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WO2018146974A1 - Photorécepteur d'électrophotographie - Google Patents

Photorécepteur d'électrophotographie Download PDF

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Publication number
WO2018146974A1
WO2018146974A1 PCT/JP2017/047012 JP2017047012W WO2018146974A1 WO 2018146974 A1 WO2018146974 A1 WO 2018146974A1 JP 2017047012 W JP2017047012 W JP 2017047012W WO 2018146974 A1 WO2018146974 A1 WO 2018146974A1
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Prior art keywords
carbon atoms
group
general formula
photosensitive layer
alkyl group
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Japanese (ja)
Inventor
岡田　英樹
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Kyocera Document Solutions Inc
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Kyocera Document Solutions Inc
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Priority to CN201780083456.0A priority Critical patent/CN110178088B/zh
Priority to JP2018566795A priority patent/JP6702444B2/ja
Publication of WO2018146974A1 publication Critical patent/WO2018146974A1/fr
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    • 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

Definitions

  • the present invention relates to an electrophotographic photoreceptor.
  • the electrophotographic photoreceptor is used in an electrophotographic image forming apparatus.
  • the electrophotographic photosensitive member includes a conductive substrate and a photosensitive layer.
  • As the electrophotographic photosensitive member for example, a multilayer electrophotographic photosensitive member or a single layer type electrophotographic photosensitive member is used.
  • the single layer type electrophotographic photosensitive member includes a single layer type photosensitive layer having a charge generation function and a charge transport function as a photosensitive layer.
  • the photosensitive layer provided in the electrophotographic photoreceptor described in Patent Document 1 includes, for example, a compound represented by the chemical formula (E-1).
  • the present invention has been made in view of the above problems, and an object of the present invention is to provide an electrophotographic photoreceptor excellent in sensitivity characteristics.
  • the electrophotographic photoreceptor of the present invention comprises a conductive substrate and a photosensitive layer.
  • the photosensitive layer is a single layer.
  • the photosensitive layer includes a charge generating agent, a hole transporting agent, an electron transporting agent, and a binder resin.
  • the electron transfer agent includes a compound represented by the general formula (1).
  • R 1 and R 2 each independently have a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms. And an aryl group having 6 to 14 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms.
  • the electrophotographic photoreceptor of the present invention is excellent in sensitivity characteristics.
  • 1 is a schematic cross-sectional view illustrating an example of an electrophotographic photosensitive member according to an embodiment of the present invention.
  • 1 is a schematic cross-sectional view illustrating an example of an electrophotographic photosensitive member according to an embodiment of the present invention.
  • 1 is a schematic cross-sectional view illustrating an example of an electrophotographic photosensitive member according to an embodiment of the present invention.
  • a compound and its derivatives may be generically named by adding “system” after the compound name.
  • “polymer” is added after the compound name to indicate the polymer name, it means that the repeating unit of the polymer is derived from the compound or a derivative thereof.
  • a halogen atom an alkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, carbon
  • An aryl group having 6 to 14 atoms, an aralkyl group having 7 to 12 carbon atoms, and a cycloalkyl group having 3 to 10 carbon atoms have the following meanings unless otherwise specified.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • alkyl group having 1 to 6 carbon atoms is linear or branched and unsubstituted.
  • Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, t-butyl group, pentyl group, isopentyl group, A neopentyl group or an n-hexyl group may be mentioned.
  • An alkyl group having 1 to 3 carbon atoms is linear or branched and unsubstituted.
  • Examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.
  • alkoxy group having 1 to 6 carbon atoms is linear or branched and unsubstituted.
  • Examples of the alkoxy group having 1 to 6 carbon atoms include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, s-butoxy group, t-butoxy group, pentoxy group, and hexyloxy. Groups.
  • An alkoxy group having 1 to 3 carbon atoms is linear or branched and unsubstituted.
  • Examples of the alkoxy group having 1 to 3 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, and an isopropoxy group.
  • An aryl group having 6 to 14 carbon atoms is unsubstituted.
  • the aryl group having 6 to 14 carbon atoms include, for example, an unsubstituted aromatic monocyclic hydrocarbon group having 6 to 14 carbon atoms, and an unsubstituted aromatic condensed bicycle having 6 to 14 carbon atoms. It is a hydrocarbon group or an unsubstituted aromatic condensed tricyclic hydrocarbon group having 6 to 14 carbon atoms.
  • Examples of the aryl group having 6 to 14 carbon atoms include a phenyl group, a naphthyl group, an anthryl group, and a phenanthryl group.
  • An aralkyl group having 7 to 12 carbon atoms is linear or branched and unsubstituted.
  • Examples of the aralkyl group having 7 to 12 carbon atoms include a group in which a phenyl group and an alkyl group having 1 to 6 carbon atoms are bonded, or a group in which a naphthyl group is bonded to a methyl group or an ethyl group. .
  • a cycloalkyl group having 3 to 10 carbon atoms is unsubstituted.
  • the cycloalkyl group having 3 to 10 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, and a cyclodecyl group.
  • the electrophotographic photoreceptor (hereinafter sometimes referred to as a photoreceptor) according to an embodiment of the present invention is excellent in sensitivity characteristics. The reason is presumed as follows.
  • the photoreceptor according to this embodiment includes a conductive substrate and a photosensitive layer.
  • the photosensitive layer includes a charge generating agent, a hole transport agent, an electron transport agent, and a binder resin.
  • the electron transport agent includes a compound represented by the general formula (1) (hereinafter sometimes referred to as an isatin derivative (1)).
  • the isatin derivative (1) has a structure in which a heterocycle is condensed to isatin.
  • the isatin derivative (1) has high planarity and has a ⁇ -conjugated system.
  • the isatin derivative (1) has a relatively long carrier (electron) movement distance in the molecule and a relatively short carrier movement distance between the molecules. Therefore, the isatin derivative (1) is considered to have excellent carrier acceptability and transportability.
  • the isatin derivative (1) has an asymmetric structure, it has superior solubility in a solvent for forming a photosensitive layer. Further, the isatin derivative (1) is excellent in compatibility with the binder resin in the photosensitive layer and dispersibility in the photosensitive layer. From the above, it is considered that the electrophotographic photosensitive member according to this embodiment is excellent in sensitivity characteristics.
  • FIGS. 1A to 1C are schematic sectional views showing examples of the photoreceptor 1 according to the present embodiment.
  • the photoreceptor 1 includes a conductive substrate 2 and a photosensitive layer 3.
  • the photosensitive layer 3 is a single layer (single layer).
  • the single-layer photosensitive layer 3 may be referred to as a single-layer type photosensitive layer 3a.
  • a single-layer type photosensitive layer 3 a may be provided directly on the conductive substrate 2.
  • the single-layer type photosensitive layer 3 a may be provided as the outermost surface layer of the photoreceptor 1.
  • the photoreceptor 1 may include a conductive substrate 2, a single-layer type photosensitive layer 3a, and an intermediate layer (undercoat layer) 4.
  • the intermediate layer 4 is provided between the conductive substrate 2 and the single-layer type photosensitive layer 3a.
  • An intermediate layer 4 is provided on the conductive substrate 2, and a single-layer type photosensitive layer 3 a is provided on the intermediate layer 4.
  • a protective layer 5 may be provided on the single-layer type photosensitive layer 3a.
  • the thickness of the single-layer type photosensitive layer 3a is not particularly limited as long as the function as the photosensitive layer can be sufficiently expressed.
  • the thickness of the single-layer type photosensitive layer 3a is preferably 5 ⁇ m or more and 100 ⁇ m or less, and more preferably 10 ⁇ m or more and 50 ⁇ m or less.
  • the photosensitive layer 3 includes a charge generator, a hole transport agent, an electron transport agent, and a binder resin.
  • the photosensitive layer 3 may contain an additive as necessary.
  • the conductive substrate is not particularly limited as long as it can be used as the conductive substrate of the photoreceptor.
  • the conductive substrate may be formed of a material having at least a surface portion having conductivity.
  • An example of the conductive substrate is a conductive substrate formed of a conductive material.
  • Another example of the conductive substrate is a conductive substrate coated with a conductive material.
  • the conductive material include aluminum, iron, copper, tin, platinum, silver, vanadium, molybdenum, chromium, cadmium, titanium, nickel, palladium, and indium. These materials having conductivity may be used alone or in combination of two or more. Examples of the combination of two or more types include alloys (more specifically, aluminum alloys, stainless steel, brass, etc.). Among these materials having conductivity, aluminum or an aluminum alloy is preferable because charge transfer from the photosensitive layer to the conductive substrate is good.
  • the shape of the conductive substrate is appropriately selected according to the structure of the image forming apparatus.
  • Examples of the shape of the conductive substrate include a sheet shape or a drum shape.
  • the thickness of the conductive substrate is appropriately selected according to the shape of the conductive substrate.
  • the electron transport agent includes an isatin derivative (1).
  • the isatin derivative (1) is represented by the general formula (1).
  • R 1 and R 2 may each independently have a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms.
  • R 1 and R 2 may be the same as or different from each other.
  • the halogen atom represented by R 1 and R 2 is preferably a fluorine atom.
  • the alkyl group having 1 to 6 carbon atoms represented by R 1 and R 2 is preferably an alkyl group having 1 to 3 carbon atoms, and more preferably an ethyl group.
  • the alkoxy group having 1 to 6 carbon atoms represented by R 1 and R 2 is preferably an alkoxy group having 1 to 3 carbon atoms, and more preferably a methoxy group.
  • R 1 and R 2 preferably each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms. .
  • R 1 and R 2 each independently represent a hydrogen atom, a fluorine atom, an ethyl group or a methoxy group.
  • At least one of R 1 and R 2 preferably represents an alkyl group having 1 to 3 carbon atoms, and more preferably represents an ethyl group.
  • Examples of the isatin derivative (1) include compounds represented by the chemical formula (1-1), the chemical formula (1-2), the chemical formula (1-3), or the chemical formula (1-4) (hereinafter referred to as the isatin derivative ( 1-1) to (1-4)).
  • isatin derivatives (1) are preferred.
  • the isatin derivative (1) is produced, for example, according to a reaction formula represented by the reaction formula (R-1) (hereinafter sometimes referred to as reaction (R-1)) or by a method analogous thereto.
  • the method for producing the isatin derivative (1) includes, for example, the reaction (R-1).
  • R 1 and R 2 in the general formula (A) are the same meanings as R 1 and R 2 in the general formula (1).
  • X in the general formula (A) represents a halogen atom, and preferably represents a bromine atom.
  • reaction time for reaction (R-1) is preferably 2 hours or longer and 10 hours or shorter.
  • the reaction temperature of reaction (R-1) is preferably raised from a low temperature (more specifically, from ⁇ 100 ° C. to ⁇ 30 ° C.).
  • the ultimate temperature is preferably 0 ° C. or higher and 30 ° C. or lower, for example.
  • the solvent include polar solvents.
  • Examples of the polar solvent include ether (more specifically, tetrahydrofuran, diethyl ether and the like) or aprotic polar solvent (more specifically, dimethylformamide, dimethyl sulfoxide and the like).
  • Examples of the alkyl lithium include n-butyl lithium.
  • the reaction (R-1) can proceed under an atmosphere of an inert gas (more specifically, an argon gas or the like).
  • a purification step In the production of the isatin derivative (1), other steps (for example, a purification step) may be included as necessary.
  • An example of such a process is a purification process.
  • the purification method include known methods (more specifically, filtration, chromatography, crystal folding, etc.).
  • the content of the isatin derivative (1) is preferably 10 parts by mass or more and 200 parts by mass or less, more preferably 10 parts by mass or more and 100 parts by mass or less, with respect to 100 parts by mass of the binder resin. It is particularly preferable that the amount is not less than 75 parts by mass and not more than 75 parts by mass.
  • the photosensitive layer may contain only one kind of isatin derivative (1) as an electron transport agent.
  • the photosensitive layer may contain two or more isatin derivatives (1) as an electron transport agent.
  • the photosensitive layer may contain only the isatin derivative (1) as an electron transport agent.
  • the photosensitive layer may further contain another electron transport agent as an electron transport agent.
  • electron transporting agents include, for example, quinone compounds, diimide compounds, hydrazone compounds, malononitrile compounds, thiopyran compounds, trinitrothioxanthone compounds, 3,4,5,7-tetranitro-9-fluorenone compounds
  • Examples thereof include compounds, dinitroanthracene compounds, dinitroacridine compounds, tetracyanoethylene, 2,4,8-trinitrothioxanthone, dinitrobenzene, dinitroacridine, succinic anhydride, maleic anhydride, or dibromomaleic anhydride.
  • quinone compounds include diphenoquinone compounds, azoquinone compounds, anthraquinone compounds, naphthoquinone compounds, nitroanthraquinone compounds, and dinitroanthraquinone compounds. These electron transport agents may be used alone or in combination of two or more.
  • the hole transporting agent examples include diamine derivatives (more specifically, benzidine derivatives, N, N, N ′, N′-tetraphenylphenylenediamine derivatives, N, N, N ′, N′-tetraphenylnaphthyl).
  • Range amine derivatives or N, N, N ′, N′-tetraphenylphenanthrylenediamine derivatives, etc. oxadiazole compounds (more specifically, 2,5-di (4-methylaminophenyl) -1 , 3,4-oxadiazole, etc.), styryl compounds (more specifically, 9- (4-diethylaminostyryl) anthracene, etc.), carbazole compounds (more specifically, polyvinylcarbazole, etc.), organic polysilane compounds, Pyrazoline compounds (more specifically, 1-phenyl-3- (p-dimethylaminophenyl) pyrazoline etc.), hydrazone compounds Indole-based compounds, oxazole compounds, isoxazole compounds, thiazole compounds, thiadiazole compounds, imidazole compounds, pyrazole compound, or triazole-based compounds.
  • These hole transport agents may be used alone or in combination of two or more. These hole transport agents may be used
  • R 21 , R 22 , R 23 , R 24 , R 25 and R 26 are each independently an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. Represents a group.
  • p, q, v and w each independently represent an integer of 0 or more and 5 or less.
  • m and n each independently represents an integer of 0 or more and 4 or less.
  • R 21 , R 22 , R 23 , R 24 , R 25 and R 26 preferably represent an alkyl group having 1 to 6 carbon atoms, and has 1 to 3 carbon atoms. More preferably, it represents an alkyl group, and more preferably a methyl group.
  • p, q, v, w, m and n preferably represent 1.
  • a compound represented by the chemical formula (H-1) (hereinafter sometimes referred to as the compound (H-1)) is preferable.
  • the content of the hole transport agent is preferably 10 parts by mass or more and 200 parts by mass or less, more preferably 10 parts by mass or more and 100 parts by mass or less, with respect to 100 parts by mass of the binder resin.
  • the amount is particularly preferably 90 parts by mass or less.
  • the photosensitive layer may contain only the compound represented by the general formula (3) as a hole transport agent.
  • a photosensitive layer may contain only 1 type of the compound represented by General formula (3) as a hole transport agent.
  • the photosensitive layer may contain two or more compounds represented by the general formula (3) as a hole transport agent.
  • the charge generator is not particularly limited as long as it is a charge generator for a photoreceptor.
  • the charge generator include phthalocyanine pigments, perylene pigments, bisazo pigments, trisazo pigments, dithioketopyrrolopyrrole pigments, metal-free naphthalocyanine pigments, metal naphthalocyanine pigments, squaraine pigments, indigo pigments, azurenium pigments, cyanine Pigments, inorganic photoconductive materials (more specifically, selenium, selenium-tellurium, selenium-arsenic, cadmium sulfide, amorphous silicon, etc.) powders, pyrylium pigments, ansanthrone pigments, triphenylmethane pigments, selenium pigments , Toluidine pigments, pyrazoline pigments or quinacridone pigments.
  • the photosensitive layer may contain only one type of charge generating agent or may contain two or more
  • the phthalocyanine pigment examples include metal-free phthalocyanine represented by the chemical formula (C-1) (hereinafter sometimes referred to as compound (C-1)). Another example of the phthalocyanine pigment is metal phthalocyanine. Examples of the metal phthalocyanine include titanyl phthalocyanine represented by the chemical formula (C-2) (hereinafter sometimes referred to as compound (C-2)). Another example of a metal phthalocyanine is hydroxygallium phthalocyanine or chlorogallium phthalocyanine. The phthalocyanine pigment may be crystalline or non-crystalline. The crystal shape of the phthalocyanine pigment (for example, ⁇ type, ⁇ type, Y type, V type or II type) is not particularly limited, and phthalocyanine pigments having various crystal shapes are used.
  • Examples of the crystal of metal-free phthalocyanine include a metal-free phthalocyanine X-type crystal (hereinafter sometimes referred to as X-type metal-free phthalocyanine).
  • Examples of the crystal of titanyl phthalocyanine include ⁇ -type, ⁇ -type, and Y-type crystals of titanyl phthalocyanine (hereinafter sometimes referred to as ⁇ -type, ⁇ -type, or Y-type titanyl phthalocyanine).
  • Examples of the crystal of hydroxygallium phthalocyanine include a V-type crystal of hydroxygallium phthalocyanine.
  • Examples of chlorogallium phthalocyanine crystals include chlorogallium phthalocyanine type II crystals.
  • the charge generator is preferably a phthalocyanine pigment, more preferably a metal-free phthalocyanine or titanyl phthalocyanine.
  • the isatin derivative (1) is included in the photosensitive layer, in order to further improve the electrical characteristics (particularly sensitivity characteristics) of the photoreceptor, X-type metal-free phthalocyanine or Y-type titanyl phthalocyanine is more preferable as the charge generator. .
  • Y-type titanyl phthalocyanine has a main peak at 27.2 ° of the Bragg angle (2 ⁇ ⁇ 0.2 °) in the CuK ⁇ characteristic X-ray diffraction spectrum, for example.
  • the main peak in the CuK ⁇ characteristic X-ray diffraction spectrum is a peak having the first or second highest intensity in a range where the Bragg angle (2 ⁇ ⁇ 0.2 °) is 3 ° or more and 40 ° or less.
  • a sample (titanyl phthalocyanine) is filled in a sample holder of an X-ray diffractometer (for example, “RINT (registered trademark) 1100” manufactured by Rigaku Corporation), and an X-ray diffraction spectrum is measured.
  • the measurement conditions are an X-ray tube Cu, a tube voltage of 40 kV, a tube current of 30 mA, and a CuK ⁇ characteristic X-ray wavelength of 1.542 mm.
  • the measurement range (2 ⁇ ) is 3 ° to 40 ° (start angle 3 °, stop angle 40 °), and the scanning speed is 10 ° / min.
  • An santhrone pigment is preferably used as a charge generating agent in a photoreceptor applied to an image forming apparatus using a short wavelength laser light source.
  • the wavelength of the short wavelength laser light is, for example, not less than 350 nm and not more than 550 nm.
  • the content of the charge generating agent is preferably 0.1 parts by mass or more and 50 parts by mass or less, more preferably 0.5 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the binder resin.
  • the amount is particularly preferably 0.5 parts by mass or more and 6.0 parts by mass or less.
  • binder resin examples include a thermoplastic resin, a thermosetting resin, and a photocurable resin.
  • thermoplastic resin examples include polycarbonate resin, polyarylate resin, styrene-butadiene resin, styrene-acrylonitrile resin, styrene-maleic acid resin, acrylic acid resin, styrene-acrylic acid resin, polyethylene resin, and ethylene-vinyl acetate.
  • Resin chlorinated polyethylene resin, polyvinyl chloride resin, polypropylene resin, ionomer resin, vinyl chloride-vinyl acetate resin, alkyd resin, polyamide resin, urethane resin, polysulfone resin, diallyl phthalate resin, ketone resin, polyvinyl butyral resin, polyester resin Or a polyether resin is mentioned.
  • a thermosetting resin a silicone resin, an epoxy resin, a phenol resin, a urea resin, or a melamine resin is mentioned, for example.
  • the photocurable resin examples include an epoxy-acrylic acid resin (more specifically, an acrylic acid derivative adduct of an epoxy compound) or a urethane-acrylic acid resin (more specifically, an acrylic acrylic resin). Acid derivative adducts, etc.).
  • the photosensitive layer may contain only one type of binder resin or may contain two or more types.
  • a polycarbonate resin is preferable because a photosensitive layer having an excellent balance of workability, mechanical strength, optical characteristics, and abrasion resistance can be obtained.
  • the polycarbonate resin include a bisphenol Z-type polycarbonate resin having a repeating unit represented by the following chemical formula (PC-1) (hereinafter sometimes referred to as a polycarbonate resin (PC-1)).
  • PC-1 polycarbonate resin
  • bisphenol ZC type polycarbonate resin, bisphenol C type polycarbonate resin or bisphenol A type polycarbonate resin can be mentioned.
  • the viscosity average molecular weight of the binder resin is preferably 40,000 or more, and more preferably 40,000 or more and 52,500 or less.
  • the viscosity average molecular weight of the binder resin is 40,000 or more, it is easy to improve the wear resistance of the photoreceptor.
  • the viscosity average molecular weight of the binder resin is 52,500 or less, the binder resin is easily dissolved in a solvent during formation of the photosensitive layer, and the viscosity of the coating solution for the photosensitive layer does not become too high. As a result, it becomes easy to form a photosensitive layer.
  • the photosensitive layer of the photoreceptor may contain an additive as necessary.
  • Additives include, for example, deterioration inhibitors (more specifically, antioxidants, radical scavengers, quenchers or ultraviolet absorbers), softeners, surface modifiers, extenders, thickeners, dispersions. Stabilizers, waxes, donors, surfactants, plasticizers, sensitizers or leveling agents can be mentioned.
  • a coating solution for a photosensitive layer (hereinafter sometimes referred to as a coating solution) is applied onto a conductive substrate to form a coating film. It is manufactured by drying the coating film. Dissolve or disperse a charge generator, a hole transport agent, an isatin derivative (1) as an electron transport agent, a binder resin, and a component (for example, an additive) added as necessary in a solvent. Thus, the photosensitive layer coating solution is produced.
  • the solvent contained in the coating solution is not particularly limited as long as each component contained in the coating solution can be dissolved or dispersed.
  • the solvent include alcohol (more specifically, methanol, ethanol, isopropanol, butanol, etc.), aliphatic hydrocarbon (more specifically, n-hexane, octane, cyclohexane, etc.), aromatic hydrocarbon (more specifically, Benzene, toluene, xylene, etc.), halogenated hydrocarbons (more specifically, dichloromethane, dichloroethane, carbon tetrachloride, chlorobenzene, etc.), ethers (more specifically, dimethyl ether, diethyl ether, tetrahydrofuran, Ethylene glycol dimethyl ether, diethylene glycol dimethyl ether or propylene glycol monomethyl ether), ketones (more specifically, acetone, methyl ethyl ketone, cyclohexanone, etc
  • Methyl acetate dimethylformamide, dimethylformamide or dimethyl sulfoxide and the like. These solvents are used alone or in combination of two or more. In order to improve the workability during the production of the photoreceptor, it is preferable to use a non-halogen solvent (a solvent other than the halogenated hydrocarbon) as the solvent.
  • a non-halogen solvent a solvent other than the halogenated hydrocarbon
  • the coating solution is prepared by mixing each component and dispersing in a solvent.
  • a bead mill, a roll mill, a ball mill, an attritor, a paint shaker, or an ultrasonic disperser can be used.
  • the coating liquid may contain, for example, a surfactant in order to improve the dispersibility of each component.
  • the method for applying the coating solution is not particularly limited as long as the coating solution can be uniformly applied on the conductive substrate.
  • the coating method include a dip coating method, a spray coating method, a spin coating method, and a bar coating method.
  • the method for drying the coating solution is not particularly limited as long as the solvent in the coating solution can be evaporated.
  • the method of heat-processing hot-air drying
  • the heat treatment conditions are preferably, for example, a temperature of 40 ° C. or higher and 150 ° C. or lower and a time of 3 minutes or longer and 120 minutes or shorter.
  • the method for producing a photoreceptor may further include one or both of a step of forming an intermediate layer and a step of forming a protective layer as necessary.
  • a known method is appropriately selected in the step of forming the intermediate layer and the step of forming the protective layer.
  • Photosensitive Material> The following hole transporting agent, charge generating agent, binder resin, and electron transporting agent were prepared as materials for forming the single layer type photosensitive layer of the single layer type photoreceptor.
  • Electron transport agent> As electron transporting agents, isatin derivatives (1-1) to (1-4) were produced by the following methods, respectively.
  • an isatin derivative represented by the chemical formula (A-1) (hereinafter sometimes referred to as an isatin derivative (A-1)) is cyclized to produce an isatin derivative (1-1 )
  • 0.32 g (1 mmol) of isatin derivative (A-1) and 30 mL of tetrahydrofuran were charged into a reaction vessel to prepare a tetrahydrofuran solution.
  • the inert gas was continuously introduced into the reaction vessel, and an inert gas stream was set.
  • the temperature in the reaction vessel was -78 ° C. Under these conditions, a 1.6 M n-butyllithium hexane solution (0.76 mL) was dropped into the reaction vessel. Subsequently, the temperature in the reaction vessel was gradually raised to room temperature (25 ° C.). Next, the contents in the reaction vessel were stirred for 8 hours.
  • Table 1 shows the isatin derivative (A) and the isatin derivative (1) in the reaction (r-1).
  • the isatin derivative (A) is a reactant in the reaction (r-1).
  • Table 1 shows the yield and yield of the isatin derivative (1).
  • Isatin derivative (1-1) 7.33-7.47 (m, 3H), 6.92-7.05 (m, 2H), 5.13 (s, 2H).
  • Compound (C-1) was a metal-free phthalocyanine (X-type metal-free phthalocyanine) represented by the chemical formula (C-1) and having an X-type crystal structure.
  • Compound (C-2) was titanyl phthalocyanine (Y-type titanyl phthalocyanine) represented by chemical formula (C-2) and having a Y-type crystal structure.
  • Y-type titanyl phthalocyanine represented by chemical formula (C-2)
  • Binder resin As the binder resin, the polycarbonate resin (PC-1) described in the present embodiment (“Panlite (registered trademark) TS-2050” manufactured by Teijin Ltd., viscosity average molecular weight 50,000) was prepared.
  • Photoconductors (A-1) to (A-8) and photoconductors (B-1) to (B-2) were produced using materials for forming the photosensitive layer.
  • photoconductor (A-1) > 5 parts by weight of the compound (C-1) as a charge generating agent, 50 parts by weight of the compound (H-1) as a hole transporting agent, 30 parts by weight of an isatin derivative (1-1) as an electron transporting agent, 100 parts by mass of polycarbonate resin (PC-1) as a binder resin and 800 parts by mass of tetrahydrofuran as a solvent were put in a container. The contents of the container were mixed for 50 hours using a ball mill, and the materials (compound (C-1), compound (H-1), isatin derivative (1-1) and polycarbonate resin (PC-1)) were mixed in the solvent. Was dispersed. This obtained the coating liquid for photosensitive layers.
  • a photosensitive layer coating solution was applied on an aluminum drum-shaped support (diameter 30 mm, total length 238.5 mm) as a conductive substrate using a dip coating method to form a coating film.
  • the coating film was dried with hot air at 100 ° C. for 60 minutes.
  • a single-layer type photosensitive layer thickness 30 ⁇ m was formed on the conductive substrate.
  • a photoreceptor A-1 was obtained.
  • Table 2 shows the structures of the photoconductors (A-1) to (A-8) and the photoconductors (B-1) to (B-2).
  • CGM, HTM, and ETM represent a charge generator, a hole transport agent, and an electron transport agent, respectively.
  • x-H 2 Pc and Y-TiOPc in the column “CGM” indicate X-type metal-free phthalocyanine and Y-type titanyl phthalocyanine, respectively.
  • HTM H-1 represents the compound (H-1).
  • ETM 1-1 to 1-4 and E-1 represent the isatin derivatives (1-1) to (1-4) and the compound (E-1), respectively.
  • monochromatic light (wavelength 780 nm, half-value width 20 nm, light intensity 16 ⁇ W / cm 2 ) was extracted from the white light of the halogen lamp using a bandpass filter.
  • the extracted monochromatic light was irradiated onto the surface of the photoreceptor (irradiation time: 80 milliseconds).
  • the surface potential of the photoreceptor was measured when 330 milliseconds had elapsed after the start of irradiation (exposure).
  • the measured surface potential was defined as a sensitivity potential (V L , unit V).
  • Table 2 shows the measured sensitivity potential (V L ) of the photoreceptor. The smaller the absolute value of the sensitivity potential (V L ), the better the sensitivity characteristic of the photoreceptor.
  • the sensitivity potential corresponds to the post-exposure potential.
  • the photosensitive layer is a single layer, and includes a charge generator, a hole transport agent, an electron transport agent, a binder resin, and the like.
  • the electron transfer agent was one of isatin derivatives (1-1) to (1-4).
  • the isatin derivatives (1-1) to (1-4) were compounds included in the general formula (1).
  • the sensitivity potential V L was + 114V or more and + 126V or less.
  • crystallization on the surface of the photosensitive layer was not visually confirmed.
  • the photosensitive layer contained the compound (E-1) as an electron transport agent.
  • the compound (E-1) was not a compound represented by the general formula (1).
  • the sensitivity potential V L was +130 V or more and +135 V or less.
  • crystallization on the surface of the photosensitive layer was slightly confirmed visually.
  • the photoconductor according to the present invention can be used in an image forming apparatus.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Photoreceptors In Electrophotography (AREA)

Abstract

L'invention concerne un photorécepteur d'électrophotographie contenant un substrat électroconducteur et une couche photosensible. La couche photosensible est une couche unique. La couche photosensible contient un agent de génération de charge, un agent de transfert de trous positifs, un agent de transfert d'électrons et une résine liante. L'agent de transfert d'électrons contient un composé représenté par la formule générale (1). Dans la formule générale (1), R1 et R2 désignent chacun indépendamment un atome d'hydrogène, un atome d'halogène, un groupe alkyle comptant de 1 à 6 atomes de carbone, un groupe aryle comptant de 6 à 14 atomes de carbone et pouvant contenir un groupe alkyle comptant de 1 à 6 atomes de carbone, un groupe aralkyle comptant de 7 à 12 atomes de carbone, un groupe cycloalkyle comptant de 3 à 10 atomes de carbone ou un groupe alcoxy comptant de 1 à 6 atomes de carbone.
PCT/JP2017/047012 2017-02-09 2017-12-27 Photorécepteur d'électrophotographie Ceased WO2018146974A1 (fr)

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JPH0940644A (ja) * 1995-07-26 1997-02-10 Mita Ind Co Ltd イサチン誘導体およびそれを用いた電子写真感光体
JP2002148836A (ja) * 2000-11-07 2002-05-22 Kyocera Mita Corp 電子写真感光体
JP2002148834A (ja) * 2000-11-07 2002-05-22 Kyocera Mita Corp 電子写真感光体

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JP3448411B2 (ja) * 1994-11-29 2003-09-22 京セラミタ株式会社 トリプトアントリンイミン誘導体およびこれを用いた電子写真感光体
EP0718298A1 (fr) * 1994-11-29 1996-06-26 Mita Industrial Co. Ltd. Composés de tryptoanthrinime comme agents de transport d'électron
CN104761563A (zh) * 2014-01-06 2015-07-08 北京大学 含有吸电子基团的对苯撑乙烯类化合物及其制备和应用
CN106750196B (zh) * 2017-01-06 2019-02-01 天津大学 基于异靛蓝衍生物的电子传输型聚合物及有机场效应晶体管

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JPH0940644A (ja) * 1995-07-26 1997-02-10 Mita Ind Co Ltd イサチン誘導体およびそれを用いた電子写真感光体
JP2002148836A (ja) * 2000-11-07 2002-05-22 Kyocera Mita Corp 電子写真感光体
JP2002148834A (ja) * 2000-11-07 2002-05-22 Kyocera Mita Corp 電子写真感光体

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NITTI, ANDREA ET AL.: "Conjugated Thiophene-Fused Isatin Dyes through Intramolecular Direct Arylation", THE JOURNAL OF ORGANIC CHEMISTRY, vol. 81, no. 22, 6 October 2016 (2016-10-06), pages 11035 - 11042, XP055532846, Retrieved from the Internet <URL:DOI:10.1021/acs.joc.6b01922> *

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