WO1993007540A1 - Electrophotographic photoreceptor - Google Patents

Electrophotographic photoreceptor Download PDF

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Publication number
WO1993007540A1
WO1993007540A1 PCT/JP1992/001241 JP9201241W WO9307540A1 WO 1993007540 A1 WO1993007540 A1 WO 1993007540A1 JP 9201241 W JP9201241 W JP 9201241W WO 9307540 A1 WO9307540 A1 WO 9307540A1
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WIPO (PCT)
Prior art keywords
layer
reactive
compound
group
composition
Prior art date
Application number
PCT/JP1992/001241
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English (en)
French (fr)
Japanese (ja)
Inventor
Akihiko Kurahashi
Original Assignee
Idemitsu Petrochemical Co., Ltd.
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Filing date
Publication date
Application filed by Idemitsu Petrochemical Co., Ltd. filed Critical Idemitsu Petrochemical Co., Ltd.
Publication of WO1993007540A1 publication Critical patent/WO1993007540A1/ja

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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/14—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, in particular, by coating the surface with a protective layer made of a specific composition, or by including the above composition in a photo-exclusive layer constituting the outermost layer.
  • Electrophotographic photoreceptors with greatly improved wear resistance, wear resistance, heat resistance, heat resistance, moisture resistance, etc.
  • an electrophotographic photosensitive member such as a copying machine, a laser beam printer, or a light emitting diode printer
  • the surface of the electrophotographic photosensitive member is corona-discharged.
  • the required portion selectively removing the static charge in the exposed portion to form an electrostatic latent image, and then attaching a developer called toner to the static latent image
  • the developer is transferred and fixed to paper, whereby an electrophotograph is formed.
  • this type of electrophotographic photoreceptor has a single photoconductive layer formed on the surface of a conductive support, but the electrophotographic photoreceptor has (1) a potential of (2) that the surface potential leaks away in some places (potential holding ability), (3) the surface potential rapidly decreases during light irradiation (photo-responsiveness), etc. Characteristics are required. Therefore, in recent years, in order to meet these demands, there has been a multi-layered light-separating layer in which the functions of charge generation and load transfer (transport) are performed in separate layers. Electrophotographic photoreceptors with conductive layers have also appeared O
  • the photoconductive layer is a single layer or multiple layers
  • the printing speed of the apparatus has been further increased, and the apparatus itself has been reduced in size, and the process time per print (the time of charging, exposing, and developing / removing) tends to be shortened.
  • a large mechanical load is applied to the photoconductive layer.
  • This mechanical load is caused by the contact of the electrophotographic photoconductor with the blade brush in the cleaning device, which cleans the toner, toner, paper, and the toner slightly attached to the surface of the electrophotographic photoconductor.
  • the higher the repetition of the series of steps of charging-exposure-development-elimination ⁇ the greater the mechanical load applied to the electrophotographic photosensitive layer. Therefore, there is a problem that the surface of the electrophotographic light-sensitive device 4 becomes significantly worn and its usable life is shortened.
  • a wear-resistant protective layer on the outermost layer of the electrophotographic photosensitive member.
  • a resin for forming a protective layer a silicone resin (see Japanese Patent Application Laid-Open No. Sho 62-75460) and an epoxy resin (see Japanese Patent Application Laid-Open No. Sho 53-107341) ), Melamine resin (see Japanese Patent Application Laid-Open No. 61-217502), fluororesin (see Japanese Patent Application Laid-Open No. 60-115,644), acryl resin (ex. (Refer to the public announcement of No. 54-35 338).
  • the intended purpose of abrasion resistance may not be sufficient, the electrophotographic properties may be rather deteriorated, or the density may be reduced or capri may occur. Also, There is a problem in that the performance of the photoreceptor is remarkably changed due to environmental changes, particularly environmental humidity, and it is easy to cause image defects such as print disturbance and capri, which are called image deletion.
  • polycarbonate and a curable resin are often exemplified as a binder resin for forming a protective layer.
  • a binder resin for forming a protective layer are not fully satisfactory in terms of adhesion, strength, surface hardness, etc.
  • JP-A-63-35856 and JP-A-63-56658 disclose protection obtained by adding a fluorine-containing resin powder to polycarbonate, polyester, or the like.
  • Electrophotographic photoreceptors formed from layers have been proposed. However, according to these proposals, although the slip property of the electrophotographic photoreceptor can be improved, there is a problem that the film strength and the surface hardness are rather lowered.
  • the present inventors have conducted intensive research in order to overcome the above-mentioned problems of the conventional technology.
  • the protective layer of the electrophotographic photoreceptor contains an en-reactive phenol erythritol compound or a reactive dipentyl erythritol compound, (2) a reactive phosphazene compound, and (3) a reactive siloxane compound. It has been found that the object can be achieved by forming the outermost layer to contain the above composition instead of forming with the composition described above or forming the protective layer.
  • the present invention has been completed based on such findings.
  • the photoconductive layer formed on the conductive substrate comprises: (1) 90 to 40 mol% of a reactive penyl erythritol compound or a reactive dipentyl erythritol compound; 100 parts by weight of a mixture comprising 100 to 60 mol% of a reactive phosphazene compound and (3) O also provides an electrophotographic photoreceptor characterized by being coated with protective dust consisting of a composition containing 0.1 to 50 parts by weight of the ft-siloxane compound.
  • the present invention also provides an electrophotographic photoreceptor comprising the above composition in a photoconductive layer (especially the outermost layer thereof) instead of forming the above-mentioned protective layer.
  • the protective layer when a protective layer is formed on the surface of the photoconductive layer in the electrophotographic photoreceptor, the protective layer itself is formed using the above composition, or the surface of another protective layer is formed using the above composition. Cover with object.
  • the above-described composition is contained in the photoconductive layer (particularly, the outermost layer portion).
  • the composition used in the present invention comprises (1) a reactive benzoyl erythritol compound or a reactive dipentyl erythritol compound, (2) a reactive phosphazene compound, and (3) a reactive siloxane compound. It contains.
  • the above-mentioned (1) reactive (di) pentaerythritol compound, (2) reactive phosphazene compound and (3) reactive siloxane compound react with each other, or And cured by reacting with the compound of the formula (1).
  • the above composition in the present invention includes (1) a group derived from a reactive (di) pentaerythritol compound, (2) a group derived from a reactive phosphazene compound, and (3) a group derived from a reactive siloxane compound. It means a composition containing a group derived therefrom, particularly a cured product thereof.
  • the reactive dipentyl erythritol compound is represented by the general formula
  • R 5 to R 1 two or more, particularly three or more, of 1 — 0 C CH 2 CH 2 or
  • CH 3 an organic group containing CH 2 is preferred because of its high reactivity.
  • reactive penyl erythritol compounds or reactive dipentyl erythritol compounds may be used alone or in a mixture. Further, as long as the composition does not affect the hardness of the composition, it may contain a (di) benzoyl erythritol compound partially free of a reactive group. In general, 90 to 0 or more is reactive (di) pen-hu erythritol.
  • A represents a curable group
  • B represents a non-curable group
  • N represents an integer of 3 or more.
  • a and b indicating the number of each group are not necessarily limited to integers, but are real numbers including decimal numbers.
  • n is a real number including not only an integer in the range of 3 or more, usually 3 to 18, and preferably 3 to 4, but also a decimal number.
  • phosphazene compounds having a repeating unit represented by the above general formula (I) depending on the type of each substituent.
  • A represents a curable group, which is an ultraviolet ray, a visible ray, It means a functional group that cures by irradiation with light or electron beam, use of a chemical curing agent, or heating, etc. It is usually a group having a reactive double bond.
  • the functional group containing an acryloyl group or the 7-functional group containing a methacryloyl group is an acryloyloxy group ⁇ a methacryloyloxy group, or a compound represented by the general formula (II)
  • R 13 represents a hydrogen atom or a methyl group
  • R 14 represents an alkylene group having 1 to 12 (preferably 1 to 5) carbon atoms (including a branched alkylene group).
  • Specific examples of the group represented by the general formula (II) include 2-hydroxypropyl methacrylate, 2-hydroxypropyl methacrylate, and 3-hydroxypropyl methacrylate.
  • R 13 is the same as above.
  • R 15 and R 16 each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • M represents an oxygen atom, sulfur J3 ⁇ 4i- ⁇ ⁇ or an imino group
  • R 17 represents an alkyl group having 1 to 18 carbon atoms or a 1 to 18 carbon atom. Shows a halogenated alkyl group.
  • alkoxy groups such as methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, and halogens (eg, fluorine, chlorine, bromine, etc.)
  • Alkylthio groups such as alkoxy group, methylthio group, ethylthio group, propylthio group, butylthio group, pentylthio group, heptylthio group, octylthio group, halogen (eg, fluorine, salt:, bromine, etc.) )),
  • Alkyl imino groups such as mino groups, hal
  • the formula (IX) medium M is as defined above, R 1 8 ⁇ R 2 2 Waso respectively independently a hydrogen atom, a halogen atom, 1 to 4 carbon atoms the alkyl group or the number of 1 to 4 carbon Shows a halogenated alkyl group.
  • the group of the formula (IX) is a phenoxy group, a thiophenyl group, a halogenated phenoxy group (2, 4, 6-tribromophenoxy group, a 4-bromobromooxy group, a 2—clo Phenoxy groups, 2,4-dichlorophenoxy groups, etc.
  • halogenated thiophenyl groups eg, 4-chlorophenylthio groups
  • some compounds phthalocyanine and halogenated anilines (2-chloro) Residues obtained by removing the hydrogen atom from the amino group of aniline, 2,4-dichloroaniline, 2,4,6-tribromoaniline, etc. can be mentioned.
  • a + b 2 It should be a real number that satisfies, and is usually a compound having two or more curable groups, preferably 0 ⁇ a ⁇ 2, 0 ⁇ b ⁇ 2.
  • the phosphazene compound having a repeating unit represented by the following formula can be used as a component of the composition of the present invention.
  • the reactive phosphazene compound in the present invention is a compound having a recurring unit of the above general formula (I).
  • the force n is in the range of 3 to 18, especially 3 to 4 or a mixture thereof.
  • the repeating unit of the general formula (I) may be linked in a chain form, but is preferably linked cyclically.
  • R 11 and R 12 each represent an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, and Z 1 and Z 2 represent These represent hydrogen or organic residues, respectively.
  • the compound represented by is also preferable.
  • a block copolymer is shown for convenience, but other random copolymers may be used.
  • k and p are integers from 0 to 400
  • q is an integer from 10 to 100
  • r is an integer from 2 to 100.
  • Y is a group derived from a diisocyanate compound, for example, a group derived from 2,4-tolylene diisocyanate or a group derived from methylene diphenyl diisocyanate.
  • X is a group containing (meta) acrylate, for example, 2-hydroxyhexyl (meta) acrylate, pentaerythritol monohydride, pheasant (meta) acrylate There are groups derived from erythritol monohydroxypentyl (meta) acrylate.
  • R 23 is a straight-chain or branched alkyl group or a single bond (S and Si are ⁇ -bonded), and R 24 and R 25 each have 1 carbon atom.
  • S and Si are ⁇ -bonded
  • reactive siloxane compounds may be used alone or as a mixture. Further, as long as the composition does not affect the hardness of the composition, the composition may contain a siloxane compound having no reactive group. In general, the reactive siloxane compound is above 90%.
  • the composition used in the present invention comprises (1) a reactive pentaerythritol compound or a reactive dipentyl erythritol compound, (2) an anti-I-phosphazene compound and (3) a reactive siloxane compound as main components.
  • the mixing ratio of these (1) to (3) is (1) based on the total of (1) the reactive (di) pentaerythritol compound and (2) the reactive phosphazene compound.
  • the proportion of the reactive siloxane compound should be adjusted to 0.1 to 50 parts by weight, preferably 0.5 to 30 parts by weight.
  • the pen-erythritol compound is effective in increasing the hardness of the formed protective debris ⁇ and contributes to the improvement of wear resistance. However, if the compounding ratio is too large, the curing rate is too high, and cracks are likely to occur. Furthermore, separation 1 when used as an electrophotographic photoreceptor may be reduced.
  • the electrophotographic photoreceptor can be provided with abrasion resistance, slipperiness, release property, heat resistance, moisture resistance, and the like. Can be provided in a well-balanced manner.
  • the conductive substrate constituting the electrophotographic photoreceptor of the present invention various substrates can be used as long as they have conductivity and can ground the photoconductive layer.
  • the conductive substrate include aluminum, aluminum alloy, copper, zinc, stainless steel, vanadium, molybdenum, chromium, titanium, nickel, indium, gold, and platinum.
  • Other conductive substrates include, for example,
  • Plastics eg, polyethylene, aluminum, aluminum alloy, indium oxide, tin oxide, indium oxide alloy, tin oxide alloy
  • a coating layer of various metals or compounds for example, aluminum, aluminum alloy, indium oxide, indium oxide alloy, tin oxide alloy
  • Conductive particles (aluminum powder, titanium oxide, tin oxide, zinc oxide, carbon black, etc.) together with a suitable binder are made of a plastic substrate or the same material as the conductive substrate. Such as a structure that is coated on a base
  • a plastic having a conductive polymer can be used.
  • An undercoat (adhesive layer) having a barrier function and an undercoat function may be present on the surface of the substrate.
  • This undercoat layer improves the adhesion of the photoconductive layer, improves coating properties, protects the substrate, covers defects on the substrate, Various forms such as improvement of charge injection property from the body and protection against electrical breakdown of the photoconductive layer can be formed according to the purpose.
  • Materials for forming the undercoat layer include polyvinyl alcohol and poly-vinyl alcohol.
  • Examples include N-vinylimidazo, polyethylene oxide, ethylcellulose, methylcellulose, ethylene-acrylic acid copolymer, casein, polyamide, copolymerized nylon, nylon, and gelatin.
  • the undercoat layer can be formed by a known method.
  • a photoconductive layer is formed on the conductive substrate as described above.
  • the photoconductive layer is formed in a single layer or a multilayer.
  • the photoconductive layer when the photoconductive layer is formed as a single layer, its components include, for example, Se, Se—Te alloy, Se—As alloy, Se—Sb alloy, and Se—B.
  • An organic photoreceptor such as an i-alloy vapor-deposited film such as a polypinylcarbazole / trinitole / fluorenone or amorphous silicon can be used.
  • the composition that is, (1) reactive (di) pentaerythritol compound, (2) reactive The cured product of the phosphazene compound and (3) a composition containing a reactive siloxane compound) is preferably used as the binder.
  • a photoconductive layer is formed from a cured product of this composition
  • the content of the organic photoconductor in the photoconductive layer is arbitrarily determined according to the desired photosensitivity.
  • a photoconductive layer is formed using the composition, a monofunctional monomer or a polyfunctional monomer may be added to the composition as necessary.
  • this composition is used by mixing with a solvent if necessary.
  • the solvent used in the process include ketones such as methylethyl ketone, methyl isobutyl ketone, and cyclohexanone; aromatic hydrocarbons such as benzene, toluene, and xylene; Halogenated hydrocarbons such as form and methylene chloride, alcohols such as methanol, ethanol, propanol and butanol, and ethers such as tetrahydrofuran and dioxane.
  • Organic solvents such as ethyl ethyl solvent and ethyl cellosolve, and the like. These solvents may be used alone or in combination of two or more.
  • ketones, alcohols or a mixed solvent thereof are preferred, and particularly, methylisobutylketone is preferably a mixed solvent with isopropyl alcohol or butyl alcohol.
  • the composition serves as a cured body for protecting the photoconductive layer.
  • the curing means includes an active energy ray (visible light ray, ultraviolet ray, electron beam, X-ray, Irradiation (light curing), heat curing, and room temperature curing can be used as appropriate.
  • an organic photoreceptor is used as the photoconductive layer, it is preferable that the photocurable layer be cured with active energy in order to prevent deterioration of organic substances.
  • photo-curing for example, when a curing method using ultraviolet light or visible light is used, ⁇ 1-hydroxycyclohexyl phenyl ketone, dibenzoyl, benzoinolemethyl ether, benzol as a polymerization initiator It is possible to add ylethyl ether, p-chlorobenzophenone, p-methoxybenzophenone, benviyl peroxide, di-tert-butyl benzoxide and camphuaquinone. I like it. These photopolymerization initiators may be used alone or in combination of two or more.
  • the amount of the curing accelerator used is usually 100 parts by weight of the composition. It is selected in the range of 0.05 to 10.0 parts by weight.
  • a peroxide compound or an amine O compound may be used alone or in combination as a polymerization initiator.
  • peroxide-based compounds include benzoyl peroxide; P- ⁇ benzoyl peroxide: 2,4-dichlorobenzoic oxide; t-butyl hydroperoxide; t-butyl hydroperoxide; —Oxide; Dicumyl peroxyside; t—Butyl veroxy acetate; Diacetate; t Monobutyl peroxybenzoate.
  • amide-based compounds include N,!
  • the total im amount of the peroxide-based compound and the amine-based compound is selected in a range of 0.05 to 5.0 parts by weight Pff based on 100 parts by weight of the composition. Is preferred.
  • the composition In order to form a photoconductive layer by curing the composition of the present invention, the composition, and if necessary, a monofunctional monomer or a polyfunctional monomer, the photoreceptor, a solvent, and a curing initiator are used.
  • a photoconductive layer composition is prepared, and the composition is cured directly on the surface of the conductive substrate or through an undercoat layer.
  • the thickness of the photoconductive layer formed using the composition of the present invention is usually
  • the single-layer photoconductive layer can be formed by using another binder resin without forming the cured product of the composition.
  • the photoconductive layer is formed on the photoconductive layer.
  • the function-separated type photoconductive layer formed in the multilayer includes a charge generation layer and a charge transfer layer (charge transfer layer).
  • the charge generation layer and the charge transfer layer are sequentially laminated on the conductive substrate (that is, the conductive substrate ⁇ the charge generation layer and the charge transfer layer), but are laminated in the reverse order ( That is, the conductive substrate (charge transfer layer / charge generation layer) may be used.
  • the charge generation layer contains a charge generation material of an organic or inorganic pigment and a binder tree Hi !.
  • the charge-generating substance examples include azoxybenzene, disazo, trisazo, benzimidazole, polycyclic quinoline, indigoide, quinacridone, phthalocyanine, and periphery.
  • Pigments and dyes that are known to generate charges such as len-based, perinon-based, cyanine dyes, (thio) pyrilyum salts, and square-riium dyes, can be mentioned. These pigments are described in, for example,
  • 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 blending ratio of the binder resin in the load generating layer is 5 to 400 parts by weight, more preferably 10 to 300 parts by weight, based on 100 parts by weight of the charge generating agent. If the amount is less than 5 parts by weight, the density of the charge generation layer with the conductive substrate is poor, and the film of the charge generation layer may be uneven or the image may be deteriorated. If it exceeds, the sensitivity tends to decrease and the residual potential tends to increase.
  • additives such as a plasticizer, an antifoaming agent, a fluidity improving agent, a pinhole controlling agent, a coupling agent, and an antioxidant may be added to the charge generating layer.
  • a dispersion is prepared by dispersing the charge generation agent, the binder resin, and an additive that is added as necessary in a solvent, and dip coating or roll coating is performed. It can be formed by coating on a conductive substrate by a method such as one-time application of apriquet, one-time application of wire, or the like.
  • Examples of the solvent include acetate, methylethylketone, and tetrahydrogen. Mouth furan; Toluene; Kyzylene; Dichloromethane; 1,2-Dichloroethane; 1,1,2—Trichloroethane; Methasol; Isopropyl alcohol.
  • the thickness of the charge generation layer is from 0.001 to 10 1m, preferably from 0.01 to 5 // m. If it is less than 0.01 / m, it may not be possible to form the charge generation layer uniformly, while if it exceeds 10 m, the above-mentioned performance such as chargeability may be reduced. .
  • the charge transfer layer is formed to include a charge transfer substance (charge transfer substance) and a binder resin.
  • the charge transfer material include fluorene; fluorenone; 2,7-dinitro-9-fluorenone; 3,7-dinitrodibenzothiophene-5-oxide; 1-bromopyrene; 2-vinyl; carnoxol; 3—phenylcarnoxole; 2—phenylindole; 2—phenylnaphthalene; oxazole; oxaziazol; oxatriazole; Rifenylamin; imidazole; chrysene; tetraphene; acridene; various hydrazones; styryl compounds; 1, 1-bis (p-pethylethylaminophenyl) 1-4, 4-Diphenyl 1, 3-Bubuten; 1 Ferro-3 — (4-Jetilaminostyryl)-5-(4-Jetilaminophen
  • the compounding ratio of the composition of the present invention and the charge transfer material is preferably selected so that the ratio of the charge transfer material is usually 20 to 80 parts by weight based on the sum of these.
  • the thickness of the charge transfer layer formed of the cured product of the composition is usually 5 to 50 m, preferably 8 to 30 fim. If it is less than 50 ⁇ m, the chargeability may decrease, and if it exceeds 50 m, the sensitivity and the light responsiveness tend to decrease.
  • the method for forming the charge transfer layer using the composition of the present invention is the same as that for forming a single photoconductive layer.
  • the thickness of the charge transfer layer formed using this composition is usually 5 to 50 m, preferably 8 to 30 m. If it is less than 5 m, the chargeability may be reduced, and if it is more than 50 m, sensitivity and photoresponsiveness may be reduced.
  • a binder resin as described below.
  • a protective layer formed using the composition of the present invention on the surface of the charge transfer layer.
  • Binder resins other than the composition of the present invention include, for example, polycarbonate resins, polyester carbonate resins, styrene resins, acrylic resins, silicone resins, polyester resins, phenoxy resins, and polyrelate. Resin, polysulfone resin, polyetherimide resin, vinyl acetate / vinyl chloride copolymer resin, poly (N-vinylcarbazole) resin, and the like. One of these can be used alone, or two or more of them can be used in combination.
  • the compounding amount of the binder resin is usually 20 to 80% by weight based on the total amount of the charge transfer material and the binder resin. If the amount is less than 20% by weight, the photoresponsiveness may decrease. If the amount exceeds 80% by weight, the durability may be poor.
  • additives such as a plasticizer, an antifoaming agent, a fluidity improver, a pinhole controlling agent, a coupling agent, and an antioxidant may be added to the charge transfer layer.
  • a dispersion is prepared by dispersing the charge transfer agent, the binder resin, and an additive to be added as necessary in a solvent, and dip coating or roll coating the dispersion. It can be formed by coating on the charge generating layer by a method such as coating, coating of apricot, coating of a wire, coating of a wire, or the like.
  • the same solvent as used for forming the charge generation layer can be used.
  • the thickness of the charge transfer layer is usually 5 to 50 / m, and preferably 8 to 30 m. If it is less than 5 Aim, the chargeability may decrease, and if it exceeds 50 m, sensitivity and photoresponsiveness may decrease.
  • the protective layer is not essential, but when formed, is formed on the surface of the photoconductive layer. However, when the protective layer is not formed, the composition of the present invention is always contained in the photoconductive layer (particularly, the outermost layer).
  • the protective layer may be formed of a cured product of the composition, or may be a coating layer formed of another material, and a cured layer of the composition formed on the surface thereof. It may be formed by. If the case where the protective layer is formed of a cured body of the composition is described, It is as follows. In this case, the types and mixing ratios of the constituent components of the composition, or the types of monofunctional or polyfunctional monomers, solvents, and curing initiators that are optionally added to the composition are as described above. It is. In order to further improve the lubrication, a lubricant such as silicone wax may be added. Alternatively, the charge transfer material and the additives exemplified in the description of the charge transfer layer may be appropriately compounded.
  • a powder of a metal or a metal oxide may be dispersed during the protection.
  • Metals dispersed in the protective layer include, for example, aluminum and aluminum alloys, and metal oxides dispersed in the protective layer include tin dioxide, antimony dioxide, zinc oxide, titanium oxide, tin oxide, and oxides. Indium, bismuth oxide, and the like can be given.
  • These metal or metal oxide powders preferably have an average particle size of 0.3 m or less.
  • the content of these metals or metal oxides is usually at most 80% by weight, preferably at most 60% by weight. Addition of a powder of these metals or metal oxides provides a static elimination effect and improves electrophotographic properties.
  • the protective layer formed of the cured product of the composition of the present invention may contain, for example, a fluorine-containing resin powder as a lubricant.
  • a fluorine-containing resin powder include tetrafluoroethylene, ethylene trifluoride, ethylene hexafluoride, propylene hexafluoride, vinyl fluoride, vinylidene fluoride, ethylene dichloride diethylene chloride, and trifluoropropyl methyl dichloride.
  • Examples include polymers such as lucirane, copolymers thereof, and powders of copolymer resins with vinyl chloride.
  • the thickness of the protective layer is Adjust to an arbitrary thickness in the range of 0.01 to 100 mm, preferably 0.5 to 15 mm, or more preferably 1.5 to 10 mm as necessary I can do it.
  • the thickness is less than 0.01 m, the function as a protective layer is not sufficiently exhibited, and the abrasion resistance may be reduced.
  • the thickness exceeds 100 m, sensitivity and light responsiveness are reduced. However, the residual potential may increase.
  • the protective layer formed by the cured product of the composition may be a laminate composed of a plurality of layers.
  • protective layer comprising a coating layer formed of another material and a cured layer of the composition of the present invention formed on the surface thereof.
  • the explanation is as follows.
  • Other materials from which the coating film can be formed include: polyurethane tree) jl, polycarbonate resin, polyacrylate resin, polymethacrylate resin, polyisocyanate.
  • a reaction product of an isocyanate and a polyester or polyether containing a hydroxyl group, or a reaction product of a polyisocyanate and an acrylic or epoxy resin containing a hydroxy group, or a polyisocyanate and a temporarily masked isocyanate group Reaction products with the polyisocyanate-containing prepolymer can be mentioned.
  • This coating layer can be formed by a coating method, a dipping method, a spraying method, a post-drying method, a curing method, or the like.
  • the thickness of the coating layer is usually 0.5 to 10 m.
  • the coating layer may contain the above-mentioned metal or metal sulphate.
  • the cured layer formed on the surface of the coating layer is the same as the case where the protective layer itself is formed from the cured product of the composition of the present invention.
  • the thickness of the cured layer of the composition is 0.2 to 10 ⁇ m, and preferably, 0.5 to 5 ⁇ m.
  • the shape of the electrophotographic photoreceptor of the present invention described in detail above is not particularly limited, it is usually formed in a drum shape.
  • Hexachlorocyclotriphosphazene was placed in a 1-liter flask equipped with a thermometer, stirrer, dropping funnel and condenser.
  • the photoreceptor having this protective layer was measured in the same manner as in Comparative Example 1. Table 1 shows the results.
  • the edge band surface potential: -1,100 ⁇ 100 V
  • static elimination static elimination light wave After repeating the length of 500 nm and the exposure amount of 50 mJZm 2 ) 100,000 times, the electrophotographic characteristics were measured and compared with the initial values.
  • the surface of the same photoreceptor sample that was used for the evaluation of the electrophotographic characteristics was tested with a urethane rubber blade (load: 200 g) with a rubber hardness of 70. The sample was slid 200 times per minute, and the weight of the photoreceptor sample worn for 20 minutes was measured.
  • the contact angle of water was measured using a contact angle meter CA-D manufactured by Kyowa Interface Science Co., Ltd.
  • the reactive phosphazene compound (1,1,3,3,5,5—hexa (methacryloylethylenedioxy) cyclotriphosphazene) obtained in Synthesis Example 1 above was added to 1 liter flask. g (255 mm), Penyu Erythritol Tonolate Crylate 250 g (839 mimol), and 10 g of the reaction mixture obtained in Synthesis Example 2 above. , And the mixture was heated to 60 ° C in a warm bath and reacted for 24 hours with stirring to obtain an I ⁇ pulverized body. No isolated group was observed in this dense body. Next, 10 g of this viscous body was added to a photoinitiator (Daroc, Merck).
  • a photoinitiator (Irgacure 907, manufactured by Ciba Geigy Co., Ltd.) 1, 3 g of conductive powder (tin oxide), 20 g of methylethylketone, and 30 g of isobutanol were added. And a coating agent.
  • Photoconductor No. 2 having a protective film was obtained in the same manner as in Example 1 above.
  • the thin protective layer when a protective layer is formed, there is no separation or damage of the protective film, the thin protective layer has sufficient strength, but only the distortion of the protective layer, etc. And has excellent electrophotographic properties.
  • the photoconductive layer is formed by adding the composition of the present invention, the photoconductive layer is not damaged, the thin photoconductive layer has sufficient strength, and the photoconductive layer can be distorted. There is no such thing.
  • the electrophotographic photoreceptor of the present invention has significantly improved abrasion resistance, surface slippage, heat resistance 11 :, moisture resistance, and the like, and its practical value is extremely high.

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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)
PCT/JP1992/001241 1991-09-30 1992-09-29 Electrophotographic photoreceptor WO1993007540A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP3/250843 1991-09-30
JP25084391A JPH0588382A (ja) 1991-09-30 1991-09-30 電子写真感光体

Publications (1)

Publication Number Publication Date
WO1993007540A1 true WO1993007540A1 (en) 1993-04-15

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Application Number Title Priority Date Filing Date
PCT/JP1992/001241 WO1993007540A1 (en) 1991-09-30 1992-09-29 Electrophotographic photoreceptor

Country Status (3)

Country Link
EP (1) EP0564655A1 (enrdf_load_stackoverflow)
JP (1) JPH0588382A (enrdf_load_stackoverflow)
WO (1) WO1993007540A1 (enrdf_load_stackoverflow)

Families Citing this family (2)

* 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
JP6060706B2 (ja) * 2013-01-29 2017-01-18 コニカミノルタ株式会社 有機感光体および画像形成装置

Citations (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
JPS5789764A (en) * 1980-08-30 1982-06-04 Hoechst Ag Electronic photographic recording material

Family Cites Families (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
DE3121563A1 (de) * 1981-05-30 1983-02-03 Hoechst Ag, 6000 Frankfurt Elektrophtographisches aufzeichnungsmaterial und verfahren zu seiner herstellung
JPS6423259A (en) * 1987-07-20 1989-01-25 Canon Kk Electrophotographic sensitive body
JPH03246553A (ja) * 1990-02-23 1991-11-01 Idemitsu Petrochem Co Ltd 電子写真感光体

Patent Citations (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
JPS5789764A (en) * 1980-08-30 1982-06-04 Hoechst Ag Electronic photographic recording material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP0564655A4 *

Also Published As

Publication number Publication date
EP0564655A4 (enrdf_load_stackoverflow) 1995-06-07
JPH0588382A (ja) 1993-04-09
EP0564655A1 (en) 1993-10-13

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