EP0564655A1 - Photorecepteur electrophotographique - Google Patents

Photorecepteur electrophotographique Download PDF

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Publication number
EP0564655A1
EP0564655A1 EP92920384A EP92920384A EP0564655A1 EP 0564655 A1 EP0564655 A1 EP 0564655A1 EP 92920384 A EP92920384 A EP 92920384A EP 92920384 A EP92920384 A EP 92920384A EP 0564655 A1 EP0564655 A1 EP 0564655A1
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EP
European Patent Office
Prior art keywords
reactive
group
compound
layer
composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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EP92920384A
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German (de)
English (en)
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EP0564655A4 (fr
Inventor
Akihiko Idemitsu Petrochemical Co. Kurahashi
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Idemitsu Petrochemical Co Ltd
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Idemitsu Petrochemical Co Ltd
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Publication of EP0564655A1 publication Critical patent/EP0564655A1/fr
Publication of EP0564655A4 publication Critical patent/EP0564655A4/xx
Withdrawn legal-status Critical Current

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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
    • G03G5/14—Inert intermediate or cover layers for charge-receiving layers
    • G03G5/147—Cover layers
    • G03G5/14708—Cover layers comprising organic material
    • G03G5/14713—Macromolecular material
    • G03G5/14791—Macromolecular compounds characterised by their structure, e.g. block polymers, reticulated polymers, or by their chemical properties, e.g. by molecular weight or acidity
    • 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
    • G03G5/14—Inert intermediate or cover layers for charge-receiving layers
    • G03G5/147—Cover layers
    • G03G5/14708—Cover layers comprising organic material
    • G03G5/14713—Macromolecular material
    • G03G5/14747—Macromolecular material obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • G03G5/14769—Other polycondensates comprising nitrogen atoms with or without oxygen atoms in the main chain
    • 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
    • G03G5/14—Inert intermediate or cover layers for charge-receiving layers
    • G03G5/147—Cover layers
    • G03G5/14708—Cover layers comprising organic material
    • G03G5/14713—Macromolecular material
    • G03G5/14747—Macromolecular material obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • G03G5/14773—Polycondensates comprising silicon atoms in the main chain
    • 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
    • G03G5/14—Inert intermediate or cover layers for charge-receiving layers
    • G03G5/147—Cover layers
    • G03G5/14708—Cover layers comprising organic material
    • G03G5/14713—Macromolecular material
    • G03G5/14786—Macromolecular compounds characterised by specific side-chain substituents or end groups

Definitions

  • the present invention relates to an electrophotographic photoreceptor. More particularly it relates to an electrophotographic photoreceptor which comprises coating the surface thereof with a protective layer made of a specific composition or incorporating said composition into an outermost photoconductive layer, having the markedly improved abrasion resistance, surface slip properties, heat resistance, moisture resistance and the like.
  • the surface of an electrophotographic photoreceptor is charged with a corona discharge at first. Necessary parts of the charged photoreceptor are exposed and the surface charge of the exposed parts is selectively destaticized to form an electrostatic latent image. Then, a developer, i.e. a toner is adhered to said electrostatic latent image. The developer is transferred to and fixed in a paper to provide an electrophotographic picture.
  • a conventional electrophotographic photoreceptor comprises a single-ply photoconductive layer formed on the surface of a conductive substrate.
  • the electrophotographic photoreceptor is required to have various properties: (1) it should be charged at a desired potential in a dark place (the charging properties), (2) it should not be accompanied by a leakage surface potential in a dark place (the ability to retain the charge), (3) its surface potential is quickly attenuated when a light is irradiated (the optical responsivity) and the like.
  • the printing speed of these such apparatuses has for years been made unusually faster, whether the photoconductive layers are single-ply or multi-ply. There has been a tendency that the apparatuses are miniaturized and that the processing time per print is made shorter (to deal with charging, exposing, developing and destaticizing).
  • the photoconductive layers have come to take a high mechanical load. This mechanical load is generated as the electrophotographic photoreceptors come into contact with a blade or a brush of a cleaning device operated to scavenge the developer, the toner and a small amount of toner adhered to the surface of papers and electrophotographic photoreceptors.
  • the electrophotographic photoreceptors bear higher mechanical loads, the greater is the speed to repeat the process of charging, exposing, developing and destaticizing.
  • the electrophotographic photoreceptors wear out on the surface quickly, resulting in a reduction of their useful life.
  • an abrasion resistant protective layer as the outermost layer of the electrophotographic photoreceptors.
  • a silicone resin Japanese Patent Application Laid-Open No. 75460/1987
  • an epoxy resin Japanese Patent Application Laid-Open No. 103741/1978
  • a melamine resin Japanese Patent Application Laid-Open No. 217052/1986
  • a fluororesin Japanese Patent Application Laid-Open No. 115944/1985
  • an acrylic resin Japanese Patent Application Laid-Open No. 3538/1979
  • the Japanese Patent Application Laid-Open Nos. 30856/1988 and 56658/1988 have proposed el ectrophotographic photoreceptors comprising a protective layer combining a polycarbonate, a polyester or the like with a fluorine-containing resin powder. According to these proposals, the electrophotographic photoreceptors have the much improved slip properties but are poorer in the film strength and the surface hardness.
  • the present inventors have made intensive studies with a view to overcoming said shortcomings of the related arts.
  • the objectives can be achieved by forming a protective layer on an electrophotographic photoreceptor with a composition comprising (1) a reactive pentaerythritol compound or a reactive dipentaerythritol compound, (2) a reactive phosphazene compound and (3) a reactive siloxane compound or incorporating said composition into an outermost layer of said electrophotographic photoreceptor instead of forming said protective layer.
  • the present invention has been completed on the basis of this finding.
  • the present invention provides an electrophotographic photoreceptor wherein a photoconductive layer formed on a conductive substrate is coated with a protective layer comprising a composition containing 100 parts by weight of a mixture of (1) 90 to 40 mole% of a reactive pentaerythritol compound or a reactive dipentaerythritol compound and (2) 10 to 60 mole% of a reactive phosphazene compound; and (3) 0.1 to 50 parts by weight of a reactive siloxane compound.
  • the present invention also provides an electrophotographic photoreceptor wherein said photoconductive layer (particularly an outermost layer thereof) contains said composition instead of forming said protective layer.
  • a protective layer is prepared from said composition or the surface of the other protective layer is coated with said composition on the surface of a photoconductive layer. If such a protective layer is not intended, said composition is incorporated into the photoconductive layer (particularly, the outermost ply thereof).
  • the composition to be used in the present invention comprises (1) a reactive pentaerythritol compound or a reactive dipentaerythritol compound, (2) a reactive phosphazene compound and (3) a reactive siloxane compound. Meanwhile, this composition is a cured product resulting from the mutual reaction among the reactive (di)pentaerythritol compound (1), the reactive phosphazene compound (2) and the reactive siloxane compound (3) or the reaction between these three and the other compounds.
  • said composition of the present invention is a composition containing a group derived from the reactive (di)pentaerythritol (1), a group derived from the reactive phosphazene compound (2) and a group derived from the reactive siloxane compound (3), or particularly a cured product thereof.
  • reactive pentaerythritol compounds or reactive dipentaerythritol compounds can be used singly or in their mixture. They may partially include a (di)pentaerythritol compound without having a reactive group to such an extent that hardness of said composition remains adversely unaffected. Ordinarily, 90% or more of them are the reactive (di) pentaerythritol.
  • the general formula (I) does not represent a single compound but is expressed in terms of a mean value of several compounds. Therefore, a and b representing the number of two different groups are each not limited to an integer but may as well be a real number including a decimal.
  • n is 3 or more, ordinarily in a range of 3 to 18, preferably 3 to 4 and each of these numbers is not limited to an integer but may as well be a real number including a decimal.
  • phosphazene compounds having the repeating unit represented by the general formula (I), depending upon the kind of substituent groups.
  • A is a curable group.
  • the curable group is a functional group which is cured due to the reaction in response to the irradiation of an ultraviolet ray, a visible ray, an electron beam, the use of a chemically curable agent, the application of heat or the like. Ordinarily it has a reactive double bond.
  • Examples of said functional group containing the acryloyl group or the methacryloyl group are an acryloyloxy group, a methacryloyloxy group and further a group represented by the general formula (II): wherein R13 is a hydrogen atom or a methyl group; R14 is an alkylene group having 1 to 12 (preferably 1 to 5) carbon atoms (including a branched chain alkylene group).
  • Specific examples of the group represented by the general formula (II) include a 2-hydroxyethyl methacrylate; a 2-hydroxypropyl methacrylate; a 3-hydroxypropyl methacrylate; a 2-hydroxybutyl methacrylate; a 3-hydroxybutyl methacrylate; a 4-hydroxybutyl methacrylate; a 5-hydroxypentyl methacrylate; a 6-hydroxy-3-methylhexyl methacrylate; a 5-hydroxyhexyl methacrylate; a 3-hydroxy-2-t-butylpropyl methacrylate; a 3-hydroxy-2,2-dimethylhexyl methacrylate; a 3-hydroxy-2-methyl-2-ethylpropyl methacrylate and a residue obtained by removing hydrogen atoms from the hydroxyl groups of the methacrylates such as 12-hydroxydodecyl methacrylate; as well as a 2-hydroxyethyl acrylate; a 2-hydroxypropyl acrylate;
  • examples of the functional group containing the acryloyl group or the methacryloyl group include a functional group represented by the general formula (III): wherein R13 and R14 are as defined above, i.e. a residue obtained by removing hydrogen atoms from the hydroxyl groups of a hydroxyalkyl-substituted acrylamide or a hydroxyalkyl-substituted methacrylamide, and further a functional group represented by the general formula (IV): wherein R13 is as defined above, i.e. a residue obtained by removing a hydrogen atom from an amino group of an acrylamide or a methacrylamide.
  • their examples include functional groups represented by the general formulae (V) to (VII): wherein R13 is as defined above; R15 and R16 are each a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, i.e. a residue obtained by removing the hydrogen atoms from an only hydroxyl group of an allyl compound.
  • B of the general formula (I) is not particularly limited but is, for example groups represented by the following general formulae: R17M- (VIII) or In the general formula (VIII), M is an oxygen atom, a sulfur atom or an imino group; R17 is an alkyl group having 1 to 18 carbon atoms or a halogenated alkyl group having 1 to 18 carbon atoms.
  • alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, and an octyloxy group
  • a halogen for example, fluorine, chlorine, bromine and the like
  • alkylthio group such as a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a pentylthio group, a heptylthio group, and an octylthio group
  • a halogen for example, fluorine, chlorine, bromine and the like
  • alkylimino group such as a methylimino group, an ethylimin
  • M is as defined above; R18 to R22 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms or a halogenated alkyl group having 1 to 4 carbon atoms.
  • the groups of the general formula (IX) are a phenoxy group, a thiophenyl group, a halogenated phenoxy group (2, 4, 6-tribromophenoxy group, 4-bromophenoxy group, 2-chlorophenoxy group, 2, 4-dichlorophenoxy group and the like) and a halogenated thiophenyl group (4-chlorophenylthio group and the like), as well as a residue obtained by removing hydrogen atoms from an amino group of an aniline or a halogenated aniline (2-chloroaniline, 2, 4-dichloroaniline, 2, 4, 6-tribromoaniline and the like).
  • the substituent group A is meant to act when a film containing the phosphazene compound of the general formula (I) is cured.
  • the substituent group B is to adjust the physical properties of said cured film, along with the action to control the curing performance thereof.
  • the various physical properties of the cured film containing this phosphazene compound are determined, depending upon the optional choice of a and b; provided that a phosphazene compound entirely free from the curable group A is not curable and should be excluded as the component to be incorporated into the composition of the present invention.
  • the phosphazene compounds of the present invention has the repeating units represented by said general formula (I) wherein n is in a range of 3 to 18. Particularly, the phosphazene compounds wherein n is 3 to 4 and a mixture of them are best suitable.
  • the repeating units represented by the general formula (I) may be bonded in the form of a chain. But those bonded in a cyclic form are preferred.
  • k and p are each an integer of 0 to 4000; q is an integer of 10 to 1000; r is an integer of 2 to 100; Y is a group derived from a diisocyanate compound, for example a group derived from a 2, 4-tolylene diisocyanate or a group derived from a methylene diphenyl diisocyanate; X is a (meth)acrylate-containing group, for example groups derived from a 2-hydroxyethyl (meth)acrylate, a pentaerythritolmonohydroxy tri(meth)acrylate and a dipentaerythritolmonohydroxy penta(meth)acrylate; R23 is a straight chain or branched chain alkyl group or a single bond (where
  • reactive siloxane compounds can be used singly or in their mixture. They may partially include a siloxane compound without having the reactive group to such an extent that hardness of said composition remain adversely unaffected. Ordinarily, 90% or more of the compounds are a reactive siloxane compound.
  • the composition of the present invention contains a reactive pentaerythritol compound or a reactive dipentaerythritol compound (1), a reactive phosphazene compound (2) and a reactive siloxane compound (3) as the essential components.
  • These components (1) to (3) are mixed in the composition, as follows: the reactive (di)pentaerythritol compound (1) and the reactive phosphazene compound (2) are mixed at a ratio of 90 to 40 mole% of (1) to 10 to 60 mole% of (2), preferably 80 to 50 mole% of (1) to 20 to 50 mole% of (2), based on the total of these two.
  • the ratio of the reactive siloxane compound (3) is adjusted to 0.1 to 50 parts by weight, preferably 0.5 to 30 parts by weight, based on 100 parts by weight of a total of the reactive (di)pentaerythritol compound (1) and the reactive phosphazene compound (2).
  • the reactive (di)pentaerythritol compound (1) is effective to provide higher hardness to the protective layer to be formed, contributing to the improvement of the abrasion resistance. If it is mixed too much, the protective layer is cured too fast, liable to develop cracks. It is not unlikely that the so formed protective layer is poor in the release properties when used as the electrophotographic photoreceptor.
  • the reactive phosphazene compound (2) is effective to prevent these cracks.
  • the reactive siloxane compound (3) acts to improve the slip properties and the release properties effectively. Therefore, the electrophotographic photoreceptor using the composition mixing the components (1) to (3) at said ratio can have a well balanced combination of the abrasion resistance, the slip properties, the release properties, the heat resistance, the moisture resistance and the like.
  • Various conductive substrates can be used to build the electrophotographic photoreceptor of the present invention if they are electrically conductive and can ground the photoconductive layer.
  • the conductive substrate include an aluminum, an aluminum alloy, a copper, a zinc, a stainless steel, a vanadium, a molybdenum, a chromium, a titanium, a nickel, an indium, a gold, a platinum and the like.
  • the other conductive substrate include:
  • an undercoat layer having the barrier function and the undercoating function may as well be provided on the surface of said substrate.
  • This undercoat layer can be used for the various purposes, e.g. to improve the adhesiveness of the photoconductive layer, to improve the coating properties, to protect the substrate, to cover the defects on the substrate, to improve the properties of injecting the charge from the substrate and to protect the photoconductive layer from the electrical destruction.
  • the undercoat layer is made from a polyvinyl alcohol, a poly-N-vinylimidazole, a polyethylene oxide, an ethyl cellulose, a methyl cellulose, an ethylene acrylate copolymer, a casein, a polyamide, a copolymerized nylon, a glue, a gelatin and the like.
  • the undercoat layers are formed according to the known methods.
  • the electrophotographic photoreceptor comprises a photoconductive layer formed on a conductive substrate as described above.
  • the photoconductive layer is either single-ply or multi-ply.
  • a single-ply photoconductive layer is made of a deposited film of Se, Se-Te alloy, Se-As alloy, Se-Sb alloy and Se-Bi alloy or an organic photoreceptor comprising a polyvinyl carbazole and a trinitrofluorene, or an amorphous silicone.
  • the organic photoreceptor photoconductive layer
  • the cured product of said composition i.e., the composition containing the reactive (di)pentaerythritol compound (1), the reactive phosphazene compound (2) and the reactive siloxane compound (3)
  • the cured product of said composition is preferably used as a binder.
  • the content of said organic photoreceptor in the photoconductive layer is optionally determined in proportion to the desired photosensitivity.
  • the photoconductive layer made of said composition may be added with a monofunctional monomer or a multifunctional monomer if necessary.
  • this composition can be used in the form of a mixture with a solvent, if necessary.
  • the solvent to be used herein include organic solvents including ketones such as methylethyl ketone, methylisobutyl ketone and cyclohexanone, an aromatic hydrocarbon such as benzene, toluene and xylene, a halogenated hydrocarbon such as chloroform and methylene chloride, alcohols such as methanol, ethanol, propanol and butanol, ethers such as tetrahydrofuran and dioxane, or cellosolves such as ethylcellosolve and butylcellosolve and the like. These solvents can be used singly or in their two or more mixture.
  • Preferred among them is a mixed solvent of ketones, alcohols or these two.
  • a mixed solvent containing a methylisobutyl ketone or an isopropyl alcohol or a butyl alcohol is more preferred.
  • Said composition is meant to protect the photoconductive layer in the form of a cured product.
  • the method for curing the composition is selected from the irradiation (photo-setting) of an activation energy ray (visible ray, ultraviolet ray, electron beam, Xray, ⁇ ray and the like), the heat curing, the cold curing and the like.
  • an activation energy ray visible ray, ultraviolet ray, electron beam, Xray, ⁇ ray and the like
  • the composition is preferably cured with an activation energy ray to prevent changes in the properties of the organic substances.
  • a photopolymerization initiator such as 1-hydroxycyclohexyl phenylketone, dibenzoyl, benzoylmethyl ether, benzoylethyl ether, p-chlorobenzophenone, p-methoxybenzophenone, benzoyl peroxide, di-tert-butyl peroxide, camphorquinone and the like.
  • photopolymerization initiators can be used singly or in their two or more mixture.
  • the cure promoter of this kind is used in an amount selected from a range of 0.05 to 10.0 parts by weight, based on 100 parts by weight of the composition.
  • the composition when the composition is subjected to heat setting, i.e. the method for heat curing or cold curing, it is preferable to use a peroxide-based compound and an amine-based compound singly or in combination as the polymerization initiator.
  • the peroxide-based compound include a benzoylperoxide; a p-chlorobenzoylperoxde; a 2, 4,-dichlorobenzoylperoxide; a t-butylhydroperoxide; a di-t-butylperoxide; a dicumylperoxide; a t-butylperoxyacetate; a diacetate; a t-butylperoxybenzoate and the like.
  • Examples of the amine-based compound include a N, N-diethanol-p-toluidine; a dimethyl-p-toluidine; a p-toluidine; a methylamine; a t-butylamine; a methylethylamine; a diphenylamine; a 4, 4'-dinitrodiphenylamine; an o-nitroaniline; a p-bromoaniline; a 2, 4, 6-tribromoaniline and the like.
  • the peroxide-based compound and the amine-based compound are used in a total amount selected from a range of 0.05 to 5.0 parts by weight, based on 100 parts by weight of the composition.
  • composition of the present invention is cured to form a photoconductive layer, as follows: at first, a photoconductive layer composition is prepared by mixing said composition, a monofunctional or multifunctional monomer if necessary, said organic photoreceptor, a solvent and a cure initiator. The so prepared composition is coated on the surface of the conductive substrate directly or via the undercoat layer. Then, the coated composition is cured.
  • the coating is carried out according to known conventional methods such as spinner method, spray method, roll coater method, dipping method and brushing method and if a solvent is used together, it is removed after the coating is over.
  • said curable composition is cured to form a cured film by means of cold curing or heat curing or by irradiating an ultraviolet ray, an electron beam, an X ray, a ⁇ ray or the like.
  • the photoconductive layer comprising the composition of the present invention ordinarily has a thickness of 0.01 to 100 ⁇ m.
  • this single-ply photoconductive layer can be formed by using a binder resin other than the cured product of said composition.
  • a protective layer comprising the cured product of the composition of the present invention is preferably provided on top of the photoconductive layer.
  • the multi-ply photoconductive layer is a sectionalized function type photoconductive layer.
  • This multi-ply, sectionalized function type photoconductive layer comprises a charge generation layer and a charge transfer layer (a charge carrying layer).
  • the charge generation layer and the charge transfer layer are laminated one after another on the conductive substrate (i.e. in the order of the substrate, the charge generation layer and the charge transfer layer), but they may be laminated the other way around (i.e. in the order of the substrate, the charge transfer layer and the charge generation layer).
  • the charge generation layer contains a charge generating substance such as organic or inorganic pigment and a binder resin.
  • This charge generating substance is, for example pigments and coloring matters which are known as the source of electric charge, including those of an azoxybenzene series, a diazo series, a trisazo series, a benzimidazole series, a polycyclic quinoline series, an indigoid series, a quinacridone series, a phthalocyanine series, a perylene series, a perinone series, a cyanine pigment, a (thio)pyrylium salt, a squarylium pigment and the like.
  • Those pigments are illustrated, for example in Japanese Patent Application Laid Open Nos.
  • a pigment of the phthalocyanine series is a pigment of the phthalocyanine series.
  • Particularly preferred among the phthalocyanine pigments is a ⁇ , ⁇ ', ⁇ or ⁇ ' type metal-free phthalocyanine pigment described in Japanese Patent Application Laid Open No. 182640/1983 and EP-A-0 92,255.
  • the pigment has high sensitivity even to long wavelengths.
  • binder resin examples include a polycarbonate resin, a polyester resin, an acrylic resin, a polyvinyl formal, a polyvinyl butyral, an epoxy resin and a urethane resin.
  • the binder resin is mixed in a charge generation layer at a ratio of 5 to 400 parts by weight, preferably 10 to 300 parts by weight, based on 100 parts by weight of the charge generator. If the ratio is less than 5 parts by weight, the adhesiveness between the charge generation layer and the conductive substrate is poor, often causing the charge generation layer to have an uneven film and the picture quality to deteriorate. If it exceeds 400 parts by weight, there is a tendency of a low sensitivity and a high residual potential.
  • the charge generation layer may as well be added with an additive such as plasticizer, defoaming agent, liquidity improver, pinhole control agent, coupling agent and antioxidant, if necessary.
  • an additive such as plasticizer, defoaming agent, liquidity improver, pinhole control agent, coupling agent and antioxidant, if necessary.
  • the charge generation layer is prepared as follows: at first a dispersant is prepared by dispersing said charge generator and a binder resin and an additive to be added if necessary in a solvent. The so prepared dispersant is coated on the conductive substrate according to dip coating, roller coating, applicator coating, wire wound bar coating and the like.
  • Examples of said solvent include an acetone; a methyletylketone; a tetrahydrofuran; a toluene; a xylene; a dichloromethane; a 1, 2-dichloroethane; a 1, 1, 2-trichloroethane; a methanol; an isopropylalcohol and the like.
  • the said charge generation layer has a thickness of 0.001 to 10 ⁇ m, preferably 0.01 to 5 ⁇ m. If it is less than 0.001 ⁇ m, a uniform charge generation layer cannot be obtained. If it exceeds 10 ⁇ m, the electrifying properties and the like are often poor.
  • the charge transfer layer (the charge carrying layer) is formed from a charge transferring substance (a charge carrying substance) and a binder resin.
  • the charge transferring substance include a fluorene; a fluorenone; a 2, 7-dinitro-9-fluorenone; a 3, 7-dinitro-dibenzothiophene-5-oxide; a 1-bromopyrene; a 2-phenylpyrene; a carbazole; a 3-phenylcarbazole; a 2-phenylindole; a 2-phenylnaphthalene; an oxazole; an oxadiazole; an oxatriazole; a triphenylamine; an imidazole; a chrysene;a tetraphene; an acridine; various hydrazones; a styryl compound; a 1, 1-bis(p-diethylaminophenyl) -4, 4-diphenyl-1
  • composition of the present invention is suitable as the binder resin in the charge transfer layer just as it is suitable in the single-ply photoconductive layer.
  • the composition of the present invention and the charge transferring substance are mixed at a ratio selected to permit the charge transferring substance to have the content of ordinarily 20 to 80 parts by weight, based on the total amount of these two.
  • the charge transfer layer formed of the cured product of said composition ordinarily has a thickness of 5 to 50 ⁇ m, preferably 8 to 30 ⁇ m. If it is less than 5 ⁇ m, the charging properties often are poor. If it exceeds 50 ⁇ m, there is a tendency of a low sensitivity and a poor optical responsivity.
  • the charge transfer layer comprising the composition of the present invention can be formed by repeating the procedure for preparing the single-ply photoconductive layer.
  • the charge transfer layer comprising the composition of the present invention ordinarily has a thickness of 5 to 50 ⁇ m, preferably 8 to 30 ⁇ m. If it is less than 5 ⁇ m, the charging properties often are poor. If it exceeds 50 ⁇ m, there is a tendency of a low sensitivity and a poor optical responsivity.
  • binder resins When it is intended not to use the composition of the present invention as the binder resin to form the charge transfer layer, it is preferable to use binder resins as described hereunder. On the surface of the charge transfer layer prepared with the binder resins as set forth below, there is preferably provided a protective layer formed of the composition of the present invention (will be described later).
  • binder resin other than the composition of the present invention examples include a polycarbonate resin, a polyestercarbonate resin, a styrene resin, an acrylic resin, a silicone resin, a polyester resin, a phenoxy resin, a polyarylate resin, a polysulfone resin, a polyetherimide resin, a vinyl acetate-vinyl chloride copolymer resin, a poly-N-vinylcarbazole resin and the like. They can be used singly or in their two or more mixture.
  • the binder resin is mixed in an amount of ordinarily 20 to 80% by weight, based on the total of the charge transferring substance and the binder resin. If the mixed amount is less than 20% by weight, the optical responsivity is poor. If it exceeds 80% by weight, the durability often is poor.
  • this charge transfer layer may as well be added with an additive such as plasticizer, defoaming agent, liquidity improver, pinhole control agent, coupling agent and antioxidant if necessary.
  • an additive such as plasticizer, defoaming agent, liquidity improver, pinhole control agent, coupling agent and antioxidant if necessary.
  • the charge transfer layer is prepared, as follows: at first a dispersant is prepared by dispersing said charge transferring agent and the binder resin and an additive to be added if necessary in a solvent. The so obtained dispersant is coated on top of said charge generation layer according to the dip coating, the roll coating, the applicator coating, the wire wound bar coating and the like.
  • those used to form said charge generation layer can be used.
  • the said charge transfer layer has ordinarily a thickness of 5 to 50 ⁇ m, preferably 8 to 30 ⁇ m. If it is less than 5 ⁇ m, the charging properties often are poor. If it exceeds 50 ⁇ m, there is a tendency of a low sensitivity and a poor optical responsivity.
  • the protective layer is not always necessary but should be situated on the surface of the photoconductive layer when it is needed; provided, however, that the composition of the present invention must be incorporated into the photoconductive layer (particularly the outermost layer thereof), if the protective layer is not provided.
  • the protective layer can be formed of the cured product of said composition of the present invention. It also can be formed by combining a film of other material and a cured layer of said composition provided on the surface of said film.
  • a powder of metal or metal oxide can suitably be dispersed in the protective layer.
  • the metal to be dispersed in the protective layer is, for example an aluminum, an aluminum alloy and the like.
  • the metal oxide to be dispersed in the protective layer is, for example a tin dioxide, an antimony dioxide, a zinc oxide, a titanium oxide, a tin oxide, an indium oxide, a bismuth oxide and the like.
  • these metal powders and metal oxide powders have a mean particle size of 0.3 ⁇ m or less.
  • the content of these metals or metal oxides is ordinarily 80% by weight or less, preferably 60% by weight or less.
  • the addition of these metal or metal oxide powders is effective in the destaticization, improving the electrophotographic properties.
  • a fluorine-containing resin powder or the like is suitably contained as the lubricant in the protective layer formed of the cured product of the composition of the present invention.
  • the fluorine-containing resin powder are powders each comprising an ethylene tetrafluoride, an ethylene trifluoride chloride, a propylene hexafluoride, a vinyl fluoride, a vinylidene fluoride, an ethylene difluoride dichloride, a polymer such as trifluoropropyl methyldichlorosilane or a copolymer thereof, a copolymer resin comprising a vinyl chloride and the like.
  • the protective layer can be adjusted to have a thickness of 0.01 to 100 ⁇ m, preferably 0.5 to 15 ⁇ m and more preferably 1.5 to 10 ⁇ m according to the need. If the thickness is less than 0.01 ⁇ m, there cannot be developed a sufficiently high function as the protective layer, resulting in a low abrasion resistance. On the other hand, if it exceeds 100 ⁇ m, the sensitivity and optical reponsivity are poor, along with the residual potential at a high side. Furthermore, the protective layer formed of the cured product of said composition may as well be a laminate comprising a plurality of plies.
  • the protective layer of the present invention is a combination of a film made from the other materials and a cured layer of the composition of the present invention which is situated on the surface of said film.
  • This protective layer will be described in detail below.
  • the other materials for use in preparing said film are, for example a polyurethane resin, a polycarbonate resin, a polyacrylate resin, a polymethacrylate resin, a polyisodcyanate, a reaction product between a polyisodcyanate and a hydroxyl group-containing polyester or polyether, a reaction product between a polyisocyanate and a hydroxyl group-containing acrylate or epoxy resin, a reaction product between a polyisocyanate and a polyisocyanate prepolymer containing an isocyanate group with a transient masking and the like.
  • the film can be formed according to the application method, the dipping method, the spraying method, the after-drying method, the curing method and the like. Ordinarily the film has a thickness of 0.5 to 10 ⁇ m. This film layer may as well contain said metals or metal oxides.
  • a cured layer to be situated on the surface of the film can be prepared by repeating the procedure for preparing the protective layer per se from the cured product of the composition of the present invention, provided that the cured layer of said composition has a thickness of 0.2 to 10 ⁇ m, preferably 0.5 to 5 ⁇ m.
  • the electrophotographic photoreceptor of the present invention as described above is not particularly limited relative to the form thereof. Usually it takes the form of a drum, however.
  • a ⁇ type metal-free phthalocyanine 2.5 parts by weight of a ⁇ type metal-free phthalocyanine, 5.0 parts by weight of a silicone resin (brandname: KR-255 (having a solid content of 50% by weight), supplied by Shin-Etsu Chemical CO., LTD.) and 92.5 parts by weight of a methylethylketone were mixed to obtain a mixed solution.
  • the mixed solution was introduced into a ball mill (a pot mill supplied by Nippon Kagaku Togyo Co., Ltd.), kneaded and dispersed over 24 hours to obtain a dispersant intended for use in the formation of a charge generation layer. This dispersant was dip-coated on said interlayer and dried at 120°C over 60 minutes and a charge generation layer having a thickness of 0.3 ⁇ m was formed.
  • the coating composition was applied to the surface of the charge transfer layer of said photoreceptor (No. R1) and the solvent was removed, followed by the irradiation of a UV ray (for 30 seconds). Thus a protective layer having a thickness of 4 ⁇ m was formed.
  • a photoreceptor having this protective layer was analyzed by repeating the procedure of said Comparative Example 1 and the results are given in Table 1.
  • the durability test was conducted by using the sample which was used in the evaluation of the electrophotographic properties as set forth in (1) above.
  • a sample was charged with a corona discharge (a surface potential: -1,000 ⁇ 100V) and destaticized (a destaticizing light wave length of 500nm, and an exposure of 50mJ/m2) 10,000 times, then the electrophotographic properties were determined and the results thereof were compared with the initial values.
  • a steel wool (#0000) at a load of 500g/cm2 was caused to go and come back over the surface of a sample 100 times on a HEIDON surface scanner supplied by Shinto Scientific Co., Ltd. and then the results were analyzed with eye.
  • the abrasion test was conducted by using the sample which was used in the evaluation of the electrophotographic properties as set forth in (1) above and an abrasion test machine supplied by Hitachi Chemical Co., Ltd.
  • a urethane rubber blade having a rubber hardness of 70 (at a load of 200g) was caused to abrade the surface of a sample at a rate of 200 times per minute for 20 minutes and the weight of the so abraded photoreceptor sample was measured.
  • the contact angle of water was obtained by measurement with a contact angle meter CA-D model supplied by Kyowa Surface Chemistry Co., Ltd.
  • a peel test was conducted by the use of a checkered cellophane tape according to JIS K5400
  • the so obtained coating composition was applied to the surface of the charge transfer layer of said photoreceptor (No. R1), the solvent was removed from the coating composition and an UV ray was irradiated thereto to form a protective layer having a thickness of 4 ⁇ m.
  • a code No. 1 was assigned to the photoreceptor having this protective layer.
  • a photo-initiator (Irgacure 907, supplied by Ciba Geigy)
  • 20g of a methylethylketone and 30g of an isobutanol were added to obtain a coating composition.
  • a photoreceptor having a protective layer No. 2 was obtained by using this coating composition and repeating the procedure of said Example 1.
  • the electrophotographic photoreceptor of the present invention has a protective layer
  • said protective layer is free from peeling and flaws, has a sufficiently high strength though it is made of a thin film and further is not liable to have strains to provide the excellent electrophotographic properties.
  • the photoconductive layer is formed by incorporating the composition of the present invention, said photoconductive layer is flaw-free, has a sufficiently high strength though it is made of a thin film and further is not liable to have strains.
  • the abrasion resistance, the surface slip properties, the heat resistance, the moisture resistance and the like are markedly improved relative to the electrophotographic photoreceptor of the present invention. It has been found highly useful in relevant industrial segments.

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Photoreceptors In Electrophotography (AREA)

Abstract

Un photorécepteur électrophotographique comporte une couche photoconductrice formée sur un substrat conducteur et revêtue d'une couche protectrice préparée à partir d'une composition renfermant un composé réactif de (di)pentaérythritol, un composé réactif de phosphazène et un composé réactif de siloxane. Ce photorécepteur présente d'excellentes caractéristiques de résistance à l'abrasion, d'uniformité de surface, de résistance à la chaleur et à l'humidité, etc.
EP92920384A 1991-09-30 1992-09-29 Photorecepteur electrophotographique Withdrawn EP0564655A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP25084391A JPH0588382A (ja) 1991-09-30 1991-09-30 電子写真感光体
JP250843/91 1991-09-30

Publications (2)

Publication Number Publication Date
EP0564655A1 true EP0564655A1 (fr) 1993-10-13
EP0564655A4 EP0564655A4 (fr) 1995-06-07

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EP92920384A Withdrawn EP0564655A1 (fr) 1991-09-30 1992-09-29 Photorecepteur electrophotographique

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EP (1) EP0564655A1 (fr)
JP (1) JPH0588382A (fr)
WO (1) WO1993007540A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014145891A (ja) * 2013-01-29 2014-08-14 Konica Minolta Inc 有機感光体および画像形成装置

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4566834B2 (ja) * 2005-06-20 2010-10-20 株式会社リコー 静電潜像担持体、並びにプロセスカートリッジ、画像形成装置及び画像形成方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5764243A (en) * 1980-10-08 1982-04-19 Canon Inc Electrophotographc receptor
EP0066215A2 (fr) * 1981-05-30 1982-12-08 Hoechst Aktiengesellschaft Matériau d'enregistrement électrophotographique et procédé pour sa production
EP0300426A2 (fr) * 1987-07-20 1989-01-25 Canon Kabushiki Kaisha Elément photosensible électrophotographique
EP0443626A2 (fr) * 1990-02-23 1991-08-28 Idemitsu Petrochemical Co. Ltd. Elément photosensible électrophotographique

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5430036A (en) * 1977-08-11 1979-03-06 Canon Inc Image holding member
JPS5598755A (en) * 1978-01-05 1980-07-28 Ricoh Co Ltd Electrophotographic receptor
DE3032774A1 (de) * 1980-08-30 1982-05-06 Hoechst Ag, 6000 Frankfurt Elektrophotographisches aufzeichnungsmaterial

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5764243A (en) * 1980-10-08 1982-04-19 Canon Inc Electrophotographc receptor
EP0066215A2 (fr) * 1981-05-30 1982-12-08 Hoechst Aktiengesellschaft Matériau d'enregistrement électrophotographique et procédé pour sa production
EP0300426A2 (fr) * 1987-07-20 1989-01-25 Canon Kabushiki Kaisha Elément photosensible électrophotographique
EP0443626A2 (fr) * 1990-02-23 1991-08-28 Idemitsu Petrochemical Co. Ltd. Elément photosensible électrophotographique

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 6, no. 141 (P-131) (1019) 30 July 1982 & JP-A-57 064 243 (CANON) 19 April 1982 *
See also references of WO9307540A1 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014145891A (ja) * 2013-01-29 2014-08-14 Konica Minolta Inc 有機感光体および画像形成装置

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Publication number Publication date
WO1993007540A1 (fr) 1993-04-15
EP0564655A4 (fr) 1995-06-07
JPH0588382A (ja) 1993-04-09

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