WO2018230110A1 - Photorécepteur électrophotographique, cartouche de traitement, et dispositif de formation d'images - Google Patents

Photorécepteur électrophotographique, cartouche de traitement, et dispositif de formation d'images Download PDF

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Publication number
WO2018230110A1
WO2018230110A1 PCT/JP2018/014312 JP2018014312W WO2018230110A1 WO 2018230110 A1 WO2018230110 A1 WO 2018230110A1 JP 2018014312 W JP2018014312 W JP 2018014312W WO 2018230110 A1 WO2018230110 A1 WO 2018230110A1
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general formula
integer
less
represent
same
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PCT/JP2018/014312
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English (en)
Japanese (ja)
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智文 清水
敬司 丸尾
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京セラドキュメントソリューションズ株式会社
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Priority to JP2019525121A priority Critical patent/JP6741156B2/ja
Priority to CN201880034962.5A priority patent/CN110709780B/zh
Publication of WO2018230110A1 publication Critical patent/WO2018230110A1/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
    • 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
    • G03G5/05—Organic bonding materials; Methods for coating a substrate with a photoconductive layer; Inert supplements for use in photoconductive layers
    • 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 photosensitive member, a process cartridge, and an image forming apparatus.
  • the electrophotographic photosensitive member is used as an image carrier in an electrophotographic image forming apparatus (for example, a printer and a multifunction machine).
  • the electrophotographic photoreceptor includes a photosensitive layer.
  • Examples of the electrophotographic photosensitive member include a single layer type electrophotographic photosensitive member and a laminated type electrophotographic photosensitive member.
  • the single-layer type electrophotographic photosensitive member includes a photosensitive layer having a charge generation function and a charge transport function.
  • the multilayer electrophotographic photosensitive member includes a photosensitive layer including a charge generation layer having a charge generation function and a charge transport layer having a charge transport function.
  • Patent Document 1 describes a polycarbonate resin having a repeating unit represented by the following chemical formula (RA) as a binder resin for an electrophotographic photoreceptor.
  • the present invention has been made in view of the above problems, and an object of the present invention is to provide an electrophotographic photosensitive member provided with a photosensitive layer excellent in sensitivity characteristics and fog resistance. Another object of the present invention is to provide a process cartridge and an image forming apparatus that suppress the occurrence of image defects.
  • the electrophotographic photoreceptor of the present invention is an electrophotographic photoreceptor provided with a conductive substrate and a photosensitive layer.
  • the photosensitive layer is a single layer and includes a charge generating agent, a hole transporting agent, an electron transporting agent, and a binder resin.
  • the binder resin includes a polycarbonate resin.
  • the polycarbonate resin has a repeating unit represented by the following general formula (1-1) and a repeating unit represented by the following general formula (1-2).
  • the hole transport agent is represented by the following general formula (HTM1), general formula (HTM2), general formula (HTM3), general formula (HTM4), general formula (HTM5), general formula (HTM6), or general formula (HTM7).
  • the scratch-resistant depth of the photosensitive layer is 0.50 ⁇ m or less.
  • the photosensitive layer has a Vickers hardness of 17.0 HV or more.
  • Q 1 and Q 2 each represent a hydrogen atom
  • Q 3 and Q 4 each independently represent an alkyl group having 1 to 6 carbon atoms
  • Q 1 and Q 2 each independently represents an alkyl group having 1 to 6 carbon atoms
  • Q 3 and Q 4 each represents a hydrogen atom
  • R 1 , R 2 , R 3 and R 4 each independently represents an alkyl group having 1 to 6 carbon atoms. a1, a2, a3 and a4 each independently represent an integer of 0 or more and 5 or less.
  • a1 represents an integer of 2 or more and 5 or less
  • the plurality of R 1 may be the same as or different from each other.
  • a2 represents an integer of 2 or more and 5 or less
  • the plurality of R 2 may be the same as or different from each other.
  • a3 represents an integer of 2 or more and 5 or less
  • the plurality of R 3 may be the same as or different from each other.
  • a4 represents an integer of 2 or more and 5 or less
  • the plurality of R 4 may be the same as or different from each other.
  • R 5 , R 6 , R 7 and R 8 each independently represents an alkyl group having 1 to 6 carbon atoms or a hydrogen atom.
  • R 9 , R 10 , R 11 and R 12 each independently represents an alkyl group having 1 to 6 carbon atoms.
  • b1, b2, b3 and b4 each independently represent an integer of 0 or more and 5 or less.
  • the plurality of R 9 may be the same as or different from each other.
  • the plurality of R 10 may be the same as or different from each other.
  • the plurality of R 11 may be the same as or different from each other.
  • b4 represents an integer of 2 or more and 5 or less
  • the plurality of R 12 may be the same as or different from each other.
  • R 13 , R 14 , R 15 and R 16 each independently represents an alkyl group having 1 to 6 carbon atoms.
  • c1, c2, c3 and c4 each independently represents an integer of 0 or more and 5 or less.
  • c1 represents an integer of 2 or more and 5 or less
  • the plurality of R 13 may be the same as or different from each other.
  • c2 represents an integer of 2 to 5
  • a plurality of R 14 may be the same as or different from each other.
  • c3 represents an integer of 2 or more and 5 or less
  • the plurality of R 15 may be the same as or different from each other.
  • c4 represents an integer of 2 to 5
  • a plurality of R 16 may be the same as or different from each other.
  • R 17 , R 18 , R 19 , R 20 and R 21 each independently represents an alkyl group having 1 to 6 carbon atoms or a hydrogen atom.
  • R 22 , R 23 and R 24 each independently represents an alkyl group having 1 to 6 carbon atoms.
  • d1, d2 and d3 each independently represent an integer of 0 or more and 5 or less.
  • d1 represents an integer of 2 or more and 5 or less
  • the plurality of R 22 may be the same as or different from each other.
  • d2 represents an integer of 2 or more and 5 or less
  • the plurality of R 23 may be the same as or different from each other.
  • d3 represents an integer of 2 or more and 5 or less
  • the plurality of R 24 may be the same as or different from each other.
  • R 25 represents an alkyl group having 1 to 6 carbon atoms or a hydrogen atom.
  • R 26 , R 27 and R 28 each independently represents an alkyl group having 1 to 6 carbon atoms.
  • e1, e2 and e3 each independently represents an integer of 0 or more and 5 or less.
  • the plurality of R 26 may be the same as or different from each other.
  • the plurality of R 27 may be the same as or different from each other.
  • the plurality of R 28 may be the same as or different from each other.
  • R 29 , R 30 and R 31 each independently represents an aryl group having 6 to 14 carbon atoms or a hydrogen atom.
  • the process cartridge of the present invention includes the above-described electrophotographic photosensitive member.
  • the image forming apparatus of the present invention includes an image carrier, a charging unit, an exposure unit, a developing unit, and a transfer unit.
  • the image carrier is the above-described electrophotographic photosensitive member.
  • the charging unit charges the surface of the image carrier.
  • the charging polarity of the charging unit is positive.
  • the exposure unit exposes the charged surface of the image carrier to form an electrostatic latent image on the surface of the image carrier.
  • the developing unit develops the electrostatic latent image as a toner image.
  • the transfer unit transfers the toner image from the image carrier to the transfer target while the surface of the image support and the transfer target are in contact with each other.
  • the electrophotographic photoreceptor of the present invention is excellent in sensitivity characteristics and fog resistance.
  • the process cartridge and the image forming apparatus of the present invention can suppress the occurrence of image defects.
  • FIG. 6 is a cross-sectional view taken along line IV-IV in FIG. 5.
  • FIG. 6 is a side view of the fixing base, the scratching needle, and the electrophotographic photosensitive member shown in FIG. 5. It is a figure which shows the scratch formed in the surface of the photosensitive layer.
  • a compound and its derivative may be named generically by attaching "system” after a compound name.
  • system the name of a polymer is expressed by adding “system” after the compound name, it means that the repeating unit of the polymer is derived from the compound or a derivative thereof.
  • an alkyl group having 1 to 6 carbon atoms an alkyl group having 1 to 3 carbon atoms, and an aryl group having 6 to 14 carbon atoms have the following meanings.
  • An 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, ethyl, propyl, isopropyl, n-butyl, s-butyl, t-butyl, pentyl, isopentyl, and neopentyl groups. , And hexyl groups.
  • 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, a propyl group, and an isopropyl 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. Examples thereof include a hydrocarbon group and an unsubstituted aromatic condensed tricyclic hydrocarbon group having 6 to 14 carbon atoms. More specific 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.
  • the photoreceptor 1 includes a conductive substrate 2 and a photosensitive layer 3.
  • the photosensitive layer 3 is a single layer.
  • the photosensitive layer 3 may be provided directly on the conductive substrate 2.
  • the photoreceptor 1 may include, for example, a conductive substrate 2, an intermediate layer 4 (for example, an undercoat layer), and a photosensitive layer 3.
  • the photosensitive layer 3 is indirectly provided on the conductive substrate 2 via the intermediate layer 4.
  • the photoreceptor 1 may include a protective layer 5 as an outermost surface layer.
  • the elements of the photoreceptor 1 (conductive substrate 2, photosensitive layer 3, and intermediate layer 4) will be described. Further, a method for manufacturing the photoreceptor 1 will be described.
  • the conductive substrate 2 is not particularly limited as long as it can be used as the conductive substrate of the photoreceptor 1.
  • a conductive substrate formed of a material having at least a surface portion having conductivity can be used.
  • the conductive substrate 2 include a conductive substrate made of a conductive material (conductive material) and 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 conductive materials may be used alone or in combination of two or more. Examples of combinations of two or more include alloys (more specifically, aluminum alloys, stainless steel, brass, etc.). Among these conductive materials, aluminum and aluminum alloys are preferable because charge transfer from the photosensitive layer 3 to the conductive substrate 2 is good.
  • the shape of the conductive substrate 2 can be appropriately selected according to the structure of the image forming apparatus to be used. Examples of the shape of the conductive substrate 2 include a sheet shape and a drum shape. Further, the thickness of the conductive substrate 2 can be appropriately selected according to the shape of the conductive substrate 2.
  • the photosensitive layer 3 contains a charge generating agent, a hole transport agent, an electron transport agent, and a binder resin.
  • the photosensitive layer 3 may further contain an additive.
  • the thickness of the photosensitive layer 3 is not particularly limited as long as the function as the photosensitive layer can be sufficiently expressed. Specifically, the thickness of the photosensitive layer 3 may be 5 ⁇ m or more and 100 ⁇ m or less, and is preferably 10 ⁇ m or more and 50 ⁇ m or less.
  • the Vickers hardness of the photosensitive layer 3 is measured by a method according to Japanese Industrial Standard (JIS) Z2244.
  • JIS Japanese Industrial Standard
  • a hardness meter for example, “Micro Vickers hardness meter DMH-1 type” manufactured by Matsuzawa Co., Ltd.
  • Vickers hardness is measured, for example, at a temperature of 23 ° C., a diamond indenter load (test force) of 10 gf, a time required to reach the test force of 5 seconds, a diamond indenter approach speed of 2 mm / second, and a test force holding time of 1 This can be done under seconds.
  • the Vickers hardness of the photosensitive layer 3 is 17.0 HV or more, preferably 17.8 HV or more, more preferably 18.2 HV or more from the viewpoint of further improving the fog resistance.
  • the upper limit of the Vickers hardness of the photosensitive layer 3 is not particularly limited as long as it can function as the photosensitive layer of the photoreceptor 1, but 25.0 HV is preferable from the viewpoint of manufacturing cost.
  • the Vickers hardness can be controlled, for example, by adjusting the type of polycarbonate resin (1) described later and the type and content of a hole transporting agent described later.
  • the scratch resistance depth of the photosensitive layer 3 (hereinafter sometimes referred to as scratch depth) is 0.50 ⁇ m or less.
  • the scratch depth of the photosensitive layer 3 is the depth of scratches formed when the photosensitive layer 3 is scratched under the specific conditions shown below.
  • the scratch depth of the photosensitive layer 3 is measured by performing the following first step, second step, third step, and fourth step using a scratch device defined in JIS K5600-5-5.
  • the scratching device includes a fixed base and a scratching needle.
  • the scratching needle has a hemispherical sapphire tip with a diameter of 1 mm.
  • the photosensitive member 1 is fixed to the upper surface of the fixing base so that the longitudinal direction of the photosensitive member 1 is parallel to the longitudinal direction of the fixing base.
  • the scratch needle is brought into perpendicular contact with the surface of the photosensitive layer 3.
  • the third step while applying a load of 10 g from the scratching needle to the photosensitive layer 3, the fixed base and the photosensitive member 1 fixed on the upper surface of the fixed base are moved by 30 mm at a speed of 30 mm / min in the longitudinal direction of the fixed base. Let By this third step, scratches are formed on the surface of the photosensitive layer 3.
  • the scratch depth that is the maximum depth of the scratch is measured.
  • the scratch depth of the photosensitive layer 3 is 0.50 ⁇ m or less, preferably 0.46 ⁇ m or less, and more preferably 0.44 ⁇ m or less from the viewpoint of further improving the fog resistance.
  • the lower limit of the scratch depth of the photosensitive layer 3 is not particularly limited as long as it can function as the photosensitive layer of the photosensitive member 1. For example, it may be 0.00 ⁇ m, but 0.09 ⁇ m from the viewpoint of manufacturing cost. preferable.
  • the scratch depth can be controlled, for example, by adjusting the type of polycarbonate resin (1) described later and the type and content of a hole transporting agent described later.
  • 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, dithioketopyrrolopyrrole pigments, metal-free naphthalocyanine pigments, metal naphthalocyanine pigments, squaraine pigments, trisazo pigments, indigo pigments, azurenium pigments, cyanine Pigments, powders of inorganic photoconductive materials (eg, selenium, selenium-tellurium, selenium-arsenic, cadmium sulfide, and amorphous silicon), pyrylium salts, ansanthrone pigments, triphenylmethane pigments, selenium pigments, toluidine pigments , Pyrazoline pigments, and quinacridone pigments.
  • inorganic photoconductive materials eg, selenium, selenium-tellurium, seleni
  • a charge generating agent may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the phthalocyanine pigment include metal-free phthalocyanine and metal phthalocyanine.
  • the metal phthalocyanine include titanyl phthalocyanine, hydroxygallium phthalocyanine, and chlorogallium phthalocyanine.
  • the phthalocyanine pigment may be crystalline or non-crystalline.
  • the crystal shape of the phthalocyanine pigment (for example, ⁇ type, ⁇ type, X type, Y type, V type and II type) is not particularly limited, and phthalocyanine pigments having various crystal shapes are used.
  • Examples of the crystal of metal-free phthalocyanine include metal-free phthalocyanine X-type crystal (hereinafter sometimes referred to as X-type metal-free phthalocyanine).
  • Examples of the titanyl phthalocyanine crystals include ⁇ -type, ⁇ -type, and Y-type crystals of titanyl phthalocyanine (hereinafter sometimes referred to as ⁇ -type, ⁇ -type, and Y-type titanyl phthalocyanine, respectively).
  • Examples of the crystal of hydroxygallium phthalocyanine include a V-type crystal of hydroxygallium phthalocyanine.
  • the photoreceptor 1 when the photoreceptor 1 is applied to a digital optical image forming apparatus, it is preferable to use a charge generating agent having sensitivity in a wavelength region of 700 nm or more.
  • the charge generator having sensitivity in the wavelength region of 700 nm or more include phthalocyanine pigments, and X-type metal-free phthalocyanine is preferable from the viewpoint of efficiently generating charges.
  • the digital optical image forming apparatus include a laser beam printer and a facsimile using a light source such as a semiconductor laser.
  • the photoreceptor 1 when the photoreceptor 1 is applied to an image forming apparatus using a short wavelength laser light source, for example, an ansanthrone pigment and a perylene pigment are preferably used as the charge generating agent.
  • the wavelength of the short wavelength laser is, for example, about 350 nm to 550 nm.
  • Examples of the charge generator include phthalocyanine pigments represented by the following chemical formulas (CGM-1) to (CGM-4) (hereinafter referred to as charge generators (CGM-1) to (CGM-4), respectively). May be included).
  • the content of the charge generating agent is preferably 0.1 parts by weight or more and 50 parts by weight or less, and 0.5 parts by weight or more and 30 parts by weight or less with respect to 100 parts by weight of the binder resin from the viewpoint of efficiently generating charges.
  • the amount is more preferably 0.5 parts by mass or less, and particularly preferably 0.5 parts by mass or more and 4.5 parts by mass or less.
  • the hole transport agent is represented by the following general formula (HTM1), general formula (HTM2), general formula (HTM3), general formula (HTM4), general formula (HTM5), general formula (HTM6), or general formula (HTM7).
  • HTM1 general formula
  • HTM2 general formula
  • HTM3 general formula
  • HTM4 general formula
  • HTM5 general formula
  • HTM6 general formula
  • HTM7 general formula
  • the photosensitive layer 3 may contain one of these hole transport agents alone, or may contain two or more kinds.
  • R 1 , R 2 , R 3 and R 4 each independently represents an alkyl group having 1 to 6 carbon atoms. a1, a2, a3 and a4 each independently represent an integer of 0 or more and 5 or less.
  • a1 represents an integer of 2 or more and 5 or less
  • the plurality of R 1 may be the same as or different from each other.
  • a2 represents an integer of 2 or more and 5 or less
  • the plurality of R 2 may be the same as or different from each other.
  • a3 represents an integer of 2 or more and 5 or less
  • the plurality of R 3 may be the same as or different from each other.
  • a4 represents an integer of 2 or more and 5 or less
  • the plurality of R 4 may be the same as or different from each other.
  • R 5 , R 6 , R 7 and R 8 each independently represents an alkyl group having 1 to 6 carbon atoms or a hydrogen atom.
  • R 9 , R 10 , R 11 and R 12 each independently represents an alkyl group having 1 to 6 carbon atoms.
  • b1, b2, b3 and b4 each independently represent an integer of 0 or more and 5 or less.
  • the plurality of R 9 may be the same as or different from each other.
  • the plurality of R 10 may be the same as or different from each other.
  • the plurality of R 11 may be the same as or different from each other.
  • b4 represents an integer of 2 or more and 5 or less
  • the plurality of R 12 may be the same as or different from each other.
  • R 13 , R 14 , R 15 and R 16 each independently represents an alkyl group having 1 to 6 carbon atoms.
  • c1, c2, c3 and c4 each independently represents an integer of 0 or more and 5 or less.
  • c1 represents an integer of 2 or more and 5 or less
  • the plurality of R 13 may be the same as or different from each other.
  • c2 represents an integer of 2 to 5
  • a plurality of R 14 may be the same as or different from each other.
  • c3 represents an integer of 2 or more and 5 or less
  • the plurality of R 15 may be the same as or different from each other.
  • c4 represents an integer of 2 to 5
  • a plurality of R 16 may be the same as or different from each other.
  • R 17 , R 18 , R 19 , R 20 and R 21 each independently represents an alkyl group having 1 to 6 carbon atoms or a hydrogen atom.
  • R 22 , R 23 and R 24 each independently represents an alkyl group having 1 to 6 carbon atoms.
  • d1, d2 and d3 each independently represent an integer of 0 or more and 5 or less.
  • d1 represents an integer of 2 or more and 5 or less
  • the plurality of R 22 may be the same as or different from each other.
  • d2 represents an integer of 2 or more and 5 or less
  • the plurality of R 23 may be the same as or different from each other.
  • d3 represents an integer of 2 or more and 5 or less
  • the plurality of R 24 may be the same as or different from each other.
  • R 25 represents an alkyl group having 1 to 6 carbon atoms or a hydrogen atom.
  • R 26 , R 27 and R 28 each independently represents an alkyl group having 1 to 6 carbon atoms.
  • e1, e2 and e3 each independently represents an integer of 0 or more and 5 or less.
  • the plurality of R 26 may be the same as or different from each other.
  • the plurality of R 27 may be the same as or different from each other.
  • the plurality of R 28 may be the same as or different from each other.
  • R 29 , R 30 and R 31 each independently represents an aryl group having 6 to 14 carbon atoms or a hydrogen atom.
  • a1 and a3 preferably represent 1 from the viewpoint of further improving sensitivity characteristics and fog resistance.
  • R 1 and R 3 each independently preferably represents an alkyl group having 1 to 3 carbon atoms, and more preferably represents a methyl group.
  • a2 and a4 preferably represent 0.
  • Examples of the hole transport agent (HTM1) represented by the general formula (HTM1) include a hole transport agent represented by the following chemical formula (HTM1-1) (hereinafter referred to as a hole transport agent (HTM1-1) and May be described.).
  • R 5 and R 6 preferably each independently represent an alkyl group having 1 to 6 carbon atoms, from the viewpoint of further improving sensitivity characteristics and fog resistance. It is more preferable to represent 1 or more and 3 or less alkyl group, and it is more preferable to represent a methyl group. From the same viewpoint, R 7 and R 8 preferably represent a hydrogen atom.
  • Examples of the hole transport agent (HTM2) represented by the general formula (HTM2) include a hole transport agent represented by the following chemical formula (HTM2-1) (hereinafter referred to as a hole transport agent (HTM2-1) and May be described.).
  • HTM3 In general formula (HTM3), b1 and b3 preferably represent 1 from the viewpoint of further improving sensitivity characteristics and fog resistance. From the same viewpoint, R 9 and R 11 each independently preferably represents an alkyl group having 1 to 3 carbon atoms, and more preferably represents a methyl group. From the same viewpoint, b2 and b4 preferably represent 0.
  • Examples of the hole transport agent (HTM3) represented by the general formula (HTM3) include a hole transport agent represented by the following chemical formula (HTM3-1) (hereinafter referred to as a hole transport agent (HTM3-1) and May be described.).
  • c1 and c2 preferably represent 1 from the viewpoint of further improving sensitivity characteristics and fog resistance.
  • R 13 and R 14 each independently preferably represents an alkyl group having 1 to 3 carbon atoms, and more preferably represents a methyl group.
  • c3 and c4 preferably represent 0.
  • Examples of the hole transport agent (HTM4) represented by the general formula (HTM4) include a hole transport agent represented by the following chemical formula (HTM4-1) (hereinafter referred to as a hole transport agent (HTM4-1) and May be described.).
  • R 17 , R 18 , R 19 , R 20 and R 21 are each independently an alkyl group having 1 to 6 carbon atoms from the viewpoint of further improving sensitivity characteristics and fog resistance. Is more preferable, an alkyl group having 1 to 3 carbon atoms is more preferable, and a methyl group is still more preferable.
  • Examples of the hole transport agent (HTM5) represented by the general formula (HTM5) include a hole transport agent represented by the following chemical formula (HTM5-1) (hereinafter referred to as a hole transport agent (HTM5-1) and May be described.).
  • HTM6 In the general formula (HTM6), d1, d2, and d3 preferably represent 0 from the viewpoint of further improving sensitivity characteristics and fog resistance. From the same viewpoint, R 25 preferably represents a hydrogen atom.
  • Examples of the hole transport agent (HTM6) represented by the general formula (HTM6) include a hole transport agent represented by the following chemical formula (HTM6-1) (hereinafter referred to as a hole transport agent (HTM6-1) and May be described.).
  • e1, e2, and e3 each independently preferably represents 0 or 1 from the viewpoint of further improving sensitivity characteristics and fog resistance.
  • R 29 , R 30 and R 31 each independently represents an aryl group having 6 to 14 carbon atoms from the viewpoint of further improving sensitivity characteristics and fog resistance. It is preferable that it represents a phenyl group.
  • R 29 , R 30 and R 31 preferably represent a hydrogen atom.
  • R 26 , R 27 and R 28 may represent an alkyl group having 1 to 3 carbon atoms. Preferably, it represents a methyl group.
  • Examples of the hole transport agent (HTM7) represented by the general formula (HTM7) include a hole transport agent represented by the following chemical formula (HTM7-1) (hereinafter referred to as hole transport agent (HTM7-1) and And a hole transporting agent represented by the chemical formula (HTM7-2) (hereinafter sometimes referred to as a hole transporting agent (HTM7-2)).
  • the hole transport agent (HTM1), the hole transport agent (HTM2) and the hole transport agent (HTM6) are preferable.
  • HTM1-1), a hole transport agent (HTM2-1) and a hole transport agent (HTM6-1) are more preferred.
  • a hole transport agent (HTM1), a hole transport agent (HTM3), a hole transport agent (HTM5) and a hole transport agent (HTM7) are preferable.
  • HTM1-1), hole transport agent (HTM3-1), hole transport agent (HTM5-1), hole transport agent (HTM7-1) and hole transport agent (HTM7-2) are more preferred.
  • the content of the hole transport agent is preferably 10 parts by mass or more and 200 parts by mass or less, 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, from the viewpoint of efficiently transporting holes. It is more preferable that In addition, the content of the hole transport agent is 100 parts by mass of the polycarbonate resin (1) from the viewpoint of suppressing crystallization while further improving the sensitivity characteristics by combining with the polycarbonate resin (1) described later. It is preferably 10 parts by mass or more and 90 parts by mass or less, and more preferably 10 parts by mass or more and 80 parts by mass or less.
  • the photosensitive layer 3 may contain other hole transport agents in addition to the hole transport agents (HTM1) to (HTM7) described above.
  • Other hole transport agents include, for example, diamine derivatives (more specifically, N, N, N ′, N′-tetraphenylphenylenediamine derivatives, N, N, N ′, N′-tetraphenylnaphthylene diene).
  • electron transfer agent examples include quinone compounds, diimide compounds, hydrazone compounds, malononitrile compounds, thiopyran compounds, trinitrothioxanthone compounds, 3,4,5,7-tetranitro-9-fluorenone compounds, Examples thereof include dinitroanthracene compounds, dinitroacridine compounds, tetracyanoethylene, 2,4,8-trinitrothioxanthone, dinitrobenzene, dinitroacridine, succinic anhydride, maleic anhydride, and dibromomaleic anhydride.
  • quinone compounds include diphenoquinone compounds, azoquinone compounds, anthraquinone compounds, naphthoquinone compounds, nitroanthraquinone compounds, and dinitroanthraquinone compounds.
  • One of these electron transport agents may be used alone, or two or more thereof may be used in combination.
  • ETM1 a compound represented by the following general formula (ETM1) is preferable, and a compound represented by the following chemical formula (ETM1-1) (hereinafter, An electron transfer agent (sometimes referred to as ETM1-1)) is more preferable.
  • R 41 and R 44 each independently represents an alkyl group having 1 to 6 carbon atoms or a hydrogen atom.
  • R 42 and R 43 each independently represents an alkyl group having 1 to 6 carbon atoms.
  • f1 and f2 each independently represent an integer of 0 or more and 4 or less. When f1 represents an integer of 2 or more and 4 or less, the plurality of R 42 may be the same as or different from each other. When f2 represents an integer of 2 or more and 4 or less, the plurality of R 43 may be the same as or different from each other.
  • the content of the electron transport agent is preferably 5 parts by mass or more and 100 parts by mass or less, and preferably 10 parts by mass or more and 80 parts by mass or less with respect to 100 parts by mass of the binder resin, from the viewpoint of efficiently transporting electrons. It is more preferable.
  • the content of the electron transport agent is 10 with respect to 100 parts by mass of the polycarbonate resin (1) from the viewpoint of suppressing crystallization while further improving sensitivity characteristics by combining with the polycarbonate resin (1) described later.
  • the mass is preferably no less than 70 parts by mass, more preferably no less than 10 parts by mass and no greater than 60 parts by mass, and still more preferably no less than 10 parts by mass and no greater than 50 parts by mass.
  • the binder resin is described as a polycarbonate resin (hereinafter referred to as polycarbonate resin (1)) having a repeating unit represented by the following general formula (1-1) and a repeating unit represented by the following general formula (1-2). May be included).
  • the photosensitive layer 3 can contain 1 type, or 2 or more types of polycarbonate resin (1).
  • Q 1 and Q 2 each represent a hydrogen atom
  • Q 3 and Q 4 each independently represent an alkyl group having 1 to 6 carbon atoms
  • Q 1 and Q 2 each independently represents an alkyl group having 1 to 6 carbon atoms
  • Q 3 and Q 4 each represents a hydrogen atom
  • the alkyl group having 1 to 6 carbon atoms represented by Q 1 , Q 2 , Q 3 and Q 4 further improves the sensitivity characteristics and fog resistance.
  • an alkyl group having 1 to 3 carbon atoms is preferable, and a methyl group is more preferable.
  • Q 1 and Q 2 represent a methyl group
  • Q 3 and Q 4 represent a hydrogen atom
  • Q 1 and Q 2 represent a hydrogen atom
  • Q 3 and Q 4 represent methyl. More preferably, it represents a group.
  • Suitable examples of the repeating unit represented by the general formula (1-1) include the following chemical formulas (11-1) and (11-2). ).
  • repeating unit (1-2) examples include the following chemical formulas (12-1) and (12-2). ).
  • Examples of the polycarbonate resin (1) include a polycarbonate resin represented by the following general formula (1).
  • Q 1 and Q 2 in the general formula (1) is the same meaning as Q 1 and Q 2 in the general formula (1-1).
  • Q 3 and Q 4 of the general formula (1) is the same meaning as Q 3 and Q 4 in the general formula (1-2).
  • r represents the number of repeating units (1-1) relative to the total number of repeating units (1-1) and repeating units (1-2) contained in the polycarbonate resin (1).
  • s represents a percentage of the number of repeating units (1-2) to the total number of repeating units (1-1) and repeating units (1-2) contained in the polycarbonate resin (1). Note that r and s are not the values obtained from one resin chain, but are the number average values obtained from the entire polycarbonate resin (1) (a plurality of resin chains) contained in the photosensitive layer 3.
  • r represents a number of 50 to 70, and s is 30 to 50. It is preferable to represent a number, r represents a number of 55 to 65, and s represents a number of 35 to 45.
  • the arrangement of the repeating units (1-1) and (1-2) in the polycarbonate resin (1) is not particularly limited. That is, the polycarbonate resin (1) may be any copolymer such as a random copolymer, an alternating copolymer, a periodic copolymer, or a block copolymer.
  • the random copolymer include a copolymer in which repeating units (1-1) and repeating units (1-2) are randomly arranged.
  • Examples of the alternating copolymer include a copolymer in which repeating units (1-1) and repeating units (1-2) are alternately arranged.
  • Examples of the periodic copolymer include a copolymer in which one or more repeating units (1-1) and one or more repeating units (1-2) are periodically arranged.
  • the block copolymer include a copolymer in which a block composed of a plurality of repeating units (1-1) and a block composed of a plurality of repeating units (1-2) are arranged.
  • the polycarbonate resin (1) may have a repeating unit other than the repeating units (1-1) and (1-2).
  • the ratio (molar fraction) of the total amount of the repeating units (1-1) and (1-2) to the total amount of all repeating units in the polycarbonate resin (1) is preferably 0.80 or more, 0.90 or more is more preferable, and 1.00 is still more preferable.
  • the polycarbonate resin (1) is: It is preferable not to include a repeating unit having a fluorine atom and a terminal group having a fluorine atom. From the same viewpoint, the polycarbonate resin (1) is preferably not terminal-modified.
  • the method for producing the binder resin is not particularly limited as long as the polycarbonate resin (1) can be produced.
  • the binder resin production method include a method of interfacial condensation polymerization of a diol compound and phosgene for constituting a repeating unit of the polycarbonate resin (1) (so-called phosgene method), and transesterification of the diol compound and diphenyl carbonate. The method of making it react is mentioned.
  • phosgene method examples include a diol compound represented by the following general formula (1-1-1) and a diol compound represented by the following general formula (1-2-1), in a molar fraction (general formula ( Examples thereof include a method of interfacial condensation polymerization of a mixture obtained by mixing so that the content ratio corresponds to r / (r + s)) of 1) and phosgene.
  • general formula (1-1-1) examples thereof include a method of interfacial condensation polymerization of a mixture obtained by mixing so that the content ratio corresponds to r / (r + s)) of 1 and phosgene.
  • Q 1 and Q 2 in the following general formula (1-1-1) is the same meaning as Q 1 and Q 2 in the general formula (1-1).
  • Q 3 and Q 4 in the following general formula (1-2-1) is the same meaning as Q 3 and Q 4 in the general formula (1-2).
  • polycarbonate resin (1) examples include polycarbonate resins represented by the following chemical formulas (R-1) and (R-2) (hereinafter referred to as polycarbonate resins (R-1) and (R-2), respectively). May be described.).
  • the binder resin only the polycarbonate resin (1) may be used alone, or the polycarbonate resin (1) and a resin other than the polycarbonate resin (1) (other resins) may be used in combination.
  • other resins include thermoplastic resins (polycarbonate resins other than polycarbonate resin (1), polyarylate resins, styrene resins, styrene-butadiene copolymers, styrene-acrylonitrile copolymers, styrene-maleic acid copolymers.
  • the content of the polycarbonate resin (1) is preferably 80% by mass or more, more
  • the viscosity average molecular weight of the binder resin is preferably 20,000 or more, more preferably 25,000 or more, and further preferably 30,000 or more. Further, the viscosity average molecular weight of the binder resin is preferably 70,000 or less, more preferably 50,000 or less, and further preferably 40,000 or less.
  • the viscosity average molecular weight of the binder resin is 30,000 or more, the abrasion resistance of the binder resin can be improved, and the photosensitive layer 3 is hardly worn.
  • the viscosity average molecular weight of the binder resin is 40,000 or less, the binder resin is easily dissolved in a solvent when the photosensitive layer 3 is formed, and the formation of the photosensitive layer 3 tends to be easy.
  • Additives that are optional components include, for example, deterioration inhibitors (more specifically, antioxidants, radical scavengers, quenchers, ultraviolet absorbers, etc.), softeners, surface modifiers, extenders, Examples include stickers, dispersion stabilizers, waxes, donors, surfactants, and leveling agents. When an additive is added, one of these additives may be used alone, or two or more may be used in combination.
  • antioxidants examples include hindered phenol compounds, hindered amine compounds, thioether compounds, and phosphite compounds. Among these antioxidants, hindered phenol compounds and hindered amine compounds are preferred.
  • the photosensitive layer 3 is formed of a hole transport agent (HTM1-1), a hole transport agent (HTM2-1), and a hole transport agent (HTM6-1). And at least one of polycarbonate resin (R-1) and polycarbonate resin (R-2) as a binder resin.
  • the photosensitive layer 3 contains one of a hole transport agent (HTM1-1), a hole transport agent (HTM2-1), and a hole transport agent (HTM6-1), and a binder resin. It is more preferable to contain a polycarbonate resin (R-2).
  • the photoreceptor 1 of this embodiment may have the intermediate layer 4 (for example, the undercoat layer).
  • the intermediate layer 4 contains, for example, inorganic particles and a resin (interlayer resin) used for the intermediate layer.
  • an increase in electrical resistance can be suppressed by smoothing the flow of current generated when the photosensitive member 1 is exposed while maintaining an insulating state capable of suppressing the occurrence of leakage.
  • the inorganic particles include metal (more specifically, aluminum, iron, copper, etc.) particles, metal oxide (more specifically, titanium oxide, alumina, zirconium oxide, tin oxide, zinc oxide, etc.). And particles of a non-metal oxide (more specifically, silica or the like). These inorganic particles may be used individually by 1 type, and may use 2 or more types together. The inorganic particles may be subjected to a surface treatment.
  • the intermediate layer resin is not particularly limited as long as it can be used as a resin for forming the intermediate layer.
  • the method for manufacturing the photoreceptor 1 includes, for example, a photosensitive layer forming step.
  • a coating solution for forming the photosensitive layer 3 (hereinafter sometimes referred to as a photosensitive layer coating solution) is prepared.
  • a photosensitive layer coating solution is applied onto the conductive substrate 2.
  • the photosensitive layer 3 is formed by removing at least a part of the solvent contained in the applied coating solution for the photosensitive layer by drying by an appropriate method.
  • the photosensitive layer coating solution includes, for example, a charge generating agent, a hole transporting agent, an electron transporting agent, a polycarbonate resin (1) as a binder resin, and a solvent.
  • a photosensitive layer coating solution is prepared by dissolving or dispersing a charge generating agent, a hole transporting agent, an electron transporting agent, and a polycarbonate resin (1) as a binder resin in a solvent.
  • Various additives may be added to the photosensitive layer coating solution as necessary.
  • the solvent contained in the photosensitive layer coating solution is not particularly limited as long as each component contained in the photosensitive layer coating solution can be dissolved or dispersed.
  • the solvent include alcohols (more specifically, methanol, ethanol, isopropanol, butanol, etc.), aliphatic hydrocarbons (more specifically, n-hexane, octane, cyclohexane, etc.), aromatic hydrocarbons ( 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, etc.), ketones (more specifically, acetone, methyl ethy
  • the photosensitive layer 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 photosensitive layer coating solution may contain, for example, a surfactant in order to improve the dispersibility of each component.
  • the method for applying the photosensitive layer coating solution is not particularly limited as long as it can uniformly apply the photosensitive layer coating solution.
  • the coating method include a dip coating method, a spray coating method, a spin coating method, and a bar coating method.
  • the method for removing at least a part of the solvent contained in the photosensitive layer coating solution is not particularly limited as long as it is a method capable of evaporating at least a part of the solvent in the photosensitive layer coating solution.
  • the removal method include heating, reduced pressure, and combined use of heating and reduced pressure. More specifically, a method of heat treatment (hot air drying) using a high-temperature dryer, a vacuum dryer, or the like can be given.
  • the heat treatment conditions are, 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 manufacturing method of the photoreceptor 1 may further include a step of forming the intermediate layer 4 as necessary.
  • a known method can be appropriately selected for the step of forming the intermediate layer 4.
  • the photoconductor of the present embodiment described above is excellent in sensitivity characteristics and fog resistance, and therefore can be suitably used in various image forming apparatuses.
  • the image forming apparatus includes an image carrier, a charging unit, an exposure unit, a developing unit, and a transfer unit.
  • the image carrier is the photoreceptor according to the first embodiment described above.
  • the charging unit charges the surface of the image carrier.
  • the charging polarity of the charging unit is positive.
  • the exposure unit exposes the charged surface of the image carrier to form an electrostatic latent image on the surface of the image carrier.
  • the developing unit develops the electrostatic latent image as a toner image.
  • the transfer unit transfers the toner image from the image carrier to the transfer target while the surface of the image support and the transfer target are in contact with each other.
  • the image forming apparatus according to the second embodiment can suppress the occurrence of image defects.
  • the reason is presumed as follows.
  • the image forming apparatus according to the second embodiment includes the photoconductor according to the first embodiment as an image carrier.
  • the photoreceptor according to the first embodiment is excellent in sensitivity characteristics and fog resistance. Therefore, the image forming apparatus according to the second embodiment can suppress image defects (more specifically, fogging or the like).
  • tandem color image forming apparatus will be described as an example of the image forming apparatus according to the second embodiment with reference to FIG.
  • the image forming apparatus 100 shown in FIG. 4 is a direct transfer type image forming apparatus.
  • an image carrier is in contact with a recording medium as a transfer medium, so that minute components are likely to adhere to the surface of the image carrier and image defects are likely to occur.
  • the image forming apparatus 100 as an example of the second embodiment includes the photoconductor according to the first embodiment as the image carrier 30.
  • the photoreceptor according to the first embodiment is excellent in sensitivity characteristics and fog resistance. Therefore, when the photoconductor according to the first embodiment is provided as the image carrier 30, even if the image forming apparatus 100 adopts the direct transfer method, it is possible to suppress the occurrence of image defects.
  • the image forming apparatus 100 includes image forming units 40a, 40b, 40c, and 40d, a transfer belt 50, and a fixing unit 52.
  • image forming units 40a, 40b, 40c, and 40d are referred to as an image forming unit 40.
  • the image forming unit 40 includes an image carrier 30, a charging unit 42, an exposure unit 44, a developing unit 46, and a transfer unit 48.
  • An image carrier 30 is provided at the center position of the image forming unit 40.
  • the image carrier 30 is provided to be rotatable in the arrow direction (counterclockwise).
  • a charging unit 42, an exposure unit 44, a developing unit 46, and a transfer unit 48 are provided in order from the upstream side in the rotation direction of the image carrier 30 with respect to the charging unit 42.
  • the image forming unit 40 may further include one or both of a cleaning unit (not shown) and a charge removal unit (not shown).
  • Each of the image forming units 40a to 40d sequentially superimposes toner images of a plurality of colors (for example, four colors of black, cyan, magenta, and yellow) on the recording medium P (transfer object) on the transfer belt 50.
  • a plurality of colors for example, four colors of black, cyan, magenta, and yellow
  • the charging unit 42 is a charging roller.
  • the charging roller charges the surface of the image carrier 30 while being in contact with the surface of the image carrier 30.
  • image defects are likely to occur.
  • the image forming apparatus 100 includes the photoconductor according to the first embodiment as the image carrier 30.
  • the photoreceptor according to the first embodiment is excellent in sensitivity characteristics and fog resistance. Therefore, even if the image forming apparatus 100 includes a charging roller as the charging unit 42, the occurrence of image defects is suppressed.
  • the image forming apparatus 100 as an example of the second embodiment employs the contact charging method. Examples of other contact charging type charging units include a charging brush.
  • the charging unit may be a non-contact type. Examples of the non-contact type charging unit include a corotron charging unit and a scorotron charging unit.
  • the voltage applied by the charging unit 42 is not particularly limited. Examples of the voltage applied by the charging unit 42 include a DC voltage, an AC voltage, and a superimposed voltage (a voltage in which an AC voltage is superimposed on a DC voltage), and among these, a DC voltage is preferable.
  • the DC voltage has the following advantages over the AC voltage and the superimposed voltage.
  • the charging unit 42 applies only a DC voltage, the voltage value applied to the image carrier 30 is constant, so that the surface of the image carrier 30 is easily charged uniformly to a constant potential. Further, when the charging unit 42 applies only a DC voltage, the wear amount of the photosensitive layer tends to decrease. As a result, a suitable image can be formed.
  • the exposure unit 44 exposes the surface of the charged image carrier 30. As a result, an electrostatic latent image is formed on the surface of the image carrier 30.
  • the electrostatic latent image is formed based on image data input to the image forming apparatus 100.
  • the developing unit 46 supplies toner to the surface of the image carrier 30 and develops the electrostatic latent image as a toner image.
  • the developing unit 46 can employ a system (contact development system) that develops the electrostatic latent image as a toner image while being in contact with the surface of the image carrier 30.
  • a system contact development system
  • image defects due to fog are likely to occur.
  • the image forming apparatus 100 includes the photoconductor according to the first embodiment as the image carrier 30.
  • the photoreceptor according to the first embodiment is excellent in fog resistance. Therefore, even if the image forming apparatus 100 including such a photoconductor employs the contact development method, the occurrence of image defects due to fogging is suppressed.
  • the developing unit 46 can clean the surface of the image carrier 30.
  • the image forming apparatus 100 can employ a so-called cleaner-less method.
  • the developing unit 46 can remove residual components on the surface of the image carrier 30.
  • a cleaning unit for example, a cleaning blade
  • residual components on the surface of the image carrier are scraped off by the cleaning unit.
  • a cleanerless type image forming apparatus residual components on the surface of the image carrier are not scraped off. For this reason, in an image forming apparatus that employs a cleaner-less method, a residual component usually tends to remain on the surface of the image carrier.
  • the image forming apparatus 100 includes the photoconductor of the first embodiment having excellent sensitivity characteristics and fog resistance as the image carrier 30. Therefore, even if the image forming apparatus 100 including such a photoconductor employs a cleaner-less method, residual components, particularly minute components (for example, paper dust) of the recording medium P hardly remain on the surface of the photoconductor. As a result, the image forming apparatus 100 can suppress the occurrence of image defects (for example, fogging).
  • condition (a) A contact developing method is employed, and a peripheral speed (rotational speed) difference is provided between the image carrier 30 and the developing unit 46.
  • the contact developing method shown in the condition (a) is adopted and a peripheral speed difference is provided between the image carrier 30 and the developing unit 46, the surface of the image carrier 30 comes into contact with the developing unit 46, and the image Residual components on the surface of the carrier 30 are removed by friction with the developing unit 46.
  • the peripheral speed of the developing unit 46 is preferably faster than the peripheral speed of the image carrier 30.
  • the development method is a reversal development method.
  • the charging polarity of the toner, the surface potential of the unexposed area of the image carrier 30, and the surface potential of the exposed area of the image carrier 30 It is preferable that both the potential of the developing bias and the potential of the developing bias are positive.
  • the surface potential of the unexposed area of the image carrier 30 and the surface potential of the exposed area are determined by the charging unit 42 after the transfer unit 48 transfers the toner image from the image carrier 30 to the recording medium P. Measured before charging 30 surfaces.
  • the transfer belt 50 conveys the recording medium P between the image carrier 30 and the transfer unit 48.
  • the transfer belt 50 is an endless belt.
  • the transfer belt 50 is provided to be rotatable in the arrow direction (clockwise).
  • the transfer unit 48 transfers the toner image developed by the developing unit 46 from the surface of the image carrier 30 to the recording medium P.
  • the image carrier 30 is in contact with the recording medium P.
  • An example of the transfer unit 48 is a transfer roller.
  • the fixing unit 52 heats and / or pressurizes the unfixed toner image transferred to the recording medium P by the transfer unit 48.
  • the fixing unit 52 is, for example, a heating roller and / or a pressure roller.
  • the toner image is fixed on the recording medium P by heating and / or pressurizing the toner image. As a result, an image is formed on the recording medium P.
  • the example of the image forming apparatus according to the second embodiment has been described above, but the image forming apparatus according to the second embodiment is not limited to the image forming apparatus 100 described above.
  • the above-described image forming apparatus 100 is a tandem image forming apparatus, but the image forming apparatus according to the second embodiment is not limited to this, and a rotary system or the like may be employed.
  • the image forming apparatus according to the second embodiment may be a monochrome image forming apparatus. In this case, the image forming apparatus may include only one image forming unit, for example.
  • the image forming apparatus according to the second embodiment may employ an intermediate transfer method. When the image forming apparatus according to the second embodiment employs an intermediate transfer method, the transfer target corresponds to an intermediate transfer belt.
  • the process cartridge according to the third embodiment includes the photoconductor according to the first embodiment as an image carrier. Next, an example of the process cartridge according to the third embodiment will be described with reference to FIG.
  • the process cartridge according to the third embodiment corresponds to each of the image forming units 40a to 40d (FIG. 4), for example.
  • These process cartridges include a unitized portion.
  • the unitized portion includes the image carrier 30. Further, the unitized portion may include at least one selected from the group consisting of the charging unit 42, the exposure unit 44, the developing unit 46, and the transfer unit 48 in addition to the image carrier 30.
  • the process cartridge may further include one or both of a cleaning unit (not shown) and a charge removal unit (not shown).
  • the process cartridge is designed to be detachable from the image forming apparatus 100, for example.
  • the process cartridge in this case is easy to handle, and when the sensitivity characteristics of the image carrier 30 are deteriorated, the process cartridge including the image carrier 30 can be easily and quickly replaced.
  • the process cartridge according to the third embodiment described above includes the photoconductor according to the first embodiment as an image carrier, thereby suppressing image defects.
  • the charge generating agent (CGM-1) described in the first embodiment was prepared.
  • the charge generating agent (CGM-1) was a metal-free phthalocyanine represented by the chemical formula (CGM-1), and its crystal structure was X-type. That is, the charge generating agent (CGM-1) used was X-type metal-free phthalocyanine.
  • Hole transport agents (HTM1-1), (HTM2-1), (HTM3-1), (HTM4-1), (HTM5-1), (HTM6-1), (HTM7-1) described in the first embodiment 1) and (HTM7-2) were prepared. Furthermore, hole transport agents (HTM8-1) and (HTM9-1) were also prepared.
  • the hole transport agents (HTM8-1) and (HTM9-1) are hole transport agents represented by the following chemical formulas (HTM8-1) and (HTM9-1), respectively.
  • the electron transport agent (ETM1-1) described in the first embodiment was prepared.
  • polycarbonate resins (R-10) to (R-14) were prepared as binder resins.
  • Polycarbonate resins (R-10) to (R-14) are polycarbonate resins represented by the following chemical formulas (R-10) to (R-14), respectively.
  • the polycarbonate resin (R-14) is a polycarbonate resin containing a terminal group having a fluorine atom (a fluorine atom-containing terminal group) as shown in the chemical formula (R-14).
  • the polycarbonate resins (R-1), (R-2), and (R-10) to (R-13) are all polycarbonate resins that do not contain a fluorine atom-containing end group.
  • This photosensitive layer coating solution was applied on an aluminum drum-like support as a conductive substrate by a dip coating method.
  • the applied photosensitive layer coating solution was dried with hot air at 100 ° C. for 40 minutes.
  • a photosensitive layer film thickness: 25 ⁇ m
  • a photoreceptor (A-1) which is a single-layer photoreceptor was obtained.
  • the surface of the obtained photoreceptor (A-1) was visually observed to confirm that it was not crystallized.
  • Photoconductors (A-2) to (A-11) and photosensitive members (B-1) to (B-7) Photoconductors (A-2) to (A-11) and photoconductors were prepared in the same manner as the photoconductor (A-1) except that the binder resins and hole transport agents listed in Table 1 were used. Forms (B-1) to (B-7) were obtained. It was confirmed that the obtained photoreceptors (A-2) to (A-11), (B-1) and (B-3) to (B-7) were not crystallized by visual observation of the surface. did. On the other hand, it was confirmed that the photoreceptor (B-2) was crystallized by visual observation of the surface.
  • binder resin polycarbonate resins (R-1), (R-2) and (R ⁇ 10) to (R-14) are shown.
  • the “molecular weight” in the column “binder resin” indicates the viscosity average molecular weight of the binder resin.
  • FIG. 5 is a diagram illustrating an example of the configuration of the scratching device 200.
  • the scratching device 200 includes a fixing base 201, a fixing tool 202, a scratching needle 203, a support arm portion 204, two shaft support portions 205, a base 206, two rail portions 207, and a weight plate 208. And a constant speed motor (not shown). A weight 209 is placed on the weight plate 208.
  • the X-axis direction and the Y-axis direction are horizontal directions, and the Z-axis direction is a vertical direction.
  • the X-axis direction indicates the longitudinal direction of the fixed base 201.
  • the Y-axis direction indicates a direction orthogonal to the X-axis direction within a plane parallel to the upper surface 201a (mounting surface) of the fixed base 201. Note that the X-axis direction, the Y-axis direction, and the Z-axis direction in FIGS. 6 to 8 described later are the same as those in FIG.
  • the fixing table 201 corresponds to the test plate fixing table in JIS K5600-5-5.
  • the fixed base 201 includes an upper surface 201a, one end 201b, and the other end 201c.
  • the upper surface 201a of the fixed base 201 is a horizontal plane.
  • One end 201b faces the two shaft support portions 205.
  • the fixing tool 202 is provided on the side of the other end 201c on the upper surface 201a of the fixing base 201.
  • the fixing tool 202 fixes the measurement target (photosensitive member 1) to the upper surface 201a of the fixing base 201.
  • the scratch needle 203 has a tip 203b (see FIG. 6).
  • the structure of the tip 203b is a hemisphere having a diameter of 1 mm.
  • the material of the tip 203b is sapphire.
  • the support arm unit 204 supports the scratch needle 203.
  • the support arm 204 rotates around the support shaft 204a in a direction in which the scratch needle 203 approaches and separates from the photoreceptor 1.
  • the two shaft support parts 205 support the support arm part 204 in a rotatable manner.
  • the base 206 includes an upper surface 206a.
  • Two shaft support portions 205 are provided on one end side of the upper surface 206a.
  • the two rail portions 207 are provided on the other end side of the upper surface 206a.
  • the two rail portions 207 are provided so as to face each other in parallel.
  • the two rail portions 207 are each provided in parallel with the longitudinal direction (X-axis direction) of the fixed base 201.
  • a fixed base 201 is attached between the two rail portions 207.
  • the fixed base 201 can move horizontally in the longitudinal direction (X-axis direction) of the fixed base 201.
  • the weight pan 208 is provided on the scratching needle 203 through the support arm 204.
  • a weight 209 is placed on the weight plate 208.
  • the constant speed motor moves the fixed base 201 along the rail portion 207 in the X-axis direction.
  • the method for measuring the scratch depth includes a first step, a second step, a third step, and a fourth step.
  • a surface property measuring machine (“HEIDON TYPE 14” manufactured by Shinto Kagaku Co., Ltd.) was used as the scratch device 200.
  • the scratch depth was measured in an environment of a temperature of 23 ° C. and a humidity of 50% RH.
  • the shape of the photoreceptor 1 was a drum shape (cylindrical shape).
  • the photosensitive member 1 is fixed to the upper surface 201 a of the fixing base 201 so that the longitudinal direction of the photosensitive member 1 is parallel to the longitudinal direction of the fixing base 201.
  • the photoconductor 1 was attached so that the central axis L 2 (rotation axis) direction of the photoconductor 1 was parallel to the longitudinal direction of the fixed base 201.
  • FIG. 6 is a cross-sectional view taken along the line IV-IV in FIG. 5, and is a cross-sectional view when the scratch needle 203 is brought into contact with the photoreceptor 1.
  • FIG. 7 is a side view of the fixing base 201, the scratching needle 203, and the photoreceptor 1 shown in FIG.
  • the scratching needle 203 was brought close to the photoreceptor 1 so that the extension line of the central axis A 1 of the scratching needle 203 was perpendicular to the upper surface 201 a of the fixed base 201.
  • the tip 203 b of the scratching needle 203 is brought into contact with a point (contact point P 2 ) farthest from the upper surface 201 a of the fixed base 201 in the vertical direction (Z-axis direction) I let you.
  • the center axis A 1 of the scratching needle 203 to be perpendicular to the tangent A 2, the tip 203b of the scratching needle 203 is in contact with the photosensitive member 1.
  • the tangent line A 2 is a tangent line at the contact point P 2 of the outer circumference circle formed by the cross section of the photoreceptor 1 perpendicular to the central axis L 2 .
  • the third step Next, the third step will be described with reference to FIGS.
  • a load W of 10 g was applied from the scratching needle 203 to the photosensitive layer 3 with the scratching needle 203 in contact with the surface 3a of the photosensitive layer 3 perpendicularly.
  • 10 g weight 209 was placed on the weight pan 208.
  • the fixed base 201 was moved.
  • the constant speed motor was driven, and the fixed base 201 was moved horizontally in the X-axis direction along the rail portion 207. That is, one end 201b of the fixed base 201, is moved from the first position N 1 to the second position N 2.
  • the second position N 2 was located downstream from the first position N 1 .
  • the downstream side is a side where the fixed base 201 is positioned in a direction away from the two shaft support portions 205 in the longitudinal direction of the fixed base 201.
  • the photosensitive member 1 With the movement of the fixed base 201 in the longitudinal direction, the photosensitive member 1 also moved horizontally in the longitudinal direction of the fixed base 201.
  • the moving speed of the fixed base 201 and the photosensitive member 1 was 30 mm / min. Further, the moving distance of the fixed base 201 and the photosensitive member 1 was 30 mm.
  • the scratch S was formed on the surface 3 a of the photosensitive layer 3 of the photoreceptor 1 by the scratch needle 203.
  • FIG. 8 shows a scratch S formed on the surface 3 a of the photosensitive layer 3. Scratches S, to the upper surface 201a and tangential A 2 of the fixing table 201, are respectively vertically formed. Moreover, scratches S was formed so as to pass through the line L 3 shown in FIG.
  • the line L 3 is a plurality of lines consisting of the contact point P 2.
  • the line L 3 was parallel to the upper surface 201 a of the fixed base 201 and the central axis L 2 of the photoreceptor 1.
  • the line L 3 was perpendicular to the central axis A 1 of the scratch needle 203.
  • the scratch depth which is the maximum value of the depth Ds of the scratch S was measured.
  • the photoreceptor 1 was removed from the fixed base 201.
  • the scratch S formed on the photosensitive layer 3 of the photoreceptor 1 is observed at a magnification of 5 times, and the depth Ds of the scratch S is measured. did.
  • the depth Ds of the scratch S was the distance from the tangent line A 2 to the valley of the scratch S.
  • the maximum value among the depths Ds of the scratches S was defined as the scratch depth.
  • the measured scratch depth is shown in Table 1.
  • the Vickers hardness of the photosensitive layer was measured for each of the obtained photoreceptors (A-1) to (A-11) and photoreceptors (B-1) to (B-7).
  • the Vickers hardness of the photosensitive layer was measured by a method based on Japanese Industrial Standard (JIS) Z2244.
  • JIS Japanese Industrial Standard
  • a hardness meter (“Micro Vickers hardness meter DMH-1 type” manufactured by Matsuzawa Co., Ltd.) was used.
  • Vickers hardness is measured at a temperature of 23 ° C., a diamond indenter load (test force) of 10 gf, a time required to reach the test force of 5 seconds, a diamond indenter approach speed of 2 mm / second, and a test force holding time of 1 second. I went there. Table 1 shows the measured Vickers hardness.
  • the sensitivity characteristics of each of the obtained photoreceptors (A-1) to (A-11) and the photoreceptors (B-1) to (B-7) were evaluated.
  • the sensitivity characteristics were evaluated in an environment of a temperature of 23 ° C. and a humidity of 50% RH.
  • the surface of the photoreceptor was charged to +700 V using a drum sensitivity tester (manufactured by Gentec Corporation).
  • monochromatic light (wavelength 780 nm, half-value width 20 nm, light intensity 1.5 ⁇ J / m 2 ) was extracted from the white light of the halogen lamp using a bandpass filter.
  • the surface of the photoreceptor was irradiated with the extracted monochromatic light.
  • the surface potential of the photoreceptor was measured when 0.5 seconds had elapsed from the start of irradiation.
  • the measured surface potential was defined as a post-exposure potential V L (unit V).
  • Table 1 shows the measured post-exposure potential VL of the photoreceptor. The smaller the absolute value of the post-exposure potential V L, the better the sensitivity characteristic of the photoreceptor.
  • Each of the obtained photoreceptors (A-1) to (A-11) and photoreceptors (B-1) to (B-7) was evaluated for fog resistance in the formed image.
  • an image forming apparatus (a modified machine of “monochrome printer FS-1300D” manufactured by Kyocera Document Solutions Inc.) was used. This image forming apparatus employs a direct transfer method, a contact development method, and a cleaner-less method. In this image forming apparatus, the developing unit cleans the toner remaining on the photoreceptor.
  • the charging unit of the image forming apparatus is a charging roller.
  • “Kyocera Document Solutions Brand Paper VM-A4” (A4 size) sold by Kyocera Document Solutions Inc. was used. A one-component developer (prototype) was used for evaluation by the evaluation machine.
  • the image I was continuously printed on 12,000 sheets of paper at a charging potential of +600 V at a rotational speed of the photoconductor of 168 mm / sec.
  • Image I was an image with a printing rate of 1%.
  • a blank image was printed on one sheet.
  • Printing was performed in an environment of a temperature of 32.5 ° C. and a humidity of 80% RH.
  • the image density at three locations in the blank paper image was measured using a reflection densitometer (“RD914” manufactured by X-rite). The sum of the image densities at three locations on the blank paper image was divided by the number of measurement locations. Thereby, the number average value of the image density of the blank paper image was obtained.
  • the value obtained by subtracting the image density of the base paper from the number average value of the image density of the blank paper image was defined as the fog density.
  • the measured fog density was determined according to the following criteria. A photoreceptor having a determination of A or B was evaluated as having good fog resistance. In addition, a photoreceptor having a determination of C was evaluated as having poor fog resistance. Table 1 shows the fog density (FD value) and the determination results. In Table 1, the fog density (FD value) of Comparative Example 2 and the determination result “ ⁇ ” indicate that the sensitivity characteristic of the photoconductor (B-2) used in Comparative Example 2 is higher than that of other photoconductors. Since it is extremely inferior, it shows that the fog resistance could not be evaluated under the same conditions.
  • Determination A The fog density is 0.010 or less.
  • Determination B The fog density is larger than 0.010 and 0.020 or less.
  • Determination C The fog density is greater than 0.020.
  • the photoreceptors (A-1) to (A-11) contain any of the polycarbonate resins (R-1) and (R-2) included in the general formula (1). It was.
  • the photoreceptors (A-1) to (A-11) are represented by the general formula (HTM1), general formula (HTM2), general formula (HTM3), general formula (HTM4), general formula (HTM5), and general formula (HTM6).
  • HTM1-1) to (HTM7-1) and (HTM7-2) included in the general formula (HTM7) was contained.
  • the scratch depth of the photosensitive layer was 0.28 ⁇ m or more and 0.46 ⁇ m or less.
  • the Vickers hardness of the photosensitive layer was 17.8 HV or higher and 20.2 HV or lower.
  • the photoreceptors (A-1) to (A-11) had a post-exposure potential V L of + 112V to + 137V.
  • Photosensitive members (A-1) to (A-11) had a determination result of fog resistance of A (good).
  • the photoconductors (B-1) to (B-4) contain any of the polycarbonate resins (R-10) to (R-13) not included in the general formula (1). It was.
  • the photoreceptors (B-5) and (B-6) are represented by the general formula (HTM1), general formula (HTM2), general formula (HTM3), general formula (HTM4), general formula (HTM5), and general formula (HTM6).
  • a hole transfer agent (HTM8-1) and (HTM9-1) not included in the general formula (HTM7) In the photoreceptors (B-1), (B-3), (B-4) and (B-7), the scratch depth of the photosensitive layer exceeded 0.50 ⁇ m.
  • the Vickers hardness of the photosensitive layer was less than 17.0 HV.
  • the photoreceptor (B-2) had a post-exposure potential V L of +193 V.
  • the determination result of fog resistance was C (poor).
  • the photoconductors (A-1) to (A-11) were superior in sensitivity characteristics to the photoconductor (B-2). Further, the photoconductors (A-1) to (A-11) were excellent in fog resistance as compared with the photoconductors (B-1) and (B-3) to (B-7).
  • the electrophotographic photosensitive member according to the present invention can be used in an image forming apparatus such as a multifunction machine.

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

Abstract

L'invention concerne un photorécepteur électrophotographique (1) comprenant un substrat conducteur (2) et une couche photosensible (3), la couche photosensible (3) étant une monocouche et contenant un agent de génération de charges, un agent de transport de trous, un agent de transport d'électrons et une résine de polycarbonate. La résine de polycarbonate comprend une unité de répétition représentée par la formule générale (1-1), et une unité de répétition représentée par la formule générale (1-2). Dans les formules générales (1-1) et (1-2), Q1 et Q2 représentent des atomes d'hydrogène, et Q3 et Q4 représentent des groupes alkyle ; ou, Q1 et Q2 représentent des groupes alkyle, et Q3 et Q4 représentent un atome d'hydrogène. L'agent de transport d'électrons contient des composés représentés par les formules générales (HTM1) à (HTM7). La profondeur de résistance aux rayures de la couche photosensible (3) est inférieure ou égale à 0,50 µm. La dureté Vickers de la couche photosensible (3) est d'au moins 17,0 HV.
PCT/JP2018/014312 2017-06-12 2018-04-03 Photorécepteur électrophotographique, cartouche de traitement, et dispositif de formation d'images WO2018230110A1 (fr)

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