JP4709014B2 - Electrophotographic photosensitive member, process cartridge, and electrophotographic apparatus - Google Patents

Description

  The present invention relates to an electrophotographic photosensitive member, and more particularly, to an electrophotographic photosensitive member containing a compound having a specific structure in a constituent layer, and a process cartridge and an electrophotographic apparatus having the electrophotographic photosensitive member.

  Conventionally, as an electrophotographic photosensitive member, an inorganic photosensitive member mainly composed of an inorganic photoconductive compound such as selenium, zinc oxide, cadmium sulfide has been widely used. In recent years, various proposals have been made regarding a laminated organic electrophotographic photoreceptor having a layer separated into two functions, which has a charge transport layer and a charge generation layer in which an organic photoconductive substance is bound with a resin or the like. (For example, Patent Documents 1 to 5).

  In particular, an electrophotographic photosensitive member having a layer structure in which a charge transport layer is provided on a charge generation layer is excellent in durability and is currently mainstream. For example, a photoconductor having a charge transfer layer containing triallyl pyrazoline (Patent Document 6), a charge generation layer made of a derivative of perylene pigment, and a charge transfer layer made of a condensate of 3-propylene and formaldehyde. A photoreceptor (Patent Document 7) and the like are disclosed. In addition, there are photoreceptors using disazo pigments or trisazo pigments as charge generating substances (for example, Patent Documents 8 and 9). Furthermore, the organic photoconductive compound can freely select the photosensitive wavelength region of the electrophotographic photosensitive member depending on the compound. For example, regarding azo organic pigments, those showing high sensitivity in the visible region (for example, Patent Documents 10 and 11) are disclosed, and those having sensitivity in the infrared region (for example, Patent Documents 12 and 13). There is also.

  Among these materials, materials having sensitivity in the red or infrared region are used in laser beam printers and LED printers that have been remarkably advanced in recent years, and the frequency of demand thereof is increasing. Conventionally, copper phthalocyanine (for example, Patent Document 14), metal-free phthalocyanine, and the like are given as materials having sensitivity in the infrared region. Furthermore, in a multilayer organic electrophotographic photoreceptor, it has been proposed to increase the sensitivity by adding an organic acceptor to the charge generation layer (Patent Document 15), but this is not sufficient. Oxytitanium phthalocyanine pigments (Patent Documents 16 and 17), gallium phthalocyanine pigments (Patent Documents 18 and 19), chlorogallium phthalocyanine pigments (Patent Documents 20 and 21) and the like have attracted attention as materials that can handle high sensitivity in recent years. . Photoconductors using these realize high quantum efficiency.

  However, the development of today's electrophotographic technology is remarkable, and a very high level is required for the characteristics required for the electrophotographic photosensitive member. For example, the process speed is increasing year by year, and charging characteristics, sensitivity, durability stability, and the like have been demanded. In particular, in recent years, there has been a demand for higher image quality, as represented by colorization, and black-and-white images that are character-centered images have become halftone images and solid images that are typified by photographs due to colorization. Their image quality is increasing year by year. In particular, acceptable standards for so-called positive ghost images and negative ghost images are becoming stricter than those for monochrome printers and monochrome copying machines. Because these ghost images use a highly sensitive charge generation material, the absolute number of carriers is large, and electrons after holes are injected into the charge transport layer tend to remain in the charge generation layer, resulting in memory. It is believed that. Therefore, ghost images are considered to be a particularly remarkable phenomenon in recent high-sensitivity charge generation materials. Note that the positive ghost phenomenon is that when a halftone latent image is generated at the next rotation in a portion irradiated with light in one image, only the above-mentioned portion irradiated with light last time has a high density. A phenomenon. Further, the negative ghost phenomenon refers to a phenomenon in which the density of only the above-mentioned portion irradiated with light last time becomes thin.

  For example, regarding these ghost images, Patent Document 22 discloses an electrophotographic photosensitive member containing an acceptor compound in a charge generation layer having oxytitanium phthalocyanine. Patent Document 22 states that by adopting this configuration, a reduction in residual potential and a reduction in ghost are achieved, but after leaving the photoconductor charged at +500 V for 5 hours to make the phenomenon noticeable. Has a ghost evaluation. This shows a ghost effect by a positively charged memory, which is different from a normal ghost. In addition, the addition of an electron transporting material, an electron acceptor or an electron withdrawing substance to the charge generation layer (for example, Patent Documents 23 to 30) has been disclosed, but ghost improvement is achieved until the above strict tolerance standards are cleared. It was not effective. Patent Document 31 discloses a method for producing a phthalocyanine pigment which is produced by adding an electron transporting material during the phthalocyanine pigmentation step. This document discloses that it is important that the electron transporting material is disposed in the vicinity of the charge generation material, thereby achieving high sensitivity. However, this is also not effective in improving the ghost so that the strict evaluation criteria as described above can be cleared.

In addition, the electrophotographic apparatus has entered the market that has conventionally been a printing area such as offset printing and screen printing, and an improvement in printing speed is required. Along with this, the process speed is increasing year by year, and a stable image quality free from ghosting is demanded at a higher level.
JP-A-57-54942 JP 60-59355 A JP-A-61-203461 JP-A 62-47054 JP-A 62-67094 US Pat. No. 3,837,851 US Pat. No. 3,871,882 JP 60-29108 A JP 56-46237 A JP 60-272754 A JP 56-167759 A JP-A-57-195767 Japanese Patent Laid-Open No. 61-228453 Japanese Patent Laid-Open No. 50-38543 JP-A-61-2157 JP-A-63-366 JP-A-1-319934 JP-A-5-249716 Japanese Patent Laid-Open No. 5-263007 JP-A-5-188615 JP-A-5-194523 JP 7-104495 A Japanese Patent Laid-Open No. 2-136860 JP-A-2-136661 Japanese Patent Laid-Open No. 2-146048 Japanese Patent Laid-Open No. 2-146049 JP-A-2-146050 JP-A-5-150498 JP-A-6-313974 JP 2000-39730 A JP 2001-040237 A

  The present invention has been made in view of the above circumstances, and provides an electrophotographic photosensitive member capable of suppressing generation of a ghost image even when repeatedly used in a high-speed process without causing memory while maintaining high sensitivity. The purpose is to do. 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, the present inventors have found that the above-described object can be achieved by including a compound having a specific structure in the layer constituting the electrophotographic photosensitive member.

That is, the present invention provides an electrophotographic photosensitive member having a layer structure including a photosensitive layer on a conductive support.
The layer structure has a polycyclic aromatic compound,
The polycyclic aromatic compound is formed by bonding two different molecular groups, and the two different molecular groups include the following molecular groups (D) and (A), or the following molecular groups ( An electrophotographic photosensitive member characterized by being D) and (C) .

In the formula , Z ²¹ , Z ²² , Z ³¹ , Z ³² , Z ⁴¹ and Z ⁴² are each independently an oxygen atom, C (CN) ₂ , N—R, C (CN) COR, C (CN) COOR. , shows the C (CN) R or C _{(COOR) 2.} R is shows the substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. At least one of ^{X 11, X 12, X 13} , X 14, X 15 and ^{X 16,} at least one of ^{X 21, X 22, X 23} , X 24, X 25 and ^{X 26, X 31, X 32} , X ^33, at least one of ^{X 34, X 35} and at least one and ^{X 41, X 42, X 43} , X 44, X 45, X 46, X 47 and ^{X 48} in ^{X 36} is an consolidated group In addition, each independently represents a hydrogen atom, a halogen atom, a nitro group, a perfluoroalkyl group, a hydroxyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. .

R and X ¹¹ , X ¹² , X ¹³ , X ¹⁴ , X ¹⁵ and X ¹⁶ , X ²¹ , X ²² , X ²³ , X ²⁴ , X ²⁵ and X ²⁶ , X ³¹ , X ³² , X ³³ , X ³⁴ , Examples of the alkyl group according to X ³⁵ and X ³⁶ and X ⁴¹ , X ⁴² , X ⁴³ , X ⁴⁴ , X ⁴⁵ , X ⁴⁶ , X ⁴⁷ and X ⁴⁸ (hereinafter also simply referred to as X) include a methyl group and an ethyl group. And a propyl group. Examples of the aryl group related to R and X include a phenyl group and a naphthyl group. Furthermore, examples of the halogen atom for X include fluorine, chlorine, bromine and iodine. In addition, examples of the alkoxy group related to X include a methoxy group, an ethoxy group, and a butoxy group.

  The polycyclic aromatic compound is preferably a compound represented by the following general formulas (1) to (3).

Where
¹ E and ² E are each independently monovalent or divalent containing at least one molecular group (B) to (D) among molecular groups selected from the group consisting of molecular groups (A) to (D). The molecular group of
ⁿ Q represents an n-valent linking group,
l represents an integer of 0 or more and 4 or less,
n represents an integer of 3 to 6,
m represents an integer of 0 or more and 6 or less.

  Furthermore, a process cartridge and an electrophotographic apparatus according to the present invention include the above-described electrophotographic photosensitive member.

  While maintaining high sensitivity, it does not cause memory and can suppress ghost images even during repeated use in high-speed processes.

  Hereinafter, the present invention will be described in more detail. First, the configuration of the electrophotographic photoreceptor of the present invention will be described.

  Examples of the conductive support used in the electrophotographic photoreceptor according to the present invention include metals or alloys such as aluminum, nickel, copper, gold, and iron. Moreover, what formed the thin films of metals, such as aluminum, silver, gold | metal | money, indium oxide, tin oxide, etc. on insulating supports, such as polyester, a polycarbonate, a polyimide, glass, is mentioned. Further, carbon and conductive fillers dispersed in a resin to impart conductivity can be used. These support surfaces may be subjected to an electrochemical treatment such as anodization in order to improve electrical characteristics or adhesion. In addition, the support surface may be subjected to chemical treatment with a solution obtained by dissolving a metal salt compound or a fluorine compound metal salt in an acidic aqueous solution mainly composed of alkali phosphate, phosphoric acid, tannic acid or the like. Good.

  In addition, when the electrophotographic photosensitive member according to the present invention is used in a printer having optical means such as a single wavelength laser beam, the surface of the conductive support may be appropriately roughened in order to suppress interference fringes. is necessary. Specifically, a support whose surface is subjected to honing, blasting, cutting, electropolishing, and the like, and a support in which a conductive film made of a conductive metal oxide and a binder resin is coated on aluminum and an aluminum alloy. Must be used.

  Examples of the honing treatment include various known treatment methods such as dry and wet. Among these, the wet honing treatment may be roughened by suspending a powdery abrasive in a liquid such as water and spraying it on the surface of the substrate at a high speed. In this case, the surface roughness can be controlled by spraying pressure, speed, amount of abrasive, type, shape, size, hardness, specific gravity, suspension temperature, and the like. In the dry honing process, the surface of the conductive substrate may be roughened by spraying an abrasive with air at a high speed, and the surface roughness can be controlled in the same manner as the wet honing process. Examples of the abrasive used in these wet or dry honing processes include particles such as silicon carbide, alumina, iron, and glass beads.

  In a conductive support in which a conductive film made of a conductive metal oxide and a binder resin is applied to a support made of aluminum or aluminum alloy, the conductive film has a powder made of conductive fine particles as a filler. . This method has the effect of dispersing the fine particles in the film to diffusely reflect the laser beam to prevent interference fringes and to conceal the scratches and protrusions on the support before coating. For the fine particles, titanium oxide, barium sulfate, or the like is used, and if necessary, a conductive coating layer may be provided on the fine particles with tin oxide or the like so as to have an appropriate specific resistance as a filler. The specific resistance of the conductive fine particle powder is preferably 0.1 Ω · cm to 1000 Ω · cm, more preferably 1 Ω · cm to 1000 Ω · cm. The content of the filler is preferably 1.0% by mass or more and 90% by mass or less, and more preferably 5.0% by mass or more and 80% by mass or less with respect to the conductive film layer. The coating layer may contain fluorine or antimony as necessary.

  As the binder resin used for the above-described conductive film, for example, phenol resin, polyurethane, polyamide, polyimide, polyamideimide, polyamic acid, polyvinyl acetal, epoxy resin, acrylic resin, melamine resin, or polyester is preferable. These resins may be used alone or in combination of two or more. These resins have good adhesion to the support, improve the dispersibility of the filler used in the present invention, and have good solvent resistance after film formation. Of the above-mentioned resins, phenol resin, polyurethane and polyamic acid are particularly preferable.

The conductive film may be formed by a solvent coating method using, for example, immersion or a Mayer bar. The thickness of the conductive film is preferably 0.1 μm or more and 30 μm or less, and more preferably 0.5 μm or more and 20 μm or less. The volume resistivity of the conductive coating, ^{10 13} [Omega] cm or less, and more preferably not more than 10 ⁵ Ω · cm or more ^{10 12 Ω} · cm. The conductive film may contain a filler made of powder such as zinc oxide or titanium oxide in addition to the powder made of barium sulfate fine particles having a coating layer. Furthermore, a leveling agent may be added to enhance the surface property.

  The electrophotographic photoreceptor according to the present invention has a photosensitive layer on a conductive support. The photosensitive layer of the present invention comprises a single layer type containing both a charge generation material and a charge transport material in the same layer, a charge generation layer containing a charge generation material, and a charge transport layer containing a charge transport material. It is roughly divided into a laminated type consisting of As a stacked type structure, there are a normal layer type in which a charge generation layer and a charge transport layer are stacked in this order on a substrate, and a reverse layer type in which a charge transport layer and a charge generation layer are stacked in this order. The electrophotographic photoreceptor according to the present invention may have the above-mentioned polycyclic aromatic compound in any of the above-mentioned layers and the following layers, in any of the above-described layer structures, From the viewpoint, it is preferred that the above-mentioned polycyclic aromatic compound is contained in the normal charge generation layer.

  Further, in the electrophotographic photoreceptor according to the present invention, an intermediate layer may be provided between the photosensitive layer and the conductive support, if necessary. It is preferable to contain a ring aromatic compound. The intermediate layer may be formed by dissolving a resin such as polyamide, polyvinyl alcohol, polyethylene oxide, ethyl cellulose, casein, polyurethane, or polyether urethane in an appropriate solvent, and applying and drying the solution on a support or a conductive layer. Good. The thickness of the intermediate layer is preferably 0.05 μm or more and 5 μm or less, and more preferably 0.3 μm or more and 1 μm or less. When the intermediate layer has the polycyclic aromatic compound, the content of the polycyclic aromatic compound is preferably 5% by mass or more and 95% by mass or less, more preferably 25% by mass or more and 80% by mass with respect to the entire intermediate layer. % Or less.

  Specific examples of the compounds represented by the general formulas (1) to (3) among the polycyclic aromatic compounds described above are shown below. In the present invention, the polycyclic aromatic compound is not limited to these.

Examples of compounds of general formula (1)

Example of compound of general formula (2)

Example of compound of general formula (3)

  In the case of the stacked type, the charge that can be transported differs depending on the charge polarity, and thus the materials that can be used are different. The forward layer type charge transport layer used for negative charge and the reverse layer type charge transport layer used for positive charge contain a hole transport material. The forward layer type used for positive charge and the reverse layer type charge transport layer used for negative charge Some contain an electron transport material.

  In the electrophotographic process using an organic electrophotographic photosensitive member, the above-described charge transport generally adopts a negative charging method, and a normal layer type is adopted from the viewpoint of durability. Is common.

  In the present invention, the reason why generation of a ghost image is suppressed by containing the above-mentioned polycyclic aromatic compound is not clear, but is considered as follows. The ghost image is considered to be due to a potential difference occurring during the next rotational exposure due to the difference in the number of carriers remaining in the exposed portion and the unexposed portion.

Charge is generated in the charge generation layer by exposure, and the separated hole and electron carriers move through the binder resin. In the case of a negatively charged laminated photoreceptor, holes are injected into the charge transport layer containing the hole transport material, but electrons are injected into the charge generation layer, the interface between the charge generation layer and the intermediate layer, and the intermediate layer. It is considered that this is likely to cause a potential difference at the time of charging during the next rotation and exposure. It is considered that a ghost image is generated by this potential difference. The above-mentioned polycyclic aromatic compound has 2 to 6 molecular groups (A) to (D) each having a functional site (including one or more molecular groups (B) to (D)). Therefore, it is considered that the above-mentioned remaining electrons are efficiently received or transported.

  Hereinafter, an electrophotographic photosensitive member having a laminated (normal layer) photosensitive layer used for negative charging will be described.

  Examples of the charge generating material used in the present invention include the following (1) to (17).

(1) Azo pigments such as monoazo, disazo and trisazo (2) Phthalocyanine pigments such as metal phthalocyanine and non-metal phthalocyanine (3) Indigo pigments such as indigo and thioindigo (4) Perylene acid anhydride and perylene imide, etc. Perylene pigments (5) Polycyclic quinone pigments such as anthraquinone and pyrenequinone (6) Squaryllium dyes (7) Pyryllium salts and thiapyrylium salts (8) Triphenylmethane dyes (9) Selenium, selenium tellurium, amorphous silicon, etc. Inorganic materials (10) Quinacridone pigments (11) Azurenium salt pigments (12) Cyanine dyes (13) Xanthene dyes (14) Quinone imine dyes (15) Styryl dyes (16) Cadmium sulfide (17) Zinc oxide, etc.

  In particular, metal phthalocyanine pigments are preferable, and oxytitanium phthalocyanine crystals, chlorogallium phthalocyanine crystals, dichlorotin phthalocyanine crystals, and hydroxygallium phthalocyanine pigments are particularly preferable. Furthermore, hydroxygallium phthalocyanine pigments are particularly preferred.

  As the oxytitanium phthalocyanine pigment, oxytitanium phthalocyanine having a strong diffraction peak at the Bragg angle (2θ ± 0.2 °) shown in the following (101) and (102) in characteristic X-ray diffraction using CuKα as a radiation source Pigments are preferred.

(101) 9.0 °, 14.2 °, 23.9 ° and 27.1 °
(102) 9.5 °, 9.7 °, 11.7 °, 15.0 °, 23.5 °, 24.1 ° and 27.3 °

  As the chlorogallium phthalocyanine crystal, chlorogallium phthalocyanine having a strong diffraction peak at the Bragg angle (2θ ± 0.2 °) shown in the following (111) to (113) in characteristic X-ray diffraction using CuKα as a radiation source Crystals are preferred.

(111) 7.4 °, 16.6 °, 25.5 ° and 28.2 °
(112) 6.8 °, 17.3 °, 23.6 ° and 26.9 °
(113) 8.7-9.2 °, 17.6 °, 24.0 °, 27.4 ° and 28.8 °

  As the dichlorotin phthalocyanine crystal, dichlorotin phthalocyanine having a strong diffraction peak at the Bragg angle (2θ ± 0.2 °) shown in the following (121) to (124) in characteristic X-ray diffraction using CuKα as a radiation source Crystals are preferred.

(121) 8.3 °, 12.2 °, 13.7 °, 15.9 °, 18.9 ° and 28.2 °
(122) 8.5 °, 11.2 °, 14.5 ° and 27.2 °
(123) 8.7 °, 9.9 °, 10.9 °, 13.1 °, 15.2 °, 16.3 °, 17.4 °, 21.9 ° and 25.5 °
(124) 9.2 °, 12.2 °, 13.4 °, 14.6 °, 17.0 ° and 25.3 °

  As the hydroxygallium phthalocyanine crystal, a hydroxygallium phthalocyanine crystal having a diffraction peak strong in the Bragg angle (2θ ± 0.2 °) shown in the following (131) in the characteristic X-ray diffraction using CuKα as a radiation source is preferable.

  (131) 7.5 °, 9.9 °, 12.5 °, 16.3 °, 18.6 °, 25.1 ° and 28.3 °

  As the binder resin contained in the charge generation layer of the electrophotographic photosensitive member according to the present invention, various compounds known in the art can be used. Examples thereof include polymers and copolymers of vinyl compounds such as styrene, vinyl acetate, vinyl chloride, acrylic acid ester, methacrylic acid ester, vinylidene fluoride, and trifluoroethylene. In addition, examples include polyvinyl alcohol, polyvinyl acetal, polycarbonate, polyester, polysulfone, polyphenylene oxide, polyurethane, cellulose resin, phenol resin, melamine resin, silicon resin, and epoxy resin. Of these, polyester, vinyl acetate, and polyvinyl acetal are preferable, and polyvinyl acetal is more preferable. The weight average molecular weight Mw is preferably 60,000 or more and 150,000 or less.

  The thickness of the charge generation layer is preferably from 0.01 μm to 2 μm, and more preferably from 0.05 μm to 0.5 μm. The ratio between the charge generation material and the binder resin in the charge generation layer is preferably from 0.5 / 1 to 4/1, and more preferably from 1/1 to 1/3.

In the present invention, the charge generation layer preferably has the above-mentioned polycyclic aromatic compound. The addition amount of the polycyclic aromatic compound is preferably 1% by mass or more and 100% by mass or less, more preferably 10% by mass or more and 50% by mass or less of the charge generation material. Polycyclic aromatic compounds, as described above, of the molecular group (A) to (D) molecular group that will be selected from the group consisting of, one selected from the group consisting of molecular group (B) to (D) The above molecular group may be included. In particular, a polycyclic aromatic compound containing two or more different molecular groups selected from the group consisting of the molecular groups (A) to (D) is more preferable than including only the same molecular group. The polycyclic aromatic compound may be contained alone or in combination. Moreover, you may contain an additive for the purpose of improving an electrical property, film formability, etc.

  In the present invention, the charge generation layer is prepared by first dispersing a pigmented charge generation material together with a binder resin and other compounds and a solvent with a homogenizer, ultrasonic dispersion, ball mill, vibration ball mill, sand mill, attritor, roll mill, and the like. May be. Thereafter, this dispersion is applied and dried. The polycyclic aromatic compound and / or the binder resin may be added after dispersion.

  The hole transport layer contains a hole transport material in a molecular dispersion state and a binder resin, and is applied with a solution in which the binder resin having a film forming property and the hole transport material are dissolved and dried. It is formed by doing.

  Examples of the hole transporting material include heterocyclic compounds such as carbazole, indole, imidazole, oxazole, thiazole, oxadiazole, pyrazole, pyrazoline, thiadiazole and triazole. Further, hydrazone compounds such as p-diethylaminobenzaldehyde-N, N-diphenylhydrazone and N, N-diphenylhydrazino-3-methylidene-9-ethylcarbazole can be mentioned. Further examples include styryl compounds such as α-phenyl-4′-N, N-diaminostilbene and 5- [4- (di-p-tolylamino) benzylidene] -5H-dibenzo [a, d] dicycloheptene. In addition, a benzidine compound, a triarylamine compound, triphenylamine, or a polymer having a group composed of these compounds in the main chain or side chain (for example, poly-N-vinylcarbazole and polyvinylanthracene) can be used. The hole transport material is not limited to these.

  Examples of the resin having a film-forming property include, but are not limited to, polyester, polycarbonate, polymethacrylic acid ester, polyarylate, polysulfone, and polystyrene. Of these, polycarbonate and polyarylate having a carbonate bond are particularly preferable.

  The ratio between the hole transport material and the binder resin is preferably 10/2 or more and 2/10 or less, and more preferably 10/6 or more and 6/10 or less.

  Furthermore, the electrophotographic photoreceptor according to the present invention may have a surface protective layer on the hole transport layer. The surface protective layer may be configured to contain conductive particles or a charge transport material in the binder resin. Moreover, you may contain additives, such as a lubricant. Further, the binder resin may have conductivity or charge transportability. In this case, it is not necessary to include conductive particles / charge transporting materials and the like in addition to the resin. The resin may be a curable resin curable by heat / light / radiation or the like, or a non-curable known thermoplastic resin.

  Examples of the method for preparing the layers constituting these electrophotographic photosensitive members include a dip coating method, a spray coating method, a curtain coating method, and a spin coating method after preparing a coating solution. Of these, the dip coating method is preferable in terms of efficiency / productivity.

(Process cartridge and electrophotographic apparatus according to the present invention)
Next, a process cartridge and an electrophotographic apparatus according to the present invention will be described.

  FIG. 1 shows an example of a schematic configuration of an electrophotographic apparatus provided with a process cartridge having the electrophotographic photosensitive member of the present invention.

  In FIG. 1, reference numeral 1 denotes a drum-shaped electrophotographic photosensitive member according to the present invention, which is rotated about a shaft 2 in the direction of an arrow at a predetermined peripheral speed. In the rotating process, the electrophotographic photoreceptor 1 is uniformly charged with a predetermined positive or negative potential on the peripheral surface thereof by the charging unit 3, and then from an exposure unit (not shown) such as slit exposure or laser beam scanning exposure. The exposure light 4 is received. In this way, electrostatic latent images are sequentially formed on the peripheral surface of the electrophotographic photosensitive member 1.

  The formed electrostatic latent image is then developed with toner by the developing means 5. The developed toner developed image is transferred to a transfer material P fed from a paper 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 images are sequentially transferred by the transfer means 6.

  The transfer material P that has received the image transfer is separated from the surface of the electrophotographic photosensitive member, introduced into the image fixing means 8, and subjected to image fixing to be printed out as a copy (copy).

  The surface of the electrophotographic photosensitive member 1 after the image transfer is cleaned by the transfer unit 7 after removal of the transfer residual toner, and is repeatedly used for image formation.

  The charging means 3 may be a scorotron charger or a corotron charger using corona discharge, or a contact type charger using a known form such as a roller shape, a blade shape, or a brush shape.

  In the present invention, the above-described electrophotographic photosensitive member 1 and a plurality of components such as the charging unit 3, the developing unit 5, and the cleaning unit 7 are integrally coupled as a process cartridge. The process cartridge may be configured to be detachable from an electrophotographic apparatus main body such as a copying machine or a laser beam printer.

  For example, at least one of the charging unit 3, the developing unit 5 and the cleaning unit 7 is integrally supported together with the electrophotographic photosensitive member 1 to form a cartridge. This can be a process cartridge that is detachable from the apparatus main body using guide means 10 such as a cartridge insertion guide / rail of the apparatus main body.

  Further, when the electrophotographic apparatus is a copying machine or a printer, the exposure light 4 may be reflected light or transmitted light from a document. The exposure light 4 may be light emitted by reading a document with a sensor, converting it into a signal, scanning with a laser beam performed according to this signal, driving an LED array, driving a liquid crystal shutter array, and the like.

  The electrophotographic photosensitive member according to the present invention can be applied to general electrophotographic apparatuses such as copying machines, laser printers, LED printers, and liquid crystal shutter printers. Further, the electrophotographic photosensitive member according to the present invention can be widely applied to apparatuses such as a display, recording, light printing, plate making and facsimile using the electrophotographic technology.

Hereinafter, the present invention will be described in more detail according to examples. In addition, "part" shows a mass part.
(Synthesis Example 1)
(Synthesis of Exemplified Compound 3-7)
10 mL of 20% aqueous sodium carbonate solution containing 5.0 g of 5-bromoacenaphthenequinone, 1.5 g of 1,4-phenylenebisboronic acid and 0.5 g of tetrakistripheniphosphine palladium was heated to reflux in 200 mL of tetrahydrofuran (THF) for 5 hours. Went. After cooling, THF was distilled off under reduced pressure, ethanol was added to the resulting residue, crystals were precipitated, and fractionated by filtration.

The obtained crude crystals were produced by silica gel column chromatography (developing solvent: toluene: THF = 10: 1) to obtain compound 3-7. In addition, it was m / z = 438.1 (M < ^- >) when the mass-spectrometric spectrum (The product made from BRUKER, measured in NEGA ion mode using REFLEXIII-TOF) of this compound 3-7 was measured.

(Synthesis Example 2)
(Synthesis of Exemplified Compound 3-8)
1.0 g of Exemplified Compound 3-7 and 0.3 g of malononitrile were heated to reflux in 100 mL of THF for 1 hour. After cooling, THF was distilled off under reduced pressure, and the resulting residue was recrystallized from ethanol to give Exemplary Compound 3-8. It was m / z = 534.1 (M < ^- >) when the mass-spectrometry spectrum (The product made from BRUKER, measured in NEGA ion mode using REFLEXIII-TOF) of this compound 3-8 was measured.

(Synthesis Example 3)
(Synthesis of Exemplified Compound 1-7)
1.0 g of 2-aminophenanthrenequinone, 1.0 g of 1,4,5,8-naphthalenetetracarboxylic anhydride and 0.6 g of 2-ethyl-6-methylaniline were added to 1,3-dimethyl-2-imidazolidinone. The mixture was heated to reflux in 50 mL for 6 hours. After cooling, the residue obtained by distilling off the solvent under reduced pressure was recrystallized with THF, and further purified by silica gel column chromatography (developing solvent: toluene: THF = 10: 1) to give Example Compound 1- 7 was obtained. It was m / z = 590.1 (M < ^- >) when the mass-spectrometry spectrum (The product made from BRUKER, measured by NEGA ion mode using REFLEXIII-TOF) of this compound 1-7 was measured.

(Synthesis Example 4)
(Synthesis of Exemplified Compound 1-9)
1.0 g of Exemplified Compound 1-7 and 0.1 g of malononitrile were heated to reflux in 100 mL of THF for 1 hour. After cooling, THF was distilled off under reduced pressure, and the resulting residue was recrystallized from ethanol to give Exemplary Compound 1-9. It was m / z = 638.2 (M < ^- >) when the mass-spectrometry spectrum (The product made from BRUKER, measured by NEGA ion mode using REFLEXIII-TOF) of this compound 1-9 was measured.

  In the present invention, other compounds can be synthesized by the same method.

( Reference Example 1)
[Creation of photoconductor]
First, a coating material for the conductive layer was prepared by the following procedure. The following components were dispersed for 2 hours in a sand mill using φ1 mm glass beads to prepare a paint.

Conductive titanium oxide powder coated with tin oxide containing 10% antimony oxide
50 parts Resol type phenol resin 25 parts (Pryofen J-325, manufactured by Dainippon Ink & Chemicals, Inc.)
Methyl cellosolve 20 parts Methanol 5 parts Silicone compound 0.002 parts (Polydimethylsiloxane polyoxyalkylene copolymer)

  This paint was applied by dip coating on an aluminum cylinder having a diameter of 30 mm and a length of 260 mm, and dried at 150 ° C. for 30 minutes to form a conductive layer having a thickness of 15 μm.

  Next, 15 parts of an alcohol-soluble polyamide resin (Amilan CM8000: manufactured by Toray) was dissolved in a liquid consisting of 200 parts of methanol and 150 parts of benzyl alcohol to prepare an intermediate layer coating material. This solution was applied onto the conductive layer by the dip coating method and dried at 100 ° C. for 10 minutes to form an intermediate layer having a thickness of 0.6 μm.

  Next, the following components were dispersed for 3 hours in a sand mill using φ1 mm glass beads.

5 parts of hydroxygallium phthalocyanine pigment (HOGaPc) (Strong peaks at 7.3 °, 24.9 ° and 28.1 ° at the Bragg angle (2θ ± 0.2 °) in the characteristic X-ray diffraction of CuKα as the charge generation material) What you have)
Polyvinyl butyral 2.5 parts (trade name S REC BX-1, manufactured by Sekisui Chemical Co., Ltd.)
Tetrahydrofuran 25 parts Cyclohexanone 10 parts

  To the obtained composition, 200 parts of tetrahydrofuran, 100 parts of cyclohexanone, and 1.5 parts of the exemplified compound 3-8 were added to prepare a charge generation layer coating material having an average particle size of 0.17 μm. The average particle size was measured by a centrifugal sedimentation method using CAPA700 manufactured by Horiba.

  This paint was applied on the above-mentioned intermediate layer by a dip coating method and dried at 100 ° C. for 10 minutes to form a charge generation layer having a thickness of 0.18 μm.

  Next, the following components were dissolved in 250 parts of monochlorobenzene and 200 parts of tetrahydrofuran.

50 parts of allylamine compound having the following structural formula (4) (as a hole transport compound)
60 parts of polyarylate resin having a structural unit represented by the following structural formula (5) (weight average molecular weight Mw = 100,000, terephthalic acid structure of phthalic acid moiety: isophthalic acid structure = 1: 1 (molar ratio))

  This solution was applied onto the charge generation layer by a dip coating method and dried at 120 ° C. for 60 minutes to form a hole transport layer having a thickness of 18 μm to obtain an electrophotographic photosensitive member.

  In addition, the above-mentioned weight average molecular weight is a value obtained by converting a value obtained by measurement under the following conditions into polystyrene.

Measuring instrument: Gel permeation chromatography “HLC-8120”
(Made by Tosoh Corporation)
Developing solvent: 0.1 mass% THF solution Column: “TSKgel SuperHM-N” manufactured by Tosoh Corporation
Detector: RI
Column temperature: 40 ° C
Injection volume: 20μL
Flow rate: 1.0 ml / min

[Evaluation]
For the evaluation, the electrophotographic photosensitive member produced as described above was introduced into LBP “Laser Jet 4600” manufactured by Hewlett-Packard Co. as an evaluation device modified as described below. Using this, a ghost image was evaluated immediately after 3000 sheets were durable printed with an image density of 4% in an environment of 15 ° C./10% RH.

Process speed: 190 mm / sec Pre-exposure: Not lit Charging condition: Variable Laser exposure: Variable

  Ghost images are created in magenta, cyan, yellow, and black, respectively. In the case of black, as shown in FIG. 2, a black square image is output at the head of the image, and then one dot is set. As shown in FIG. 3, a halftone image was created using a pattern arranged in a Keima-like pattern. The order of image creation is to take a solid white image as the first image, then take five consecutive ghost images, then take one solid black image and then take five ghost images again for a total of ten images. Evaluation was performed using a ghost image. The evaluation of the ghost image is carried out by measuring the density difference between the Keima pattern image density and the image density of the ghost part with a spectral densitometer X-Rite 504/508 (manufactured by X-Rite Co., Ltd.) at 10 points with one ghost image The average of these 10 points was taken as one result. Further, all of the above-described ten ghost images were measured in the same manner, and the average value of the density differences was obtained. This method was similarly performed for the other three colors, and evaluation was performed using an average value of these values. The measurement result of each color is displayed as a result of each color of magenta color, cyan color, yellow color and black color of the spectral densitometer X-Rite, and the value of the same color as the image color is used as the measurement value.

( Reference Example 2)
An electrophotographic photoreceptor was prepared in the same manner as in Reference Example 1 except that the amount of Example Compound 3-8 added to the charge generation layer coating material was changed to 2.5 parts, and evaluation was performed in the same manner.

(Example 3)
The electrophotographic photosensitive member is the same as in Reference Example 1 except that the compound to be added to the charge generation layer coating material is the above exemplified compound 1-9 instead of the exemplified compound 3-8, and the addition amount is 0.5 parts. Were prepared and evaluated in the same manner.

Example 4
The compound to be added to the paint for the charge generating layer, exemplified compounds instead of 3-8 and Example Compound 1-9 described above, similarly electrophotographic photosensitive member and the reference example 1 except that the amount added with 0.25 parts of Were prepared and evaluated in the same manner.

( Reference Example 5)
The electrophotographic photosensitive member was prepared in the same manner as in Reference Example 1 except that the compound to be added to the charge generation layer coating material was changed to Exemplified Compound 1-20 instead of Exemplified Compound 3-8, and the addition amount was 5 parts. The same evaluation was made.

( Reference Example 6)
The electrophotographic photosensitive member is the same as Reference Example 1 except that the compound to be added to the charge generation layer coating material is the above-mentioned Exemplified Compound 1-30 instead of Exemplified Compound 3-8, and the addition amount is 0.25 part. Were prepared and evaluated in the same manner.

( Reference Example 7)
An electrophotographic photosensitive member was produced in the same manner as in Reference Example 1 except that the compound added to the charge generation layer coating material was changed to the above exemplified compound 2-3 instead of the exemplified compound 3-8, and evaluated in the same manner. .

( Reference Example 8)
An electrophotographic photosensitive member was prepared in the same manner as in Reference Example 1 except that the compound added to the charge generation layer coating material was changed to the above exemplified compound 3-1, instead of the exemplified compound 3-8, and evaluated in the same manner. .

( Reference Example 9)
An electrophotographic photoreceptor was prepared in the same manner as in Reference Example 1 except that the compound to be added to the charge generation layer coating material was changed to Exemplified Compound 3-7 instead of Exemplified Compound 3-8, and evaluated in the same manner. .

( Reference Example 10)
The electrophotographic photosensitive member is the same as in Reference Example 1 except that the compound added to the charge generation layer coating material is the above-described exemplary compound 2-9 instead of exemplary compound 3-8, and the addition amount is 0.25 part. Were prepared and evaluated in the same manner.

( Reference Example 11)
In Reference Example 1, the following components (referred to as solid components in Table 14; the same applies hereinafter) were dissolved in a liquid composed of 200 parts of methanol and 150 parts of benzyl alcohol to prepare an intermediate layer coating material. This solution was applied onto the conductive layer described in Reference Example 1 by a dip coating method and dried at 100 ° C. for 10 minutes to form an intermediate layer having a thickness of 0.6 μm.

Compound 3-8 2 parts Alcohol-soluble polyamide resin 8 parts (Amilan CM8000: manufactured by Toray)

On this intermediate layer, the charge generation layer coating material prepared in the same manner as in the charge generation layer coating material of Reference Example 1 except that the compound 3-8 was not added, was applied by a dip coating method. And dried for 10 minutes to form a charge generation layer having a thickness of 0.18 μm. Further, a hole transport layer was formed thereon in the same manner as in Reference Example 1 and evaluated in the same manner.

( Reference Example 12)
In the same manner as in Reference Example 11 except that the following components were dissolved in a liquid consisting of 200 parts of methanol and 150 parts of benzyl alcohol instead of the intermediate layer paint of Reference Example 11 and used as the intermediate layer paint. Photoconductors were prepared and evaluated in the same manner.

Compound 3-8 5 parts Alcohol-soluble polyamide resin 5 parts (Amilan CM8000: manufactured by Toray)

( Reference Example 13)
An intermediate layer was formed in the same manner as in Reference Example 11, and a charge generation layer and a hole transport layer were formed on this intermediate layer in the same manner as in Example 1 to produce an electrophotographic photosensitive member. went.

(Example 14)
An electrophotographic photoreceptor was prepared in the same manner as in Reference Example 13 except that the compound added to the charge generation layer coating material was changed to Exemplified Compound 1-9 described above in place of Exemplified Compound 3-8, and evaluated in the same manner. .

(Example 15)
An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 14 except that the compound added to the intermediate layer coating material was changed to Exemplified Compound 1-9 instead of Exemplified Compound 3-8.

(Example 16)
An electrophotographic photosensitive member was produced in the same manner as in Reference Example 1 except that the compound added to the charge generation layer coating material was changed to Exemplified Compound 1-10, instead of Exemplified Compound 3-8, and evaluated in the same manner. .

(Example 17)
An electrophotographic photosensitive member was prepared in the same manner as in Reference Example 1 except that the compound added to the charge generation layer coating material was changed to Exemplified Compound 1-9, instead of Exemplified Compound 3-8, and evaluated in the same manner. .

( Reference Example 18)
The electrophotographic photosensitive member is the same as in Reference Example 1 except that the compound to be added to the charge generation layer coating material is the above exemplified compound 1-20 instead of the exemplified compound 3-8, and the addition amount is 0.25 part. Were prepared and evaluated in the same manner.

( Reference Example 19)
The compound to be added to the charge generation layer coating material is the above exemplified compound 1-20 instead of the exemplified compound 3-8, and the electrophotographic photosensitive member is the same as the reference example 1 except that the addition amount is 0.5 part. Were prepared and evaluated in the same manner.

( Reference Example 20)
The electrophotographic photoreceptor is the same as in Reference Example 1 except that the compound added to the charge generation layer coating material is the above-described exemplary compound 1-20 instead of exemplary compound 3-8, and the addition amount is 2.5 parts. Were prepared and evaluated in the same manner.

(Comparative Example 1)
An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Reference Example 1 except that Compound 3-8 was not used in the charge generation layer.

(Comparative Example 2)
An electrophotographic photoreceptor was prepared in the same manner as in Reference Example 1 except that the following structural formula (6) was used instead of Compound 3-8 added to the charge generation layer coating material in Reference Example 1, and evaluation was performed in the same manner. .

(Comparative Example 3)
An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Reference Example 11 except that the structural formula (6) was used in place of the compound 3-8 added to the intermediate layer coating material in Reference Example 11.

(Comparative Example 4)
In Reference Example 12, a high molecular compound (weight average molecular weight 15,400) of the following structural formula (7) was used instead of the compound 3-8 added to the intermediate layer coating material. In Reference Example 12, 1.5 parts of the structural formula (6) was added to the charge generation layer coating material. Except for these, an electrophotographic photoreceptor was prepared in the same manner as in Reference Example 12, and evaluated in the same manner.

1 shows an example of a schematic configuration of an electrophotographic apparatus including a process cartridge having the electrophotographic photosensitive member of the present invention. The schematic of the image used for evaluation of the electrophotographic photoreceptor of this invention is shown. The pattern of the halftone image used for evaluation of the electrophotographic photosensitive member of the present invention is shown.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Electrophotographic photoreceptor 2 Axis 3 Charging means 4 Exposure light 5 Developing means 6 Transfer means 7 Cleaning means 8 Fixing means 9 Process cartridge 10 Guide means P Transfer material

Claims (7)

On a conductive support, an electrophotographic photosensitive member having a layer structure including a photosensitive layer,
The layer structure has a polycyclic aromatic compound,
The polycyclic aromatic compound is formed by bonding two different molecular groups, and the two different molecular groups include the following molecular groups (D) and (A), or the following molecular groups ( An electrophotographic photosensitive member characterized by being D) and (C) .

(Wherein Z ³¹ , Z ³² , Z ⁴¹ and Z ⁴² are each independently an oxygen atom, C (CN) ₂ , N—R, C (CN) COR, C (CN) COOR, C (CN) R represents C or (COOR) _2. R represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, at least one of X ¹¹ , X ¹² , X ¹³ , X ¹⁴ , X ¹⁵ and X ¹⁶ At least one of one , X ³¹ , X ³² , X ³³ , X ³⁴ , X ³⁵ and X ³⁶ and at least one of X ⁴¹ , X ⁴² , X ⁴³ , X ⁴⁴ , X ⁴⁵ , X ⁴⁶ , X ⁴⁷ and X ⁴⁸ One is a linking group, and the others are independently a hydrogen atom, a halogen atom, a nitro group, a perfluoroalkyl group, a hydroxyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkyl group. Group or a substituted or unsubstituted aryl group.) The layer structure, the photosensitive layer and an intermediate layer provided between the conductive support and the photosensitive layer, 請 Motomeko 1 intermediate layer, you containing the polycyclic aromatic compound The electrophotographic photoreceptor described in 1. The photosensitive layer is a photosensitive layer formed by laminating a charge generation layer containing a charge generation material and a charge transport layer containing a charge transport material in order, and the charge generation layer contains the polycyclic aromatic compound. containing an electrophotographic photosensitive member according to claim 1 or 2. The electrophotographic photosensitive member according to claim 3 , wherein the content of the polycyclic aromatic compound in the charge generation layer is 10% by mass or more and 50% by mass of the charge generation material. The electrophotographic photosensitive member according to any one of claims 1 to 4, wherein the polycyclic aromatic compound is represented by the following formula (1-9) or (1-10).
An electrophotographic photosensitive member according to any one of claims 1 to 5, charging means, and at least one means selected from the group consisting of the developing means and cleaning means integrally supported, detachably attached to an electrophotographic apparatus main body Process cartridge characterized by being. The electrophotographic photosensitive member according to any one of claims 1 to 5, a charging means, an exposure means, the electrophotographic apparatus, characterized in that it comprises a developing means and a transfer means.