EP0319992A2 - Matériau photosensible électrophotographique - Google Patents

Matériau photosensible électrophotographique Download PDF

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Publication number
EP0319992A2
EP0319992A2 EP88120607A EP88120607A EP0319992A2 EP 0319992 A2 EP0319992 A2 EP 0319992A2 EP 88120607 A EP88120607 A EP 88120607A EP 88120607 A EP88120607 A EP 88120607A EP 0319992 A2 EP0319992 A2 EP 0319992A2
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EP
European Patent Office
Prior art keywords
phenyl
compound
charge
layer
sensitive material
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP88120607A
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German (de)
English (en)
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EP0319992A3 (en
EP0319992B1 (fr
Inventor
Tomokazu Kobata
Yosuke Matsui
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Bando Chemical Industries Ltd
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Bando Chemical Industries Ltd
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Publication date
Application filed by Bando Chemical Industries Ltd filed Critical Bando Chemical Industries Ltd
Publication of EP0319992A2 publication Critical patent/EP0319992A2/fr
Publication of EP0319992A3 publication Critical patent/EP0319992A3/en
Application granted granted Critical
Publication of EP0319992B1 publication Critical patent/EP0319992B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording-members for original recording by exposure, e.g. to light, to heat or to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
    • G03G5/0601—Acyclic or carbocyclic compounds
    • G03G5/0612—Acyclic or carbocyclic compounds containing nitrogen
    • G03G5/0616—Hydrazines; Hydrazones

Definitions

  • This invention relates to an electrophotographic light-sensitive material. More particularly, it is an electrophotographic light-sensitive material having a composite light-sensitive layer formed by a layer of a charge transporting substance and a layer of a charge produc­ing substance on an electrically conductive support.
  • a light-sensitive material having a layer of selenium is low in flexibility and its handling involves quite a bit of difficulty, as selenium is a highly toxic substance.
  • a light-sensitive material having a layer of zinc oxide can only poorly be charged with electricity, shows a high degree of charge attenuation in the dark, and is low in sensitivity.
  • a light-sensitive material having an organic light-sensitive layer formed by a charge transfer complex composed of poly­vinylcarbazole and trinitrofluorenone This material is also low in sensitivity and the toxicity of trinitrofluore­none presents a difficult problem, too.
  • a composite or laminated type electrophotographic light-sensitive material has been developed to improve the prior materials as hereinabove described.
  • This type of light-sensitive material is disclosed in, for example, Japanese Patent Publications Nos. 42380/1980 and 34099/­1985. It comprises an electrically conductive support 3 having a layer of aluminum 2 deposited on a polyester film 1, a layer 4 of a charge producing substance formed on the aluminum layer 2, and a layer 5 of a charge transporting substance formed on the layer 4, as shown by way of example in FIGURE 18.
  • Examples of the charge transporting substance include p-N,N-dialkylaminobenzaldehyde-N′,N′-diphenylhydra­zone, particularly p-N,N-diethylaminobenzaldehyde-N′,N′-­diphenylhydrazone, p-N,N-diphenylaminobenzaldhyde-N′-­methyl-N′-phenylhydrazone and p-N-ethyl-N-phenyl-aminobenz­aldehyde-N′-methyl-N′-phenylhydrazone.
  • the layer of any such substance and the layer of a charge producing sub­stance are laid on the electrically conductive support.
  • the layer of a charge transporting substance is formed by, for example, dissolving it in an organic solvent to prepare a solution containing a binding resin, which may further contain a plasticizer, etc. as required, applying the solu­tion onto the support or the layer of a charge producing substance, and drying it, whereby a layer having a thick­ness of, say, 5 to 100 microns is formed.
  • the charge transporting substance has a decisive bearing on the performance or quality of any electrophoto­graphic light-sensitive material of the type to which this invention pertains.
  • the manufacture of an electrophoto­graphic light-sensitive material having high sensitivity requires the provision of a layer containing a charge transporting substance in a relatively high concentration and therefore the use of a charge transporting substance which is highly compatible with the resin used as a bonding agent.
  • the substance must also be one from which any such layer can be formed easily.
  • the charge trans­porting substance is required to have an appropriately low oxidation potential and a high charge transfer rate, so that the charge which is produced in the layer of the charge producing substance may be effectively injected into the layer of the charge transporting substance.
  • organic compounds having a low oxidation potential are generally liable to oxidation and unstable.
  • an object of this invention to provide an electrophotographic light-­sensitive material of the composite or laminated type including a layer of a charge transporting substance which is highly compatible with a bonding agent, has an appro­priately low oxidation potential, is stable and has a high charge transfer rate, and having a high degree of sensiti­vity.
  • the object of this invention is, therefore, attained by an electrophotographic light-sensitive material having a layer of a charge transporting substance and a layer of a charge producing substance formed on an electrically conductive support, characterized in that the charge trans­porting substance is an arylaldehydehydrazone derivative of the general formula: where R1, R2 and R3 are each an alkyl or aryl group.
  • the arylaldehydehydrazone derivative is highly compatible with an organic solvent and a resin used as a bonding agent, has an appropriately low oxidation poten­tial, exhibits a completely reversible oxidation-reduction reaction and is, therefore, very stable, and also has a high charge transfer rate.
  • the electrophotographic light-­sensitive material of this invention containing any such derivative as a charge transporting substance has, there­fore, a high degree of sensitivity and a high degree of printing resistance.
  • the electrophotographic light-sensitive material of this invention contains as a charge transporting sub­stance an arylaldehydehydrazone derivative of the general formula shown above, in which R1, R2 and R3 are each an alkyl or aryl group.
  • the alkyl group may, for example, be a methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl or dodecyl group. It may be in the form of a straight or branched chain.
  • the aryl group may, for example, be an unsubstituted or substituted phenyl, naphthyl, anthryl, pyrenyl, acenaph­thenyl or fluorenyl group.
  • the substituent may, for example, be an alkyl group such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, or dodecyl, an alkoxy group such as methoxy, ethoxy, propoxy or butoxy, a halogen such as chlorine, bromine or fluorine, an aryloxy group such as phenoxy or tolyloxy, or a dialkylamino group such as dimethylamino, diethylamino or dipropylamino.
  • an alkyl group such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, or dodecyl
  • an alkoxy group such as methoxy, ethoxy, propoxy or butoxy
  • a halogen such as chlorine, bromine or fluorine
  • an aryloxy group such as phen
  • R1, R2 and R3 are each a methyl, ethyl, propyl, butyl, phenyl, tolyl or chlorophenyl group.
  • arylaldehydehydrazone derivatives can be manufactured by reacting the corresponding aryl­aldehyde with hydrazine appropriately in accordance with any customary process that is employed for producing aldehydehydrazone.
  • the electrophotographic light-sensitive material of this invention can be manufactured if a solution or dis­persion of a charge producing substance in an organic solvent containing a resin as a bonding agent, which may further contain a plasticizer, etc. as required, is applied onto an electrically conductive support and dried to form a charge producing layer, and if a solution of an aryl­aldehydehydrazone derivative in an organic solvent contain­ing a resin as a bonding agent, which may further contain a plasticizer, etc. as required, is applied onto the charge producing layer and dried to form a charge trans­porting layer.
  • the order in which the two layers are formed can, however, be reversed, so that the charge trans­porting layer may be formed on the support.
  • the charge transporting layer preferably contains 10 to 60% by weight of the arylaldehydehydrazone derivative and has a thickness of 5 to 100 microns.
  • the charge producing layer may usually contain 5 to 50% by weight of the resin as a bonding agent, though its content had better be lowered as far as possible within that range. Its thickness is usually from 0.05 to 20 mic­rons, and preferably from 0.1 to 10 microns.
  • the charge producing layer can also consist solely of a charge produc­ing substance.
  • the resin used as a bonding agent is of the type which is soluble in an organic solvent and is highly com­patible with a charge producing or transporting substance, so that a stable solution or dispersion thereof can be prepared easily. Moreover, it is preferable to use a resin which is inexpensive and can form a film of high mechanical strength, transparency and electrical insulating property.
  • Preferred examples of the resin are poly­carbonate, polystyrene, polyester and polyvinyl chloride resins.
  • the organic solvent it is possible to use any solvent with any limitation in particular. Preferred examples of the organic solvent are, however, chloroform, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane and tetrahydrofuran.
  • FIGURE 1 The infrared absorption spectrum of the compound is shown in FIGURE 1.
  • FIGURE 2 The results of its cyclic voltam­metric analysis are shown in FIGURE 2 to show one of its electrochemical properties. It shows the complete rever­sibility of the compound in an oxidation-reduction reaction.
  • the solution was subjected twice to recrystallization from a mixed solvent consisting of benzene and ethanol in a ratio of 2:3, where­by the captioned compound was obtained as fine crystals having a light yellow color.
  • the compound weighed 50 g and showed, therefore, a yield of 46.1%.
  • FIGURE 3 The infrared absorption spectrum of the comppund is shown in FIGURE 3, and the results of its cyclic voltam­metric analysis in FIGURE 4. It showed complete reversi­bility in a oxidation-reduction reaction.
  • FIGURE 5 shows the charge transfer rate of the composition which was obtained by dissolving the compound in polycarbonate in equal proportions by weight.
  • FIGURE 5 also shows the charge transfer rate of the polycarbonate composition which was likewise prepared by employing p-­diethylaminobenzaldehydediphenylhydrazone as a charge transporting substance for the sake of comparison.
  • the compound (2) showed a higher charge transfer rate than that of the comparative composition.
  • the compound (2) further showed the following data: Melting point: 193.5°C to 195.0°C; Mass analysis: Molecular ion peak 634; Elemental analysis: C H N Calculated value 85.14 6.03 8.83 Measured value 85.16 6.08 8.76
  • FIGURE 6 The infrared absorption spectrum of the compound is shown in FIGURE 6, and the results of its cyclic voltam­metric analysis in FIGURE 7. It showed complete reversi­bility in a oxidation-reduction reaction.
  • a compatibilized composition was prepared by dissolving the compound in poly­carbonate in equal proportions by weight and its charge transfer rate is shown in TABLE 1 below.
  • FIGURE 8 The infrared absorption spectrum of the compound is shown in FIGURE 8, and the results of its cyclic voltam­metric analysis in FIGURE 9. It showed complete reversi­bility in an oxidation-reduction reaction.
  • a compatibi­lized composition was prepared by dissolving the compound in polycarbonate in equal proportions by weight and its charge transfer rate is shown in TABLE 1.
  • the oily matter was refined and separated by silica gel chromatography employ­ing a mixed solvent consisting of benzene and hexane in a ratio of 1:1. Then, it was recrystallized twice from a mixed solvent consisting of benzene and ethanol in a ratio of 3:2, whereby the captioned compound was obtained as fine crystals having a light yellow color.
  • the com­pound weighed 95 g and showed, therefore, a yield of 72%.
  • FIGURE 10 The infrared absorption spectrum of the compound is shown in FIGURE 10, and the results of its cyclic voltam­metric analysis in FIGURE 11. It showed complete reversi­bility in an oxidation-reduction reaction.
  • a compatibi­lized composition was prepared by dissolving the compound in polycarbonate in equal proportions by weight and its charge transfer rate is shown in TABLE 1.
  • FIGURE 12 The infrared absorption spectrum of the compound is shown in FIGURE 12, and the results of its cyclic voltam­metric analysis in FIGURE 13. It showed complete reversi­bility in an oxidation-reduction reaction.
  • a compatibi­lized composition was prepared by dissolving the compound in polycarbonate in equal proportions by weight and its charge transfer rate is shown in TABLE 1.
  • the oily matter was refined and separated by silica gel chromatography employ­ing a mixed solvent consisting of benzene and hexane in a ratio of 1:1. Then, it was recyrstallized from a mixed solvent consisting of benzene and ethanol in a ratio of 1:5, whereby the captioned compound was obtained as leaf-­shaped crystals having a light yellow color.
  • the compound weighed 7.3 g and showed, therefore, a yield of 48%.
  • FIGURE 14 The infrared absorption spectrum of the compound is shown in FIGURE 14, and the results of its cyclic voltammetric analysis in FIGURE 15. It showed complete reversibility in an oxidation-reduction reaction.
  • a com­patibilized composition was prepared by dissolving the com­pound in polycarbonate in equal proportions by weight and its charge transfer rate is shown in TABLE 1.
  • FIGURE 16 The infrared absorption spectrum of the compound is shown in FIGURE 16, and the results of its cyclic voltammetric analysis in FIGURE 17. Its oxidation-reduction reactions were completely reversible.
  • a compatibilized composition was prepared by dissolving the compound in polycarbonate in equal proportions by weight and its charge transfer rate was as shown in TABLE 1 above.
  • a laminated light-sensitive material was made by following the procedures of EXAMPLE 1, except that p-[(p-­phenyl-p-tolylamino)phenyl)-p-tolyl]aminobenzaldehyde­diphenylhydrazone [Compound (2)] was used as the charge transporting substance.
  • a laminated light-sensitive material was made by following the procedures of EXAMPLE 1, except that N,N-­diethylaminobenzaldehydediphenylhydrazone was used as the charge transporting substance.
  • a solution was prepared by dissolving six parts by weight of p-[(p-diphenylaminophenyl)phenyl]aminobenz­aldehydediphenylhydrazone [Compound (1)] and six parts by weight of polycarbonate (the same product as had been used in EXAMPLE 1) in 88 parts by weight of chloroform. It was applied onto the charge producing layer by a doctor blade having a clearance of 100 microns. After the coat­ing had been allowed to dry at room temperature, it was dried by heating at 80°C for an hour to form a charge transporting layer having a thickness of 15 microns, where­by a laminated light-sensitive material was obtained.
  • a laminated light-sensitive material was made by following the procedures of EXAMPLE 3, except that p-[(p-­(phenyl-p-tolylamino)phenyl)-p-tolyl]aminobenzaldehyde­diphenylhydrazone [Compound (2)] was used as the charge transporting substance.
  • a laminated light-sensitive material was made by repeating EXAMPLE 3, except that N,N-diethylaminobenzalde­hydediphenylhydrazone was used as the charge transporting substance.
  • a laminated light-sensitive material was made by repeating EXAMPLE 3, except that p-[(p-(diphenylaminophenyl)-­phenyl]aminobenzaldehydemethylphenylhydrazone [Compound (5)] was used as the charge transporting substance.
  • a laminated light-sensitive material was made by repeating EXAMPLE 3, except that p-[(p-(phenyl-p-tolyl­amino)phenyl)-p-tolyl]aminobenzaldehydemethylphenylhydra­zone [Compound (4)] was used as the charge transporting substance.
  • a laminated light-sensitive material was made by repeating EXAMPLE 3, except that p-[(p-(phenyl-p-chloro­phenyl)phenyl)-p-chlorophenyl]aminobenzaldehydediphenyl­hydrazone [Compound (8)] was used as the charge transport­ing substance.
  • a laminated light-sensitive material was made by repeating EXAMPLE 3, except that p-[(p-(phenyl-p-chloro­phenyl)phenyl)-p-chlorophenyl]aminobenzaldehydemethylphenyl­hydrazone [Compound (9)] was used as the charge transport­ing substance.
  • a laminated light-sensitive material was made by repeating EXAMPLE 9, except that p-[(p-(phenyl-p-tolyl­amino)phenyl)-p-tolyl]aminobenzaldehydemethylphenylhydra­zone [Compound (4)] was used as the charge transporting substance.
  • a laminated light-sensitive material was made by repeating EXAMPLE 9, except that p-[(p-(phenyl-p-chloro­phenyl)phenyl)-p-chlorophenyl]aminobenzaldehyde diphenyl­hydrazone [Compound (8)] was used as the charge transport­ing substance.
  • a laminated light-sensitive material was made by repeating EXAMPLE 9, except that p-[(p-(phenyl-p-chloro­phenyl)phenyl-p-chlorophenyl]aminobenzaldehydemethylphenyl­hydrazone [Compound (9)] was used as the charge transport­ing substance.
  • a laminated light-sensitive material was made by repeating EXAMPLE 9, except that N,N-diethylaminobenzalde­hydediphenylhydrazone was used as the charge transporting substance.
  • a laminated light-sensitive material was made by repeating EXAMPLE 9, except that p-[(p-(methylphenylamino)-­phenyl)methyl]aminobenzaldehydediphenylhydrazone [Compound (10)] was used as the charge transporting substance.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Photoreceptors In Electrophotography (AREA)
EP19880120607 1987-12-10 1988-12-09 Matériau photosensible électrophotographique Expired - Lifetime EP0319992B1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP31380587 1987-12-10
JP313805/87 1987-12-10
JP25425588A JPH01257850A (ja) 1987-12-10 1988-10-07 電子写真感光体
JP254255/88 1988-10-07

Publications (3)

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EP0319992A2 true EP0319992A2 (fr) 1989-06-14
EP0319992A3 EP0319992A3 (en) 1989-11-29
EP0319992B1 EP0319992B1 (fr) 1993-04-14

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EP19880120607 Expired - Lifetime EP0319992B1 (fr) 1987-12-10 1988-12-09 Matériau photosensible électrophotographique

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EP (1) EP0319992B1 (fr)
JP (1) JPH01257850A (fr)
DE (1) DE3880277T2 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0410285A1 (fr) * 1989-07-19 1991-01-30 Bando Chemical Industries, Limited Matériau photosensible organique, laminé
EP0410439A3 (en) * 1989-07-28 1991-04-24 Bando Chemical Industries, Ltd. Laminated organic photosensitive material

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3201202A1 (de) * 1982-01-16 1983-07-28 Basf Ag, 6700 Ludwigshafen Neue phenylhydrazone und deren verwendung
JPS62244060A (ja) * 1986-04-17 1987-10-24 Canon Inc 電子写真感光体

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0410285A1 (fr) * 1989-07-19 1991-01-30 Bando Chemical Industries, Limited Matériau photosensible organique, laminé
EP0410439A3 (en) * 1989-07-28 1991-04-24 Bando Chemical Industries, Ltd. Laminated organic photosensitive material

Also Published As

Publication number Publication date
JPH01257850A (ja) 1989-10-13
DE3880277T2 (de) 1993-08-26
JPH0466506B2 (fr) 1992-10-23
DE3880277D1 (de) 1993-05-19
EP0319992A3 (en) 1989-11-29
EP0319992B1 (fr) 1993-04-14

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