Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
  • G03G5/02—Charge-receiving layers
  • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
  • G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
  • G03G5/0664—Dyes
  • G03G5/0666—Dyes containing a methine or polymethine group
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
  • C07C39/02—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring monocyclic with no unsaturation outside the aromatic ring
  • C07C39/06—Alkylated phenols
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
  • G03G5/02—Charge-receiving layers
  • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
  • G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
  • G03G5/0601—Acyclic or carbocyclic compounds
  • G03G5/0612—Acyclic or carbocyclic compounds containing nitrogen
  • G03G5/0614—Amines
  • G03G5/06142—Amines arylamine
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
  • G03G5/02—Charge-receiving layers
  • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
  • G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
  • G03G5/0601—Acyclic or carbocyclic compounds
  • G03G5/0612—Acyclic or carbocyclic compounds containing nitrogen
  • G03G5/0614—Amines
  • G03G5/06142—Amines arylamine
  • G03G5/06147—Amines arylamine alkenylarylamine
  • G03G5/061473—Amines arylamine alkenylarylamine plural alkenyl groups linked directly to the same aryl group
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
  • G03G5/02—Charge-receiving layers
  • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
  • G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
  • G03G5/0601—Acyclic or carbocyclic compounds
  • G03G5/0612—Acyclic or carbocyclic compounds containing nitrogen
  • G03G5/0614—Amines
  • G03G5/06149—Amines enamine

Definitions

• Electrophotographic photoreceptor and image forming apparatus including the same
• the present invention relates to an electrophotographic photosensitive member and an image forming apparatus including the same.
• An electrophotographic image forming apparatus (hereinafter, also simply referred to as “electrophotographic apparatus") is frequently used for a copying machine, a printer, a facsimile machine, and the like.
• an image is formed through the following electrophotographic process.
• an electrophotographic photosensitive member hereinafter, also simply referred to as “photosensitive member”
• the surface of the charged photoconductor is exposed according to image information to form an electrostatic latent image.
• the formed electrostatic latent image is developed with a developer containing toner and the like, and is visualized as a toner image.
• the formed toner image is transferred from the surface of the photoconductor onto a recording medium such as paper, and the transferred toner image is fixed to form an image.
• Toner remaining on the photoreceptor surface without being transferred to the recording medium after the transfer operation is removed by a cleaning blade or the like. Thereafter, the surface charge of the photoreceptor is removed by light from the discharge lamp, so that the electrostatic latent image on the surface of the photoreceptor disappears.
• the electrophotographic photosensitive member includes a conductive support made of a conductive material, and a photosensitive layer provided on the conductive support.
• a conductive support made of a conductive material
• a photosensitive layer provided on the conductive support.
• an electrophotographic photoreceptor an inorganic photoreceptor having a photosensitive layer mainly composed of an inorganic photoconductive material such as selenium, zinc oxide or cadmium has been widely used.
• Inorganic photoreceptors have some basic properties as a photoreceptor, but have problems such as difficulty in forming a photosensitive layer, poor plasticity and high production cost.
• inorganic photoconductive materials are generally highly toxic and have significant restrictions on production and handling.
• an organic photoreceptor using an organic photoconductive material has good film forming properties of a photosensitive layer, is excellent in flexibility, and is lightweight and has an appropriate sensitization method in which transparency is also improved. It has the advantage that it can easily design a photoreceptor that shows good sensitivity over a wide wavelength range. Therefore, it has been gradually developed as a mainstay of the electrophotographic photosensitive member.
• the early organic photoconductors had drawbacks in sensitivity and durability, these drawbacks were attributed to the development of a function-separated electrophotographic photoconductor in which charge generation and charge transport functions were shared by different substances. It has been significantly improved.
• Function-separated type photoconductors are classified into a stacked type and a single-layer type.
• a charge generation layer containing a charge generation material having a charge generation function and a charge transport material having a charge transport function A photoconductive layer formed by laminating a charge transporting layer containing the compound is provided as a photosensitive layer.
• a single photoconductive layer containing a charge generating substance and a charge transporting substance is provided as a photosensitive layer.
• the function-separated type photoreceptor also has the advantage that an electrophotographic photoreceptor having arbitrary characteristics can be manufactured relatively easily, which allows a wide selection range of materials such as a charge generating substance and a charge transporting substance constituting the photosensitive layer. ing.
• Examples of the charge generating substance used in such a function-separated type photoreceptor include various types of phthalocyanine pigments, squarylium dyes, azo pigments, perylene pigments, polycyclic quinone pigments, cyanine dyes, squaric acid dyes and pyrylium salt dyes. Are being studied, and various materials with high light resistance and high charge generation ability have been proposed.
• examples of the charge transporting substance include pyrazoline compounds (for example, see Japanese Patent Publication No. 52-4188), hydrazonyi conjugates (for example, JP-A-54-150128, JP-B-55-42380 and JP-A-55-52063, triphenylamine compounds (for example, see JP-B-58-32372 and JP-A-2-190862) and stilbene compounds (for example, JP-A-54-151955) And JP-A-58-198043).
• pyrazoline compounds for example, see Japanese Patent Publication No. 52-4188
• hydrazonyi conjugates for example, JP-A-54-150128, JP-B-55-42380 and JP-A-55-52063
• triphenylamine compounds for example, see JP-B-58-32372 and JP-A-2-190862
• stilbene compounds for example, JP-A-54-151955) And JP-A-58-198043
• Charge transport materials include:
• the charge transporting material is required to have high charge transporting ability among the above requirements.
• the charge transport material is required to have high charge transport capability in order to ensure sufficient photoresponsiveness. .
• a part of the surface layer of the photoconductor When the photoconductor is used by being mounted on an electrophotographic apparatus such as a copying machine or a laser beam printer, a part of the surface layer of the photoconductor must be scraped off by a contact member such as a cleaning blade or a charging roller. Is done. If the surface layer of the photoreceptor is scraped off, the charge retention ability of the photoreceptor is reduced, and it becomes impossible to provide a high quality image. Therefore, in order to increase the durability of a copying machine, a laser beam printer, or the like, a surface layer that is strong against the above-mentioned contact member, that is, a small amount of abraded by the above-mentioned contact member, is a surface layer with high printing durability. A highly durable photoreceptor having the following is required.
• This decrease in photoresponsiveness is due to the low charge transport ability of the charge transport material.
• the charge generated by the charge-generating substance due to light absorption is transported to the photoreceptor surface by the charge transporting material, thereby erasing the surface charge of the photoreceptor in the irradiated area. . Therefore, when the content of the charge transport material in the charge transport layer relatively decreases with an increase in the content of the binder resin, if the charge transport capability of the charge transport material is low, the charge transport capability of the charge transport layer is reduced. Is further reduced, and the light responsiveness is descend. Therefore, in order to prevent this decrease in photoresponsiveness and secure sufficient photoresponsiveness, the charge transporting material is required to have a high charge transport ability.
• electrophotographic devices such as digital copiers and printers have been reduced in size and increased in speed, and as photoconductor characteristics, higher sensitivity has been required to cope with the higher speed of electrophotographic devices.
• Materials are required to have ever higher charge transport capabilities.
• the time from exposure to development is short, so a photoreceptor with high photoresponsiveness is required. Since the photoresponsiveness of the photoreceptor depends on the charge transporting ability of the charge transporting substance as described above, a charge transporting substance having a higher charge transporting ability is required from such a viewpoint.
• the photoconductor is exposed to active gases such as ozone and NOx generated during charging by corona discharge, ultraviolet rays and heat included in light used for exposure and static elimination.
• active gases such as ozone and NOx generated during charging by corona discharge, ultraviolet rays and heat included in light used for exposure and static elimination.
• the photoreceptor is exposed to the above-described active gas, ultraviolet rays, heat, and the like, free radicals are generated in the photosensitive layer, and the material constituting the photosensitive layer is decomposed or deteriorated. Therefore, the charge transport material is required to be stable against light, heat, and active gases such as ozone and NOx as described above.
• An antioxidant or a light stabilizer is combined with a specific charge transporting material as in the photoreceptors described in JP-A-64-44946, JP-A-11-271995 and JP-A-2001-51434. Also, when used with good initial sensitivity, the deterioration due to repeated use is not sufficiently improved, and those with little deterioration due to repeated use have a problem that the initial sensitivity and chargeability are insufficient.
• an antioxidant or a light stabilizer is used in combination with the above-mentioned JP-A-2-51162, JP-A-6-43674 or JP-A-10-69107, which is used in combination with a high charge-mobility enamine conjugate.
• JP-A-7-134430 has high charge transport ability by containing polysilane
• the photoreceptor using polysilane is a light stabilizer which is weak to light exposure. Even if is added to the photosensitive layer, there is a problem that various characteristics as a photoreceptor are deteriorated due to exposure to light during maintenance or the like. Disclosure of the invention
• An object of the present invention is to provide high sensitivity, excellent photoresponse, and that their characteristics do not deteriorate even when used in a low-temperature environment or a high-speed electronic photography process or when exposed to light. And a highly reliable electrophotographic photoreceptor that is stable to active gases such as ozone and NOx, ultraviolet rays and heat, and that causes little fatigue deterioration when used repeatedly, and an image forming apparatus including the same It is to provide.
• the present invention provides a conductive support comprising a conductive material, And a photosensitive layer provided on the conductive support and containing at least one of an antioxidant and a light stabilizer, which is represented by the following general formula (1):
• Ar 1 and Ar 2 each represent an aryl group which may have a substituent or a heterocyclic group which may have a substituent.
• Ar 3 is an aryl group which may have a substituent group, yo Le also have a substituent, a heterocyclic group, yo Le may have a substituent, an alkyl group but it may also have a Ararukiru group or substituent.
• Ar 4 and Ar 5 A hydrogen atom, an aryl group which may have a substituent, a heterocyclic group which may have a substituent, an aralkyl group which may have a substituent, or an alkyl group which may have a substituent However, Ar 4 and Ar 5 are not both hydrogen atoms.
• Ar 4 and Ar 5 may be bonded to each other via an atom or an atomic group to form a ring structure.
• m represents an integer of 16. When m is 2 or more, a plurality of a may be the same or different.
• R 1 represents a hydrogen atom, a halogen atom or an alkyl group which may have a substituent
• R 2 , R 3 and R 4 represent Each may have a hydrogen atom, an alkyl group which may have a substituent, an alkyl group which may have a substituent, an aryl group, an aryl group which may have a substituent, a heterocyclic group or a substituent
• n represents an integer of 0 to 3.
• n is 2 or 3
• a plurality of R 2 may be the same or different
• a plurality of R 3 may be the same or different, provided that n When is 0, Ar 3 represents a heterocyclic group which may have a substituent.
• the electrophotographic photosensitive member has a conductive support and a photosensitive layer, and the photosensitive layer And an enamine compound represented by the general formula (1), and at least one of an antioxidant and a light stabilizer.
• the photosensitive layer is a photosensitive layer composed of a single photoconductive layer containing a charge generating substance and a charge transporting substance, and contains a charge generating layer containing a charge generating substance and a charge transporting substance. Any of a photosensitive layer composed of a photoconductive layer formed by laminating a charge transport layer and a photosensitive layer obtained by further laminating a surface protective layer on these photoconductive layers may be used.
• the enamel compound represented by the general formula (1) Since the enamine conjugate represented by the general formula (1) has a high charge mobility, the enamel compound represented by the general formula (1) is included in the photosensitive layer as a charge transporting substance, so that the chargeability is improved.
• An electrophotographic photoreceptor having high sensitivity, high photoresponsiveness, and which does not decrease in the above-described characteristics even when used in a low-temperature environment or in a high-speed electrophotographic process can be obtained. Further, since the high charge transporting ability can be realized without including the polysilane in the photosensitive layer, the above-mentioned characteristics do not deteriorate even when the electrophotographic photosensitive member is exposed to light.
• the photosensitive layer contains at least one of an antioxidant and a light stabilizer, it is possible to reduce fatigue deterioration upon repeated use and improve the durability of the electrophotographic photosensitive member. it can. This is because the antioxidant and light stabilizer contained in the photosensitive layer
• active gases such as ozone and NO generated during charging by corona discharge
• the photosensitive layer contains at least one of an antioxidant and a light stabilizer
• the coating solution contains the antioxidant and the light stabilizer. Since at least one of them is contained, the stability of the coating solution can be improved. Therefore, regardless of whether the photosensitive layer is formed immediately after the preparation of the coating solution or when the photosensitive layer is formed after a long period of time, the electrophotographic photosensitive member having substantially the same level of characteristics and characteristics can be obtained. Therefore, the quality stability and productivity of the electrophotographic photoreceptor can be improved.
• the electrophotographic photoreceptor of the present invention contains the enamine compound having a high charge mobility represented by the general formula (1) in the photosensitive layer as a charge transporting substance. Even if a light stabilizer is contained in the photosensitive layer, the sensitivity and the light responsiveness do not decrease.
• the photosensitive layer a combination of the enamine compound represented by the general formula (1) and at least one of an antioxidant and a light stabilizer, the chargeability, Even when used in low-temperature environments with high sensitivity and photoresponsiveness, or in high-speed electrophotographic processes, or when exposed to light, the above-mentioned characteristics do not degrade, and active gases such as ozone and NOx Therefore, it is possible to obtain a highly reliable electrophotographic photoreceptor that is stable to ultraviolet light, heat, and the like, and has little fatigue deterioration when used repeatedly.
• the present invention is characterized in that the enamine compound represented by the general formula (1) is an enamine disulfide compound represented by the following general formula (2).
• b, c and d each represent an alkyl group which may have a substituent, an alkoxy group which may have a substituent, a dialkylamino group which may have a substituent
• i represents a aryl group, a halogen atom or a hydrogen atom
• i, k and j each represent an integer of 115.
• a plurality of b may be the same or different.
• k is 2 or more, a plurality of cs may be the same or different, and may be bonded to each other to form a ring structure.
• a plurality of d may be the same or different and may be bonded to each other to form a ring structure
• Ar 4 , Ar 5 , a and m are as defined in the above general formula (1) It is synonymous with what was done.
• the photosensitive layer contains, among the enamine conjugates represented by the general formula (1), an enamine compound represented by the general formula (2) having a particularly high level and charge mobility. Therefore, it is possible to obtain an electrophotographic photosensitive member having higher sensitivity and photoresponsiveness.
• the enamine compound represented by the general formula (2) is relatively easy to synthesize and has a high yield. Can be. Therefore, the electrophotographic light-sensitive material of the present invention having excellent characteristics as described above can be manufactured at low cost and at low manufacturing cost.
• the present invention is characterized in that the enamine compound represented by the general formula (1) is an enamine compound represented by the following general formula (1a).
• Ar 1 and Ar 2 each represent a phenyl group.
• Ar 3 represents a tolyl group, a p-methoxyphenyl group, a naphthyl group, or a 5-methyl-2-phenyl group.
• Ar 4 A hydrogen atom, a lower alkyl group or a phenyl group,
• Ar 5 represents a phenyl group or a p-methoxyphenyl group, and n represents an integer of 112.
• the compound of the general formula (la) can easily be synthesized by force with a high charge mobility and its yield is high, so that it can be produced at low cost. Therefore, the electrophotographic photoreceptor of the present invention containing these compounds has high sensitivity, excellent responsiveness, and excellent cost.
• the present invention is characterized in that the antioxidant is a hindered phenol compound having a hindered phenol structural unit.
• the invention is characterized in that the hindered phenol compound is a compound represented by the following structural formula (Ia).
• the photosensitive layer contains, as an antioxidant, a hindered phenol compound having a hindered phenol structural unit, preferably a hindered phenol compound represented by the structural formula (I-a). .
• a hindered phenol compound particularly a hindered phenolic conjugate represented by the structural formula (I-a)
• the compound represented by the general formula (1) contained in the photosensitive layer as a charge transport material is contained.
• the decomposition and deterioration of the enameled conjugate shown can be particularly suppressed to further reduce the fatigue deterioration when used repeatedly and to further improve the durability of the electrophotographic photoconductor.
• the stability of the coating solution when the photosensitive layer is formed by coating can be further enhanced, and the quality stability and productivity of the electrophotographic photosensitive member can be further improved.
• the present invention is characterized in that the antioxidant is a phosphorus-based antioxidant.
• the photosensitive layer contains a phosphorus-based antioxidant.
• the phosphorous antioxidant was repeatedly used while suppressing decomposition and deterioration of the enamined product represented by the general formula (1) contained in the photosensitive layer as a charge transporting substance.
• the fatigue deterioration at the time can be further reduced, and the durability of the electrophotographic photosensitive member can be further improved.
• the stability of the coating solution when forming the photosensitive layer by coating can be further enhanced, and the quality stability and productivity of the electronic photoconductor can be further improved.
• the present invention is characterized in that the antioxidant is an organic antioxidant.
• the photosensitive layer contains an organic antioxidant.
• an organic iodine-based antioxidant in the photosensitive layer, the enamine compound represented by the above general formula (1) contained in the photosensitive layer as a charge transporting substance can be used repeatedly while particularly suppressing decomposition and deterioration.
• the ability to further reduce the fatigue deterioration of the photoreceptor and further improve the durability of the electrophotographic photoreceptor can be achieved.
• the stability of the coating solution when the photosensitive layer is formed by coating can be further enhanced, and the quality stability and productivity of the electrophotographic photosensitive member can be further improved.
• the present invention is characterized in that the light stabilizer is a hindered amine compound having a hinderdamine structural unit.
• the invention is characterized in that the hinderdamine compound is a compound represented by the following structural formula (II-a).
• the photosensitive layer contains a hinderdamine compound having a hinderdamine structural unit, preferably a hindered amine conjugate represented by the structural formula (II-a), as a light stabilizer.
• a hinderdamine compound particularly a hinderedamine compound represented by the above structural formula (II-a)
• an enamine disulfide compound represented by the above general formula (1) contained in the photosensitive layer as a charge transporting substance is contained.
• the stability of the coating solution when the photosensitive layer is formed by coating can be further enhanced, and the quality stability and productivity of the electrophotographic photosensitive member can be further improved.
• the present invention is characterized in that the light stabilizer is a benzotriazole derivative.
• the photosensitive layer contains a benzotriazole derivative as a light stabilizer.
• a benzotriazole derivative in the photosensitive layer, the degradation and degradation of the enamine compound represented by the general formula (1) contained in the photosensitive layer as a charge transporting substance is particularly suppressed, and the fatigue deterioration when the compound is repeatedly used.
• the durability of the electrophotographic photoreceptor can be further improved.
• the stability of the coating solution when forming the photosensitive layer by coating can be further enhanced, and the quality stability and productivity of the electrophotographic photosensitive member can be further improved.
• the photosensitive layer preferably contains 0.1 to 15% by weight of the antioxidant.
• the content of the antioxidant contained in the photosensitive layer is selected in a suitable range, sufficient effects for improving the durability of the electrophotographic photoreceptor and the stability of the coating solution can be obtained. In addition to this, it is possible to minimize the deterioration of the characteristics of the electrophotographic photosensitive member due to the inclusion of an antioxidant.
• the invention is characterized in that the photosensitive layer contains the light stabilizer in an amount of 0.1 to 10% by weight.
• the content of the light stabilizer contained in the photosensitive layer is selected in a suitable range, sufficient effects for improving the durability of the electrophotographic photoreceptor and the stability of the coating solution can be obtained. In addition to this, it is possible to minimize the deterioration of the characteristics of the electrophotographic photosensitive member due to the inclusion of the light stabilizer.
• the present invention also provides the electrophotographic photoreceptor of the present invention,
• a developing unit for developing an electrostatic latent image formed by exposure for developing an electrostatic latent image formed by exposure.
• an image forming apparatus includes the electrophotographic photoreceptor of the present invention, a charging unit, an exposing unit, and a developing unit.
• the electrophotographic photoreceptor of the present invention has the above-described characteristics degraded even when used in a low-temperature environment where chargeability, sensitivity and photoresponsiveness are high or in a high-speed electrophotographic process. It is stable to active gases such as ozone and NOx, ultraviolet rays and heat, and has high reliability with little fatigue deterioration when used repeatedly. Therefore, it is possible to obtain a highly reliable image forming apparatus capable of stably providing high-quality images over a long period under various environments.
• the above-described electrophotographic photoreceptor of the present invention does not deteriorate in the above-described characteristics even when exposed to light, so that the electrophotographic photoreceptor is exposed to light during maintenance or the like. It is possible to prevent the image quality from deteriorating and improve the reliability of the image forming apparatus.
• FIG. 1A is a perspective view showing a simplified configuration of an electrophotographic photosensitive member 1 according to a first embodiment of the present invention.
• FIG. 1B is a partial cross-sectional view showing a simplified configuration of the electrophotographic photoreceptor 1.
• FIG. 2 is a schematic cross-sectional view showing a simplified configuration of an electrophotographic photosensitive member 2 according to a second embodiment of the present invention.
• FIG. 3 is a schematic cross-sectional view showing a simplified configuration of an electrophotographic photosensitive member 3 according to a third embodiment of the present invention.
• FIG. 4 is a side view showing the configuration of the image forming apparatus 100 in a simplified manner.
• FIG. 5 is a diagram showing a 1 H-NMR spectrum of a product of Production Examples 1-3.
• FIG. 6 is an enlarged view of 6 ppm and 9 ppm of the spectrum shown in FIG.
• FIG. 7 is a view showing a 13 C-NMR spectrum of the product of Production Examples 1-3 by ordinary measurement.
• FIG. 8 is an enlarged view of lOppm-160ppm of the spectrum shown in FIG.
• FIG. 9 is a diagram showing a 13 C-NMR spectrum of the product of Production Examples 1-3 measured by DEPT135.
• FIG. 10 is an enlarged view of lOppm-160 ppm of the spectrum shown in FIG.
• FIG. 11 is a chart showing a 1 H-NMR spectrum of the product of Production Example 2.
• FIG. 12 is an enlarged view showing 6 to 9 ppm of the spectrum shown in FIG.
• FIG. 13 is a diagram showing a 13 C-NMR spectrum of the product of Production Example 2 by normal measurement.
• FIG. 14 is an enlarged diagram showing 11 O ppm to 160 ppm of the spectrum shown in FIG.
• FIG. 15 shows a 13 C-NMR spectrum of the product of Production Example 2 measured by DEPT135.
• FIG. 16F is an enlarged view of FIG. 15 showing 11 Oppm to 160 ppm of the starch paste shown in FIG. BEST MODE FOR CARRYING OUT THE INVENTION
• FIG. 1A is a perspective view showing a simplified configuration of an electrophotographic photosensitive member 1 according to a first embodiment of the present invention.
• FIG. 1B is a partial cross-sectional view showing a simplified configuration of the electrophotographic photoreceptor 1.
• the electrophotographic photoreceptor 1 (hereinafter, also simply referred to as “photoreceptor”) includes a cylindrical conductive support 11 made of a conductive material and a photosensitive layer 14 provided on the outer peripheral surface of the conductive support 11. It is comprised including.
• the photosensitive layer 14 includes a charge generating layer 15 containing a charge generating substance 12 that generates charges by absorbing light, and a charge transporting substance 13 capable of receiving charges generated by the charge generating substance 12 and transporting the same.
• a charge transport layer 16 containing a photoconductive layer which is laminated on the outer peripheral surface of the conductive support 11 in this order. That is, the electrophotographic photoreceptor 1 is a laminated photoreceptor.
• the photosensitive layer 14 contains at least one of an antioxidant and a light stabilizer.
• the antioxidant and the light stabilizer may be contained in the charge generating layer 15 and the charge transporting layer 16 constituting the photosensitive layer 14, and may be contained in the charge generating layer 15 and the charge transporting layer 16. It may be contained.
• At least the charge transport layer 16 preferably contains an antioxidant and a light stabilizer.
• an enamine compound represented by the following general formula (1) is used as the charge transport material 13 contained in the charge transport layer 16.
• Ar 2 each represent an aryl group which may have a substituent or a heterocyclic group which may have a substituent.
• Ar 3 is an aryl group which may have a substituent, a heterocyclic group which may have a substituent, an aralkyl group which may have a substituent or an alkyl group which may have a substituent Is shown.
• Ar 4 and Ar 5 are each a hydrogen atom, It represents an aryl group which may have a substituent, a heterocyclic group which may have a substituent, an aralkyl group which may have a substituent or an alkyl group which may have a substituent. However, both Ar 4 and Ar 5 cannot be hydrogen atoms.
• Ar 4 and Ar 5 may be bonded to each other via an atom or an atomic group to form a ring structure.
• a represents an alkyl group optionally having a substituent, an alkoxy group optionally having a substituent, a dialkylamino group optionally having a substituent, an aryl group optionally having a substituent, halogen Represents an atom or a hydrogen atom, and m represents an integer of 1 to 6. When m is 2 or more, a plurality of a may be the same or different and may be bonded to each other to form a ring structure.
• R 1 represents a hydrogen atom, a halogen atom or an alkyl group which may have a substituent.
• R 2 , R 3 and R 4 each represent a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, a heterocyclic group which may have a substituent, Represents an aralkyl group which may have a substituent.
• n represents an integer of 0 to 3. When n is 2 or 3, a plurality of R 2 may be the same or different, and a plurality of R 3 may be the same or different. However, when n is 0, Ar 3 represents a heterocyclic group which may have a substituent.
• aryl group represented by Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 , a, R 2 , R 3 or R 4 include, for example, phenyl, naphthyl, pyrenyl And the ability to raise anthril and so on.
• Substituents which these aryl groups may have include, for example, alkyl groups such as methyl, ethyl, propyl and trifluoromethyl, alkenyl groups such as 2-propenyl and styryl, methoxy, ethoxy and propoxy.
• Alkoxy groups amino groups such as methylamino and dimethylamino, halogen groups such as fluoro, chloro and bromo, aryl groups such as phenyl and naphthyl, aryloxy groups such as phenoxy, and arylthio groups such as thiophenoxy.
• aryl groups having a substituent include, for example, tolyl, methoxyphenyl, biphenyl, terphenyl, phenoxyphenyl, p- (phenylthio) phenyl, p-styrylphenyl and the like. Can be.
• heterocyclic group represented by Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 , R 2 , R 3 or R 4 include, for example, furyl, chenyl, thiazolyl, benzofuryl Benzothiophenyl, benzothiazolyl and benzoxazolyl.
• substituent which these heterocyclic groups may have include aryl groups such as Ar 1 described above.
• specific examples of the heterocyclic group having a substituent include N-methylindolyl and N-ethylcarbazolyl. Can be.
• specific examples of the aralkyl group represented by Ar 3 , Ar 4 , Ar 5 , R 2 , R 3 or R 4 include, for example, benzinole and 1_naphthylmethyl.
• substituent which the aralkyl group may have include the same substituents as the above-mentioned aryl group such as Ar 1 which the aryl group may have.
• Specific examples of the aralkyl group having a substituent Examples include p-methoxybenzyl and the like.
• the alkyl group represented by Ar 3 , Ar 4 , Ar 5 , a, R 1 , R 2 , R 3 or R 4 preferably has 1 to 16 carbon atoms
• Examples thereof include linear alkyl groups such as methyl, ethyl, n-propyl, isopropyl and t_butyl, and cycloalkyl groups such as cyclohexyl and cyclopentyl.
• substituent which these alkyl groups can have include the same substituents as those which the aryl group represented by Ar 1 and the like described above can have, and have a substituent.
• alkyl group examples include, for example, halogenated alkyl groups such as trifluoromethyl and fluoromethyl, alkoxyalkyl groups such as 1-methoxyethyl, and alkyl groups substituted with a heterocyclic group such as 2-phenylmethyl. I can do it.
• the alkoxy group represented by a is preferably an alkoxy group having 114 carbon atoms. Specific examples thereof include methoxy, ethoxy, n-propoxy and isopropoxy. Examples of the substituent which these alkoxy groups can have include the same substituents as the above-mentioned substituents such as Ar 1 which the aryl group can have.
• the dialkylamino group represented by a is preferably a group substituted by an alkyl group having 114 carbon atoms. Specific examples thereof include, for example, dimethinoleamino, acetylamino and diisopropylamino. Can be mentioned. Examples of the substituent which these dialkylamino groups may have include aryl groups such as Ar 1 described above. And the same substituents as those which can be used.
• halogen atom represented by a or R 1 include, for example, a fluorine atom and a chlorine atom.
• specific examples of the atom bonding Ar 4 and Ar 5 include an oxygen atom, a sulfur atom, and a nitrogen atom.
• the nitrogen atom can bond Ar 4 and Ar 5 as a divalent group such as an imino group or an N-alkylimino group.
• Specific examples of the atomic group that binds Ar 4 and Ar 5 include, for example, an alkylene group such as methylene, ethylene and methylmethylene, an alkenedylene group such as vinylene and propenylene, and oxymethylene (diagonal formula: 10 Alkylene containing a hetero atom such as —CH—)
• the enamine compound represented by the general formula (1) Since the enamine compound represented by the general formula (1) has high charge mobility, the enamine compound represented by the general formula (1) is contained in the photosensitive layer 14 as the charge transport material 13 by adding: Electrophotographic photoreceptor that does not degrade the above characteristics even when used in low-temperature environments or high-speed electrophotographic processes with high chargeability, sensitivity and photoresponsiveness
• the photosensitive layer 14 contains at least one of an antioxidant and a light stabilizer as described above, fatigue deterioration when repeatedly used is reduced, and the electrophotographic photosensitive member 1 Durability can be improved. This is because the antioxidant and light stabilizer contained in the photosensitive layer 14 are activated by corona discharge, such as ozone and NO.
• the photosensitive layer 14 contains at least one of an antioxidant and a light stabilizer
• the coating liquid contains the antioxidant and the light stabilizer. Contains at least one of As a result, the stability of the coating solution can be improved.
• the electrophotographic photosensitive member having substantially the same characteristics is obtained. Since the body 1 can be manufactured, the quality stability and the productivity of the electrophotographic photosensitive member 1 can be improved.
• the electrophotographic photoreceptor 1 of the present embodiment has the general Since the photosensitive layer 14 contains the enamine compound having high charge mobility represented by the formula (1) as the charge transporting substance 13, even if the photosensitive layer 14 contains an antioxidant or a light stabilizer, sensitivity and photoresponsiveness can be improved. Does not drop.
• the chargeability is improved by combining the enamine compound represented by the general formula (1) with at least one of the antioxidant and the light stabilizer in the photosensitive layer 14. Even when used in a low-temperature environment with high sensitivity and photoresponsiveness, or in a high-speed electrophotographic process, or when exposed to light, the above-mentioned characteristics do not deteriorate, and ozone and N ⁇ x It is possible to obtain a highly reliable electrophotographic photoreceptor 1 that is stable against active gases, ultraviolet rays, heat, and the like, and has little fatigue deterioration when used repeatedly.
• an enamine conjugate represented by the following general formula (2) is preferably used.
• b, c and d each represent an optionally substituted alkyl group.
• I, k and j which represent an aryl group, an optionally substituted alkoxy group, an optionally substituted dialkylamino group, an optionally substituted aryl group, a halogen atom or a hydrogen atom.
• i 2 or more
• a plurality of b's may be the same or different and may combine with each other to form a ring structure.
• k is 2 or more
• a plurality of c's may be the same or different and may combine with each other to form a ring structure.
• a plurality of ds may be the same or different and may be bonded to each other to form a ring structure.
• Ar 4 , Ar 5 , a and m have the same meaning as defined in the above general formula (1).
• the alkyl group represented by b, c or d is preferably a group having 16 carbon atoms, and specific examples thereof include linear groups such as methyl, ethyl, n-propyl and isopropyl. Examples include an alkyl group, and a cycloalkyl group such as cyclohexyl and cyclopentyl.
• Examples of the substituent which the alkyl group may have include the same substituents as the substituents which the aryl group represented by Ar 1 and the like described above may have, and specific examples of the alkyl group having a substituent Examples thereof include halogenated alkyl groups such as trifluoromethyl and fluoromethyl, alkoxyalkyl groups such as 1-methoxyl, and alkyl groups substituted with a heterocyclic group such as 2-phenylmethyl.
• the alkoxy group represented by b, c or d is preferably one having 14 to 14 carbon atoms, and specific examples include methoxy, ethoxy, n-propoxy and isopropoxy. Can be.
• substituent which these alkoxy groups can have include the same substituents as the substituents which the aryl group represented by Ar 1 and the like described above can have.
• the dialkylamino group represented by b, c or d is preferably a group substituted by an alkyl group having 14 to 14 carbon atoms. Specific examples thereof include dimethylamino, getylamino and diisopropylamino. And amino. Examples of the substituent which the dialkylamino group can have include the same substituents as the substituents which the aryl group represented by Ar 1 or the like can have.
• aryl group represented by b, c or d include, for example, phenyl and naphthyl. These aryl groups have Examples of the substituent that can be substituted include the same substituents as the substituents that the aryl group represented by Ar 1 or the like can have, and specific examples of the aryl group having a substituent include, for example, tolyl. And methoxyphenyl.
• halogen atom represented by b, c or d include, for example, a fluorine atom and a chlorine atom.
• the enamine compound represented by the general formula (2) Since the enamine compound represented by the general formula (2) has a particularly high charge mobility among the enamine compounds represented by the general formula (1), the enamine compound represented by the general formula (2) is charged. By using the transport material 13, an electrophotographic photoreceptor with higher sensitivity and photoresponsiveness can be obtained.
• the enamine compound represented by the general formula (2) is relatively easy to synthesize and has a high yield, so that it can be produced at low cost. That can be S. Therefore, the electrophotographic photoreceptor 1 of the present embodiment having the excellent characteristics as described above can be manufactured at a low manufacturing cost.
• enamine compounds represented by the general formula (1) compounds which are particularly excellent from the viewpoints of properties, cost, productivity, and the like include those in which Ar 1 and Ar 2 are both phenyl groups, and Ar 3 is phenyl. Group, tolyl group, p-methoxyphenyl group, biphenylyl group, naphthyl group or phenyl group, and at least one of Ar 4 and Ar 5 is a phenyl group, a p-tolyl group, a ⁇ -methoxyphenyl group.
• R 1 , R 2 , R 3 and R 4 are all hydrogen atoms and ⁇ is 1.
• a more preferred conjugate is an enamine compound represented by the following general formula (la).
• Ar 1 and Ar 2 each represent a phenyl group.
• Ar 3 represents a tolyl group, a p-methoxyphenyl group, a naphthyl group, or a 5-methyl-2-phenyl group.
• Ar 4 A hydrogen atom, a lower alkyl group or a phenyl group,
• Ar 5 represents a phenyl group or a p-methoxyphenyl group, and n represents an integer of 112.
• the compound of the general formula (la) has a high charge mobility, is easily available as a raw material, can be easily synthesized, has a high yield, and can be produced at low cost. Therefore, by using these compounds, the electrophotographic photoreceptor of the present invention having high sensitivity and excellent responsiveness can be manufactured at low cost.
• enamine compound represented by the general formula (1) examples include, for example, exemplified compounds No. 1 to No. 220 shown in Table 1 and Table 32 below.
• the enameled dangling products shown by are not limited to these.
• each exemplified compound is represented by a group corresponding to each group of the general formula (1).
• Exemplified Compound No. 1 shown in Table 1 is an enamine compound represented by the following structural formula (111).
• the enamine compound represented by the general formula (1) can be produced, for example, as follows. Can be.
• This dehydration condensation reaction is performed, for example, as follows.
• An aldehyde compound or a ketone conjugate represented by the general formula (3) and a secondary amine compound represented by the general formula (4) in an approximately equimolar amount with the aldehyde compound or the ketone conjugate are mixed with an aromatic solvent, alcohol or Dissolve in a solvent such as ether to prepare a solution.
• a solvent such as ether
• Specific examples of the solvent used include, for example, toluene, xylene, benzene, butanol, and diethylene glycol dimethyl ether.
• Lifting power S can.
• a catalyst for example, an acid catalyst such as p-toluenesulfonic acid, camphorsulfonic acid or pyridinium_p_toluenesulfonic acid is added to the prepared solution, and reacted under heating.
• the addition amount of the catalyst is preferably 1/10 (1Z10) / 1000 ( ⁇ ⁇ ⁇ ⁇ ) molar equivalent to the aldehyde compound or ketone compound represented by the general formula (3), more preferably. Is 1/25 (1/25)-1/500 (1Z500) molar equivalents, optimally 1/50 (1/50) 1/200 (1Z200) molar equivalents.
• water is formed as a by-product and hinders the reaction. Thereby, the enamine intermediate represented by the general formula (5) can be produced in high yield.
• the enamine intermediate represented by the general formula (5) is subjected to a formyl ridge by a Vilsmeier reaction or an acyl ridge by a Friedel-Kraft reaction, whereby the intermediate represented by the following general formula (6) is obtained.
• R 5 represents R 4 when n is 0 and R 2 when n is 1, 2 or 3 in the general formula (1).
• Ar 1 , Ar 2 , Ar 3 , R 1 , R 2 , R 4 , a, m and n have the same meanings as defined in the general formula (1).
• the Vilsmeier reaction is performed, for example, as follows.
• a solvent such as N, N-dimethylformamide (N, N_Dimethylformamide; abbreviation: DMF) or 1,2-dichloroethane
• Add phosphorus oxychloride and N, N-dimethylformamide, phosphorus oxychloride and N-methyl-N_phenylenolenomoleamide, or phosphorus oxychloride and N, N-diphenylformamide to prepare Vilsmeier reagent .
• the prepared Vilsmeier reagent 1.0 equivalent-1.3 equivalents, 1.0 equivalent of the enamine intermediate represented by the general formula (5) was added, and heated under 60-110 ° C. to obtain 2-8 Stir for hours.
• an enamine monocarbonyl intermediate in which R 5 is a hydrogen atom can be produced in high yield.
• the Friedel-Crafts reaction is performed, for example, as follows.
• a solvent such as 1,2-dichloroethane and the like
• a reagent prepared by using aluminum chloride and an acid chloride in an amount of 1.0 equivalent to 1.3 equivalents, and 1.0 equivalent of the enamine intermediate represented by the general formula (5).
• heating is performed.
• hydrolysis is carried out with an aqueous alkali solution such as an aqueous 18N sodium hydroxide solution or potassium hydroxide solution.
• an enamine-keto intermediate in which R 5 is a group other than a hydrogen atom can be produced in high yield.
• R ° represents an alkyl group which may have a substituent or an aryl which may have a substituent. Represents a group.
• Ar 4 and Ar 5 have the same meaning as defined in the general formula (1).
• R 6 represents an alkyl group which may have a substituent or an aryl group which may have a substituent.
• N represents an integer of 13; Ar 4 , Ar 5 , and R 2 , R 3 and R 4 have the same meaning as defined in formula (1).
• This Wittig-Horner reaction is performed, for example, as follows.
• a solvent such as toluene, xylene, methyl ether, tetrahydrofuran (abbreviation: THF), ethylene glycol dimethyl ether, N, N-dimethylformamide, or dimethyl sulfoxide
• the enamine-monocarbonyl intermediate represented by the general formula (6) is used.
• 1.0 equivalent and the Wittig reagent represented by the general formula (7-1) or (7-2) 1.0-1.20 equivalents and potassium t-butoxide, sodium ethoxide or sodium methoxide, etc.
• 1.0 to 1.5 equivalents of the metal alkoxide salt are added, and the mixture is stirred at room temperature or under heating at 30 ° C. for 28 hours. Thereby, the enamine compound represented by the general formula (1) can be produced in high yield.
• enamine compound represented by the general formula (1) for example, one selected from the group consisting of the exemplified compounds shown in Table 1 and Table 32 described above is used alone or in combination of two or more.
• the enamine compound represented by the general formula (1) may be used by being mixed with another charge transport substance.
• Other charge-transporting substances that are used by being mixed with the enamine conjugate represented by the general formula (1) include phorbazole derivatives, oxazole derivatives, oxadiazole derivatives, thiazole derivatives, thiadiazole derivatives, triazole derivatives, and imidazole derivatives.
• Imidazolone derivatives imidazolidine derivatives, bisimidazolidin derivatives, styryl compounds, hydrazone compounds, polycyclic aromatic compounds, indole derivatives, pyrazoline derivatives, oxazolone derivatives, benzimidazole derivatives, quinazoline derivatives And benzofuran derivatives, ataridine derivatives, phenazine derivatives, aminostilbene derivatives, triarylamine derivatives, triarylmethane derivatives, phenylenediamine derivatives, stilbene derivatives, and benzidine derivatives.
• polymers having a group derived from these compounds in the main chain or side chain such as poly_N_bulbulene rubazole, poly_1-bulpyrene and poly_9-bulanthracene are also included.
• the entire amount of the charge transporting substance 13 is the enamine compound represented by the general formula (1).
• an antioxidant generally used by adding it to a resin or the like can be used as it is, for example, a hindered phenol compound, a phosphorus-based antioxidant, or an organic oxidized agent.
• An inhibitor, a hydroquinone derivative, a paraphenylene diamine derivative or a tocopherol conjugate is used.
• antioxidants hindered phenol compounds, phosphorus-based antioxidants and organic thio-based antioxidants are preferably used.
• the degradation and degradation of the enamine compound represented by the general formula (1) contained in the photosensitive layer 14 as the charge transporting substance 13 can be particularly suppressed to reduce fatigue deterioration when the enamine compound is used repeatedly.
• the durability of the electrophotographic photosensitive member 1 can be further improved.
• the stability of the coating solution when forming the photosensitive layer 14 by coating can be further enhanced, and the quality stability and productivity of the electrophotographic photoreceptor 1 can be further improved.
• the hindered phenol compound is a compound having a hindered phenol structural unit
• the hindered phenol structural unit is a bulky atomic group near a phenolic hydroxyl group (-OH).
• Is a structural unit derived from a phenolic compound having Examples of the bulky atomic group include a branched alkyl group, an alicyclic hydrocarbon group, an aryl group, and a heterocyclic group.
• the hindered phenol structural unit is preferably represented by the following general formula (I).
• R 11 represents a branched alkyl group, a linear alkyl group having 8 or more carbon atoms, an unsaturated aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aryl group, a heterocyclic group.
• R 12 , R 13 and R 14 each represent a hydrogen atom, a halogen atom or a monovalent organic residue, and at least two of R 12 , R 13 and R 14 are bonded to each other to form a ring structure. May be.
• R 15 represents a hydrogen atom or a monovalent organic residue.
• the branched alkyl group represented by R 11 is preferably a group having 3 to 18 carbon atoms, and specific examples thereof include t-butyl, t-pentyl and t-octyl such as t-octyl.
• Alkyl groups and s-alkyl groups such as s-butyl, s-octyl and s-octadecyl can be mentioned.
• Preferred examples of the unsaturated aliphatic hydrocarbon group represented by R 11 include those having 2 to 12 carbon atoms, such as 2_propenyl, 1,3-butagenyl, 2_pentenyl, and 1,4 Alkenyl groups such as 1-hexenyl, alkynyl groups such as ethynyl and 2-hexyl, and carbon-carbon double and triple bonds such as 2-pentene-141-inyl and 1-heptene-15-inyl And the like.
• Preferred examples of the alicyclic hydrocarbon group represented by R 11 include those having 5 to 8 carbon atoms, such as cycloalkyl such as cyclopentyl, cyclohexyl, cycloheptyl and 1-methylcyclohexyl.
• cycloalkyl such as cyclopentyl, cyclohexyl, cycloheptyl and 1-methylcyclohexyl.
• cycloalkenyl groups such as 2-cyclopentene-1-yl and 1-cyclohexenyl
• cycloalkynyl groups such as 2-cyclohexyn-1-yl
• carbon-carbon such as 2-cyclodecene-5-in-1-yl
• aryl group represented by R 11 include, for example, phenyl, naphthyl, anthryl and biphenylyl.
• heterocyclic group represented by R 11 may for example thienyl, furyl, benzofuryl, and the like base Nzochiofeniru and downy Nzochiazoriru.
• polysubstituted silyl group represented by R 11 include, for example, trisubstituted silyl groups such as trimethylsilyl and triisopropylsilyl, and disubstituted silyl groups such as dimethylsilyl and diphenylsilyl.
• a monovalent group containing a cyclic group represented by R 11 as cyclic group preferably contains an alicyclic hydrocarbon group, ⁇ Li Lumpur group or a heterocyclic group described above.
• Specific examples of the monovalent group containing a cyclic group represented by R 11 include, for example, aralkyl groups such as benzyl, phenethyl, 1_naphthylmethyl and 1-methylbenzyl, phenylphosphino, diphenylphosphino and ethylphenyl.
• Phosphino groups substituted with aryl groups such as phosphino, cycloalkylalkyl groups such as cyclohexylmethyl and 1-cyclohexyl-1-methylethyl, aryloxy groups such as phenoxy, arylaryl groups such as thiophenoxy, and furfuryl, piperidinomethyl and Examples thereof include an alkyl group substituted with a heterocyclic group such as chenylmethyl.
• univalent embodiment containing alkyl group having 4 or more carbon atoms indicated by R 11 is, heptyl carbonyl ⁇ amino Contact and N- methyl O-lipped ylcarbonyl ⁇ amino alkylcarbonyl ⁇ amino group such as the example, Okuchi Ruchiomechiru, Deshiruchioechiru And alkylthioalkyl groups such as pentylthioethyl, and alkoxyalkyl groups such as heptyloxymethyl, 2-dodecyloxethyl and hexyloxethyl.
• examples of the halogen atom represented by R 12 , R 13 or R 14 include a fluorine atom and a chlorine atom.
• Examples of the monovalent organic residue represented by R 12 , R 13 or R ′′ include alkyl groups such as methyl, ethyl, t-butyl, t_pentyl, hexyl and octyl, phenyl, naphthinole And aryl groups such as anthryl and biphenyl, aralkyl groups such as benzyl, phenethyl, 1-naphthylmethyl and 1-methylbenzyl, pyridyl, phenyl, phenyl, benzoyl, benzothioyl, benzothiazolyl and N-indolyl.
• amino groups such as getylamino, dimethylamino and diisopropylamino.
• a hydroxyl group, an alkoxy group, a carboxylic acid group, an acyl group, an ester group, an amide group, a siloxane group and a silyl group can also be mentioned.
• the alkyl group represented by R 12 , R 13 or R 14 preferably has 1 to 40 carbon atoms.
• the monovalent organic residue represented by R 12 , R 13 or R 14 may have a substituent, and examples of the substituent include an ester group, a carboxylic acid group, a phosphoric acid group and a thioether group. That can be S.
• examples of the monovalent organic residue represented by R 15 include an alkyl group such as methyl, ethyl, propyl, hexyl and octyl; an aryl group such as phenyl, naphthyl and anthryl; Examples include an aralkyl group such as benzyl, phenethyl and 1-naphthylmethyl, a heterocyclic group such as pyridinole, phenyl, furyl, benzofuryl and benzothiophenyl, and an acyl group such as atariloyl and acetyl.
• Alkyl group represented by R 15 are the rather preferable than it is preferred instrument a carbon number of 1 one 40 1 one 18 carbon atoms.
• the hindered phenol compound may have two or more hindered phenol structural units represented by the general formula (I) or the like.
• the plurality of hindered phenol structural units may be the same or different.
• the hindered phenol compound contains a plurality of hindered phenol structural units as described above, the plurality of hindered phenol structural units may be directly bonded or may be bonded via an atom or an atomic group.
• Specific examples of the atoms bonding a plurality of hindered phenol structural units include an oxygen atom, a sulfur atom, and a carbon atom.
• the atomic groups linking a plurality of hindered phenol structural units include polyvalent groups such as divalent and trivalent groups derived from saturated aliphatic hydrocarbons, unsaturated aliphatic hydrocarbons, aromatic hydrocarbons or heterocyclic compounds. Can be mentioned. Arising from saturated aliphatic hydrocarbons Specific examples of the polyvalent group include a divalent group such as an alkylene group such as methylene, ethylene and propylene and an alkylidene group such as ethylidene, propylidene and butylidene; And a trivalent group such as an alkanthryl group such as 1,3,6-hexanetolyl.
• polyvalent groups generated from unsaturated aliphatic hydrocarbons include alkenylene groups such as vinylene and propenylene, alkadierenylene groups such as 1,3-butenylene, 1,4-hexenenylene, and 3_pentynylene. And divalent groups such as anolequinylene groups such as 1,2-hexylene and trivalent groups such as alkenylidene groups such as 2_pentyl-15-ylidene.
• polyvalent groups derived from aromatic hydrocarbons include arylene groups such as phenylene, naphthylene, biphenylurylene and 2,7-phenanthrylene, trivalent groups such as 1,3,5_benzenetolyl, and the like.
• Tetravalent groups such as 1,4,5,8_anthracenetetrayl and the like can be mentioned.
• Specific examples of the polyvalent group generated from the heterocyclic compound include divalent groups such as 3,5_pyridinediyl and 2,6-quinolinediyl, 1,3,5-triazine-2,4,6_tolyl and 1,3 Trivalent groups such as 1,5, -triazine-1,2,4,6-triene-1,3,5, triinole and tetravalent groups such as Pico 1,4,5,8-ataridintetrayl Can be mentioned.
• hindered phenol compound examples include, for example, the exemplified compounds HP-1 -—- 80 shown in Tables 33 to 39 below, but the hindered phenol compounds are not limited to these. Absent.
• t_Bu represents a t-butyl group (_C (CH) C)
• t-C H represents a t-pentyl group (_C (CH) C H)
• C H represents a t-octyl group (—C (CH 2) C H).
• the exemplified compound HP-1 shown in Table 33 that is, the hindered phenol compound shown by the following structural formula (I-a) is preferably used.
• phosphorus antioxidant known compounds can be used. Specific examples include, for example, exemplified compounds P-11 and P-47 shown in Tables 40 to 44 below. The phosphorus-based antioxidants are not limited to these.
• the exemplified compound P-39 shown in Table 43 is commercially available, for example, as JPH-3800 (trade name, manufactured by Johoku Chemical Co., Ltd.).
• organic antioxidant known ones can be used. Specific examples include, for example, exemplified compounds S-1-S-14 shown in Tables 45 and 46 below. The organic antioxidant is not limited to these.
• a light stabilizer that is generally used by being added to a resin or the like can be used as it is, for example, a hindered amine compound, a benzotriazole derivative, a benzophenone derivative, or a tertiary amine compound is used. .
• hinderdamine compounds such as hinderdamine compounds, benzotriazole derivatives or benzophenone derivatives are preferably used.
• the degradation and degradation of the enamine compound represented by the general formula (1) contained in the photosensitive layer 14 as the charge transporting substance 13 can be particularly suppressed to reduce the fatigue deterioration when used repeatedly. Further, the durability of the electrophotographic photosensitive member 1 can be further improved.
• the photosensitive layer such as hinderdamine compounds, benzotriazole derivatives or benzophenone derivatives are preferably used.
• a hinderdamine compound is a compound having a hinderdamine structural unit
• a hinderdamine structural unit is a structural unit derived from an amine compound having a bulky atomic group near an amino nitrogen atom. It is.
• the bulky atomic group include a branched alkyl group, an alicyclic hydrocarbon group, an aryl group, and a heterocyclic group.
• the hinderdamine structural unit may be either an aromatic amine or an aliphatic amine, but is preferably an aliphatic amine.
• the hinderdamine structural unit is preferably represented by the following general formula (II).
• R lb , R 1 , R and R 19 each represent a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group or an aralkyl group.
• R 2 ° represents a hydrogen atom or a monovalent organic residue.
• W represents a group required to form a ring structure containing an amino nitrogen atom.
• R 16 , R 17 , R 18 and R 19 are never hydrogen atoms.
• the alkyl group represented by R 16 , R 17 , R 18 or R 19 is preferably an alkyl group having 118 carbon atoms.
• the alkyl group represented by R 16 , R 17 , R 18 or R 19 may have a substituent. Examples of the substituent include an aryl group, an alkoxy group, a carboxylic acid group, an amide group, a halogen group and a thioether group. And the like.
• aryl group represented by R 16 , R 17 , R 18 or R 19 include phenyl, naphthyl, anthryl and P-tolyl.
• heterocyclic group represented by R 16 , R 17 , R 18 or R 19 include, for example, phenyl, furyl, benzofuryl and benzothiofurnyl.
• aralkyl group represented by R 16 , R 17 , R 18 or R 19 include, for example, benzyl, phenethyl, 1-naphthylmethyl and 1-methylbenzyl.
• Examples of the monovalent organic residue represented by R 2 ° include methyl, ethyl, t-pentyl, and hexyl.
• Alkyl groups such as octyl and octyl; acyl groups such as acetyl, propionyl and butyryl; aryl groups such as phenyl and naphthyl; aralkyl groups such as benzyl, phenethyl and 1-naphthylmethyl; Heterocyclic groups such as benzothiophenidyl and the like can be mentioned.
• the alkyl group represented by R 2 ° preferably has 118 carbon atoms.
• the ring structure including an amino nitrogen atom formed by W is preferably a 5- or 6-membered ring.
• Specific examples thereof include piperidine, piperazine, and morpholine. , Pyrrolidine, imidazolidin, oxazolidin, thiazolidine, selenazolidin, pyrroline, imidazoline, isoindoline, tetrahydroisoquinoline, tetrahydropyridine, dihydropyridine, dihydroisoquinoline, oxazoline, thiazoline, selenazoline and pyrrole. Of these, piperidine, piperazine and pyrrolidine rings are particularly preferred.
• W has one bond chain, but may have two or more bond chains without being limited thereto.
• the ring containing an amino nitrogen atom formed by W may have a substituent such as an alkyl group such as methyl, ethyl and octyl, an aryl group such as phenyl and naphthyl, and a benzyl group.
• aralkyl groups such as phenethyl, heterocyclic groups such as pyridyl, phenyl, phenyl, furyl, benzofuryl and benzothiophenidyl; and amino groups such as methinoleamino, dimethylamino and diphenylamino.
• an ester group, a hydroxy group, a silyl group and the like can also be mentioned.
• the hinderdamine compound may have two or more hinderdamine structural units represented by the general formula (II) and the like. In this case, the plurality of hinderdamine structural units may be the same or different.
• the hindered amine conjugate contains a plurality of hinderdamine structural units as described above, the plurality of hindered amine structural units may be directly bonded to each other via an atom or an atomic group.
• Specific examples of the atoms bonding a plurality of hinderdamine structural units include an oxygen atom, a sulfur atom, and a carbon atom.
• Specific examples of the atomic group linking a plurality of hinderdamine structural units include a multivalent group such as a divalent group and a trivalent group generated from a saturated aliphatic hydrocarbon, an unsaturated aliphatic hydrocarbon, an aromatic hydrocarbon, or a heterocyclic compound. Valent groups can be mentioned.
• polyvalent groups generated from saturated aliphatic hydrocarbons include alkylene groups such as methylene, ethylene and propylene, and divalent groups such as alkylidene groups such as ethylidene, propylidene and butylidene, and 1-propanyl-3_ylidene. And trivalent groups such as alkanthryl groups such as 1,3,6-hexanetolyl.
• polyvalent groups generated from unsaturated aliphatic hydrocarbons include alkenedylene groups such as vinylene and propenylene; anorecadienedylene groups such as 1,3-butagenylene and 1,4-hexagenylene; and 3_ Examples thereof include divalent groups such as an anolequinylene group such as pentynylene and 2-hexylene, and trivalent groups such as an alkenylidene group such as 2-pentenyl 5-ylidene.
• polyvalent groups generated from aromatic hydrocarbons include arylene groups such as phenylene, naphthylene, biphenylylene and 2,7-phenanthrylene, and trivalent groups such as 1,3,5-benzentyryl.
• tetravalent groups such as 1,4,5,8-anthracenetetrayl.
• Specific examples of the polyvalent group generated from the heterocyclic compound include divalent groups such as 3,5-pyridinyl and 2,6-quinolindyl, and 1,3,5-triazine-2,4,6_tolyl. It can include trivalent groups and tetravalent groups such as 1,4,5,8-ataridintetrayl.
• the hindered amine conjugate may have the aforementioned hindered phenol structural unit in addition to the hindered amine structural unit.
• hinderdamine compound examples include, for example, the exemplified compounds HA-11 and HA-15 shown in Tables 47 to 49 below, but the hinderdamine compounds are not limited thereto.
• the exemplified compound HA-12 shown in Table 49 is commercially available, for example, as TINUVIN622 (trade name, manufactured by Ciba Geigy Japan KK).
• Exemplary compound HA-14 is, for example, it is commercially available as CHIMASSORB944 (trade name, manufactured by Nippon Ciba Geigy Co., Ltd.).
• the exemplified compound HA-15 is commercially available, for example, as CHIMASSORB119 (trade name, manufactured by Nippon Ciba Geigy Co., Ltd.).
• the exemplified compound HA_3 shown in Table 47 that is, the hindered amine conjugate shown by the following structural formula (II-a) is preferably used.
• benzotriazole derivative examples include, for example, exemplified compounds TZ-1-TZ-28 shown in Tables 50 to 52 below, but the benzotriazole derivative is not limited thereto.
• the antioxidants and light stabilizers shown in Table 33 and Table 55 above can be synthesized by various methods and can be obtained as commercial products.
• antioxidant and the light stabilizer for example, one kind selected from the group consisting of the exemplified compounds shown in Tables 33 to 55 described above is used alone, or two or more kinds are used in combination.
• the antioxidant is preferably contained in the photosensitive layer 14 in a range of 0.1% by weight to 15% by weight, more preferably in a range of 0.1% by weight to 5% by weight.
• the light stabilizer is preferably contained in the photosensitive layer 14 in a range of 0.1% by weight to 10% by weight, more preferably in a range of 0.1% by weight to 5% by weight. .
• the total content of the antioxidant and the light stabilizer in the photosensitive layer 14 is 0.1% by weight or more and 20% by weight or less. It is more preferably below 0.1% by weight or more and 10% by weight or less.
• the durability of the electrophotographic photosensitive member 1 is improved.
• a sufficient effect for improving the stability of the coating solution can be obtained.
• deterioration of the characteristics of the electrophotographic photoreceptor 1 caused by including an antioxidant and a light stabilizer can be minimized.
• the content of the antioxidant, the content of the light stabilizer, or the total content of the antioxidant and the light stabilizer in the photosensitive layer 14 is less than 0.1% by weight, the durability of the photoconductor 1 is reduced. And a sufficient effect cannot be obtained for improving the stability of the coating solution.
• the antioxidant content in the light-sensitive layer 14 exceeds 15% by weight, the light stabilizer content exceeds 10% by weight, or the total content of the antioxidant and the light stabilizer is 20% by weight. If it exceeds, the properties of the photoreceptor are adversely affected. Therefore, the above range is set.
• the charge transport layer 16 is formed in such a manner that a charge transport material 13 containing an enamine compound represented by the general formula (1) is bound to a binder resin 17.
• a resin having excellent compatibility with the charge transport material 13 is selected.
• Specific examples of the resin used for the binder resin 17 include, for example, two or more of a vinyl polymer resin such as a polymethyl methacrylate resin, a polystyrene resin, a polyvinyl chloride resin, and a repeating unit constituting the same.
• Copolymer resins including the above, as well as polycarbonate resins, polyester resins, polyester carbonate resins, polysulfone resins, phenoxy resins, epoxy resins, silicone resins, polyarylate resins, polyamide resins, polyether resins, polyurethane resins, and polyacrylamide resins And phenolic resin. Further, a thermosetting resin obtained by partially cross-linking these resins may also be used. One of these resins may be used alone, or two or more thereof may be used as a mixture.
• polystyrene resin, polycarbonate resin, polyarylate resin or polyphenylene oxide has a volume resistivity of 10 13 ⁇ 'cm or more, has excellent electrical insulation properties, and has good film properties and potential. It is particularly preferable to use these as the binder resin 17 because of their excellent properties.
• the weight A of the charge transport material 13 in the charge transport layer 16 and the weight B of the binder resin 17 The ratio A / B is preferably 10/12 (10/12)-10/30 (10/30). When a conventionally known charge transport material is used, if the ratio A / B is set to 10/12 or less and the ratio of the binder resin 17 is increased, the photoresponsiveness may be reduced. It is about. However, in the electrophotographic photoreceptor 1 of the present embodiment, as described above, the enamine compound having a high charge mobility represented by the general formula (1) is used for the charge transport material 13 as described above.
• the ratio A / B which does not lower the photoresponsiveness, is set to 10 / 12-10 / 30, and the content of the binder resin 17 in the charge transport layer 16 is increased to improve the printing durability of the charge transport layer 16.
• the durability of the electrophotographic photoreceptor 1 can be improved.
• the ratio A / B is set to 10 / 12-10 / 30.
• additives such as a plasticizer or a leveling agent may be added to the charge transport layer 16 in order to improve film formability, flexibility and surface smoothness.
• plasticizer include dibasic acid esters such as phthalic acid esters, fatty acid esters, ester phosphates, chlorinated paraffins, and epoxy-type plasticizers.
• leveling agent include a silicone leveling agent.
• fine particles of an inorganic compound or an organic compound may be added to the charge transport layer 16 in order to enhance mechanical strength and improve electrical characteristics.
• the charge transport layer 16 is formed by, for example, dissolving or dispersing a charge transport material 13 containing an enamine compound represented by the general formula (1) and a binder resin 17 in a suitable solvent. It is formed by preparing a coating solution for the transport layer and applying the obtained coating solution on the outer peripheral surface of the charge generation layer 15.
• the charge transport layer 16 contains an antioxidant or a light stabilizer
• the above-described antioxidant or light stabilizer is dissolved in a suitable solvent together with the charge transport material 13 and the binder resin 17 to transfer the charge.
• a coating solution for a layer is prepared. If necessary, the above-mentioned additives such as a plasticizer, a leveling agent, or fine particles are added to the coating solution for the charge transport layer.
• Examples of the solvent for the coating solution for the charge transport layer include aromatic hydrocarbons such as benzene, toluene, xylene and monochlorobenzene, halogenated hydrocarbons such as dichloromethane and dichloroethane, and ethers such as tetrahydrofuran (THF), dioxane and dimethoxymethyl ether. And aprotic polar solvents such as N, N-dimethylformamide.
• aromatic hydrocarbons such as benzene, toluene, xylene and monochlorobenzene
• halogenated hydrocarbons such as dichloromethane and dichloroethane
• ethers such as tetrahydrofuran (THF), dioxane and dimethoxymethyl ether.
• aprotic polar solvents such as N, N-dimethylformamide.
• One of these compounds lj may be used alone, or two or more thereof may be used as a mixture
• Examples of the method for applying the charge transport layer coating solution include a spray method, a bar coating method, a roll coating method, a blade method, a ring method, and a dip coating method. From these coating methods, an optimum method can be selected in consideration of the physical properties and productivity of the coating.
• the dip coating method forms a layer on the surface of a substrate by immersing the substrate in a coating tank filled with a coating solution and then pulling the substrate at a constant speed or a gradually changing speed. This method is relatively simple, is excellent in terms of productivity and cost, and is widely used in the production of electrophotographic photoreceptors, and is also widely used in forming the charge transport layer 16. ing.
• Film thickness of the charge transport layer 16 is preferably from preferably not more 50 zm less than 5 M m device is 10 xm than 40 zm less. If the thickness of the charge transport layer 16 is less than 5 ⁇ m, the charge retention ability on the surface of the photoconductor is reduced. When the thickness of the charge transport layer 16 exceeds, the resolution of the photoconductor 1 is reduced. Therefore, it was set to 5 m or more and 50 zm or less.
• the charge generation layer 15 contains the charge generation substance 12 as a main component.
• Substances effective as the charge generating substance 12 include monoazo pigments, bisazo pigments, and trisazo pigments. Azo pigments, indigo pigments such as indigo and thioindigo, perylene pigments such as perylene imide and perylene anhydride, polycyclic quinone pigments such as anthraquinone and pyrenequinone, and phthalocyanine pigments such as metal phthalocyanine and metal-free phthalocyanine Pigments, squarylium dyes, pyrylium salts and thiopyrylium salts, triphenylmethane dyes, and inorganic materials such as selenium and amorphous silicon can be mentioned.
• One of these charge generating substances may be used alone, or two or more thereof may be used in combination.
• oxotitanium phthalocyanine is a charge generating substance having high charge generation efficiency and high charge injection efficiency, it generates a large amount of charge by absorbing light and accumulates the generated charge inside. And efficiently inject it into the charge transport material 13. Further, as described above, since the enamine compound having a high charge mobility represented by the general formula (1) is used as the charge transporting substance 13, the oxotitanium phthalocyanine which is the charge generating substance 12 by light absorption is used.
• the generated charges are efficiently injected into the enamine compound represented by the general formula (1), which is the charge transporting substance 13, and are smoothly transported to the surface of the photosensitive layer 14. Therefore, by using oxotitanium phthalocyanine as the charge generating substance 12, a high-sensitivity and high-resolution electrophotographic photoreceptor 1 can be obtained.
• the charge generating substance 12 includes methyl violet, crystal violet, night blue, and Victoria.
• Triphenylmethane dyes such as blue, erythrocyte synth, rhodamine 8, rhodamine 3R, ataridin dyes such as ataridine orange and flaveosin, thiazine dyes such as methylene blue and methylene green, It may be used in combination with a sensitizing dye such as an oxazine dye, a cyanine dye, a styryl dye, a pyrylium salt dye or a thiopyrylium salt dye represented by Liblue and Meldable.
• a sensitizing dye such as an oxazine dye, a cyanine dye, a styryl dye, a pyrylium salt dye or a thiopyrylium salt dye represented by Liblue and Meldable.
• a method for forming the charge generation layer 15 a method in which the charge generation substance 12 is vacuum-deposited on the outer peripheral surface of the conductive support 11, or a charge generation layer obtained by dispersing the charge generation substance 12 in an appropriate solvent
• a method of applying a coating liquid for use on the outer peripheral surface of the conductive support 11. Let's do it.
• a charge generation material 12 is dispersed by a conventionally known method in a binder resin solution obtained by mixing a binder resin as a binder in a solvent to prepare a coating solution for a charge generation layer.
• a method of applying the applied coating solution on the outer peripheral surface of the conductive support 11 is preferably used. Hereinafter, this method will be described.
• binder resin used for the charge generation layer 15 examples include a polyester resin, a polystyrene resin, a polyurethane resin, a phenol resin, an alkyd resin, a melamine resin, an epoxy resin, a silicone resin, an acrylic resin, a methacryl resin, a polycarbonate resin, and a polystyrene resin.
• resins such as arylate resins, phenoxy resins, polybutyral resins, and polybutylformal resins, and copolymer resins containing two or more of the repeating units constituting these resins.
• the copolymer resin examples include insulating resins such as a vinyl chloride-vinyl acetate copolymer resin, a vinyl chloride-vinyl acetate-maleic anhydride copolymer resin, and an acrylonitrile-styrene copolymer resin. be able to.
• the binder resin is not limited to these, and a commonly used resin can be used as the binder resin. One of these resins may be used alone, or two or more thereof may be used as a mixture.
• Solvents for the coating solution for the charge generation layer include, for example, halogenated hydrocarbons such as dichloromethane or dichloroethane, ketones such as acetone, methyl ethyl ketone or cyclohexanone, esters such as ethyl acetate or butyl acetate, and tetrahydrofuran (THF ) Or dioxane; alkyl ethers of ethylene glycol such as 1,2-dimethoxyethane; aromatic hydrocarbons such as benzene, toluene or xylene; or N, N-dimethylformamide or N, N —Aprotic polar solvents such as dimethylacetamide are used. Also, a mixed solvent in which two or more of these solvents are mixed can be used.
• halogenated hydrocarbons such as dichloromethane or dichloroethane
• ketones such as acetone, methyl ethyl ketone or cyclohe
• the compounding ratio of the charge generating material 12 to the binder resin is preferably such that the ratio of the charge generating material 12 is in the range of 10% by weight to 99% by weight. If the proportion of the charge generating substance 12 is less than 10% by weight, the sensitivity is reduced. When the ratio of the charge generating substance 12 exceeds 99% by weight, not only the film strength of the charge generating layer 15 is reduced but also the dispersibility of the charge generating substance 12 is reduced, so that coarse particles increase and are erased by exposure. Surface charge in parts other than power Therefore, the number of image defects, particularly the fogging of an image called black spots, in which toner adheres to a white background and minute black spots are formed, increases. Therefore, it was set to 10% by weight-99% by weight.
• the charge generating substance 12 may be pulverized by a pulverizer in advance.
• a pulverizer used for the pulverization treatment include a ball mill, a sand mill, an attritor, a vibration mill, and an ultrasonic disperser.
• Examples of the dispersing machine used for dispersing the charge generating substance 12 in the binder resin solution include a paint mill, a ball mill and a sand mill. Appropriate conditions for the dispersion are selected so that impurities are not mixed due to abrasion of the container used and members constituting the disperser.
• the antioxidant or the light stabilizer is dissolved together with the charge generation material 12 in a suitable solvent or a binder resin solution. To prepare a charge generation layer coating solution.
• Examples of the method of applying the charge generation layer coating solution include a spray method, a bar coating method, a roll coating method, a blade method, a ring method, and a dip coating method.
• the dip coating method is particularly excellent in various points as described above, and is therefore often used for forming the charge generation layer 15.
• the apparatus used for the dip coating method may be provided with a coating liquid dispersing apparatus represented by an ultrasonic generator in order to stabilize the dispersibility of the coating liquid.
• the film thickness of the charge generation layer 15 is preferably 0.05 ⁇ or more and 5 ⁇ or less, more preferably 0.1 ⁇ or more and 1 ⁇ or less. If the thickness of the charge generation layer 15 is less than 0.05 ⁇ , the efficiency of light absorption is reduced and the sensitivity is reduced. When the thickness of the charge generation layer 15 exceeds 5 zm, the charge transfer inside the charge generation layer becomes a rate-determining step in the process of erasing the charge on the photoreceptor surface, and the sensitivity decreases. Therefore, it was set to 0.05 ⁇ m or more and 5 ⁇ m or less.
• the photoconductive layer constituting the photosensitive layer 14 has a laminated structure of the charge generation layer 15 and the charge transport layer 16 formed as described above.
• the charge generation function and the charge transport function are assigned to different layers, so that it is possible to select the most suitable material for the charge generation function and the charge transport function for the material constituting each layer. , It is possible to obtain the electrophotographic photoreceptor 1 having higher sensitivity and high durability with increased stability during repeated use.
• a metal such as aluminum, copper, zinc or titanium, or a metal material such as an aluminum alloy or an alloy such as stainless steel can be used.
• metallic materials such as polyethylene terephthalate, polymeric materials such as nylon or polystyrene, hard paper or glass, laminated metal foil, metal material deposited, or conductive material
• a material obtained by depositing or coating a layer of a conductive compound such as a polymer, tin oxide, or indium oxide can also be used.
• These conductive materials are used after being processed into a predetermined shape.
• the shape of the conductive support 11 is cylindrical in the present embodiment, but may be cylindrical, sheet, endless belt, or the like, which is not limited thereto.
• the surface of the conductive support 11 may be subjected to an anodic oxide film treatment, a surface treatment with a chemical or hot water, a coloring treatment, or a roughening of the surface, if necessary, within a range that does not affect the image quality. Irregular reflection processing may be performed.
• the wavelength of the laser light is uniform, so that the incident laser light and the light reflected within the photoreceptor cause interference, and interference fringes due to this interference appear on the image. Image defects may occur.
• the photosensitive layer 14 is constituted by the photoconductive layer formed by stacking the charge generation layer 15, the charge transport layer 16, and the force on the outer peripheral surface of the conductive support 11 in this order.
• the present invention is not limited to this, and the charge transport layer 16 and the charge generation layer 15 may be formed of a photoconductive layer laminated on the outer peripheral surface of the conductive support 11 in this order.
• FIG. 2 is a schematic cross-sectional view showing a simplified configuration of an electrophotographic photosensitive member 2 according to a second embodiment of the present invention.
• the electrophotographic photoreceptor 2 of the present embodiment is similar to the electrophotographic photoreceptor 1 of the first embodiment, and the corresponding portions are denoted by the same reference numerals and description thereof will be omitted.
• an intermediate layer 18 is provided between the conductive support 11 and the photosensitive layer 14. If there is no intermediate layer 18 between the conductive support 11 and the photosensitive layer 14, charges are injected from the conductive support 11 into the photosensitive layer 14, and the chargeability of the photosensitive layer 14 is reduced, and the photosensitive layer 14 is erased by exposure. It has the ability to reduce surface charge in areas other than the areas where it should be removed, and to cause defects such as fog on images. In particular, when an image is formed using the reversal development process, a toner image is formed in a portion where the surface charge has been reduced by exposure, so if the surface charge is reduced by a factor other than exposure, the toner adheres to a white background.
• Image fogging called black spots in which minute black spots are formed, occurs, and the image quality is remarkably deteriorated. That is, when there is no intermediate layer 18 between the conductive support 11 and the photosensitive layer 14, the chargeability in a minute area is reduced due to a defect in the conductive support 11 or the photosensitive layer 14, and Image fogging such as black spots occurs, resulting in significant image defects.
• the intermediate layer 18 is provided between the conductive support 11 and the photosensitive layer 14 as described above, so that the charge from the conductive support 11 to the photosensitive layer 14 is transferred. Injection can be prevented. Therefore, it is possible to prevent a decrease in the chargeability of the photosensitive layer 14, suppress a decrease in surface charge in a portion other than a portion to be erased by exposure, and prevent a defect such as a fog from occurring in an image. it can.
• the intermediate layer 18 defects on the surface of the conductive support 11 can be covered and a uniform surface can be obtained, so that the film forming property of the photosensitive layer 14 can be improved. Further, peeling of the photosensitive layer 14 from the conductive support 11 can be suppressed, and the adhesiveness between the conductive support 11 and the photosensitive layer 14 can be improved.
• the intermediate layer 18 a resin layer having various resin materials or an alumite layer is used.
• the resin material constituting the resin layer examples include polyethylene resin, polypropylene resin, polystyrene resin, acrylic resin, vinyl chloride resin, vinyl acetate resin, polyurethane resin, epoxy resin, polyester resin, melamine resin, silicone resin, and polybutylene resin.
• resins such as Lal resin and polyamide resin, and copolymer resins containing two or more of the repeating units constituting these resins.
• gelatin, polybutyl alcohol, ethyl cellulose and the like can also be mentioned.
• a fat is used.
• Preferred alcohol-soluble nylon resins include, for example, so-called copolymerized nylon obtained by copolymerizing 6 nylon, 6,6 nylon, 6,10 nylon, 11 nylon, 2 nylon, and 12 nylon, and N-alkoxymethyl-modified. Examples thereof include resins obtained by chemically modifying nylon, such as nylon and N_alkoxyethyl-modified nylon.
• the intermediate layer 18 may contain particles such as metal oxide particles. By including these particles in the intermediate layer 18, the effect of preventing charge injection into the conductive support 11 and the photosensitive layer 14 can be enhanced by adjusting the volume resistance value of the intermediate layer 18 and various properties. In this environment, the electrical characteristics of the photoconductor can be maintained.
• metal oxide particles examples include particles such as titanium oxide, aluminum oxide, aluminum hydroxide, and tin oxide.
• the intermediate layer 18 is formed by, for example, dissolving or dispersing the above-described resin in an appropriate solvent to prepare a coating liquid for an intermediate layer, and applying the coating liquid on the outer peripheral surface of the conductive support 11. You.
• the intermediate layer 18 contains particles such as the above-mentioned metal oxide particles, for example, these particles are dispersed in a resin solution obtained by dissolving the above-mentioned resin in an appropriate solvent to form an intermediate layer.
• the intermediate layer 18 can be formed by preparing a coating liquid for a layer and applying the coating liquid on the outer peripheral surface of the conductive support 11.
• Water, various organic solvents, or a mixed solvent thereof is used as the solvent of the coating solution for the intermediate layer.
• single solvents such as water, methanol, ethanol or butanol, or water and alcohols, two or more alcohols, acetone or dioxolane, etc. and alcohols, chlorinated solvents such as dichloroethane, black form or trichloroethane.
• a mixed solvent such as alcohols is preferably used.
• a general method using a ball mill, a sand mill, an attritor, a vibration mill, an ultrasonic disperser, or the like can be used.
• the total content C of the resin and the metal oxide in the coating liquid for the intermediate layer is C / D in a weight ratio of 1/99 to 40 / with respect to the content D of the solvent used in the coating liquid for the intermediate layer.
• it is 60, more preferably 2Z98 30Z70.
• the ratio of resin to metal oxide is preferably 90 / 10-1 / 99 by weight, more preferably 70 / 30-5 / 95.
• Examples of the method of applying the coating solution for the intermediate layer include a spray method, a bar coating method, a roll coating method, a blade method, a ring method, and a dip coating method.
• the dip coating method is relatively simple and excellent in productivity and cost as described above, it is often used for forming the intermediate layer 18.
• the thickness of the intermediate layer 18 is preferably 0.01 xm or more and 20 xm or less, more preferably 0.05 x m or more and 10 ⁇ or less.
• the thickness of the intermediate layer 18 is thinner than the thickness of 01 ⁇ m and practically no longer functions as the intermediate layer 18, and covers the defects of the conductive support 11 to obtain a uniform surface. As a result, the injection of charges from the conductive support 11 into the photosensitive layer 14 cannot be prevented, and the chargeability of the photosensitive layer 14 decreases.
• the thickness of the intermediate layer 18 is greater than 20 ⁇ m, it becomes difficult to form the intermediate layer 18 when the intermediate layer 18 is formed by the dip coating method, and the photosensitive layer is exposed on the outer peripheral surface of the intermediate layer 18. This is not preferable because the layer 14 cannot be formed uniformly and the sensitivity of the photoreceptor decreases.
• FIG. 3 is a schematic cross-sectional view showing a simplified configuration of an electrophotographic photosensitive member 3 according to a third embodiment of the present invention.
• the electrophotographic photoreceptor 3 of the present embodiment is similar to the electrophotographic photoreceptor 2 of the second embodiment, and the corresponding portions are denoted by the same reference numerals and description thereof will be omitted.
• the photosensitive layer 140 is composed of a single photoconductive layer containing the charge generating substance 12 and the charge transporting substance 13. That is, the electrophotographic photoconductor 3 is a single-layer photoconductor.
• an enamine compound represented by the general formula (1) is used for the charge transporting substance 13.
• the photosensitive layer 140 contains at least one of an antioxidant and a light stabilizer. Therefore, similar to the first and second embodiments, when used in a low-temperature environment with high chargeability, sensitivity and photoresponsiveness or in a high-speed electrophotographic process, or when exposed to light
• the characteristics described above do not deteriorate, and are stable against active gases such as ozone and NOx, ultraviolet rays, heat, etc., and cause less fatigue deterioration when used repeatedly.
• a highly reliable electrophotographic photosensitive member 3 can be obtained.
• the content of the antioxidant, the content of the light stabilizer, and the total content of the antioxidant and the light stabilizer in the photosensitive layer 140 are determined by the content of the antioxidant in the photosensitive layer 14 of the first embodiment. , The content of the light stabilizer, and the total content of the antioxidant and the light stabilizer.
• the photosensitive layer 140 is formed in the same manner as the charge transport layer 16 provided on the electrophotographic photosensitive member 1 of the first embodiment.
• the photosensitive layer 140 can be formed by coating the outer peripheral surface of the intermediate layer 18 by a method or the like.
• the ratio A ′ / B ′ between the weight A ′ of the charge transport material 13 in the photosensitive layer 140 and the weight B ′ of the binder resin 17 is represented by the weight A of the charge transport material 13 in the charge transport layer 16 of the first embodiment. Like the ratio A / B to the weight B of the binder resin 17, it is preferably 10/12 to 10/30.
• the thickness of the photosensitive layer 140 is preferably 5 ⁇ or more and 100 / im or less, more preferably 10/1 111 or more and 50/1 111 or less. If the thickness of the photosensitive layer 140 is less than 5 ⁇ , the charge holding ability of the surface of the photoreceptor decreases. When the thickness of the photosensitive layer 140 exceeds 100 ⁇ , productivity decreases. Therefore, it was set to 5 ⁇ m or more and 100 ⁇ m or less.
• the photosensitive layers 14, 140 provided in the electrophotographic photoreceptors 1, 2, and 3 of the first to third embodiments described above are provided with improved sensitivity to increase residual potential during repeated use and reduce fatigue.
• One or more electron accepting substances or dyes may be further added in order to suppress such problems.
• the electron acceptor examples include acid anhydrides such as succinic anhydride, maleic anhydride, phthalic anhydride and 4-chloronaphthalic anhydride; cyano compounds such as tetracyanoethylene and terephthalmalon nitrile; Aldehydes such as dunzaldehyde, anthraquinones, anthraquinones such as 1-nitroanthraquinone, polycyclic or heterocyclic such as 2,4,7_trinitrofluorenone, 2,4,5,7-tetranitrofluorenone Ring nitro compounds, also For example, an electron-withdrawing material such as a diphenoquinone compound can be used. In addition, those obtained by polymerizing these electron-withdrawing materials can also be used.
• acid anhydrides such as succinic anhydride, maleic anhydride, phthalic anhydride and 4-chloronaphthalic anhydride
• cyano compounds such as tetracyanoethylene and terephthalmalon
• an organic photoconductive compound such as a xanthene pigment, a thiazine pigment, a triphenylmethane pigment, a quinoline pigment, or copper phthalocyanine can be used. These organic photoconductive compounds function as optical sensitizers.
• the electrophotographic photoreceptor according to the present invention can have various layer configurations without being limited to the configurations of the electrophotographic photoreceptors 1, 2, and 3 of the first to third embodiments described above.
• the photosensitive layer 14 composed of a photoconductive layer formed by laminating the charge generation layer 15 and the charge transport layer 16 or the charge generation layer
• a photosensitive layer 140 composed of a single photoconductive layer containing the substance 12 and the charge transport substance 13 is provided
• a surface protection layer is further laminated on these photoconductive layers without being limited thereto.
• a photosensitive layer may be provided.
• the surface protective layer By providing the surface protective layer on the photoconductive layer in this way, the printing durability of the photosensitive layer can be improved, and the ozone and nitrogen oxides ( Chemical adverse effects of the active gas such as NOx) on the photosensitive layer can be further prevented.
• a layer made of, for example, a resin, a resin containing an inorganic filler, or an inorganic oxide is used.
• the aforementioned antioxidant and light stabilizer may be contained in either the photoconductive layer or the surface protective layer. It may be contained in both the photoconductive layer and the surface protective layer.
• FIG. 4 is a side view showing the configuration of the image forming apparatus 100 in a simplified manner.
• the image forming apparatus 100 includes a photoreceptor 1 rotatably supported by an apparatus main body (not shown), and a driving unit (not shown) for driving the photoreceptor 1 to rotate around a rotation axis 44 in the direction of an arrow 41.
• the driving means includes, for example, a motor as a power source, and transmits the power from the motor to a support constituting the core of the photoreceptor 1 via a gear (not shown) to thereby provide a photosensitive member.
• the body 1 is driven to rotate at a predetermined peripheral speed.
• a charger 32, exposure means (not shown), a developing unit 33, a transfer unit 34, and a cleaner 36 are arranged from the upstream side in the rotation direction of the photoreceptor 1 indicated by an arrow 41. It is provided in this order toward the downstream side.
• the cleaner 36 is provided together with a static elimination lamp (not shown).
• the charger 32 is a charging unit that charges the outer peripheral surface 43 of the photoconductor 1 to a predetermined potential.
• the charger 32 is a contact-type charging unit such as a roller charging system.
• the exposure means includes, for example, a semiconductor laser or the like as a light source, and irradiates light 31 such as a laser beam output from the light source to the outer peripheral surface 43 of the photoconductor 1 located between the charger 32 and the developing device 33.
• light 31 such as a laser beam output from the light source
• the outer peripheral surface 43 of the photoconductor 1 located between the charger 32 and the developing device 33.
• the developing device 33 is a developing unit that develops an electrostatic latent image formed on the outer peripheral surface 43 of the photoreceptor 1 by exposure with a developer, and is provided to face the photoreceptor 1.
• a developing roller 33a for supplying toner to the developing roller 3; a casing 33b for rotatably supporting the developing roller 33a about a rotation axis parallel to the rotation axis 44 of the photoreceptor 1 and accommodating a developer containing toner in its internal space; Is provided.
• the transfer device 34 supplies a toner image, which is a visible image formed on the outer peripheral surface 43 of the photoconductor 1 by development, to a direction indicated by an arrow 42 by a conveying means (not shown) between the photoconductor 1 and the transfer device 34.
• the transfer unit 34 is, for example, a non-contact transfer unit that includes a charging unit and transfers a toner image onto the transfer paper 51 by applying a charge having a polarity opposite to that of the toner to the transfer paper 51.
• the cleaner 36 is a cleaning unit that removes and collects toner remaining on the outer peripheral surface 43 of the photoconductor 1 after the transfer operation by the transfer unit 34, and removes the toner remaining on the outer peripheral surface 43 of the photoconductor 1 from the outer peripheral surface 43. It has a cleaning blade 36a to be peeled off, and a collecting casing 36b for storing the toner peeled off by the cleaning blade 36a.
• a fixing device 35 as fixing means for fixing the transferred image is provided.
• the fixing device 35 is provided with a heating roller 35a having heating means (not shown) and a heating roller 35a. And a pressure roller 35b pressed by the heating roller 35a to form a contact portion.
• light 31 is applied to the outer peripheral surface 43 of the photoreceptor 1 from the exposure means.
• Light 31 from the light source is repeatedly scanned in the longitudinal direction of the photoconductor 1, which is the main scanning direction.
• the outer peripheral surface 43 of the photoconductor 1 is exposed according to the image information. This exposure removes the surface charge of the portion irradiated with the light 31, causing a difference between the surface potential of the portion irradiated with the light 31 and the surface potential of the portion not irradiated with the light 31.
• An electrostatic latent image is formed on the outer peripheral surface 43 of the camera.
• the toner is transferred from the developing roller 33a of the developing unit 33 provided downstream of the image forming point of the light 31 from the light source in the rotation direction of the photoconductor 1 to the outer peripheral surface 43 of the photoconductor 1 on which the electrostatic latent image is formed.
• One is supplied.
• the electrostatic latent image is developed, and a toner image is formed on the outer peripheral surface 43 of the photoconductor 1.
• the transfer paper 51 is supplied between the photoconductor 1 and the transfer unit 34 by a conveying means in a direction indicated by an arrow 42 in synchronization with the exposure of the photoconductor 1.
• the transfer device 34 gives the transfer paper 51 a charge having a polarity opposite to that of the toner.
• the toner image is transferred onto the transfer paper 51 formed on the outer peripheral surface 43 of the photoconductor 1.
• the transfer paper 51 on which the toner image has been transferred is conveyed to the fixing device 35 by the conveying means, and is heated and calorie-pressed when passing through the contact portion between the heating roller 35a and the pressure roller 35b of the fixing device 35. .
• the toner image on the transfer paper 51 is fixed on the transfer paper 51 and becomes a robust image.
• the transfer paper 51 on which the image has been formed in this way is discharged to the outside of the image forming apparatus 100 by the conveying means.
• the toner remaining on the outer peripheral surface 43 of the photoconductor 1 after the transfer operation by the transfer unit 34 is separated from the outer peripheral surface 43 of the photoconductor 1 by the cleaning blade 36a of the cleaner 36, Collected in the collecting casing 36b.
• the charge on the outer peripheral surface 43 of the photoreceptor 1 from which the toner has been removed in this manner is removed by light from the discharging lamp, and the electrostatic latent image on the outer peripheral surface 43 of the photoreceptor 1 disappears.
• the photoconductor 1 is further driven to rotate, and a series of operations starting from charging of the photoconductor 1 is repeated again. As described above, images are continuously formed.
• the photoreceptor 1 provided in the image forming apparatus 100 contains the enamine compound represented by the general formula (1) as the charge transporting substance 13, and further includes at least one of an antioxidant and a light stabilizer. Having the photosensitive layer 14 containing one of them, the above-mentioned characteristics are not degraded even when used in a low-temperature environment where the chargeability, sensitivity and photoresponsiveness are high or in a high-speed electrophotographic process, and It is stable against active gases such as ozone and N ⁇ x, ultraviolet rays and heat, and has high reliability with little fatigue deterioration when used repeatedly. Therefore, it is possible to obtain a highly reliable image forming apparatus 100 capable of stably providing a high-quality image for a long time under various environments.
• the reliability of the image forming apparatus 100 can be improved.
• the image forming apparatus 100 of the present embodiment includes the electrophotographic photoreceptor 1 of the first embodiment, but is not limited to the electrophotographic photoreceptor 1 of the second embodiment.
• the electrophotographic photoreceptor 3 of the second or third embodiment or the electrophotographic photoreceptor having a different layer configuration from the electrophotographic photoreceptors 2 and 3 of the first to third embodiments may be provided.
• the charger 32 is a contact-type charging unit, but may be a non-contact type charging unit such as a corona charging system without being limited thereto.
• the transfer unit 34 is a non-contact type transfer unit that includes a charging unit and transfers a toner image onto the transfer paper 51 by applying a charge having a polarity opposite to that of the toner to the transfer paper 51, but is not limited thereto.
• a contact type transfer unit that includes a roller and transfers the toner image onto the transfer sheet 51 by pressing the transfer sheet 51 and the photosensitive body 1 using the roller may be used.
• reaction solution was concentrated to about one tenth (1/10) and gradually dropped into 100 mL of vigorously stirred hexane to form crystals.
• the generated crystals were separated by filtration and washed with cold ethanol to obtain 36.2 g of a pale yellow powdery compound.
• the obtained compound was analyzed by Liquid Chromatography-Mass Spectrometry (abbreviation: LC-MS), and as a result, an enamine intermediate represented by the following structural formula (10) (calculated molecular weight: 411. The peak corresponding to the molecular ion [M + H] + with proton added to 20) was observed at 412.5, indicating that the obtained compound is an enamine intermediate represented by the following structural formula (10). (Yield: 88%).
• LC-MS As a result, the purity of the obtained enamine intermediate was found to be 99.5%.
• an enamine intermediate represented by the structural formula (10) was obtained.
• the enamine intermediate represented by the structural formula (10) is subjected to formylation by a Vilsmeier reaction to obtain an enamine monoaldehyde intermediate represented by the structural formula (11). did it.
• the toluene solution was transferred to a separatory funnel, washed with water, and then the organic layer was taken out.
• the organic layer taken out was dried over magnesium sulfate. After drying, the organic layer from which solids were removed was concentrated and subjected to silica gel column chromatography to obtain 10.lg of yellow crystals.
• FIG. 5 is a diagram showing a 1 H-NMR spectrum of a product of Production Examples 1-3
• FIG. 6 is a diagram showing 6 ppm to 9 ppm of the spectrum shown in FIG. 5 in an enlarged manner
• FIG. 7 is a diagram showing a 13 C-NMR spectrum of the product of Production Example 1-3 by a normal measurement
• FIG. 8 is an enlarged view of ⁇ ⁇ m 160 ppm of Statonore shown in FIG. 7. is there.
• FIG. 5 is a diagram showing a 1 H-NMR spectrum of a product of Production Examples 1-3
• FIG. 6 is a diagram showing 6 ppm to 9 ppm of the spectrum shown in FIG. 5 in an enlarged manner
• FIG. 7 is a diagram showing a 13 C-NMR spectrum of the product of Production Example 1-3 by a normal measurement
• FIG. 8 is an enlarged view of ⁇ ⁇ m 160 ppm of Statonore shown in FIG. 7. is there.
• FIG. 8 is an
• FIG. 9 is a diagram showing a 13 C-NMR spectrum of the product of Production Example 1-3 by DEPT135 measurement
• FIG. 10 is an enlarged diagram showing 1 lOppm-160 ppm of the spectrum shown in FIG. 5 and 10, the horizontal axis represents the chemical shift value ⁇ (ppm).
• the value between the signal and the horizontal axis is the relative integrated value of each signal when the integrated value of the signal indicated by reference numeral 500 in FIG. 5 is set to 3. It is.
• N_ represented by the structural formula (8) (p-tolyl) Ichihi - Nafuchiruamin 23. Instead of 3 g (l 0 eq.), N-(p-Metokishifue sulfonyl) - Fei -. Nafuchiruamin 4 9 g (l Eq.), And the production of an enamine intermediate by a dehydration condensation reaction (yield: 94%) and the production of an enamine-aldehyde intermediate by a Vilsmeier reaction in the same manner as in Production Example 1 (yield: 85%), and further subjected to Wittig-Horner reaction to obtain 7.9 g of a yellow powdery compound.
• the equivalent relation between the reagent and the substrate used in each reaction is the same as the equivalent relation between the reagent and the substrate used in Production Example 1.
• the obtained compound was analyzed by LC-MS, and as a result, the molecular ion [M +] obtained by adding a proton to the desired enamine compound of Exemplified Compound No. 61 shown in Table 9 (calculated molecular weight: 555.26) was obtained.
• a peak corresponding to [H] + was observed at 556.7.
• FIG. 11 is a diagram showing a 1 H-NMR spectrum of the product of Production Example 2
• FIG. 12 is an enlarged diagram showing 6 ppm to 9 ppm of the spectrum shown in FIG.
• FIG. 13 is a diagram showing 13 C-NMR spectrum obtained by normal measurement of the product of Production Example 2
• FIG. 14 is a diagram showing an enlarged view of 160 ppm of lOppm in the spectrum shown in FIG.
• FIG. 15 is a diagram showing a 13 C-NMR spectrum of the product of Production Example 2 measured by DEPT135, and FIG.
• FIG. 16 is a diagram showing, in an enlarged manner, 160 ppm of lOppm of the statonore shown in FIG.
• the horizontal axis represents the chemical shift value ⁇ (ppm).
• the value between the signal and the horizontal axis is the relative value of each signal when the signal integration value indicated by reference numeral 501 in FIG. 11 is set to 3. This is the integral value.
• azo compound represented by the following structural formula (15), which is the charge generating substance 12 was added to 97 parts by weight of THF with a polybutyral resin (Slec BX— 1) 1 part by weight was dissolved in a resin solution, and the mixture was dispersed for 10 hours with a paint sieve to prepare a coating solution for a charge generation layer.
• the obtained coating solution for a charge generation layer was applied onto the previously formed intermediate layer 18 using a bailing applicator, and then dried to form a charge generation layer 15 having a thickness of 0.3 ⁇ m.
• Example 1 instead of Exemplified Compound No. 1 as the charge transporting substance 13, Exemplified Compound No. 3 shown in Table 1, Exemplified Compound No. 61 shown in Table 9, and Exemplified Compound No. 106 shown in Table 16
• Exemplified Compound No. 146 shown in Table 21 or Exemplified Compound No. 177 shown in Table 26 was used, five kinds of electrophotographic photoconductors satisfying the requirements of the present invention were obtained. Produced.
• Example 1 the requirements for the present invention were the same as in Example 1, except that Comparative Compound A represented by the following structural formula (16) was used instead of Exemplified Compound No. 1 as the charge transporting substance 13. The electrophotographic photoreceptor was not satisfied.
• Example 1 the requirements for the present invention were the same as in Example 1, except that Comparative Compound B represented by the following structural formula (17) was used instead of Exemplified Compound No. 1 as the charge transporting substance 13. The electrophotographic photoreceptor was not satisfied.
• Example 1 a requirement of the present invention was obtained in the same manner as in Example 1, except that Comparative Compound C represented by the following structural formula (18) was used instead of Exemplified Compound No. 1 as the charge transporting substance 13. The electrophotographic photoreceptor was not satisfied.
• an intermediate layer 18 having a thickness of 1 ⁇ m was formed on an aluminum substrate having a thickness of 0.2 mm as the conductive support 11.
• Example 1 the requirements of the present invention were the same as in Example 1 except that the X-type metal-free phthalocyanine was used instead of the azo compound represented by the structural formula (15) as the charge generating substance 12.
• An electrophotographic photoreceptor satisfying the above was prepared.
• Example 1 an X-type metal-free phthalocyanine was used instead of the azo compound represented by the structural formula (15) as the charge generating substance 12, and the charge transporting substance 13 was replaced with Exemplified Compound No. 1, Exemplary compound No. 3 shown in Table 1, Exemplary compound No. 61 shown in Table 9, Exemplary compound No. 106 shown in Table 16, Exemplary compound No. 146 shown in Table 21, or Exemplary compound No. 177 shown in Table 26 In the same manner as in Example 1 except for using 5, electrophotographic photosensitive members satisfying the requirements of the present invention were produced.
• Example 1 an X-type metal-free phthalocyanine was used in place of the azo compound represented by the structural formula (15) as the charge generating material 12, and Exemplified Compound No.
• the comparative compound A represented by the structural formula (16) the comparative compound B represented by the structural formula (17) or the comparative compound C represented by the structural formula (18) was used.
• three types of electrophotographic photosensitive members not satisfying the requirements of the present invention were produced.
• Example 1 an X-type metal-free phthalocyanine was used instead of the azo compound represented by the structural formula (15) as the charge generating material 12, and Example Compound No. 1 was used as the charge transporting material 13. Then, an electrophotographic photoreceptor that does not satisfy the requirements of the present invention was produced in the same manner as in Example 1, except that Comparative Compound D represented by the following structural formula (19) was used.
• Example 1 An X-type metal-free phthalocyanine was used instead of the azo compound represented by the structural formula (15) as the charge generating substance 12, and the charge transporting substance 13 was replaced with Exemplified Compound No. 1, An electrophotographic photoreceptor that does not satisfy the requirements of the present invention was produced in the same manner as in Example 1, except that Comparative Compound E represented by the following structural formula (20) was used.
• the surface of the photoconductor was charged by applying a voltage of minus (1) 5 kV to the photoconductor, and the surface potential of the photoconductor at this time was measured as a charging potential V (V).
• V charging potential
• the surface of the photoreceptor was charged by applying a voltage of plus (+) 5 kV.
• the charged photoreceptor surface was exposed to light, and the exposure amount required to reduce the surface potential of the photoreceptor to half the charging potential V was measured as a half-decreased exposure amount E (Aij / cm 2 ).
• the surface potential of the photoreceptor 10 seconds after the start of exposure was measured as a residual potential Vr (V).
• V residual potential
• the photoreceptors of Example 117 and Comparative Example 113 using the azo compound represented by the structural formula (15) as the charge generating substance 12 had an intensity of 1 ⁇ W / cm 2.
• the photoconductors of Examples 8-13 and Comparative Example 4-18 using white light of Example 2 and X-type non-metallic phthalocyanine as the charge generating substance 12 the wavelength 780 nm obtained by spectroscopy with a monochromator was used. Light intensity of 1 ⁇ W / cm 2 was used. These measurement results were used as initial measurement results.
• Table 56 shows the measurement results at the initial stage and after repeated use.
• Table 56 shows that the difference between the initial measurement result and the measurement result after repeated use was small for both the photoconductors of Example 113 and Comparative Example 18 containing the antioxidant in the photosensitive layer. It was found that the fatigue deterioration when used was small. Further, of the photoconductors of Example 113 and Comparative Example 118, the photoconductor of Example 113 using the enamine compound represented by the general formula (1) as the charge transporting substance 13 has a charge transporting property. Comparative Example 18 using Comparative Compound A, B, C, D or E for Substance 13 Compared with the photoreceptor of Example 18, half-exposure E power, high sensitivity, and low absolute value of residual potential Vr responsiveness
• the photoreceptor of Example 113 has excellent characteristic stability against environmental changes where the difference between the measurement result under the N / N environment and the measurement result under the LZL environment is small, While the characteristics do not decrease, the photoreceptor of Comparative Example 18 has a large difference between the measurement results under the N / N environment and the measurement results under the L / L environment. It was found to decrease.
• Y-type oxotitanium phthalocyanine as the charge generating substance 12 is obtained by dissolving 1 part by weight of a polyvinyl butyral resin (manufactured by Sekisui Chemical Co., Ltd .: ES REC BX-1) in 97 parts by weight of methylethylken. After being added to the resulting resin solution, the mixture was dispersed for 10 hours with a paint sieve to prepare a coating solution for a charge generation layer. The obtained coating solution for a charge generation layer was applied onto the previously formed intermediate layer 18 with a bailing force applicator, and then dried to form a charge generation layer 15 having a thickness of 0.4 zm.
• a polyvinyl butyral resin manufactured by Sekisui Chemical Co., Ltd .: ES REC BX-1
• Example 14 in place of the exemplary compound HP-1, the exemplary compound HP-9 shown in Table 33, the exemplary compound P-7 shown in Table 40, or the exemplary compound S-6 shown in Table 45 was used instead of the exemplary compound HP-1 in Example 14. Except for using, three kinds of electrophotographic photosensitive members satisfying the requirements of the present invention were produced in the same manner as in Example 14.
• Example 14 in place of Exemplified Compound HP-1 which is an antioxidant, Exemplified Compound HA-3 shown in Table 47, Exemplified Compound HA-10 shown in Table 48 or Table 50 which is a light stabilizer is used as a light stabilizer.
• Three kinds of electrophotographic photoreceptors satisfying the requirements of the present invention were produced in the same manner as in Example 14 except that Exemplified compound TZ-5 was used.
• Example 14 Example Compound No. 3 shown in Table 1 was used in place of Example Compound No. 61 as the charge transporting substance 13, and Table 35 was used instead of Example Compound HP-1 as the antioxidant.
• An electrophotographic photoreceptor satisfying the requirements of the present invention was produced in the same manner as in Example 14, except that the exemplified compound HP-26 was used.
• Example 14 the charge transporting substance 13 was replaced with the exemplified compound No. 146 shown in Table 21 instead of the exemplified compound No. 61, and was replaced with a light stabilizer instead of the exemplified compound HP-1 which is an antioxidant.
• An electrophotographic photoreceptor satisfying the requirements of the present invention was produced in the same manner as in Example 14, except that Exemplified Compound HA-10 shown in Table 48 was used.
• Example 14 The coating solution for a charge transport layer obtained in Example 14 was stored at a place under an environment of a temperature of 40 ° C. for one month, and then the coating solution for a charge transport layer was used in the same manner as in Example 14. Thus, an electrophotographic photoreceptor satisfying the requirements of the present invention was produced.
• Example 24 In the same manner as in Example 14, except that the amount of the hindered phenol compound of Exemplified Compound HP-1, which is an antioxidant, was changed to 5.4 parts by weight (about 16% by weight based on the photosensitive layer). Thus, an electrophotographic photosensitive member satisfying the requirements of the present invention was produced.
• Example 14 in place of 1.4 parts by weight of the hindered phenol compound of Exemplified Compound HP-1 which is an antioxidant, a hinderamine compound of Exemplified Compound HA-3 shown in Table 47 which is a light stabilizer, instead of 1.4 parts by weight.
• An electrophotographic photosensitive member satisfying the requirements of the present invention was produced in the same manner as in Example 14, except that 5 parts by weight (about 11% by weight based on the photosensitive layer) was used.
• An electrophotographic photoreceptor that does not satisfy the requirements of the present invention was produced in the same manner as in Example 14, except that the hindered phenol compound of Exemplified Compound HP-1 as an antioxidant was not used. .
• the coating solution for a charge transport layer obtained in Comparative Example 1 was stored for one month at a place under an environment of a temperature of 40 ° C., and then the same as in Example 14 was performed using the coating solution for a charge transport layer. Thus, an electrophotographic photosensitive member not satisfying the requirements of the present invention was produced.
• the surface of the photoconductor was charged to minus (_) 600 V while rotating the rotating disk on which the sample was placed at a rotation speed of 1100 rpm.
• the surface of the charged photoreceptor is irradiated with monochromatic light having a wavelength of 780 nm at an intensity of 1 ⁇ WZcm 2 , and the surface potential of the photoreceptor is changed from the charged potential of minus ( ⁇ ) 600 V to minus ( ⁇ ) 300 V.
• the amount of exposure required to reduce by half was measured as half-life exposure E (zj / cm 2 ).
• Table 57 shows the measurement results at the initial stage and after repeated use.
• Example 14 the photoconductor of Example 24 in which the content of the antioxidant in the photosensitive layer exceeds 15% by weight has the content of the antioxidant in the photosensitive layer of 0.1.
• the absolute value of the residual potential V is smaller than that of the photoreceptor of Example 14 in the range of one
• the light response is slightly inferior and slightly inferior.
• the photoconductor of Example 25 in which the content of the light stabilizer in the photosensitive layer exceeds 10% by weight has a light stabilizer content of 0.1 in the photosensitive layer.
• the absolute value of the residual potential V is slightly higher than that of the photoreceptor of Example 18 in the range of 1 to 10% by weight.
• An intermediate layer 18 of xm was formed on the outer peripheral surface of the conductive support 11.
• a Bragg angle of 2 ° error: 2 ⁇ ⁇ 0.2.
• Esrec II-S 97 parts by weight of methylethyl ketone
• the mixture was mixed and subjected to a dispersion treatment with a paint sieve to prepare a coating solution for a charge generation layer.
• the obtained charge generation layer coating solution is applied on the outer peripheral surface of the previously formed intermediate layer 18 by the same dip coating method as that for the above-mentioned intermediate layer 18, and then dried to obtain a charge having a thickness of 0.4 xm.
• a generation layer 15 was formed.
• the obtained coating solution for the charge transport layer is applied on the outer peripheral surface of the previously formed charge generation layer 15 by the same dip coating method as the above-mentioned intermediate layer 18, and then dried at 110 ° C for 1 hour. As a result, a charge transport layer 16 having a thickness of 23 / im was formed.
• an electrophotographic photosensitive member having the configuration shown in FIG. 2 and satisfying the requirements of the present invention was produced.
• Example 26 was repeated in the same manner as in Example 26, except that Exemplified Compound P-36 shown in Table 42 or Exemplified Compound S-12 shown in Table 46 was used instead of Exemplified Compound HP-1 as the antioxidant.
• Exemplified Compound P-36 shown in Table 42 or Exemplified Compound S-12 shown in Table 46 was used instead of Exemplified Compound HP-1 as the antioxidant.
• Example 26 is the same as Example 26 except that Example Compound HA-3 shown in Table 47 or Example Compound TZ-4 shown in Table 50 as a light stabilizer was used in place of Example Compound HP-1 as an antioxidant.
• Example Compound HP-1 as an antioxidant
• Example 26 an electron-emitting device satisfying the requirements of the present invention was prepared in the same manner as in Example 26 except that Exemplified Compound X-19 shown in Table 55 was used instead of Exemplified Compound HP-1 as an antioxidant. A photoreceptor was prepared.
• Example Compound 159 shown in Table 23 is used instead of Example Compound No. 61 as the charge transporting substance 13 in Example 26.
• a photoreceptor was prepared.
• Example 26 instead of 1.4 parts by weight of the hindered phenol compound of Exemplified Compound HP-1 which is an antioxidant, 1 part by weight of the hindered phenol compound of Exemplified Compound HP-1 and a light stabilizer were used. Except for the use of 0.4 part by weight of the hinderdamine compound of HA-3 as shown in Table 47, except that the mixture is used (total content in the photosensitive layer is about 5% by weight), the requirements of the present invention are the same as in Example 26. An electrophotographic photoreceptor satisfying the above was prepared.
• Example 26 the hindered phenol compound of Exemplified Compound HP-1 which is an antioxidant was replaced with 1.4 parts by weight, and the hindered phenol compound of Exemplified Compound HP-26 shown in Table 35 which is an antioxidant was replaced with 0.1 part by weight. Except that 3 parts by weight and 0.2 parts by weight of a hinderdamine compound of HA-10, which is a light stabilizer shown in Table 48, are mixed and used (total content of about 2% by weight in the photosensitive layer). An electrophotographic photosensitive member satisfying the requirements of the present invention was produced in the same manner as in Example 26.
• Example 26 in place of 1.4 parts by weight of the hindered phenol compound of Exemplified Compound HP-1 which is an antioxidant, 1 part by weight of a hindered phenol compound of Exemplified Compound HP-1 and the exemplification shown in Table 54 were used.
• An electrophotographic photosensitive material satisfying the requirements of the present invention was prepared in the same manner as in Example 26, except that 1 part by weight of compound X-16 was mixed and used (the total content in the photosensitive layer was about 7% by weight). The body was made.
• Example 26 35 and Comparative Example 11 Each of the electrophotographic photoreceptors produced in Example 26 35 and Comparative Example 11 was modified so that the surface potential of the photoreceptor in the image forming process could be measured with a surface electrometer (CATE751 manufactured by Gentec). Installed in a commercially available small digital copier (AR-C260 manufactured by Sharp Corporation). In an environment with a temperature of 22 ° C and a relative humidity of 20% (22 ° CZ20 / .RH), the surface potential of the photoconductor immediately after charging was measured as a charging potential V (V). Also laser
• V The surface potential of the photoconductor immediately after exposure with light was measured as the post-exposure potential V (V).
• the halftone image was formed on plain paper of Japanese Industrial Standard (IIS) A3 size.
• IIS Japanese Industrial Standard
• the halftone image is an image in which the gradation of the image is expressed by gradation using black and white dots.
• the obtained images were visually observed, and the image quality was evaluated based on the degree of image defects such as white spots, black bands, and image blurring.
• the image quality was evaluated according to the following criteria.
• Table 58 shows the measurement results at the initial stage and after the actual image aging, and the evaluation results of the image quality after the actual image aging.
• Example 26 Exemplary compound 61 HP-1 -605 -45-602 -55 A Example 27 Exemplary compound 61 P-36 -604 -48-605 -59 B Example 28 Exemplary compound 61 S-12-600-51- 603 -65 B Example 29 Exemplary compound 61 HA-3-608 -46 -605 -54 A Example 30 Exemplary compound 61 TZ-4 -604 -49-608 -61 B Example 31 Exemplary compound 61 X-19- 602 -49 -600 -61 B Example 32 Exemplary compound 159 HP-1 -608-45 -605-54 A Example 33 Exemplary compound 61 HP-1 + HA-3-607 -45 -601-52 A Example 34 Illustrative compound 61 HP-26 + HA-10 -608 -46 -605 -53 A Example 35 Illustrative compound 61 HP-1 + X-16 -604 -46-604 -52 A Comparative example 1 1 Illustrative compound 61 None -602 -48 -485 -1
• the photosensitive layer contains an antioxidant or a light stabilizer.
• the photoreceptor of Example 26-35 was exposed to ozone and NOx during charging, exposed to light and heat during exposure and static elimination, and exposed to light and heat. Absolute value does not decrease significantly, and absolute value of post-exposure potential V does not increase significantly.
• the enamine compound represented by the general formula (1) in combination with at least one of an antioxidant and a light stabilizer in the photosensitive layer, the chargeability, Even when used in a low-temperature environment where sensitivity and light response are high, the above-mentioned characteristics do not decrease, and are stable against active gases such as ozone and NOx, ultraviolet rays and heat, and are used repeatedly. It was possible to obtain a highly reliable electronic photoreceptor with little fatigue deterioration during the process.
• the photosensitive layer contains a high-energy compound having a specific structure and a high charge mobility, and at least one of an antioxidant and a light stabilizer.
• the above properties are not reduced even when used in a low-temperature environment where the chargeability, sensitivity and photoresponsiveness are high, or in a high-speed electrophotographic process, or when exposed to light.
• it is stable against active gases such as ozone and N ⁇ x, ultraviolet rays and heat, and has the ability to obtain a highly reliable electrophotographic photoreceptor with little fatigue deterioration when used repeatedly.
• the stability of the coating solution when the photosensitive layer is formed by coating can be enhanced, and the quality stability and productivity of the electrophotographic photosensitive member can be improved.
• the photosensitive layer contains an enamine compound having a specific structure, which has particularly high charge mobility, is relatively easy to synthesize, has a high yield, and can be manufactured at low cost. Therefore, an electrophotographic photoreceptor having higher sensitivity and photoresponsiveness can be produced at a low production cost.
• the specific antioxidant is contained in the photosensitive layer, the decomposition and deterioration of the enamine compound having the specific structure contained in the photosensitive layer as the charge transporting substance is particularly suppressed while suppressing repetition.
• the durability of the electrophotographic photoreceptor can be further improved, and the stability of the coating solution when forming the photosensitive layer by coating is further improved, thus enabling the electrophotographic It is possible to further improve the quality stability and productivity of the photoconductor.
• the specific light stabilizer since the specific light stabilizer is contained in the photosensitive layer, it is repeatedly used while suppressing decomposition and deterioration of the enamine compound having a specific structure contained in the photosensitive layer as the charge transporting substance.
• the durability of the electrophotographic photoreceptor can be further improved, and the stability of the coating solution when the photosensitive layer is formed by coating is further improved. It can further improve quality stability and productivity.
• the content of the antioxidant contained in the photosensitive layer is selected within a suitable range, so that sufficient effects for improving the durability of the electrophotographic photoreceptor and the stability of the coating solution can be obtained. And the deterioration of the characteristics of the electrophotographic photosensitive member due to the inclusion of an antioxidant can be minimized.
• the content of the light stabilizer contained in the photosensitive layer is selected within a suitable range, so that it is suitable for improving the durability of the electrophotographic photosensitive member and the stability of the coating solution. In addition to providing an advantageous effect, it is possible to minimize the deterioration of the characteristics of the electrophotographic photosensitive member due to the inclusion of the light stabilizer.
• the image forming apparatus has high chargeability, sensitivity, and photoresponsiveness even when used in a low-temperature environment or a high-speed electrophotographic process or when exposed to light. It has a highly reliable electrophotographic photoreceptor that is stable with respect to active gases such as ozone and N ⁇ x, ultraviolet rays and heat, and has little fatigue deterioration when used repeatedly. It can provide high-quality images stably over a long period of time in various environments, and there is no deterioration in image quality due to exposure of the electrophotographic photosensitive member to light during maintenance. It is possible to obtain a highly reliable image forming apparatus.

Priority Applications (1)

Applications Claiming Priority (2)

Publications (1)

Family

ID=33508400

Family Applications (1)

Country Status (4)

Cited By (1)

Families Citing this family (14)

Citations (4)

Family Cites Families (80)

• 2003
  • 2003-06-03 JP JP2003157688A patent/JP3718508B2/ja not_active Expired - Lifetime
• 2004
  • 2004-05-31 CN CNB2004800119369A patent/CN100510972C/zh not_active Expired - Fee Related
  • 2004-05-31 US US10/559,187 patent/US7534539B2/en not_active Expired - Fee Related
  • 2004-05-31 WO PCT/JP2004/007484 patent/WO2004109406A1/ja active Application Filing

Patent Citations (4)

Also Published As

Similar Documents

Legal Events