EP0356246B1 - Photorécepteur - Google Patents

Photorécepteur Download PDF

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Publication number
EP0356246B1
EP0356246B1 EP19890308637 EP89308637A EP0356246B1 EP 0356246 B1 EP0356246 B1 EP 0356246B1 EP 19890308637 EP19890308637 EP 19890308637 EP 89308637 A EP89308637 A EP 89308637A EP 0356246 B1 EP0356246 B1 EP 0356246B1
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EP
European Patent Office
Prior art keywords
group
substituted
carrier transport
unsubstituted
layer
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German (de)
English (en)
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EP0356246A3 (fr
EP0356246A2 (fr
Inventor
Yoshiaki Takei
Eiichi Sakai
Tadasu Ichino
Katumi Matuura
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Konica Minolta Inc
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Konica Minolta Inc
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/05—Organic bonding materials; Methods for coating a substrate with a photoconductive layer; Inert supplements for use in photoconductive layers
    • G03G5/0528—Macromolecular bonding materials
    • G03G5/0557—Macromolecular bonding materials obtained otherwise than by reactions only involving carbon-to-carbon unsatured bonds
    • G03G5/0564—Polycarbonates
    • 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
    • G03G5/043—Photoconductive layers characterised by having two or more layers or characterised by their composite structure
    • G03G5/047—Photoconductive layers characterised by having two or more layers or characterised by their composite structure characterised by the charge-generation layers or charge transport layers

Definitions

  • the present invention relates to a photoreceptor such as one to be used in electrophotography.
  • an electric charge layer is deposited on the surface of a photoreceptor and after exposure to form a latent electrostatic image, it is developed by a toner and the resulting visible image is transferred and fixed to a receiving sheet such as paper. Subsequently, the toner is removed from the surface of the photoreceptor and any residual charges are neutralized to erase the electrostatic image completely and condition the photoreceptor for another cycle, thereby enabling its cyclic use for a prolonged period.
  • the photoreceptor For successful operation of electrophotography, the photoreceptor must satisfy various requirements not only in terms of electrophotographic characteristics such as good chargeability and sensitivity plus small dark decay but also in terms of physical properties such as long run length and high resistance to wear and moisture during cyclic use, as well as in terms of resistance to environmental conditions such as ozone generated upon corona discharging and ultraviolet radiation emitted during exposure.
  • Electrophotographic photoreceptors that have been commonly used in the art are inorganic products having a photosensitive layer that is based on inorganic photoconductive materials such as selenium, zinc oxide and cadmium sulfide.
  • inorganic photoconductive materials such as selenium, zinc oxide and cadmium sulfide.
  • organic photoconductive materials as the effective component of light-sensitive layers in electrophotographic photoreceptors has been the subject of active research and development efforts in the recent years.
  • an organic photoreceptor having a light-sensitive layer containing poly-N-vinylcarbazole and 2,4,7-trinitro-9-fluorenone has been described in JP-B-50-10496 (the term "JP-B" as used hereunder means an "examined Japanese patent publication").
  • organic electrophotographic photoreceptors described above have the advantage that the light-sensitive layer can be formed by coating techniques, so not only can they be manufactured at low cost without causing environmental pollution but they can also be fabricated in various forms including sheet.
  • conventional organic electrophotographic photoreceptors have had the following problems that demand solution.
  • US-A-4 637 971 discloses a photoreceptor which uses a polycarbonate resin having one of the formulas (I) and (II) described hereinafter.
  • the document describes a photoreceptor which has good charging performance, repeatability and copy running life while avoiding the disadvantages of toner film build up and the like.
  • the photoreceptor does not have good resistance to environmental factors such as ozone, heat and moisture.
  • JP-A-60 12551 discloses a photoreceptor in which the charge transport layer is composed of two or more constituent layers and in which the weight ratio of the content of the charge transport material to the binder in a constituent layer which is closer to the electroconductive base is higher than the weight ratio of the content of the charge transport material to the binder in a constituent layer which is more remote from the base.
  • the purported object of the photoreceptor described in this document is to provide improved durability.
  • the photoreceptor does not possess satisfactory performance in hot and humid environments.
  • An object, therefore, of the present invention is to provide a photoreceptor that has a high mechanical strength and good charging potential and sensitivity characteristics, that will not experience a substantial increase in residual potential, and that exhibits high resistance to the environment including hot and humid conditions.
  • a photoreceptor having an electroconductive base, a carrier generation layer formed thereon, and carrier transport layer overlaid on the carrier generation layer and containing a carrier transport material and a binder material; the carrier transport layer comprising at least two constituent layers, so that the weight ratio of the carrier transport material to the binder material in a continuous layer which is closer to the electroconductive base is higher than the weight ratio of the carrier transport material in a constituent layer which is more remote from the electroconductive base, and a polycarbonate having as the principal recurring unit a structural unit represented by the following general formula (I) and/or a structural unit represented by the following general formula (II): (where R1 and R2 each is a hydrogen atom, a substituted or unsubstituted aliphatic group, a substituted or unsubstituted carbocyclic group, or a substituted or unsubstituted aromatic group, provided that at least one of R1 and R2 is a "bulky" group; and R3, R4, R3, R4, R3, R
  • the carrier transport layer is divided into two or more constituent layers having different concentrations of carrier transport material.
  • a constituent layer which is closer to said electroconductive base has a higher concentration of carrier transport material so that photocarriers generated in the carrier generation layer will be injected efficiently into the carrier transport layer.
  • a constituent layer which is more remote from said electroconductive base has a lower concentration of carrier transport material, so that the reduced use of the carrier transport material having a low molecular weight will contribute to a corresponding increase in the mechanical strength of the carrier transport layer.
  • a polycarbonate having a structural unit represented by the general formula (I) and/or the general formula (II) as the principal recurring unit is incorporated as a binder in a constituent layer of said carrier transport layer which is the remotest from the electroconductive base.
  • Polycarbonates having a structural unit represented by the general formula (I) and/or the general formula (II) as the principal recurring unit have high mechanical strength, good resistance to scratch and wear, long run length and desired charging performance.
  • such polycarbonates have a hard surface while providing a reasonable degree of lubricity. They also have a high degree of transparency and insulating property and are highly miscible with the carrier transport material.
  • R1 and R2 at least one of which is "bulky” are bound to the central carbon atom of the bisphenol A portion or a ring is formed of Z around said carbon atom, so that said R1 and/or R2 or Z effectively prevents the molecular chain of the polycarbonate to be oriented in a certain direction.
  • the polycarbonate will not crystallize to bleed out on the surface of the photosensitive layer being formed and deterioration of characteristics such as yield loss due to abnormal projections and defective image due to toner filming, or premature gelation of the coating solution can be prevented.
  • the polycarbonates of the general formula (I) and the general formula (II) are impermeable to ozone and will hence reduce the chance of deterioration of the carrier transport material. This advantage is particularly notable in the photoreceptor of the present invention since a constituent layer of the carrier transport layer which is more remote from the electroconductive base has a lower concentration of carrier transport material.
  • the carrier transport layer may be composed of two or three or more constituent layers. If it is made of three or more constituent layers, the content of carrier transport material is the highest in the constituent layer which is the closest to the electroconductive base, with said concentration being decreased toward the outer surface of the carrier transport layer.
  • Figs. 1 - 4 Four basic compositions of the photoreceptor of the present invention are shown schematically in Figs. 1 - 4 for illustrative purposes.
  • the photoreceptor shown in Fig. 1 comprises an electroconductive base 1 overlaid with a carrier generation layer 2 that in turn is overlaid with a carrier transport layer 3 which is composed of constituent layers 3A and 3B.
  • the electroconductive base 1 of the photoreceptor shown in Fig. 2 is formed of a flexible substrate 1A overlaid with an electroconductive layer 1B.
  • the carrier generation layer 2 is overlaid with the carrier transport layer 3 composed of three constituent layers 3A, 3B and 3C.
  • the photoreceptor shown in Fig. 4 is the same as that shown in Fig. 1 except that an intermediate layer or subbing layer 6 is provided between the carrier generation layer 2 and the electroconductive base 1.
  • the weight ratio of the content of the carrier transport material to binder material in a constituent layer of said carrier transport layer which is the remotest from the electroconductive base (hereinafter referred to as a outermost constituent layer of the carrier transport layer) (layer 3B in the examples shown in Figs. 1, 2 and 4, and layer 3C in the example shown in Fig. 3) is preferably not higher than 70 wt%, more preferably in the range of 5 - 70 wt%. If the weight ratio of the content of carrier transport material to binder material is adjusted to lie within this range, the strength of the carrier transport layer can be increased without sacrificing its ability to transport carriers.
  • the weight ratio of the content of carrier transport material to binder material in a constituent layer which is the closest to the electroconductive base is preferably at least 30 wt%, more preferably in the range of 30 - 300 wt%. If the weight ratio of the content of carrier transport material to binder material is adjusted to lie within this range, an increased amount of photocarriers can be injected into the carrier transport layer from the carrier generation layer. It is particularly noteworthy that the content of carrier transport material in this constituent layer can be increased to as high as 300 wt% and this has become possible for two reasons: first, the carrier transport layer is composed of two or more constituent layers, and second, the constituent layer the remotest from the electroconductive base has an increased strength.
  • the weight ratio of the content of carrier transport. material to binder material in a constituent layer which is the remotest from the electroconductive base preferably differs by at least 1.0 wt% from the weight ratio of the content of carrier transport material to binder material in a constituent layer which is the closest to the electroconductive base.
  • the binder in each of the constituent layers of the carrier transport layer may be made of a polycarbonate represented by the general formula (I) and/or the general formula (II). This is effective in achieving further increase in the strength of the carrier transport layer.
  • At least one of R1 and R2 be a bulky group, preferably having at least 3 carbon atoms, in order to provide steric hindrance in such a way as to prevent orientation of the molecular chain.
  • R1 and R2 When either one of R1 and R2 is a bulky group, the other may be a hydrogen atom or an alkyl group such as methyl.
  • R3 - R10 may represent not only a hydrogen atom but also a halogen atom such as Cl, Br or F, an alkyl group such as methyl, and a carbocyclic group such as cyclohexyl.
  • Z may be an atomic group that forms a 5- or 6-membered carbon ring or heterocyclic ring, such as a cyclohexyl group or a cyclopentyl group. These groups may be partly substituted by acetyl, acetylamino or other groups.
  • the polycarbonates that can be used in the present invention have as the principal recurring unit the structural unit represented by the general formula (I) and/or the structural unit represented by the general formula (II).
  • the principal recurring unit may be a single structural unit represented by general formula (I) or general formula (II) (for example, the structural unit (I-2) may be the sole recurring unit), or two or more structural units represented by general formula (I) and/or general formula (II) may be co-condensed.
  • a recurring unit represented by general formula (I) and/or general formula (II) may be co-condensed with minor amounts of different other recurring units with a view to providing improved physical, chemical and electrical characteristics.
  • the resulting polycarbonates of co-condensation type are included within the scope of the present invention as long as they are not detrimental to the purposes of the present invention.
  • polycarbonates of co-condensation type include a polycarbonate prepared by co-condensing 4,4′-dihydroxyphenyl-1,1-cyclohexane with a minor proportion of bisphenol A, and the product of polycondensation of 4,4′-dihydroxyphenyl-1,1-cyclohexane and an aromatic dicarboxylic acid such as terephthalic acid or isophthalic acid.
  • polycarbonates that can be used in the present invention are represented by the following general formulas (Ia) and (IIa): where R1, R2, R3, R4, R5, R6, R7, R8, R9 and R10 each is same as defined for formulas (I) and (II); n is 10 - 5000, preferably 50 - 2000; and where R3, R4, R5, R6, R7, R8, R9, R10, Z and n each is same as defined for general formulas (I) and (II).
  • the polycarbonate having the structural unit represented by general formula (II) as the principal recurring unit is preferred since it is capable of attaining the objects of the present invention in a more effective way.
  • Particularly advantageous structural units are those identified above by (II-2), (II-4) and (II-9) which have a cyclohexane ring bound to the central carbon atom of the bisphenol A portion, and the structural unit identified by (II-2) is most preferred.
  • the carrier transport material to be incorporated in the carrier transport layer is described below.
  • Illustrative carrier transport materials include carbazole derivatives represented by the following general formula (III) and hydrazone compounds represented by the following general formulas (IV) - (VI): (where R13 is a substituted or unsubstituted aryl group; R14 is a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, an alkoxy group, an amino group, a hydroxyl group or a substituted amino group; and R15 is a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group); (where R16 and R17 each is a hydrogen atom or a halogen atom; R18 and R19 each is a substituted or unsubstituted aryl group; and Ar1 is a substituted or unsubstituted arylene group); (where R20 is a substituted or unsubstituted aryl group, or a substituted or unsub
  • Carrier transport materials represented by the following general formulas (VII) - (IX) can also be used in the present invention: (where l is an integer of 0 or 1; R24, R25 and R26 each is a substituted or unsubstituted aryl group; R27 and R28 each is a hydrogen atom, an alkyl group having 1 - 4 carbon atoms, a substituted or unsubstituted aryl or aralkyl group, provided that R27 and R28 are not a hydrogen atom at the same time, and when l is 0, R27 is not a hydrogen atom); (where R29 and R30 is a substituted or unsubstituted alkyl or phenyl group, with the substituent being an alkyl, alkoxy or phenyl group; R31 is a substituted or unsubstituted phenyl, naphthyl, anthryl, fluorenyl or heterocyclic group, with the substituent being an alkyl group,
  • Hydrazone compounds represented by the following general formula (X) may also be used in the present invention: (where D is a substituted or unsubstituted phenyl group, or a substituted or unsubstituted carbazolyl group, as specifically illustrated by R36 and R37 each represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted aryl group (illustrative alkyl groups include methyl, ethyl, propyl and butyl; illustrative aralkyl groups include benzyl and phenethyl; illustrative aryl groups include phenyl, ⁇ -naphthyl and ⁇ -naphthyl; illustrative substituents include a halogen atom, an alkyl group, an alkoxy group and a substituted amino group such as dimethylamino, die
  • the carrier transport materials described above may be synthesized by known methods, one of which comprises performing dehydrative condensation between ⁇ , ⁇ -unsaturated ketone and phenylhydrazine in the presence of an acid catalyst.
  • the carrier generation layer (CGL) in the photoreceptor of the present invention contains a carrier generation material (CGM) and polycyclic quinone pigments represented by the following general formulas (XI), (XII) and (XIII) may be used as CGM:
  • X is a halogen atom, a nitro group, a cyano group, an acyl group or a carboxyl group
  • n is an integer of 0 to 4
  • m is an integer of 0 to 6.
  • These polycyclic quinone pigments can be synthesized by known methods.
  • CGM examples include bisazo compounds represented by the following general formula (XIV): where Ar5 and Ar6 each is a substituted or unsubstituted carbocyclic aromatic group, or a substituted or unsubstituted heterocyclic aromatic group; R47 and R48 each is an electron withdrawing group or a hydrogen atom (at least one of R47 and R48 is -CN, a halogen such as -Cl or an electron withdrawing group such as -NO2); and A is (X is a hydroxyl group, or -NHSO2-R52 (where R50, and R51 each is a hydrogen atom or a substituted or unsubstituted alkyl group; R52 is a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group); Y is a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, an alkoxy group, a carboxyl
  • Ar5 and Ar6 in formula (XIVa) each represents a substituted or unsubstituted phenyl group, with the substituent being selected from among an alkyl group such as methyl or ethyl, an alkoxy group such as methoxy or ethoxy, a halogen atom such as chlorine or bromine, a hydroxyl group and a cyano group.
  • Bisazo compounds represented by the following general formula (XV) are also useful as CGM: where A is (where Z is the atomic group necessary to form a substituted or unsubstituted aromatic carbon ring or a substituted or unsubstituted aromatic heterocyclic ring; Y is a hydrogen atom, a hydroxyl group, a carboxyl group, an ester group thereof, a sulfo group, a substituted or unsubstituted carbamoyl group, or a substituted or unsubstituted sulfamoyl group; R53 is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted carbamoyl group, a carboxyl group, an ester group thereof, a cyano group; Ar7 is a substituted or unsubstituted aryl group; and R54 is a substituted or unsubsti
  • fluorenylidene group containing bisazo compounds represented by the following general formula (XVa) are particularly effective: where R55 and R56 each is an alkyl group, an alkoxy group or an aryl group; R57, R58, R59, R60, R61 and R62 each is a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an amino group, a hydroxyl group or an aryl group; and A'' is a substituted or unsubstituted aryl group.
  • the bisazo compounds of formula (XVa) whose intramolecular carbazole group would contribute sensitizing action are capable of providing high sensitivity, particularly in the longer wavelength range.
  • the combination with the intramolecular carbamoyl group moiety provides an effective coupler which exhibits satisfactory sensitivity characteristics over a broad range of wavelengths, thereby contributing to the fabrication of an efficient photoreceptor for use with a semiconductor laser.
  • Bisazo compounds represented by the following general formula (XVI) can also be used as carrier generation materials: where X1 and X2 each is a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a nitro group, a cyano group, a hydroxyl group or a substituted or unsubstituted amino group, provided that at least one of X1 and X2 is a halogen atom; p and q each represents an integer of 0, 1 or 2, provided that p and q are not zero at the same time and that when p is 2, X1 may assume the same or different groups, and that when q is 2, X2 may assume the same or different groups; and A is a group represented by the following general formula (XVII): (where Ar8 is an aromatic carbocyclic or heterocyclic group having at least one fluorinated hydrocarbon group; Z is the nonmetallic atomic group necessary to form a substituted
  • halogen atom represented by X1 and X2 in formula (XVI) examples include chlorine, bromine, fluorine and iodine atoms. At least one of X1 and X2 has a halogen atom.
  • the alkyl group represented by X1 and X2 is preferably a substituted or unsubstituted alkyl group having 1 - 4 carbon atoms and illustrative examples include methyl, ethyl, ⁇ -cyanoethyl, iso-propyl, trifluoromethyl and t-butyl.
  • the alkoxy group represented by X1 and X2 is preferably a substituted or unsubstituted alkoxy group having 1 - 4 carbon atoms and illustrative examples include methoxy, ethoxy, ⁇ -chloroethyl and sec-butoxy.
  • the substituted or unsubstituted amino group represented by X1 and X2 include those which are substituted by an alkyl group, an aryl group (preferably phenyl), etc.
  • N-methylamino, N-ethylamino, N,N-dimethylamino, N,N-diethylamino, N-phenylamino and N,N-diphenylamino and those which are substituted by an acyl group, such as acetylamino and p-chlorobenzoylamino.
  • X1 and X2 may be the same or different.
  • A is represented by the following general formula (XVII): where Ar8 is an aromatic carbocyclic or heterocyclic group having at least one fluorinated hydrocarbon group.
  • the fluorinated hydrocarbon group preferably contains 1 - 4 carbon atoms and may be exemplified by trifluoromethyl, pentafluoroethyl, tetrafluoroethyl, heptafluoropropyl, etc. Trifluoromethyl is more preferred.
  • Illustrative aromatic carbocyclic groups include phenyl, naphthyl and anthryl, with phenyl being preferred.
  • Illustrative aromatic heterocyclic groups include carbazolyl and dibenzofuryl.
  • aromatic carbocyclic and heterocyclic groups may contain substituents other than the fluorinated hydrocarbon group, and such optional substituents include: a substituted or unsubstituted alkyl group having 1 - 4 carbon atoms such as methyl, ethyl, isopropyl, t-butyl or trifluoromethyl; a substituted or unsubstituted aralkyl group such as benzyl or phenethyl; a halogen atom such as chlorine, bromine, fluorine or iodine; a substituted or unsubstituted alkoxy group having 1 - 4 carbon atoms such as methoxy, ethoxy, isopropoxy, t-butoxy or 2-chloroethoxy; a hydroxyl group; a substituted or unsubstituted aryloxy group such as p-chlorophenoxy or 1-naphtoxy; an acyloxy group such as acetyloxy or
  • substituents the following are preferred: a substituted or unsubstituted alkyl group having 1 - 4 carbon atoms such as methyl, ethyl, isopropyl, t-butyl or trifluoromethyl; a halogen atom such as chlorine, bromine, fluorine or iodine; a substituted or unsubstituted alkoxy group having 1 - 4 carbon atoms such as methoxy, ethoxy, t-butoxy or 2-chloroethoxy; a nitro group; and a cyano group.
  • a substituted or unsubstituted alkyl group having 1 - 4 carbon atoms such as methyl, ethyl, isopropyl, t-butyl or trifluoromethyl
  • a halogen atom such as chlorine, bromine, fluorine or iodine
  • Z represents the atomic group necessary to form a substituted or unsubstituted aromatic carbon or heterocyclic ring and may specifically be exemplified by the atomic groups necessary to form a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring, a substituted or unsubstituted indole ring, a substituted or unsubstituted carbazole ring, etc.
  • the atomic groups necessary to form these rings may have substituents such as those listed in connection with Ar8 and preferred examples include a halogen atom ie., chlorine, bromine, fluorine or iodine), a sulfo group and a sulfamoyl group (e.g., aminosulfonyl, p-tolylaminosulfonyl, etc.).
  • a halogen atom ie., chlorine, bromine, fluorine or iodine
  • a sulfo group and a sulfamoyl group e.g., aminosulfonyl, p-tolylaminosulfonyl, etc.
  • XVI bisazo compounds represented by formula (XVI)
  • those which are represented by the following general formulas (XVIII), (XIX), (XX) and (XXI) are preferred: where X 1a , X 1b , X 2a and X 2b each represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a nitro group, a cyano group, a hydroxyl group or a substituted or unsubstituted amino group, provided that at least one of X 1a , X 1b , X 2a and X 2b is a halogen atom, and that X 1a and X 1b or X 2a and X 2b may be the same or different; Ar′ has the same meaning as Ar8 in formula (XVI); Y has the same meaning as the substituent on Z in formula (XVI).
  • the bisazo compounds represented by the general formula (XVI) can be easily synthesized by known methods.
  • 2,7-Diamino-4-bromo-9-fluorenone (2.89 g, 0.01 mol.) is dispersed in 10 ml of HCl and 20 ml of water. Under cooling at 5°C or below, a solution having 1.40 g (0.02 mol) of sodium nitrite dissolved in 5 ml of water is added dropwise to the dispersion. Under continued stirring for 1 h at the same temperature, the insoluble matter is removed by filtration and a solution having 4.6 g of ammonium hexafluorophosphate in 50 ml of water is added to the filtrate. The precipitating tetrazonium salt is recovered by filtration and dissolved in 100 ml of N,N-dimethylformamide (DMF). Under cooling at 5°C or below, a solution having 6.62 g (0.02 mol) of 2-hydroxy-3-naphthoic acid-3'-trifluoromethylanilide dissolved in 200 ml of DMF is added dropwise.
  • the electroconductive base for use in the present invention may be a sheet of metal selected from among, for example, aluminum, nickel, copper, zinc, palladium, silver, indium, tin, platinum, gold, stainless steel, brass, etc.
  • the electroconductive base can also be made by providing an electroconductive layer on an insulating substrate which is suitably selected from among paper, plastic sheets and other materials that are flexible and that have sufficient strength to withstand bending, tensile and other stresses.
  • the electroconductive layer may be formed by various methods including laminating a metal sheet and vacuum evaporating a metal.
  • the carrier generation layer may be composed of a carrier generation material (CGM) alone or in combination with a suitable binder resin. If desired, a carrier transport material having high mobility of carriers with a specified or unspecified polarity may be incorporated. Specific methods of forming the carrier generation layer include: vacuum evaporating CGM on the electroconductive base described above and; applying or dip-coating CGM which is dissolved or dispersed in a suitable solvent either alone or together with a suitable binder resin, and drying the coating.
  • CGM carrier generation material
  • a binder resin or a carrier transport material may be incorporated and in this case, the proportions of carrier generation material, binder resin and carrier transport material are preferably in the range of 1:(0 - 100):(0 - 500), more preferably in the range of 1:(1 - 10):(0 - 50), on a weight basis.
  • Constituent layers of the carrier transport layer may be formed by the following process: dissolving or dispersing a carrier transport material and a binder resin in a solvent; coating the solution or dispersion onto the carrier generation layer or other constituent layers of the carrier transport layer; and drying the coated layers.
  • An intermediate layer or a subbing layer can be formed by coating and drying a solution having a binder resin dissolved in a solvent.
  • solvents or dispersants that may be used in this method include: n-butylamine, diethylamine, ethylenediamine isopropanolamine, monoethanolamine, triethanolamine, triethylenediamine, N,N-dimethylformamide, acetone, methyl ethyl ketone, cyclohexanone, benzene, toluene, xylene, chloroform, 1,2-dichloroethane dichloromethane, tetrahydrofuran, dioxane, methanol, ethanol, isopropanol, ethyl acetate, butyl acetate and dimethyl sulfoxide.
  • the following resins may be used as binders either on their own or as admixtures: polycarbonates other than those described above, polyesters, methacrylic resins, acrylic resins, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyvinyl acetate, melamine resins, polyurethanes, styrene-acrylate copolymers, styrene-butadiene copolymer, vinylidene chloride-acrylonitrile copolymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, silicone resins, silicone-alkyd resins, phenolic resins, styrene-alkyd resins, poly-N-vinylcarbazole, and polyvinyl but
  • resins are transparent resins having a volume resistivity of at least 108 ⁇ cm, preferably at least 1010 ⁇ cm, more preferably at least 1013 ⁇ cm.
  • Resins that cure by the action of light or heat may also the used as binders and examples of such photo- or heat-curable resins include thermosetting acrylic resins, epoxy resins, urethane resins, urea resins, polyester resins, alkyd resins, melamine resins and photocurable cinnamic ester resins, as well as copolymerized and condensed resins thereof. All other photo- and heat-curable resins commonly employed in electrophotographic materials may be used in the present invention. In order to provide improved working and physical properties (e.g.
  • the protective layer may incorporate therein less than 50 wt% of a thermoplastic resin as required.
  • a thermoplastic resin include, for example, polypropylene, acrylic resins, methacrylic resins, vinyl chloride resin, vinyl acetate resin, epoxy resins, polycarbonate resins, copolymerized resins thereof, high-molecular weight organic semiconductors such as poly-N-vinylcarbazole, and any other thermoplastic resins that are commonly used in electrophotographic materials.
  • Binder resins that are to be used in an intermediate layer or a subbing layer may be selected from among metal oxides such as aluminum oxide and indium oxide and high-molecular weight materials such as acrylic resins, methacrylic resins, vinyl chloride resin, vinyl acetate resin, epoxy resins, polyurethane resins, phenolic resins, polyester resins, alkyd resins, polycarbonate resins, silicone resins, melamine resins, vinyl chloride-vinyl acetate copolymer resin, and vinyl chloride-vinyl acetate-maleic anhydride copolymer resin.
  • metal oxides such as aluminum oxide and indium oxide
  • high-molecular weight materials such as acrylic resins, methacrylic resins, vinyl chloride resin, vinyl acetate resin, epoxy resins, polyurethane resins, phenolic resins, polyester resins, alkyd resins, polycarbonate resins, silicone resins, melamine resins, vinyl chloride-vinyl acetate copolymer resin,
  • the constituent layers 3A, 3B and 3C of the carrier transport layer 3 may employ the same or different binder resins.
  • the topmost or outermost constituent layer 3B or 3C may use the polycarbonate of the present invention, with a bisphenol A type polycarbonate being used in the bottommost constituent layer 3A that is the closest to the electroconductive base.
  • the constituent layer 3A (or 3B) which is adjacent the outermost constituent layer 3B (or 3C) and which is closer to the electro conductive base may be designed to employ a binder resin that is hardly soluble with respect to the solvent used to coat said outermost constituent layer. This offers the advantage of preventing not only diffusion of the carrier transport material into the bottommost constituent layer 3A but also swelling of said layer.
  • the constituent layer 3B or 3C that is more remote from the electroconductive base may be coated in a different way than the bottommost constituent layer 3A is coated.
  • the constituent layer 3A may be formed by dip coating whereas the constituent layer 3B or 3C is formed by spray coating, and this is effective in preventing dissolution and swelling of the bottommost constituent layer 3A.
  • the bottommost constituent layer 3A preferably has a thickness of 5 - 50 ⁇ m, with the range of 5 - 30 ⁇ m being more preferred.
  • the outermost constituent layer 3B or 3C preferably has a thickness of 0.1 - 30 ⁇ m, with the range of 0.5 - 10 ⁇ m being more preferred.
  • the carrier generation layer preferably has a thickness of 0.01 - 10 ⁇ m, with the range of 0.1 - 5 ⁇ m being more preferred.
  • the light-sensitive layer may have a high-molecular weight semiconductor contained therein. While various high-molecular weight semiconductors may be used, poly-N-vinylcarbazole and its derivatives are preferred because of their high degree of curability. Derivatives of poly-N-vinylcarbazole are such that all or part of the carbazole rings in the recurring units have various substituents such as an alkyl group, a nitro group, an amino group, a hydroxyl group and a halogen atom.
  • the light-sensitive layer may also have at least one electron - accepting materials contained therein in order to attain various purposes such as improving sensitivity, reducing residual potential and minimizing fatigue that results from cyclic use of the photoreceptor.
  • electron-accepting materials that may be used in the photoreceptor of the present invention include: succinic anhydride, maleic anhydride, dibromomaleic anhydride, phthalic anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, 3-nitrophthalic anhydride, 4-nitrophthalic anhydride, pyromellitic anhydride, mellitic anhydride, tetracyanoethylene, tetracyanoquinodimethane, o-dinitrobenzene, m-dinitrobenzene, 1,3,5-trinitrobenzene, paranitrobenzonitrile, picryl chloride, quinone chlorimide, chloranyl, bromanyl, 2-methylnaphthoquinon
  • electron-accepting substances may be used either on their own or as admixtures.
  • fluorenone compounds, quinone compounds and benzene derivatives having electron-withdrawing substituents such as Cl, CN and NO2 may be used with particular advantage.
  • Silicone oil and fluorine containing surfactants may also be incorporated as surface modifiers in the photoreceptor of the present invention.
  • Ammonium compounds may also be incorporated as agents to provide improved durability.
  • Ultraviolet (uv) absorbers may also be incorporated and preferred examples include benzoic acid, stilbene compounds and their derivatives, and nitrogenous compounds such as triazole compounds, imidazole compounds, triazine compounds, coumarin compounds, oxadiazole compounds, thiazole compounds and derivatives thereof.
  • An antioxidant may be incorporated in the carrier transport layer, the carrier generation layer and the light-sensitive layer. This is effective not only in minimizing the adverse effects of ozone that is generated by discharging but also in preventing the increase in residual potential or decrease in charging potential that might occur during cyclic use of the photoreceptor.
  • Illustrative antioxidants include hindered phenol, hindered amines, paraphenylenediamine, arylalkanes, hydroquinone, spirochromans, spiroindanone and its derivatives, organosulfur compounds, and organo-phosphorus compounds.
  • a 100- ⁇ m thick electroconductive base made of aluminum-evaporated polyethylene terephthalate was coated with an intermediate layer ca. 0.1 ⁇ m thick that was made of a vinyl chloride-vinyl acetate-maleic anhydride copolymer.
  • ES-lac MF-10 of Sekisui Chemical Co., Ltd.
  • 4 g of a polycyclic quinone pigment having the structural formula XI-3 shown below was pulverized in a ball mill for 24 h.
  • a solution having 2 g of a bisphenol A type polycarbonate ("Panlite L-1250" of Teijin Ltd.) dissolved in 130 ml of 1,2-dichloroethane was added.
  • the mixture was stirred for an additional 24 h to form a dispersion, which was coated by doctor blading onto the previously formed intermediate layer and dried to form a carrier generation layer (CGL) in a thickness of Ca. 0.5 ⁇ m.
  • a styryl compound represented by the structural formula VIII-35 shown hereinafter and 10 g of a polycarbonate ("Panlite L-1250") were dissolved in 100 ml of 1,2-dichloroethane.
  • the resulting solution was coated by doctor blading onto the carrier generation layer and dried at 80°C for 1 h to form a constituent layer of carrier transport layer that was the closest to the electroconductive base in thickness of 18 ⁇ m.
  • the weight ratio of the content of carrier transport material to binder resin was 80 wt%.
  • a styryl compound represented by the structural formula VIII-35 and 10 g of a polycarbonate (viscosity average mol. wt. ca. 30,000) composed of recurring units represented by the structural formula II-2 were dissolved in 100 ml of monochlorobenzene.
  • the resulting solution was coated by doctor blading onto the constituent layer of carrier transport layer that was the closest to the electroconductive base to form the outermost constituent layer of carrier transport layer in a thickness of 4 ⁇ m.
  • the weight ratio of the content of carrier transport material to binder resin was 60 wt%.
  • An electrophotographic photoreceptor was fabricated as in Example 1 except that the amount of the carrier transport material in the constituent layer of carrier transport layer that was the closest to the electroconductive base was changed from 8 g to 20 g (200%).
  • Example 1 An intermediate layer and a carrier generation layer were formed as in Example 1.
  • the constituent layer of carrier transport layer that was the closest to the electroconductive base was formed as in Example 1 except that the layer thickness was changed to 19 ⁇ m.
  • the outermost constituent layer of carrier transport layer was formed as in Example 1 except that the amount of carrier transport material and the layer thickness were changed to 4 g and 3 ⁇ m, respectively.
  • Example 1 An intermediate layer and a carrier generation layer were formed as in Example 1.
  • a carrier transport material represented by the structural formula VIII-35 and 10 g of a polycarbonate "Panlite L-1250" were dissolved in 100 ml of 1,2-dichloroethane and the resulting solution was coated onto the carrier generation layer to form a single-layered carrier transport layer in a thickness of 22 ⁇ m.
  • Another comparative photoreceptor was prepared by the following procedures.
  • an intermediate layer and a carrier generation layer were formed as in Example 1.
  • the constituent layers of the carrier transport layer that was the closest to the electroconductive base and the outermost constituent layer of the carrier transport layer were successively formed as in Example 1, except that the content of the carrier transport material in the constituent layer of the carrier transport layer that was the closest to the electroconductive base and its thickness were changed to 4 g and 19 ⁇ m, respectively, and that the content of the carrier transport material in the outermost constituent layer and its thickness were changed to 8 g and 3 ⁇ m, respectively.
  • Still another comparative photoreceptor was prepared as in Example 1 except that a bisphenol A type polycarbonate "Panlite L-1250" was used as a binder resin in the outermost constituent layer of carrier transport layer.
  • An intermediate layer and a carrier generation layer were formed as in Example 1 except that a fluorenone compound represented by the structural formula XVI-71 shown hereinafter was used as a carrier generation material.
  • a coating solution for the outermost constituent layer was prepared as described above except that the content of the carrier transport material was reduced to 7 g. This solution was spray-coated onto the constituent layer of the carrier transport layer that was the closest to the electroconductive base to form the outermost constituent layer in a thickness of 5 ⁇ m.
  • An electrophotographic photoreceptor was prepared as in Example 3, except that the thickness of the constituent layer of the carrier transport layer that was the closest to the electroconductive base, the content of the carrier transport material in the outermost constituent layer and its thickness were changed to 17 ⁇ m, 5 g and 3 ⁇ m, respectively.
  • An electrophotographic photoreceptor was prepared as in Example 3, except that the thickness of the constituent layer of the carrier transport layer that was the closest to the electroconductive base, the content of the carrier transport material in the outermost constituent layer and its thickness were changed to 18 ⁇ m, 3 g and 2 ⁇ m, respectively.
  • An intermediate layer and a carrier generation layer were formed as in Example 3.
  • a coating solution of the same composition as that of the solution for forming the constituent layer of carrier transport layer that was the closest to the electroconductive base in Example 3 (containing 10 g of the carrier transport material) was coated onto the carrier generation layer by doctor blading to form a single-layered carrier transport layer in a thickness of 20 ⁇ m.
  • An additional comparative electrophotographic photoreceptor was prepared as in Comparative Example 3 except that the content of the carrier transport material in the carrier transport layer was changed to 3 g.
  • An intermediate layer was formed as in Example 1.
  • a carrier generation layer was formed as in Example 1 except that a bisazo compound represented by the structural formula XIV-5 shown hereinafter was used as a carrier generation material and that a polyester resin "Vylon-200" of Toyobo Co., Ltd. was used as a binder resin.
  • An electrophotographic photoreceptor was prepared as in Example 6, except that the thickness of the constituent layer of carrier transport layer that was the closest to the electroconductive base, the thickness of the outermost constituent layer and the weight ratio of the content of carrier transport material to binder resin in the outermost constituent layer were changed to 19 ⁇ m, 3 ⁇ m and 40%, respectively.
  • Example 6 An intermediate layer and a carrier generation layer were formed as in Example 6.
  • a coating solution of the same composition as that of the solution for forming the constituent layer of carrier transport layer that was the closest to the electroconductive base in Example 6 was prepared and coated onto the carrier generation layer by doctor blading to form a single-layered carrier transport layer in a thickness of 22 ⁇ m.
  • Example 1 An intermediate layer and a carrier generation layer were formed as in Example 1.
  • a pyrazoline compound represented by the structural formula VII-22 and 10 g of a polycarbonate composed of structural units represented by the formula II-5 were dissolved in 100 ml of monochlorobenzene, and the resulting solution was coated onto the constituent layer of carrier transport layer that was the closest to the electroconductive base by doctor blading to form the outermost constituent layer in a thickness of 4 ⁇ m.
  • black paper potential means the surface potential which developed on a photoreceptor when it was subjected to the cyclic copying test described above using a black paper original having a reflection density of 1.3.
  • white paper potential means the surface potential which developed on the same photoreceptor when used with a white paper original.
  • the photoreceptor samples prepared in Examples 1 - 8 were high in wear and scratch resistance, showed satisfactory values of both black paper and white paper potential, and permitted a great number of copies to be taken to produce image of consistent quality with minimum variations in the values of black paper and white paper potential.

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Claims (30)

  1. Photorécepteur possédant une base électroconductrice, une couche engendrant un support formée par-dessus et une couche de transport du support étalée sur la couche engendrant un support et contenant une substance de transport du support et une substance liante; la couche de transport du support comprenant au moins deux couches constitutives de façon à ce que le rapport pondéral de la substance de transport du support à la substance liante dans une couche constitutive plus proche de la base électroconductrice soit plus élevé que le rapport pondéral de la substance de transport du support dans une couche constitutive plus éloignée de la base électroconductrice, et un polycarbonate possédant, comme motif récurrent principal, un motif structurel représenté par la formule (I) ou un motif structurel représenté par la formule (II), contenu dans la substance liante dans la couche constitutive la plus externe de la couche de transport du support:
    Figure imgb0073
     dans laquelle R¹ et R² sont chacun un atome d'hydrogène, un groupe aliphatique substitué ou non substitué, un groupe aromatique substitué ou non substitué; R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹ et R¹⁰ sont chacun un atome d'hydrogène, un atome d'halogène, un groupe aliphatique substitué ou non substitué, un groupe carbocyclique substitué ou non substitué;
    Figure imgb0074
     dans laquelle Z est le groupe d'atomes nécessaire pour former un noyau carboné substitué ou non substitué ou un noyau hétérocyclique substitué ou non substitué; et l'un au moins des radicaux R¹ et R² est un des groupes (1) à (4) ci-dessous
    (1)
    Figure imgb0075
     dans lequel R¹¹ est un atome d'hydrogène, un groupe alkyle ou un groupe ester alkylique représenté par -(CH₂)mCOOR, où R est un groupe alkyle, et m ≧ 1;
    (2)
    Figure imgb0076
    (3) un groupe alkyle représenté par -CmH2m+1, où m ≧ 4; et
    (4) un groupe ester alkylique représenté par -(CH₂)mCOOR¹², où R¹² est un groupe alkyle, et m ≧ 2.
  2. Photorécepteur selon la revendication 1, caractérisé en ce que le rapport de la substance de transport du support à la substance liante dans une couche constitutive la plus proche de la base électroconductrice est plus élevé que le rapport pondéral de la substance de transport du support à la substance liante dans la couche constitutive la plus externe de la couche de transport du support, la différence entre les deux rapport pondéraux étant d'au moins 20%.
  3. Photorécepteur selon la revendication 2, caractérisé en ce que le rapport pondéral de la substance de transport du support à la substance liante dans une couche constitutive la plus proche de la base électroconductrice est plus élevé que le rapport pondéral de la substance de transport du support à la substance liante dans la couche constitutive la plus externe de la couche de transport du support, la différence entre les deux rapport pondéraux se situant dans l'intervalle de 20% à 140%.
  4. Photorécepteur selon la revendication 1, caractérisé en ce que la couche de transport du support contient un polycarbonate possédant au moins un motif structurel représenté par la formule (II) comme motif récurrent principal.
  5. Photorécepteur selon la revendication 1, caractérisé en ce que la couche constitutive la plus externe de la couche de transport du support renferme la substance de transport du support en une quantité d'au plus 70% en poids de la substance liante dans la couche constitutive la plus externe de la couche de transport du support.
  6. Photorécepteur selon la revendication 5, caractérisé en ce que la couche constitutive la plus externe de la couche de transport du support renferme la substance de transport du support en une quantité de 5% à 70% en poids de la substance liante dans la couche constitutive la plus externe de la couche de transport du support.
  7. Photorécepteur selon la revendication 1, caractérisé en ce que la couche constitutive de la couche de transport du support la plus proche de la base électroconductrice renferme la substance de transport du support en une quantité d'au plus 30% en poids de la substance liante dans la couche constitutive de la couche de transport du support la plus proche de la base électroconductrice.
  8. Photorécepteur selon la revendication 7, caractérisé en ce que la couche constitutive de la couche de transport du support la plus proche de la base électroconductrice renferme la substance de transport du support en une quantité de 30% à 300% en poids de la substance liante dans la couche constitutive de la couche de transport du support la plus proche de la base électroconductrice.
  9. Photorécepteur selon la revendication 1, caractérisé en ce que R¹ et R², dans la formule générale (I), représentent des groupes différents.
  10. Photorécepteur selon la revendication 1, caractérisé en ce que l'un au moins des groupes R¹ et R², dans la formule générale (I), est un groupe volumineux comportant au moins 3 atomes de carbone.
  11. Photorécepteur selon la revendication 1, caractérisé en ce que chacun des groupes R³ à R¹⁰, dans les formules générales (I) et (II), est un atome d'hydrogène, un atome d'halogène, un groupe méthyle ou un groupe cyclohexyle.
  12. Photorécepteur selon la revendication 1, caractérisé en ce que Z, dans la formule générale (II), forme un noyau carboné ou un noyau hétérocyclique à 5 ou 6 chaînons.
  13. Photorécepteur selon la revendication 1, caractérisé en ce que le nombre de répétitions du motif structurel représenté par les formules générales (I) ou (II) est de 10 à 5000.
  14. Photorécepteur selon la revendication 13, caractérisé en ce que le nombre de répétitions du motif structurel représenté par les formules générales (I) ou (II) est de 50 à 2000.
  15. Photorécepteur selon la revendication 1, caractérisé en ce que le polycarbonate posséde au moins un motif structurel représenté par la formule générale (II).
  16. Photorécepteur selon la revendication 12, caractérisé en ce que les groupes R³ à R¹⁰, dans la formule générale (II), sont chacun un atome d'hydrogène et Z représente le groupe d'atomes nécessaire pour former un noyau cyclohexylidène.
  17. Photorécepteur selon la revendication 1, caractérisé en ce que la substance de transport du support est l'un au moins des composés représentés par les formules générales (III) à (X) suivantes
    Figure imgb0077
     (dans laquelle R¹³ est un groupe aryle substitué ou non substitué; R¹⁴ est un atome d'hydrogène, un atome d'halogène, un groupe alkyle substitué ou non substitué, un groupe alcoxy, un groupe amino, un groupe hydroxyle ou un groupe amino substitué; et R¹⁵ est un groupe aryle substitué ou non substitué ou un groupe hétérocyclique substitué ou non substitué);
    Figure imgb0078
     (dans laquelle R¹⁶ et R¹⁷ sont chacun un atome d'hydrogène ou un atome d'halogéne; R¹⁸ et R¹⁹ sont chacun un groupe aryle substitué ou non substitué; et Ar¹ est un groupe arylène substitué ou non substitué);
    Figure imgb0079
     (dans laquelle R²⁰ est un groupe aryle substitué ou non substitué ou un groupe hétérocyclique substitué ou non substitué; R²¹ est un atome d'hydrogène, un groupe alkyle substitué ou non substitué ou un groupe aryle substitué ou non substitué; Q est un atome d'hydrogène, un atome d'halogène, un groupe alkyle, un groupe amino substitué, un groupe alcoxy ou un groupe cyano; et p est un nombre entier de 0 ou 1);
    Figure imgb0080
     (dans laquelle R²² est un groupe aryle substitué ou non substitué ou un groupe hétérocyclique substitué ou non substitué; R²³ est un atome d'hydrogène, un groupe alkyle substitué ou non substitué ou un groupe aryle substitué ou non substitué; X'₂ est un atome d'hydrogène, un atome d'halogène, un groupe alkyle, un groupe amino substitué, un groupe alcoxy ou un groupe cyano; et q est un nombre entier de 0 ou 1);
    Figure imgb0081
     (dans laquelle l est un nombre entier de 0 ou 1; R²⁴, R²⁵ et R²⁶ sont chacun un groupe aryle substitué ou non substitué; R²⁷ et R²⁸ sont chacun un atome d'hydrogène, un groupe alkyle comportant 1 à 4 atomes de carbone, un groupe aryle ou arylakyle substitué ou non substitué, à condition que R²⁷ et R²⁸ ne soient pas en même temps un atome d'hydrogène et que, lorsque l est nul, R²⁷ ne soit pas un atome d'hydrogène);
    Figure imgb0082
     (dans laquelle R²⁹ et R³⁰ sont chacun un groupe alkyle ou phényle substitué ou non substitué, le substituant étant un groupe alkyle, alcoxy ou phényle; R³¹ est un groupe phényle, naphtyle, anthryle, fluorényle ou un groupe hétérocyclique, substitué ou non substitué, le substituant étant un groupe alkyle, un groupe alcoxy, un atome d'halogène, un groupe hydroxyle ou un groupe phényle; R³¹, est un atome d'hydrogéne, un groupe alkyle ou phényle substitué ou non substitué; et R³², R³³, R³⁴ et R³⁵ sont chacun un atome d'hydrogène, un atome d'halogène, un groupe alkyle, un groupe alcoxy ou un groupe alkylamino);
    Figure imgb0083
     (dans laquelle Ar² et Ar³ sont chacun un groupe phényle substitué ou non substitué, le substituant étant un atome d'halogène, un groupe alkyle, un groupe nitro ou un groupe alcoxy; et Ar⁴ est un groupe phényle, naphtyle, anthryle, fluorényle ou hétérocyclique substitué ou non substitué, le substituant étant un groupe alkyle, un groupe alcoxy, un atome d'halogène, un groupe hydroxyle, un groupe aryloxy, un groupe aryle, un groupe amino, un groupe nitro, un groupe pipéridino, un groupe morpholino, un groupe naphtyle, un groupe anthryle ou un groupe amino substitué, dans lequel le substituant est un groupe acyle, un groupe alkyle, un groupe aryle ou un groupe arylalkyle);
    Figure imgb0084
     dans laquelle D est un groupe phényle substitué ou non substitué ou un groupe carbazolyle substitué ou non substitué, ou un groupe choisi dans les groupes
    Figure imgb0085
     dans lesquels R³⁶, R³⁷, R³⁸, R³⁹ et R⁴⁵ représentent chacun un groupe alkyle substitué ou non substitué, un groupe arylalkyle substitué ou non substitué ou un groupe aryle substitué ou non substitué; et R⁴⁰, R⁴¹, R⁴², R⁴³, R⁴⁴ et R⁴⁶ représentent chacun un groupe alkyle, un groupe alcoxy ou un atome d'halogène.
  18. Photorécepteur selon la revendication 1, caractérisé en ce que la substance engendrant le support contenue dans ladite couche engendrant le support est un pigment quinone polycyclique ou un pigment bis-azoïque.
  19. Photorécepteur selon la revendication 16, dans lequel ledit pigment quinone polycyclique est un pigment anthanthrone représenté par la formule générale (XI) suivante :
    Figure imgb0086
     dans laquelle X est un atome d'halogène, un groupe nitro, un groupe cyano, un groupe acyle ou un groupe carboxyle; n est un nombre entier de 0 à 4; et m est un nombre entier de 0 à 6.
  20. Photorécepteur selon la revendication 16, dans lequel ledit pigment bis-azoïque est un pigment fluorénylidène représenté par la formule générale (XVa) suivante
    Figure imgb0087
     dans laquelle R⁵⁵ et R⁵⁶ sont chacun un groupe alkyle, un groupe alcoxy ou un groupe aryle; R⁵⁷, R⁵⁸, R⁵⁹, R⁶⁰, R⁶¹ et R⁶² sont chacun un atome d'hydrogène, un atome d'halogène, un groupe alkyle, un groupe alcoxy, un groupe amino, un groupe hydroxyle ou un groupe aryle; et A'' est un groupe aryle substitué ou non substitué.
  21. Photorécepteur selon la revendication 16, dans lequel ledit pigment bis-azoïque est un pigment fluorénone représenté par la formule générale (XVI) suivante:
    Figure imgb0088
     dans laquelle X¹ et X² sont chacun un atome d'halogène, un groupe alkyle substitué ou non substitué, un groupe alcoxy substitué ou non substitué, un groupe nitro, un groupe cyano, un groupe hydroxyle ou un groupe amino substitué ou non substitué, à condition que l'un au moins des radicaux X¹ et X² soit un atome d'halogène; p et q représentent chacun un nombre entier de 0, 1 ou 2, à condition que p et q ne soient pas nuls en même temps et que, lorsque p est égal à 2, les radicaux X¹ puissent être des groupes identiques ou différents et que, lorsque q est égal à 2, les radicaux X² puissent être des groupes identiques ou différents; et A est un groupe représenté par la formule générale (XVII) suivante:
    Figure imgb0089
     (dans laquelle Ar⁸ est un groupe carbocyclique ou hétérocyclique aromatique possédant au moins un groupe hydrocarboné fluoré; Z représente les atomes non métalliques nécessaires pour former un noyau carboné aromatique substitué ou non substitué ou un noyau hétérocyclique aromatique substitué ou non substitué); m et n représentent chacun un nombre entier de 0, 1 ou 2, à condition que ni et n ne soient pas nuls en même temps.
  22. Photorécepteur selon la revendication 1, dans lequel une couche constitutive de ladite couche de transport du support plus proche de la base électroconductrice et adjacente à la couche constitutive la plus externe de ladite couche de transport du support contient, comme liant, un polycarbonate de type bisphénol A.
  23. Photorécepteur selon la revendication 1, dans lequel la résine liante contenue dans une couche constitutive de ladite couche de transport du support plus proche de la base électroconductrice et adjacente à la couche constitutive la plus externe de ladite couche de transport du support est très peu soluble dans le solvant utilisé pour revêtir ladite couche constitutive la plus externe.
  24. Photorécepteur selon la revendication 1, dans lequel une couche constitutive de ladite couche de transport du support la plus proche de la base électroconductrice est formée par revêtement au trempé, et une couche constitutive de ladite couche de transport du support adjacente à ladite couche constitutive et éloignée de la base électroconductrice est formée par revêtement au pistolet.
  25. Photorécepteur selon la revendication 1, dans lequel une couche constitutive de ladite couche de transport du support la plus proche de la base électroconductrice a une épaisseur de 5-50 µm.
  26. Photorécepteur selon la revendication 1, dans lequel une couche constitutive de ladite couche de transport du support la plus proche de la base électroconductrice a une épaisseur de 5-30 µm.
  27. Photorécepteur selon la revendication 1, dans lequel la couche constitutive la plus externe de ladite couche de transport du support a une épaisseur de 0,1-30 µm.
  28. Photorécepteur selon la revendication 1, dans lequel la couche constitutive la plus externe de ladite couche de transport du support a une épaisseur de 0,5-10 µm.
  29. Photorécepteur selon la revendication 1, dans lequel ladite couche engendrant le support a une épaisseur de 0,01-10 µm.
  30. Photorécepteur selon la revendication 1, dans lequel ladite couche engendrant le support a une épaisseur de 0,1-5 µm.
EP19890308637 1988-08-25 1989-08-24 Photorécepteur Expired - Lifetime EP0356246B1 (fr)

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EP0481747B1 (fr) * 1990-10-18 1998-01-07 Konica Corporation Méthode de formation d'image
US5283142A (en) * 1991-02-21 1994-02-01 Canon Kabushiki Kaisha Image-holding member, and electrophotographic apparatus, apparatus unit, and facsimile machine employing the same
DE69221064T2 (de) * 1991-10-17 1997-11-13 Canon Kk Elektrophotographisches, lichtempfindliches Element, elektrophotographische Geräteeinheit und Faksimile-Gerät mit demselben
JP3250295B2 (ja) * 1992-04-16 2002-01-28 三菱化学株式会社 電子写真感光体
DE69418356T2 (de) * 1993-02-09 2000-02-10 Canon K.K., Tokio/Tokyo Elektrophotographisches, lichtempfindliches Element und Bildherstellungsverfahren unter Anwendung desselben
KR960008432A (ko) * 1994-08-11 1996-03-22 나까자또 요시히꼬 전자사진 감광체

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6012551A (ja) * 1983-07-01 1985-01-22 Hitachi Ltd 複合型電子写真用感光体
JPS60172045A (ja) * 1984-02-16 1985-09-05 Konishiroku Photo Ind Co Ltd 電子写真感光体

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DE68913100T2 (de) 1994-07-21
EP0356246A3 (fr) 1991-07-03
DE68913100D1 (de) 1994-03-24
EP0356246A2 (fr) 1990-02-28

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