EP0001599A1 - Electrophotographic recording material and its application in a copying process - Google Patents

Electrophotographic recording material and its application in a copying process Download PDF

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Publication number
EP0001599A1
EP0001599A1 EP78101087A EP78101087A EP0001599A1 EP 0001599 A1 EP0001599 A1 EP 0001599A1 EP 78101087 A EP78101087 A EP 78101087A EP 78101087 A EP78101087 A EP 78101087A EP 0001599 A1 EP0001599 A1 EP 0001599A1
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EP
European Patent Office
Prior art keywords
recording material
charge
transport layer
electrophotographic recording
charge carrier
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP78101087A
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German (de)
French (fr)
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EP0001599B1 (en
Inventor
Howard Warren Anderson
Michael Thomas Moore
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International Business Machines Corp
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International Business Machines Corp
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Publication of EP0001599A1 publication Critical patent/EP0001599A1/en
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Publication of EP0001599B1 publication Critical patent/EP0001599B1/en
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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
    • G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
    • G03G5/0664—Dyes
    • G03G5/0666—Dyes containing a methine or polymethine group
    • G03G5/0668—Dyes containing a methine or polymethine group containing only one methine or polymethine group
    • G03G5/067—Dyes containing a methine or polymethine group containing only one methine or polymethine group containing hetero rings
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
    • G03G5/0601—Acyclic or carbocyclic compounds
    • G03G5/0612—Acyclic or carbocyclic compounds containing nitrogen
    • G03G5/0616—Hydrazines; Hydrazones
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
    • G03G5/0601—Acyclic or carbocyclic compounds
    • G03G5/0618—Acyclic or carbocyclic compounds containing oxygen and nitrogen
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
    • G03G5/0622—Heterocyclic compounds
    • G03G5/0624—Heterocyclic compounds containing one hetero ring
    • G03G5/0635—Heterocyclic compounds containing one hetero ring being six-membered
    • G03G5/0637—Heterocyclic compounds containing one hetero ring being six-membered containing one hetero atom
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
    • G03G5/0622—Heterocyclic compounds
    • G03G5/0624—Heterocyclic compounds containing one hetero ring
    • G03G5/0635—Heterocyclic compounds containing one hetero ring being six-membered
    • G03G5/0638—Heterocyclic compounds containing one hetero ring being six-membered containing two hetero atoms
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
    • G03G5/0664—Dyes
    • G03G5/0666—Dyes containing a methine or polymethine group
    • G03G5/0668—Dyes containing a methine or polymethine group containing only one methine or polymethine group

Definitions

  • the invention relates to an electrophotographic recording material and its use in a copying process.
  • Electrophotographic processes and materials are known. In these processes, a uniform electrostatic charge is applied to a normally insulating plate or element under so-called “dark" conditions. The element is then exposed imagewise, the areas of the element 3 struck by the light becoming conductive and allowing the electrostatic charge to be dissipated from the surface of the element. This creates a latent image in the form of charged surface areas in the parts of the surface that have not been struck by light. The electrostatic image on the surface of the element is then developed with an oppositely charged powder developer, a toner. This is held onto the charged areas of the element by its affinity for the opposite solution. The discharged areas of the element show no affinity of this kind for the toner. The sc-formed toner image is then transferred to another surface, for example on paper, and is fixed on this by pressure- or heat-sensitive or similar additives that are added to the toner.
  • a particularly advantageous electrophotographic element is obtained when a layer which generates charge carriers and which is sensitive to actinic radiation to form electron-hole pairs is used in conjunction with a p-type charge carrier transport layer adjacent to it.
  • Numerous layers which generate charge carriers and are sensitive to certain wavelengths of actinic radiation are known.
  • the charge carrier transport layer is not sensitive to actinic radiation under the conditions used, but it serves to remove positive charges from the charge carrier generating layer either . depending on the system used, to the surface of the negatively charged charge carrier transport layer on which the image is formed, or in a system with a positive charge to the conductive base.
  • US Pat. No. 3,837,851 describes an electrophotographic plate in which a tri-aryl-pyrazoline compound is used as the active material in the charge carrier transport layer.
  • Hydrazones of a type other than that of the present invention have already been used as a radiation-sensitive material in photoconductive layers.
  • U.S. Patent No. 3,717,462 describes the corresponding use of a hydrazone compound. Similar uses of hydrazone compounds can be found, for example, in US Pat. No. 3,765,884.
  • an electrophotographic recording material comprising an electrically conductive layer support, a charge generation layer and a charge transport layer which has a charge transport layer containing a hydrazone bath, as characterized in the claims, and a polymer binder.
  • p-diethylaminobezaldehyde (diphenylhydranzone).
  • Other preferred carrier transport materials are o-ethoxy-p-diethyl-inobenzaldehyde (diphenylhydrazone), o-methyl-p-diethylami-topzaldehyde (diphenyhydrazone), o-methyl-p-dimethylaminobenzadehyde (diphenylhydrazone), p- dipropylaminobenzaldehyde (dipenylhydrazone), p-diethylaminobenzalde hyd- (benzylphenylhydrazone), p -dibutylaminobenzaldehyde- (diphenylhydrazone) and p-dimethylaminobenzaldehyde- (diphenylhydrazone).
  • Multi-layer electrophotographic recording materials are generally known.
  • the charge carrier-generating layer which can consist of an organic or inorganic material, is sensitive to actinic radiation which strikes the material to form electron-hole pairs.
  • the charge carrier generating layer can be self-supporting, but a flexible base, such as a polymer film with a metallized surface, is preferably used. Biaxially oriented polyethylene terephthalate is preferably used as the flexible base.
  • the carrier generation layer must be in electrical contact with a conductor in order to facilitate the selective discharge of the recording material.
  • the charge carrier generating layer is preferably formed on the base and in contact with the conductive layer.
  • the layer thickness of the layer generating charge carriers is not critical, but is generally between 0.05 and 0.20 ⁇ m.
  • Materials generating inorganic charge carriers include selenium, tellurium and compounds of groups II b and VI a of the periodic system, for example cadmium sulfo selenide.
  • Materials which generate organic charge carriers include cyanine compounds, which are described, for example, in German patent application P 22 15 040.9, disazo compounds, which are described, for example, in German patent applications P 22 15 968.1 and P 26 35 887.2, or phthalocyanine compounds. Useful results are also obtained with charge generating materials that Methine dye derivatives of squaric acid include. Materials of this type are discussed in German patent application P 24 01 220.2.
  • Chlorodian blue, methylsquarylium and hydroxysquarylium dyes are particularly suitable charge-generating materials.
  • preferred materials of this type are 3,3'-dichloro-4,4'-diphenyl-bis [1 "-azo-2" -hydroxy-3 "- naphthanilide] 2,4-bis (2-methyl-4-dimethylaminophenyl) cyclobutenediylium-1,3-diolate 2,4-bis (2-hydroxy-4-dimethylaminophenyl) cyclobutenediylium 1,3-diolate
  • these dyes are referred to below as chlorodian blue, methylsquarylium and hydroxysquarylium.
  • the charge carrier transport material in most embodiments of the invention must be essentially transparent to the actinic radiation which activates the charge carrier generating material, it is preferred that the charge carrier generating material is sensitive to actinic radiation in the visible and longer-wave spectral range, i.e. is sensitive to light with a wavelength greater than 390 nm. This requirement is essential for the preferred exemplary embodiment of the invention, in which the charge carrier transport layer is arranged between the charge carrier generating layer and the radiation source, which is the case with a system with negative charging.
  • the carrier generation material is directly exposed to actinic radiation and the carrier transport material is disposed between the carrier generation material and the conductive carrier.
  • charge generating materials and radiation sources that operate at shorter wavelengths than visible light are suitable for use with the charge transport material of the present invention.
  • organic charge generating materials are used, these materials are applied in a known manner to a metallized base, for example by meniscus coating, by means of a doctor blade or in a dip coating process.
  • An adhesive layer is preferably applied to the base in order to improve the adhesion of the charge carrier-generating layer thereon. Polyester resins are preferred as adhesives.
  • the charge carrier transport layer according to the invention is preferably applied to the charge carrier generating layer and forms the uppermost or exposed layer of the recording material.
  • the charge carrier transport layer has a thickness between approximately 7 and 35 ⁇ m, but can also be thicker or thinner, for example less than 7 ⁇ m, i.e. 5 ⁇ m.
  • the charge carrier transport layer can also be arranged between the charge carrier generating layer and the base, as indicated in two figures and the associated explanations.
  • a particularly preferred charge carrier transport material is p-diethylaminobenzaldehyde (diphenylhydrazone):
  • Trans p are o-ethoxy-p-diäthylaminobenzaldehyd- (diphenylhydrazone) o-methyl-p-diethylaminobenzaldehyde- (diphenylhydrazone) o-methyl-p-dimethylaminobenzaldehyde (diphenylhydrazone) p-dipropylaminobenzaldehyde (diphenylhydrazone) p-diethylaminobenzaldehyde (benzylphenylhydrazone) p-dibutylaminobenzaldehyde (diphenylhydrazone) p-dimethylaminobenzaldehyde (diphenylhydrazone)
  • the hydrazone material is mixed with a binder in an organic solvent, applied to the charge-generating layer and dried in a forced air oven.
  • binders are polycarbonate resins, for example a resin which is available under the name M-60 from Mobay Chemical Company, polyester resins, for example a resin which is available under the name PE-200 from Goodyear and Acrylic resins, for example a resin available from Rohm and Haas under the designation A-11.
  • Various other resins are also suitable, as shown below.
  • the resins, which can be used individually or in mixtures, are mixed with one or more organic solvents, preferably with tetrahydrofuran and toluene, although other suitable solvents can also be used.
  • a silicone oil available under the trademark DC-200 from Dow Corning, is incorporated into the solution of the charge carrier transport material.
  • a multilayer electrophotographic recording material g in Fi. 1 is generally identified by reference number 10.
  • the recording material 10 comprises a charge generation layer 12 and a charge transport layer 14. As shown, a negative charge is on the surface of the charge transport layer 14. A positive charge is on the opposite side of the charge generation layer 12, ie in a conductive layer, which is not shown. Actinic radiation 16 passes through the charge carrier transport layer 14 in the region 18, penetrates into the charge carrier generating layer 12 and generates electron-hole pairs. The hole is attracted to the negative charge on the surface of the carrier transport layer 14 and, as shown in Fig. 2, is injected into the carrier transport layer and migrates through the layer 14 to discharge the region 18.
  • the carrier transport layer 14 is essentially in terms of the negative charge on it made of an insulating mate rial. In this way, a localized discharge is obtained in the area 18. The electron is attracted to the positive charge in the conductive pad (not shown).
  • FIGS. 3 and 4 A similar result is shown in FIGS. 3 and 4.
  • the charge carrier generating layer 12 is charged positively and irradiated directly with actinic radiation 16.
  • the charge carrier transport layer 14 is arranged between the charge carrier generating layer 12 and a negative charge, which is located in the conductive base, not shown.
  • Actinic radiation in turn creates 16 electron-hole pairs.
  • the area 18 of the charge carrier generating layer 12 is discharged by electrons, while the corresponding holes migrate through the charge carrier transport layer 14 and are attracted to the negative charges.
  • the recording material 10 ' has the advantage that actinic radiation 16 does not have to penetrate the charge carrier transport layer 14, on the other hand the charge carrier generating layer 12 is not protected.
  • the recording material 10 in FIG. 1 can also be exposed to actinic radiation from the opposite side, ie through the layer support.
  • a backing suitable for the present invention was made by coating an aluminized polyethylene terephthalate support with a solution of a polyester resin which was mixed in a tetrahydrofuran: toluene solvent mixture in a ratio of 9: 1 (0.7% to 1.4% solids content, weight : Weight) was solved.
  • the poly ester coating was applied using a meniscus coating process and dried in a forced air oven.
  • chlorodian blue (0.73 g% solids content) was dissolved in a mixture of ethylene diamine, n-butylamine and tetrahydrofuran in a weight ratio of 1.2: 1.0: 2.2. Silicone oil was then added in an amount of 2.3% by weight based on the chlorordian blue.
  • the resulting solution was applied to the polyester-coated support by a meniscus coating method and the resulting coated base was dried in a forced air oven.
  • the production of the layer producing chlorine dian blue on a conventional polyester base is known per se.
  • the new charge carrier transport layer according to the invention was produced by mixing a polycarbonate resin binder in an amount of 7.65 g, a polyester resin in an amount of 3.60 g and an acrylic resin in an amount of 2.25 g in 86.5 tetrahydrofuran and Toluene, the solvents being in a weight ratio of about 9: 1.
  • a polycarbonate resin binder in an amount of 7.65 g
  • a polyester resin in an amount of 3.60 g
  • an acrylic resin in an amount of 2.25 g in 86.5 tetrahydrofuran and Toluene
  • the solvents being in a weight ratio of about 9: 1.
  • p-diethylaminobenzaldehyde (diphenylhydrazone) is added in an amount of 9.0 g together with 0.02 g of silicone oil.
  • Further tetrahydrofuran can be added to adjust the viscosity, which is suitable for the chosen coating method.
  • the resulting solution was applied to the previously produced carrier generation layer and the entire film was again dried in a forced air oven to obtain a multilayer electrophotographic recording material.
  • the electrophotographic material was tested by charging the surface to -870 volts in the dark, the charged electrophotographic material with light used in commercial electrophotographic equipment under various conditions of light intensity and by determining the light intensity required to discharge the recording material to a voltage of -150 volts within 454 ms under the specified conditions. It was found that 1.10 ⁇ J / cm 2 was required to discharge the recording material of the present example. This value indicates excellent hole transport.
  • Electrophotographic recording materials identical to those of the present examples have been tested in commercial copiers and have given excellent results in terms of charge transport, resistance to toner filming, physical resistance to wear, long-term stability of electrical and physical properties and low temperature operation.
  • Multilayered electrophotographic Aufzeichnun g smateria- lien which are prepared in Example 1 similar to that made with different resins in different amounts in the charge carrier transport layer.
  • a multilayer electrophotographic recording material similar to that in Example 1 was prepared except that the solution for preparing the charge carrier transport layer contained 14.5 g of acrylic resin as the sole binder and 14.5 g of E-diethylaminobenzaldehyde (diphenylhydrazone).
  • the recording material was tested as in Example 1, it was found that 3.0 ⁇ J / cm 2 of light energy was required to discharge the recording material from a voltage in the dark from -870 V to -150 V with a response time to exposure of 454 ms .
  • a multilayer electrophotographic recording material similar to that prepared in Example 1 was made except that a different acrylic resin was used. When tested as in Example 1, it was found that 1.16 ⁇ J / cm 2 of light energy was required to discharge the recording material from a voltage in the dark from -870 V to -150 V with a response time to exposure of 454 ms.
  • Multilayer electrophotographic recording materials similar to that of Example 2 were prepared except that the following polyester resins were used in place of the polyester resin specified therein.
  • Multilayer electrophotographic recording materials similar to that in Example 1 were made except that the adhesive layers applied first were made with resins other than the polyester specified there, but in similar amounts.
  • Each recording material was charged to -870 V and discharged to -150 V in 146 ms.
  • the exposure energies given below in ⁇ J / cm 2 were required.
  • Multilayer electrophotographic recordings similar to that prepared in Example 2e were made except that 5.78 g of p-diethylaminobenzaldehyde (diphenylhydrazone) was used in the charge transport layer solution in Example 7a and 7.27 g in Example 7b.
  • p-diethylaminobenzaldehyde diphenylhydrazone
  • a multilayer electrophotographic recording medium similar to that of Example 2a was made except that 13.5 g of p-diethylaminobenzaldehyde (diphenylhydrazone) was dissolved in the solution of the Laduna carrier trans port layer were used.
  • p-diethylaminobenzaldehyde diphenylhydrazone
  • 1.37 ⁇ J / cm 2 of light energy was required to discharge the recording material from a dark voltage of -870 V to -150 V with a response time to exposure of 146 ms.
  • a multilayer electrophotographic recording material similar to that in Example 2a was prepared except that 20.25 g of p-diethylaminobenzaldehyde (diphenylhydrazone) was used in the solution of the charge transport layer.
  • p-diethylaminobenzaldehyde diphenylhydrazone
  • a multilayered electrophotographic recording materials which were similar to that given in Example 2 were prepared with the exception that 13.5 g of the following hydrazones in the solution of the charge carrier-p were used ort harsh:
  • Multilayer electrophotographic recording materials similar to that in Example 1 were prepared with the exception that the solution of the charge carrier transport layer contained 6.75 g of polyester resin, 6.75 g of polycarbonate resin and 13.5 g of the hydrazone compounds given below:
  • hydroxysquarylium in an amount of 1 g is dissolved in a mixed solvent of 1 ml of ethylenediamine, 5 ml of propylamine and 24 ml of tetrahydrofuran and applied to an aluminized polyester base by a meniscus coating method and dried to obtain a layer generating charge carriers.
  • a charge carrier transport layer in accordance with the present invention was prepared by meniscus coating the carrier-coated layer with a solution of 8.12 g of a polycarbonate resin and 8.12 g of p-diethylaminobenzaldehyde (diphenylhydrazone) in a 9: 1 mixture of tetrahydrofuran and toluene and drying to form a multilayer electrophotographic recording material.
  • a solution of 8.12 g of a polycarbonate resin and 8.12 g of p-diethylaminobenzaldehyde (diphenylhydrazone) in a 9: 1 mixture of tetrahydrofuran and toluene and drying to form a multilayer electrophotographic recording material.
  • 1.40 ⁇ J / cm 2 of light energy was required to discharge the recording material from a voltage in the dark from -870 V to -150 V with a response time to exposure of 146 ms.
  • a multilayer electrophotographic recording material similar to that in Example 13 was made except that o-ethoxy-p-diethylaminobenzaldehyde (diphenylhydrazone) was used in the charge transport layer solution.
  • o-ethoxy-p-diethylaminobenzaldehyde diphenylhydrazone
  • a multi-layer electrophotographic recording material similar to that in Example 13 was prepared except that the charge generation solution contained 0.85 g of hydroxysquarylium and 0.15 g of methylsquarylium. When tested as in Example 1, it was found that 0.86 ⁇ J / cm 2 of light energy was required to discharge the recording material from a voltage in the dark from -870 to -150 V with a response time to exposure of 116 ms.
  • a multilayered electrophotographic recording material similar to that in Example 13 was prepared except that the carrier generation layer solution was 0.15 g of hydroxysquarylium and 0.15 g Methylsquarylium and the solution of the charge carrier transport layer contained 8.12 g of polycarbonate resin and 5.42 g of p-diethylaminobenzaldehyde (diphenylhydrazone).
  • the carrier generation layer solution was 0.15 g of hydroxysquarylium and 0.15 g Methylsquarylium
  • the solution of the charge carrier transport layer contained 8.12 g of polycarbonate resin and 5.42 g of p-diethylaminobenzaldehyde (diphenylhydrazone).
  • a multilayer electrophotographic recording material was prepared by adding a charge transport layer composed of a solution of 6.75 g polyester resin, 6.75 g polycarbonate resin and 13.5 g p-diethylaminobeazalde to a charge-generating layer which was produced by vacuum deposition of selenium and tellurium - hyd (diphenylhydrazone) was applied.
  • a charge transport layer composed of a solution of 6.75 g polyester resin, 6.75 g polycarbonate resin and 13.5 g p-diethylaminobeazalde
  • the p-type charge carrier transport layer according to the present invention can be produced with various types of scavengers as well as a large number of hydrazone compounds of the specified type.
  • Both organic and inorganic charge generation layers can be used with the charge transport layer according to the present invention, and various combinations of solvents, polymeric binders, and the like, known per se, can be used.
  • Certain hydrazone compounds when used in relatively high concentrations, tend to crystallize, thereby reducing their charge carriers transport function decreases. However, if smaller amounts are used, useful results will be obtained. A selection in this direction can be made by a person skilled in the art.
  • the electrophotographic recording materials with the charge carrier transport layer according to the invention show an excellent ratio of sensitivity, especially at low temperatures, to adhesive. to neighboring layers and resistance to mechanical wear at different temperatures.
  • the recording materials also show excellent properties with regard to aging and have a considerable resistance to toner formation.

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  • Health & Medical Sciences (AREA)
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Abstract

Die Erfindung betrifft ein elektrophotographisches Aufzeichnungsmaterial (10) und dessen Verwendung in einem Kopierverfahren. Das Aufzeichnungsmaterial (10) besteht aus einem elektrisch leitenden Schichtträger, einer Ladungsträger erzeugenden Schicht (12) und einer Ladungstransportschicht (14). Letztere enthält gemäss der Erfindung als Ladungen transportierende Verbindung ein Hydrazon der allgemeinem Formel <IMAGE> in der die Reste <IMAGE> R2 = -OC2H3; -CH3; -C2H5; -H R3 = -H; -OC2H5 R4 = -H; -CH3; -C2H5 R5 = -H; -CH3 R6 = -C4H5; -CH2-C6H5; -CH3; n-C4H9 R7 = -C6H5; -CH3 <IMAGE> bedeuten, und ein polymeres Bindemittel. Eine bevorzugte, Ladungen transportierende Verbindung ist ρ-Diäthylaminobenzaldehyd- (diphenythydrazon). Als Bindemittel wird ein Polycarbonat-, Polyester-oder Acrylherz, oder Mischungen dereiben verwendet. Die Ladungsträgertransportschicht (14), die eine Dicke von mindestens 5 um aufweist, kann, je nach dem Vorzeichen der Aufladung der Landungsträger erzeugenden Schicht, auf der Landungsträger erzeugenden Schicht (12) oder zwischen derselben und dem leitenden Schichtträger angeordnet sein. Die Erfindung bezieht sich auch auf die Verwendung des mehrlagigen Aufzeichnungsmaterials in einem elektrophotographischen Kopierverfahren.The invention relates to an electrophotographic recording material (10) and its use in a copying process. The recording material (10) consists of an electrically conductive layer support, a charge generation layer (12) and a charge transport layer (14). According to the invention, the latter contains a hydrazone of the general formula <IMAGE> in which the radicals <IMAGE> R2 = -OC2H3; -CH3; -C2H5; -H R3 = -H; -OC2H5 R4 = -H; -CH3; -C2H5 R5 = -H; -CH3 R6 = -C4H5; -CH2-C6H5; -CH3; n-C4H9 R7 = -C6H5; -CH3 mean <IMAGE>, and a polymeric binder. A preferred charge transporting compound is ρ-diethylaminobenzaldehyde (diphenythydrazone). A polycarbonate, polyester or acrylic heart, or mixtures thereof, is used as the binder. The charge carrier transport layer (14), which has a thickness of at least 5 µm, can, depending on the sign of the charge of the landing carrier-generating layer, be arranged on the landing carrier-generating layer (12) or between the same and the conductive layer carrier. The invention also relates to the use of the multilayer recording material in an electrophotographic copying process.

Description

Die Erfindung betrifft ein elektrophotographisches Aufzeichnungsmaterial und dessen Verwendung in einem Kopierverfahren.The invention relates to an electrophotographic recording material and its use in a copying process.

Elektrophotographische Verfahren und Materialien sind bekannt. Bei diesen Prozessen wird eine gleichmäßige elektrostatische Ladung auf eine normalerweise isolierenden Platte oder ein Element unter sogenannten "Dunkel"-Bedingungen aufgetragen. Anschließend wird das Element bildmäßig belichtet, wobei die vom Licht getroffenen Bereiche des Element3 leitend werden und eine Ableitung der elektrostatischen Ladung von der Oberfläche des Elements ermöglichen. Dadurch wird ein latentes Bild in Form geladener Oberflächenbereiche in den Teilen der Oberfläche, die nicht von Licht getroffen wurden, gebildet. Das elektrostatische Bild auf der Oberfläche des Elements wird dann mit einem entgegengesetzt geladenen Pulverentwickler, einem Toner, entwickelt. Dieser wird an den geladenen Bereichen des Elements durch seine Affinität zu der entgegengesetzten Li.lung festgehalten. Die entladenen Bereiche des Elemeats zeigen keine Affinität dieser Art zu dem Toner. Das sc gebildete Tonerbild wird anschließend auf eine andere Oterfläche, beispielsweise auf Papier übertragen und wird auf dieser durch druck- oder hitzeempfindliche oder ähnliche Zusatzstoffe, die dem Toner beigemischt sind, fixiert.Electrophotographic processes and materials are known. In these processes, a uniform electrostatic charge is applied to a normally insulating plate or element under so-called "dark" conditions. The element is then exposed imagewise, the areas of the element 3 struck by the light becoming conductive and allowing the electrostatic charge to be dissipated from the surface of the element. This creates a latent image in the form of charged surface areas in the parts of the surface that have not been struck by light. The electrostatic image on the surface of the element is then developed with an oppositely charged powder developer, a toner. This is held onto the charged areas of the element by its affinity for the opposite solution. The discharged areas of the element show no affinity of this kind for the toner. The sc-formed toner image is then transferred to another surface, for example on paper, and is fixed on this by pressure- or heat-sensitive or similar additives that are added to the toner.

Ein besonders vorteilhaftes elektrophotographisches Element ergibt sich, wenn eine Ladungsträger erzeugende Schicht, welche gegenüber aktinischer Strahlung zur Ausbildung von Elektronen-Lochpaaren empfindlich ist, in Verbindung mit einer zu ihr benachbarten Ladungsträgertransportschicht vom p-Typ verwendet wird. Zahlreiche Ladungsträger erzeugende Schichten, die gegenüber bestimmten Wellenlängen aktinischer Strahlung empfindlich sind, sind bekannt. Die Ladungsträgertransportschicht ist unter den angewendeten Bedingungen gegenüber aktinischer Strahlung nicht empfindlich, aber sie dient dazu, positive Ladungen von der Ladungsträger erzeugenden Schicht entweder,.in Abhängigkeit von dem angewendeten System, an die Oberfläche der negativ geladenen Ladungsträgertransportschicht, auf der das Bild gebildet wird, oder in einem System mit positiver Aufladung zu der leitenden Unterlage zu transportieren. In der US-Patentschrift 3 837 851 wird eine elektrophotographische Platte beschrieben, bei der als aktives Material in der Ladungsträgertransportschicht eine Tri-aryl-pyrazolin-Verbindung verwendet wird.A particularly advantageous electrophotographic element is obtained when a layer which generates charge carriers and which is sensitive to actinic radiation to form electron-hole pairs is used in conjunction with a p-type charge carrier transport layer adjacent to it. Numerous layers which generate charge carriers and are sensitive to certain wavelengths of actinic radiation are known. The charge carrier transport layer is not sensitive to actinic radiation under the conditions used, but it serves to remove positive charges from the charge carrier generating layer either . depending on the system used, to the surface of the negatively charged charge carrier transport layer on which the image is formed, or in a system with a positive charge to the conductive base. US Pat. No. 3,837,851 describes an electrophotographic plate in which a tri-aryl-pyrazoline compound is used as the active material in the charge carrier transport layer.

Hydrazone eines anderen Typs als die der vorliegenden Erfindung wurden bereits in photoleitfähigen Schichten als strahlungsempfindliches Material verwendet. In der US-Patentschrift 3 717 462 wird die entsprechende Verwendung einer Hydrazonverbindung beschrieben. Ähnliche Verwendungen von Hydrazonverbindungen können beispielsweise der US-Patentschrift 3 765 884 entnommen werden.Hydrazones of a type other than that of the present invention have already been used as a radiation-sensitive material in photoconductive layers. U.S. Patent No. 3,717,462 describes the corresponding use of a hydrazone compound. Similar uses of hydrazone compounds can be found, for example, in US Pat. No. 3,765,884.

Zusammenfassend kann gesagt werden, daß die Verwendung von Ladungsträgertransportschichten in Verbindung mit bestimmten Ladungsträger erzeugenden Schichten bekannt ist, daß aber die Verwendung von Hydrazonverbindungen im allgemeinen und Lnsbesondere der Hydrazonverbindungen gemäß der vorliegende Erfindung als aktives Material in einer Ladungsträgertransoortschicht bisher nicht vorgeschlagen wurde. Andererseits wurden Hydrazonverbindungen, die sich von den spezifischen Verbindungen der vorliegenden Erfindung unterscheiden, Lereits als lichtempfindliche Materialien, aber nicht als ladungsträgertransportmaterialien verwendet.In summary it can be said that the use of charge carrier transport layers in connection with be certain charge-generating layers is known, but the use of hydrazone compounds in general and in particular the hydrazone compounds according to the present invention as active material in a charge carrier layer has not previously been proposed. On the other hand, hydrazone compounds other than the specific compounds of the present invention have been used as photosensitive materials but not as charge transport materials.

Aufgabe de vorliegenden Erfindung ist die Bereitstellung eines elekrophotographischen Aufzeichnungsmaterials aus mehreren Schichten, das im Vergleich mit bisher bekannten mehrlagige Aufzeichnungsmaterialien hinsichtlich seines Verhaltens bei niedriger Temperatur, der Haftung und der Widerstanesfähigkeit gegenüber Abnutzung, der Tonerfilmbildung und lterung bei gleichzeitig vorhandener hoher LichtempfindlLhkeit verbesserte Eigenschaften aufweist.It is an object of the present invention to provide a multilayered electrophotographic recording material which, compared to previously known multilayer recording materials, has improved properties with regard to its behavior at low temperature, adhesion and resistance to wear, toner film formation and aging while at the same time having high photosensitivity.

Die Autgab der Erfindung wird gelöst durch ein elektrophotographiscaes Aufzeichnungsmaterial aus einem elektrisch leitenden chichtträger, einer Ladungsträger erzeugenden Schicht und einer Ladungsträgertransportschicht, das eine Ladungsträgertransportschicht mit einem Gehalt an einer Hydrazonverbadung, wie sie in den Ansprüchen gekennzeichnet ist und einem colymeren Bindemittel aufweist.The object of the invention is achieved by an electrophotographic recording material comprising an electrically conductive layer support, a charge generation layer and a charge transport layer which has a charge transport layer containing a hydrazone bath, as characterized in the claims, and a polymer binder.

Besonders vorte thafte Ergebnisse werden bei Verwendung von p-Diäthylaminobezaldehyd-(diphenylhydranzon) erhalten. Andere bevorzugte Liungsträgertransportmaterialien sind o-Äthoxy-p-diäthyl-inobenzaldehyd-(diphenylhydrazon), o-Methyl-p-diäthylami-obenzaldehyd-(diphenyhydrazon), o-Methyl- p-dimethylaminobenzadehyd-(diphenylhydrazon), p-Dipropyl- aminobenzaldehyd-(dipenylhydrazon), p-Diäthylaminobenzaldehyd-(benzylphenylhydrazon), p-Dibutylaminobenzaldehyd-(diphenylhydrazon) und p-Dimethylaminobenzaldehyd-(diphenylhydrazon).Particularly advantageous results are obtained when using p-diethylaminobezaldehyde (diphenylhydranzone). Other preferred carrier transport materials are o-ethoxy-p-diethyl-inobenzaldehyde (diphenylhydrazone), o-methyl-p-diethylami-topzaldehyde (diphenyhydrazone), o-methyl-p-dimethylaminobenzadehyde (diphenylhydrazone), p- dipropylaminobenzaldehyde (dipenylhydrazone), p-diethylaminobenzalde hyd- (benzylphenylhydrazone), p -dibutylaminobenzaldehyde- (diphenylhydrazone) and p-dimethylaminobenzaldehyde- (diphenylhydrazone).

Mehrlagige elektrophotographische Aufzeichnungsmaterialien sind allgemein bekannt. Die Ladungsträger erzeugende Schicht, welche aus einem organischen oder anorganischen Material bestehen kann, ist gegenüber aktinischer Strahlunq, die auf das Material auftrifft zur Ausbildung von Elektronen-Lochpaaren empfindlich. Die Ladungsträger erzeugende Schicht kann selbsttragend sein, es wird jedoch vorzugsweise eine biegsame Unterlage, wie ein Polymerfilm mit einer metallisierten Oberfläche, angewendet. Als biegsame Unterlage wird vorzugsweise biaxial orientiertes Polyäthylenterephthalat verwendet. Wie oben angegeben, muß die Ladungsträger erzeugende Schicht in elektrischem Kontakt mit einem Leiter sein, um die selektive Entladung des Aufzeichnungsmaterials zu erleichtern. Wiederum im Hinblick auf die bevorzugte, aber konventionelle Ausführungsform der Erfindung ist es am vorteilhaftesten, einen aluminisierten Polyäthylenterephthalat-Film zu verwenden, wobei das Aluminium die leitende Schicht ausmacht. Die Ladungsträger erzeugende Schicht wird vorzugsweise auf der Unterlage und in Kontakt mit der leitenden Schicht gebildet. Die Schichtdicke der Ladungsträger erzeugenden Schicht ist nicht kritisch, sie liegt jedoch im allgemeinen zwischen 0,05 und 0,20 µm. Anorganische Ladungsträger erzeugende Materialien schließen Selen, Tellur und Verbindungen der Gruppen II b und VI a des periodischen Systems, beispielsweise Cadmium-sulfo-selenid ein. Organische Ladungsträger erzeugende Materialien schließen Cyaninverbindungen, die beispielsweise in der deutschen Patentanmeldung P 22 15 040.9 beschrieben sind, Disazoverbindungen, die beispielsweise in den deutschen Patentanmeldungen P 22 15 968.1 und P 26 35 887.2 beschrieben sind, oder Phthalocyaninverbindungen ein. Brauchbare Ergebnisse werden auch mit Ladungsträger erzeugenden Materialien erhalten, die Methinfarbstoffderivate der Quadratsäure umfassen. Materialien dieser Art werden in der deutschen Patentanmeldung P 24 01 220.2 diskutiert.Multi-layer electrophotographic recording materials are generally known. The charge carrier-generating layer, which can consist of an organic or inorganic material, is sensitive to actinic radiation which strikes the material to form electron-hole pairs. The charge carrier generating layer can be self-supporting, but a flexible base, such as a polymer film with a metallized surface, is preferably used. Biaxially oriented polyethylene terephthalate is preferably used as the flexible base. As indicated above, the carrier generation layer must be in electrical contact with a conductor in order to facilitate the selective discharge of the recording material. Again in view of the preferred but conventional embodiment of the invention, it is most advantageous to use an aluminized polyethylene terephthalate film, the aluminum being the conductive layer. The charge carrier generating layer is preferably formed on the base and in contact with the conductive layer. The layer thickness of the layer generating charge carriers is not critical, but is generally between 0.05 and 0.20 μm. Materials generating inorganic charge carriers include selenium, tellurium and compounds of groups II b and VI a of the periodic system, for example cadmium sulfo selenide. Materials which generate organic charge carriers include cyanine compounds, which are described, for example, in German patent application P 22 15 040.9, disazo compounds, which are described, for example, in German patent applications P 22 15 968.1 and P 26 35 887.2, or phthalocyanine compounds. Useful results are also obtained with charge generating materials that Methine dye derivatives of squaric acid include. Materials of this type are discussed in German patent application P 24 01 220.2.

Chlordianblau, Methylsquarylium- und Hydroxysquaryliumfarbstoffe sind besonders geeignete Ladungsträger erzeugende Materialien. Im einzelnen sind bevorzugte Materialien dieser Art 3,3'-Dichlor-4,4'-diphenyl- bis [1"-azo-2"-hydroxy-3"- naphtanilid]

Figure imgb0001
2,4-Bis-(2-methyl-4-dimethylaminophenyl)-cyclobutendiylium-1,3-diolat
Figure imgb0002
2,4-Bis-(2-hydroxy-4-dimethylaminophenyl)-cyclobutendiylium-1,3-diolat
Figure imgb0003
Diese Farbstoffe werden der Einfachheit halber nachfolgend mit Chlordianblau, Methylsquarylium und Hydroxysquarylium bezeichnet.Chlorodian blue, methylsquarylium and hydroxysquarylium dyes are particularly suitable charge-generating materials. In particular, preferred materials of this type are 3,3'-dichloro-4,4'-diphenyl-bis [1 "-azo-2" -hydroxy-3 "- naphthanilide]
Figure imgb0001
 2,4-bis (2-methyl-4-dimethylaminophenyl) cyclobutenediylium-1,3-diolate
Figure imgb0002
 2,4-bis (2-hydroxy-4-dimethylaminophenyl) cyclobutenediylium 1,3-diolate
Figure imgb0003
 For the sake of simplicity, these dyes are referred to below as chlorodian blue, methylsquarylium and hydroxysquarylium.

Zusammenfassend kann gesagt werden, daß eine Vielzahl anorganischer und organischer Ladungsträger erzeugender Materialien zusammen mit dem Ladungsträgertransportmaterial der vorliegenden Erfindung verwendet werden können. Da jedoch das Ladungsträgertransportmaterial in den meisten Ausführungsbeispielen der Erfindung für die aktinische Strahlung, welche das Ladungsträger erzeugende Material aktiviert, im wesentlichen transparent sein muß, wird bevorzugt, daß das Ladungsträger erzeugende Material gegenüber aktinischer Strahlung im sichtbaren und längerwelligen Spektralbereich, d.h. gegenüber Licht mit einer Wellenlänge größer 390 nm, empfindlich ist. Diese Forderung ist wesentlich für das bevorzugte Ausführungsbeispiel der Erfindung, bei dem die Ladungsträgertransportschicht zwischen der Ladungsträger erzeugenden Schicht und der Strahlungsquelle angeordnet ist, was bei einem System mit negativer Aufladung der Fall ist. Bei einem System mit positiver Aufladung wird das Ladungsträger erzeugende Material direkt aktinischer Strahlung ausgesetzt, und das Ladungsträgertransportmaterial wird zwischen Ladungsträger erzeugendem Material und dem leitenden Träger angeordnet. Im letzteren Fall sind Ladungsträger erzeugende Materialien und Strahlungsquellen, die bei kürzeren Wellenlängen als sichtbarem Licht arbeiten, zur Verwendung mit dem Ladungsträgertransportmaterial gemäß der vorliegenden Erfindung geeignet.In summary, a variety of inorganic and organic carrier generation materials can be used in conjunction with the carrier transport material of the present invention. However, since the charge carrier transport material in most embodiments of the invention must be essentially transparent to the actinic radiation which activates the charge carrier generating material, it is preferred that the charge carrier generating material is sensitive to actinic radiation in the visible and longer-wave spectral range, i.e. is sensitive to light with a wavelength greater than 390 nm. This requirement is essential for the preferred exemplary embodiment of the invention, in which the charge carrier transport layer is arranged between the charge carrier generating layer and the radiation source, which is the case with a system with negative charging. In a positive charge system, the carrier generation material is directly exposed to actinic radiation and the carrier transport material is disposed between the carrier generation material and the conductive carrier. In the latter case, charge generating materials and radiation sources that operate at shorter wavelengths than visible light are suitable for use with the charge transport material of the present invention.

In dem bevorzugten Ausführungsbeispiel gemäß der vorliegenden Erfindung, in dem organische Ladungsträger erzeugende Materialien verwendet werden, werden diese Materialien in bekannter Weise auf eine metallisierte Unterlage aufgetragen, beispielsweise durch Meniskusbeschichten, mittels einer Rakel oder in einem Tauchbeschichtungsverfahren. Es wird vorzugsweise eine Klebstoffschicht auf die Unterlage aufgetragen, um die Haftung der Ladungsträger erzeugenden Schicht auf dieser zu verbessern. Polyesterharze werden als Klebstoffe bevorzugt.In the preferred exemplary embodiment according to the present invention, in which organic charge generating materials are used, these materials are applied in a known manner to a metallized base, for example by meniscus coating, by means of a doctor blade or in a dip coating process. An adhesive layer is preferably applied to the base in order to improve the adhesion of the charge carrier-generating layer thereon. Polyester resins are preferred as adhesives.

Die Ladungsträgertransportschicht gemäß der Erfindung wird vorzugsweise auf die Ladungsträger erzeugende Schicht aufgetragen und bildet die oberste oder freiliegende Schicht des Aufzeichnungsmaterials. Die Ladungsträgertransportschicht weist eine Dicke zwischen etwa 7 und 35 µm auf, kann aber auch dicker oder dünner sein, beispielsweise weniger als 7 µm, d.h. 5 µm. Die nachfolgenden Ausführungen betreffen zwar das bevorzugte Ausführungsbeispiel gemäß der Erfindung, bei einem System mit positiver Aufladung kann jedoch die Ladungsträgertransportschicht auch zwischen der Ladungsträger erzeugenden Schicht und der Unterlage angeordnet sein, wie in zwei Abbildungen und den dazugehörigen Ausführungen angegeben ist.The charge carrier transport layer according to the invention is preferably applied to the charge carrier generating layer and forms the uppermost or exposed layer of the recording material. The charge carrier transport layer has a thickness between approximately 7 and 35 µm, but can also be thicker or thinner, for example less than 7 µm, i.e. 5 µm. Although the following explanations relate to the preferred exemplary embodiment according to the invention, in a system with positive charging, however, the charge carrier transport layer can also be arranged between the charge carrier generating layer and the base, as indicated in two figures and the associated explanations.

Das aktive Material der Ladungsträgertransportschicht vom p-Typ gemäß der vorliegenden Erfindung ist ein Hydrazon der allgemeinen Formel

Figure imgb0004
in der die Reste
Figure imgb0005
Figure imgb0006
Figure imgb0007
Figure imgb0008
Figure imgb0009

  • R2 = -OC2H5; -CH3; -C2H5; -H
  • R3 = -H; -OC2H5
  • R4 = -H; -CH3; -C2H5
  • R5 = -H; -CH3
  • R6 = -C6H5; -CH2-C6H5; -CH3; n-C4H9
  • R7 = -C6H5; -CH3
    Figure imgb0010
    bedeuten.
The active material of the p-type charge transport layer according to the present invention is a hydrazone of the general formula
Figure imgb0004
 in which the leftovers
Figure imgb0005
Figure imgb0006
Figure imgb0007
Figure imgb0008
Figure imgb0009
  • R 2 = -OC 2 H 5 ; -CH 3 ; -C 2 H 5 ; -H
  • R 3 = -H; -OC 2 H 5
  • R 4 = -H; -CH 3 ; -C 2 H 5
  • R 5 = -H; -CH 3rd
  • R 6 = -C 6 H 5 ; -CH 2 -C 6 H 5 ; -CH 3 ; nC 4 H 9
  • R 7 = -C 6 H 5 ; -CH 3rd
    Figure imgb0010
     mean.

Ein besonders bevorzugtes Ladungsträgertransportmaterial ist p-Diäthylaminobenzaldehyd-(diphenylhydrazon):

Figure imgb0011
A particularly preferred charge carrier transport material is p-diethylaminobenzaldehyde (diphenylhydrazone):
Figure imgb0011

Andere bevorzugte Ladungsträgertransportmaterialien sind o-Äthoxy-p-diäthylaminobenzaldehyd-(diphenylhydrazon)

Figure imgb0012
o-Methyl-p-diäthylaminobenzaldehyd-(diphenylhydrazon)
Figure imgb0013
 o-Methyl-p-dimethylaminobenzaldehyd-(diphenylhydrazon)
Figure imgb0014
p-Dipropylaminobenzaldehyd-(diphenylhydrazon)
Figure imgb0015
p-Diäthylaminobenzaldehyd-(benzylphenylhydrazon)
Figure imgb0016
p-Dibutylaminobenzaldehyd-(diphenylhydrazon)
Figure imgb0017
p-Dimethylaminobenzaldehyd-(diphenylhydrazon)
Figure imgb0018
 Ortmaterialien Other preferred carriers Trans p are o-ethoxy-p-diäthylaminobenzaldehyd- (diphenylhydrazone)
Figure imgb0012
 o-methyl-p-diethylaminobenzaldehyde- (diphenylhydrazone)
Figure imgb0013
 o-methyl-p-dimethylaminobenzaldehyde (diphenylhydrazone)
Figure imgb0014
 p-dipropylaminobenzaldehyde (diphenylhydrazone)
Figure imgb0015
 p-diethylaminobenzaldehyde (benzylphenylhydrazone)
Figure imgb0016
 p-dibutylaminobenzaldehyde (diphenylhydrazone)
Figure imgb0017
 p-dimethylaminobenzaldehyde (diphenylhydrazone)
Figure imgb0018

Zur Anwendung wird das Hydrazonmaterial mit einem Bindemittel in einem organischen Lösungsmittel gemischt, auf die Ladungsträger erzeugende Schicht aufgetragen und in einem Umluftofen getrocknet. Zur Verwendung sind zahlreiche polymere Bindemittel geeignet, besonders geeignete Bindemittel sind Polycarbonatharze, beispielsweise ein Harz, das unter der Bezeichnung M-60 von Mobay Chemical Company erhältlich ist, Polyesterharze, beispielsweise ein Harz, das unter der Bezeichnung PE-200 von Goodyear erhältlich ist und Acrylharze, beispielsweise ein Harz, das unter der Bezeichnung A-11 von Rohm und Haas erhältlich ist. Es sind auch verschiedene andere Harze geeignet, wie nachfolgend gezeige wird. Die Harze, die einzeln oder in Mischungen verwendet werden können, werden mit einem oder mehreren organischen Lösungsmitteln gemischt, vorzugsweise mit Tetrahydrofuran und Toluol, wobei auch andere geeignete Lösungsmittel verwendet werden können.For use, the hydrazone material is mixed with a binder in an organic solvent, applied to the charge-generating layer and dried in a forced air oven. Numerous polymeric binders are suitable for use, particularly suitable binders are polycarbonate resins, for example a resin which is available under the name M-60 from Mobay Chemical Company, polyester resins, for example a resin which is available under the name PE-200 from Goodyear and Acrylic resins, for example a resin available from Rohm and Haas under the designation A-11. Various other resins are also suitable, as shown below. The resins, which can be used individually or in mixtures, are mixed with one or more organic solvents, preferably with tetrahydrofuran and toluene, although other suitable solvents can also be used.

Andere Bestandteile können zur Erhöhung der Gleitwirkuig, der Stabilität, der Haftung, zur Beeinflussung der Üb tzugsqualität und ähnlichen Eigenschaften der Ladungsträge transportschicht einverleibt werden. So wird beispielsweise ein Siliconöl, das unter dem Warenzeichen DC-200 von Dow Corning erhältlich ist, der Lösung des Ladungsträgertrensportmaterials einverleibt.Other components can be incorporated to increase the sliding effect, the stability, the adhesion, to influence the quality of the coating and similar properties of the charge carrier transport layer. For example, a silicone oil, available under the trademark DC-200 from Dow Corning, is incorporated into the solution of the charge carrier transport material.

Die Erfindung wird anhand der nachfolgenden Figuren unt der Beschreibung näher erläutert.

  • Fig. 1 stellt einen vereinfachten Querschnitt durch eine Ladungsträger erzeugende und eine Ladungst gertransportschicht in einem bevorzugten Ausf Arungsbeispiel der Erfindung dar, wobei die Wirlangsweise bei Belichtung eines negativ geladeun Elements mit aktinischer Strahlung gezeigt vid;
  • Fig. 2 ist ein Schnittbild ähnlich Fig. 1, anhand dessen die resultierende negative Ladungsverteilung auf dem Aufzeichnungsmaterial gezeigt wird;
  • Fig. 3 ist ein Schnittbild, anhand dessen ein Aufzeichnungsmaterial für positive Aufladung gezeigt wird und
  • Fig. 4 ist ein Schnittbild ähnlich Fig. 3, anhand dessen die resultierende positive Ladungsverteilung auf der Oberfläche des positiv geladenen Aufzeichnungsmaterials gezeigt wird.
The invention is explained in more detail with reference to the following figures and the description.
  • 1 shows a simplified cross section through a charge carrier-generating and a charge carrier transport layer in a preferred embodiment of the invention, the method being shown when a negatively charged element is exposed to actinic radiation;
  • Fig. 2 is a sectional view similar to Fig. 1, showing the resultant negative charge distribution on the recording material;
  • Fig. 3 is a sectional view showing a positive charge recording material, and
  • Fig. 4 is a sectional view similar to Fig. 3, showing the resultant positive charge distribution on the surface of the positively charged recording material.

In allen Figuren sind gleiche Komponenten und Bestandteile mit den gleichen Bezugszeichen bezeichnet, ein mehrlagiges elektrophotographisches Aufzeichnungsmaterial in Fig. 1 wird im allgemeinen mit dem Bezugszzeichen 10 gekennzeichnet.In all figures, identical components and components having the same reference numerals, a multilayer electrophotographic recording material g in Fi. 1 is generally identified by reference number 10.

Das Aufzeichnungsmaterial 10 umfaßt eine Ladungsträger erzeugende Schicht 12 und eine Ladungsträgertransportschicht 14. Wie dargestellt, befindet sich eine negative Ladung auf der Oberfläche der Ladungsträgertransportschicht 14. Eine positive Ladung befindet sich auf der entgegengesetzten Seite der Ladungsträger erzeugenden Schicht 12, d.h. in einer leitenden Schicht, die nicht gezeigt ist. Aktinische Strahlung 16 passiert die Ladungsträgertransportschicht 14 im Bereich 18, dringt in die Ladungsträger erzeugende Schicht 12 ein und erzeugt Elektronen-Lochpaare. Das Loch wird von der negativen Ladung auf der Oberfläche der Ladungsträgertransportschicht 14 angezogen und wird, wie in Fig. 2 gezeigt ist, in die Ladungsträgertransportschicht injiziert und wandert durch die Schicht 14 zur Entladung des Bereichs 18. Die Ladungsträgertransportschicht 14 besteht im wesentlichen im Hinblick auf die sich darauf befindliche negative Ladung aus einem isolierenden Material. Auf diese Weise wird eine lokalisierte Entladung im Bereich 18 erhalten. Das Elektron wird durch die positive Ladung in der leitenden Unterlage (nicht gezeigt) angezogen.The recording material 10 comprises a charge generation layer 12 and a charge transport layer 14. As shown, a negative charge is on the surface of the charge transport layer 14. A positive charge is on the opposite side of the charge generation layer 12, ie in a conductive layer, which is not shown. Actinic radiation 16 passes through the charge carrier transport layer 14 in the region 18, penetrates into the charge carrier generating layer 12 and generates electron-hole pairs. The hole is attracted to the negative charge on the surface of the carrier transport layer 14 and, as shown in Fig. 2, is injected into the carrier transport layer and migrates through the layer 14 to discharge the region 18. The carrier transport layer 14 is essentially in terms of the negative charge on it made of an insulating mate rial. In this way, a localized discharge is obtained in the area 18. The electron is attracted to the positive charge in the conductive pad (not shown).

Ein ähnliches Ergebnis ist in den Figuren 3 und 4 dargestellt. In dem Aufzeichnungsmaterial 10', in dem die gleichen Schichten enthalten sind, sind diese in anderer Reihenfolge angeordnet. Die Ladungsträger erzeugende Schicht 12 wird positiv geladen und direkt mit aktinischer Strahlung 16 bestrahlt. Die Ladungsträgertransportschicht 14 wird zwischen der Ladungsträger erzeugenden Schicht 12 und einer negativen Aufladung, die sich in der nicht gezeigten leitenden Unterlage befindet, angeordnet. Wiederum erzeugt aktinische Strahlung 16 Elektronen-Lochpaare. Der Bereich 18 der Ladungsträger erzeugenden Schicht 12 wird durch Elektronen entladen, während die korrespondierenden Löcher durch die Ladungsträgertransportschicht 14 wandern und von den negativen Ladungen angezogen werden. Das Aufzeichnungsmaterial 10' weist den Vorteil auf, daß aktinische Strahlung 16 nicht die Ladungsträgertransportschicht 14 durchdringen muß, andererseits ist die Ladungsträger erzeugende Schicht 12 nicht geschützt. Es sind auch andere Ausfiihrunqsbei- spiele möglich, die nicht dargestellt sind. So kann beispielsweise das Aufzeichnungsmaterial 10 in Fig. 1 auch von der entgegengesetzten Seite, d.h. durch den Schichtträger hindurch, mit aktinischer Strahlung belichtet werden.A similar result is shown in FIGS. 3 and 4. In the recording material 10 'in which the same layers are contained, these are arranged in a different order. The charge carrier generating layer 12 is charged positively and irradiated directly with actinic radiation 16. The charge carrier transport layer 14 is arranged between the charge carrier generating layer 12 and a negative charge, which is located in the conductive base, not shown. Actinic radiation in turn creates 16 electron-hole pairs. The area 18 of the charge carrier generating layer 12 is discharged by electrons, while the corresponding holes migrate through the charge carrier transport layer 14 and are attracted to the negative charges. The recording material 10 'has the advantage that actinic radiation 16 does not have to penetrate the charge carrier transport layer 14, on the other hand the charge carrier generating layer 12 is not protected. There are also other Ausfiihrun q sbei- games possible, which are not shown. For example, the recording material 10 in FIG. 1 can also be exposed to actinic radiation from the opposite side, ie through the layer support.

Beispiel 1example 1

Eine Unterlage, die für die vorliegende Erfindung geeignet ist, wurde hergestellt durch Beschichten eines aluminisierten Polyäthylenterephthalatträgers mit einer Lösung eines Polyesterharzes, welches in einem Tetrahydrofuran:Toluol-Lösungsmittelgemisch im Verhältnis 9:1 (0,7 % bis 1,4 % Feststoffgehalt, Gewicht : Gewicht) gelöst wurde. Der Polyesterüberzug wurde mittels eines Meniskusbeschichtungsverfahrens aufgetragen und in einem Umluftofen getrocknet. Dann wurde Chlordianblau (0,73 G.% Feststoffgehalt) in einer Mischung von Äthylendiamin, n-Butylamin und Tetrahydrofuran im Gewichtsverhältnis 1,2:1,0:2,2 gelöst. Siliconöl wurde dann in einer Menge von 2,3 G.%, bezogen auf das Chlordianblau, zugegeben. Die resultierende Lösung wurde mittels eines Meniskusbeschichtungsverfahrens auf den mit Polyester beschichteten Träger aufgetragen, und die resultierende beschichtete Unterlage wurde in einem Umluftofen getrocknet. Die Herstellung der Ladungsträger erzeugenden Schicht aus Chlordianblau auf einer konventionellen Polyesterunterlage ist an sich bekannt.A backing suitable for the present invention was made by coating an aluminized polyethylene terephthalate support with a solution of a polyester resin which was mixed in a tetrahydrofuran: toluene solvent mixture in a ratio of 9: 1 (0.7% to 1.4% solids content, weight : Weight) was solved. The poly ester coating was applied using a meniscus coating process and dried in a forced air oven. Then chlorodian blue (0.73 g% solids content) was dissolved in a mixture of ethylene diamine, n-butylamine and tetrahydrofuran in a weight ratio of 1.2: 1.0: 2.2. Silicone oil was then added in an amount of 2.3% by weight based on the chlorordian blue. The resulting solution was applied to the polyester-coated support by a meniscus coating method and the resulting coated base was dried in a forced air oven. The production of the layer producing chlorine dian blue on a conventional polyester base is known per se.

Die neue Ladungsträgertransportschicht gemäß der Erfindung wurde hergestellt durch Mischen eines Polycarbonatharz-Bindemittels in einer Menge von 7,65 g, eines Polyesterharzes in einer Menge von 3,60 g und eines Acrylharzes in einer Menge von 2,25 g in 86,5 Tetrahydrofuran und Toluol, wobei die Lösungsmittel in einem Gewichtsverhältnis von etwa 9:1 vorliegen. Als bevorzugtes Hydrazon gemäß vorliegender Erfindung wird p-Diäthylaminobenzaldehyd-(diphenylhydrazon) in einer Menge von 9,0 g zusammen mit 0,02 g Siliconöl zugegeben. Zur Einstellung der Viskosität, die für das gewählte Beschichtungsverfahren geeignet ist, kann weiteres Tetrahydrofuran zugegeben werden. In dem vorliegenden Beispiel wurde die resultierende Lösung auf die zuvor hergestellte Ladungsträger erzeugende Schicht aufgetragen und der gesamte Film wiederum im einem Umluftofen getrocknet unter Erhalt eines mehrschichtigen elektrophotographischen Aufzeichnungsmaterials. Das elektrophotographische Aufzeichnungsmaterial wurde getestet, indem die Oberfläche auf -870 Volt im Dunkeln aufgeladen wurde, das geladene elektrophotographische Aufzeichnungsmaterial mit Licht, das in kommerziellen elektrophotographischen Geräten angewendet wird, unter verschiedenen Bedingungen der Lichtintensität belichtet und indem die Lichtintensität, die erforderlich ist, um das Aufzeichnungsmaterial auf eine Spannung von -150 Volt innerhalb 454 ms unter den angegebenen Bedingungen zu entladen, bestimmt wurde. Es wurde festgestellt, daß zur Entladung des Aufzeichnungsmaterials des vorliegenden Beispiels 1,10 µJ/cm2 erforderlich waren. Dieser Wert zeigt einen ausgezeichneten Löchertransport an. Elektrophotographische Aufzeichnungsmaterialien, die mit denen der vorliegenden Beipiele identisch sind, wurden in kommerziellen Kopiergeräten getestet und ergaben ausgezeichnete Ergebnisse hinsichtlich des Ladungstransports, der Widerstandsfähigkeit gegen Tonerfilmbildung, der physikalischen Widerstandsfähigkeit gegen Abnutzung, der Langzeitstabilität elektrischer und physikalischer Eigenschaften und des Arbeitens bei niedriger Temperatur.The new charge carrier transport layer according to the invention was produced by mixing a polycarbonate resin binder in an amount of 7.65 g, a polyester resin in an amount of 3.60 g and an acrylic resin in an amount of 2.25 g in 86.5 tetrahydrofuran and Toluene, the solvents being in a weight ratio of about 9: 1. As a preferred hydrazone according to the present invention, p-diethylaminobenzaldehyde (diphenylhydrazone) is added in an amount of 9.0 g together with 0.02 g of silicone oil. Further tetrahydrofuran can be added to adjust the viscosity, which is suitable for the chosen coating method. In the present example, the resulting solution was applied to the previously produced carrier generation layer and the entire film was again dried in a forced air oven to obtain a multilayer electrophotographic recording material. The electrophotographic material was tested by charging the surface to -870 volts in the dark, the charged electrophotographic material with light used in commercial electrophotographic equipment under various conditions of light intensity and by determining the light intensity required to discharge the recording material to a voltage of -150 volts within 454 ms under the specified conditions. It was found that 1.10 µJ / cm 2 was required to discharge the recording material of the present example. This value indicates excellent hole transport. Electrophotographic recording materials identical to those of the present examples have been tested in commercial copiers and have given excellent results in terms of charge transport, resistance to toner filming, physical resistance to wear, long-term stability of electrical and physical properties and low temperature operation.

Beispiele 2 a - fExamples 2 a - f

Mehrschichtige elektrophotographische Aufzeichnungsmateria- lien, die dem in Beispiel 1 hergestellten ähnlich sind, wurden hergestellt mit unterschiedlichen Harzen in unterschiedlichen Mengen in der Ladungsträgertransportschicht.

Figure imgb0019
Multilayered electrophotographic Aufzeichnun g smateria- lien which are prepared in Example 1 similar to that made with different resins in different amounts in the charge carrier transport layer.
Figure imgb0019

Versuche, die wie in Beispiel 1 angegeben durchgeführt wurden, ergaben folgende Ergebnisse:

Figure imgb0020
Experiments carried out as indicated in Example 1 gave the following results:
Figure imgb0020

Beispiel 3Example 3

Ein mehrschichtiges elektrophotographisches Aufzeichnungsmaterial, das dem im Beispiel 1 ähnlich ist, wurde hergestellt mit der Ausnahme, daß die Lösung zur Herstellung der Ladungsträgertransportschicht 14,5 g Arcylharz als einziges Bindemittel und 14,5 g E-Diäthylaminobenzaldehyd-(diphenylhydrazon) enthielt. Bei einer Prüfung des Aufzeichnungsmaterials wie in Beispiel 1 ergab sich, daß 3,0 µJ/cm2 Lichtenergie erforderlich waren, um das Aufzeichnungsmaterial von einer Spannung im Dunkeln von -870 V auf -150 V bei einer Ansprechzeit auf Belichtung von 454 ms zu entladen.A multilayer electrophotographic recording material similar to that in Example 1 was prepared except that the solution for preparing the charge carrier transport layer contained 14.5 g of acrylic resin as the sole binder and 14.5 g of E-diethylaminobenzaldehyde (diphenylhydrazone). When the recording material was tested as in Example 1, it was found that 3.0 µJ / cm 2 of light energy was required to discharge the recording material from a voltage in the dark from -870 V to -150 V with a response time to exposure of 454 ms .

Beispiel 4Example 4

Ein mehrschichtiges elektrophotographisches Aufzeichnungsmaterial, das dem in Beispiel 1 hergestellten ähnlich ist, wurde hergestellt mit der Ausnahme, daß ein anderes Acrylharz verwendet wurde. Bei einer Prüfung wie in Beispiel 1 ergab sich, daß 1,16 µJ/cm2 Lichtenergie erforderlich waren, um das Aufzeichnungsmaterial von einer Spannung im Dunkeln von -870 V auf -150 V bei einer Ansprechzeit auf Belichtung von 454 ms zu entladen.A multilayer electrophotographic recording material similar to that prepared in Example 1 was made except that a different acrylic resin was used. When tested as in Example 1, it was found that 1.16 µJ / cm 2 of light energy was required to discharge the recording material from a voltage in the dark from -870 V to -150 V with a response time to exposure of 454 ms.

Beispiele 5 a - eExamples 5 a - e

Mehrschichtige elektrophotographische Aufzeichnungsmaterialien, die denen von Beispiel 2 ähnlich waren, wurden hergestellt mit der Ausnahme, daß die folgenden Polyesterharze anstelle des dort angegebenen Polyesterharzes verwendet wurden.

Figure imgb0021
Multilayer electrophotographic recording materials similar to that of Example 2 were prepared except that the following polyester resins were used in place of the polyester resin specified therein.
Figure imgb0021

Ergebnisse, die denen von Beispiel 2e ähnlich waren, wurden in jedem Fall erhalten.Results similar to those of Example 2e were obtained in each case.

Beispiele 6 a - kExamples 6 a - k

Mehrschichtige elektrophotographische Aufzeichnungsmaterialien, die dem in Beispiel 1 ähnlich sind, wurden hergestellt mit der Ausnahme, daß die zuerst aufgetragenen Klebstoffschichten mit anderen Harzen als dem dort angegebenen Polyester, aber in ähnlichen Mengen hergestellt wurden. Jedes Aufzeichnungsmaterial wurde auf -870 V aufgeladen und auf -150 V in 146 ms entladen. Die nachfolgend angegebenen Belichungsenergien in µJ/cm2 waren erforderlich.

Figure imgb0022
Multilayer electrophotographic recording materials similar to that in Example 1 were made except that the adhesive layers applied first were made with resins other than the polyester specified there, but in similar amounts. Each recording material was charged to -870 V and discharged to -150 V in 146 ms. The exposure energies given below in µJ / cm 2 were required.
Figure imgb0022

Beispiele 7a und 7bExamples 7a and 7b

Mehrschichtige elektrophotographische Aufzeichnungsmaterialien, die dem im Beispiel 2e hergestellten ähnlich sind, wurden hergestellt mit der Ausnahme, daß 5,78 g p-Diäthylaminobenzaldehyd-(diphenylhydrazon) in der Lösung der Ladungsträgertransportschicht in Beispiel 7a und 7,27 g in Beispiel 7b verwendet wurden. Bei einer Prüfung unter den gleichen Entladungsspannungen und den gleichen Ansprechzeiten auf Belichung wie in Beispiel 1 wurde gefunden, daß für das elektrophotographische Aufzeichungsmaterial von Beispiel 7a 1,4 µJ/cm2 Lichtenergie und für dasjenige von Beispiel 7b 1,3 µJ/cm2 erforderlich waren.Multilayer electrophotographic recordings similar to that prepared in Example 2e were made except that 5.78 g of p-diethylaminobenzaldehyde (diphenylhydrazone) was used in the charge transport layer solution in Example 7a and 7.27 g in Example 7b. When tested under the same discharge voltages and response times to exposure as in Example 1, it was found that 1.4 µJ / cm 2 of light energy was required for the electrophotographic recording material of Example 7a and 1.3 µJ / cm 2 for that of Example 7b were.

Beispiel 8Example 8

Ein mehrschichtiges elektrophotographisches Aufzeichnungsmaterial, das dem von Beispiel 2a ähnlich war, wurde hergestellt mit der Ausnahme, daß 13,5 g p-Diäthylaminobenzaldehyd-(diphenylhydrazon) in der Lösung der Ladunasträgertransportschicht verwendet wurden. Bei einer Prüfung, die wie im Beispiel 1 angegeben durchgeführt wurde, waren 1,37 µJ/cm2 Lichtenergie erforderlich, um das Aufzeichnungsmaterial von einer Dunkelspannung von -870 V auf -150 V bei einer Ansprechzeit auf Belichtung von 146 ms zu entladen.A multilayer electrophotographic recording medium similar to that of Example 2a was made except that 13.5 g of p-diethylaminobenzaldehyde (diphenylhydrazone) was dissolved in the solution of the Laduna carrier trans port layer were used. In a test carried out as indicated in Example 1, 1.37 µJ / cm 2 of light energy was required to discharge the recording material from a dark voltage of -870 V to -150 V with a response time to exposure of 146 ms.

Beispiel 9Example 9

Ein mehrschichtiges elektrophotographisches Aufzeichnungsmaterial, das dem in Beispiel 2a ähnlich war, wurde hergestellt mit der Ausnahme, daß 20,25 g p-Diäthylaminobenzaldehyd-(diphenylhydrazon) in der Lösung der Ladungsträgertransportschicht verwendet wurden. Bei einer Prüfung, die wie in Beispiel 1 angegeben durchgeführt wurde, ergab sich, daß 1,37 µJ/cm2 Lichtenergie erforderlich waren, um das Aufzeichnungsmaterial von einer Dunkelspannung von -870 V auf -150 V bei einer Ansprechzeit auf Belichtung von 146 ms zu entladen.A multilayer electrophotographic recording material similar to that in Example 2a was prepared except that 20.25 g of p-diethylaminobenzaldehyde (diphenylhydrazone) was used in the solution of the charge transport layer. When tested as described in Example 1, it was found that 1.37 µJ / cm 2 of light energy was required to switch the recording material from a dark voltage of -870 V to -150 V with a response time to exposure of 146 ms to unload.

Beispiele 10a - dExamples 10a-d

Mehrschichtige elektrophotographische Aufzeichnungsmaterialien, die dem in Beispiel 2a angegebenen ähnlich waren, wurden hergestellt mit der Ausnahme, daß alternativ die folgenden Hydrazonverbindungen in den gleichen Mengen in der Lösung der Ladungsträgertransportschicht verwendet wurden:Multilayer electrophotographic recordings similar to that given in Example 2a were made except that alternatively the following hydrazone compounds were used in the same amounts in the charge transport layer solution:

Beispielexample

  • 10a o-Hethyl-p-dimethylaminobenzaldehyd-(diphenylhydrazon)10a o-ethyl-p-dimethylaminobenzaldehyde- (diphenylhydrazone)
  • 10b o-Äthoxy-p-diäthylaminobenzaldehyd-(diphenylhydrazon)10b o-ethoxy-p-diethylaminobenzaldehyde (diphenylhydrazone)
  • 10d o-Methyl-p-diäthylaminobenzaldehyd-(diphenylhydrazon)10d o-methyl-p-diethylaminobenzaldehyde (diphenylhydrazone)
  • 10d p-Dimethylaminobenzaldehyd-(diphenylhydrazon)10d p-dimethylaminobenzaldehyde (diphenylhydrazone)

Die folgenden Ergebnisse wurden erhalten:

Figure imgb0023
The following results were obtained:
Figure imgb0023

Beispiele 11a - cExamples 11a-c

Mehrschichtige elektrophotographische Aufzeichnungsmaterialien, die dem in Beispiel 2a angegebenen ähnlich waren, wurden hergestellt mit der Ausnahme, daß 13,5 g der folgenden Hydrazone in der Lösung der Ladungsträgertransportschicht verwendet wurden:A multilayered electrophotographic recording materials which were similar to that given in Example 2 were prepared with the exception that 13.5 g of the following hydrazones in the solution of the charge carrier-p were used ortschicht:

Beispielexample

  • 11a o-Methyl-p-dimethylaminobenzaldehyd-(diphenylhydrazon)11a o-methyl-p-dimethylaminobenzaldehyde- (diphenylhydrazone)
  • 11b o-Äthoxy-p-diäthylaminobenzaldehyd-(diphenylhydrazon)11b o-ethoxy-p-diethylaminobenzaldehyde (diphenylhydrazone)
  • 11c o-Methyl-p-diäthylaminobenzaldehyd-(diphenylhydrazon)11c o-methyl-p-diethylaminobenzaldehyde- (diphenylhydrazone)

Die folgenden Ergebnisse wurden erhalten:

Figure imgb0024
The following results were obtained:
Figure imgb0024

Beispiele 12a - cExamples 12a-c

Mehrschichtige elektrophotographische Aufzeichnungsmaterialien, die dem in Beispiel 1 ähnlich waren, wurden hergestellt mit der Ausnahme, daß die Lösung der Ladungsträgertransportschicht 6,75 g Polyesterharz, 6,75 g Polycarbonatharz und 13,5 g der nachfolgend angegebenen Hydrazonverbindungen enthielt:Multilayer electrophotographic recording materials similar to that in Example 1 were prepared with the exception that the solution of the charge carrier transport layer contained 6.75 g of polyester resin, 6.75 g of polycarbonate resin and 13.5 g of the hydrazone compounds given below:

Beispielexample

  • 12a p-Dimethylaminobenzaldehyd-(diphenylhydrazon)12a p-dimethylaminobenzaldehyde (diphenylhydrazone)
  • 12b p-Dipropylaminobenzaldehyd-(diphenylhydrazon)12b p-dipropylaminobenzaldehyde (diphenylhydrazone)
  • 12c p-Dibutylaminobenzaldehyd-(diphenylhydrazon)12c p-dibutylaminobenzaldehyde (diphenylhydrazone)

Die folgenden Ergebnisse wurden erhalten:

Figure imgb0025
The following results were obtained:
Figure imgb0025

Beispiel 13Example 13

Auf eine Art, die der in Beispiel 1 angegebenen ähnlich ist, wird Hydroxysquarylium in einer Menge von 1 g in einem Lösungsmittelgemisch aus 1 ml Äthylendiamin, 5 ml Propylamin und 24 ml Tetrahydrofuran gelöst und mittels eines Meniskusbeschichtungsverfahrens auf eine aluminisierte Polyesterunterlage aufgetragen und getrocknet unter Erhalt einer Ladungsträger erzeugenden Schicht. Eine Ladungsträgertransportschicht gemäß der vorliegenden Erfindung wurde hergestellt durch Meniskusbeschichten der mit der Ladungsträger erzeugenden Schicht beschichteten Unterlage mit einer Lösung von 8,12 g eines Polycarbonatharzes und 8,12 g p-Diäthylaminobenzaldehyd-(diphenylhydrazon) in einer 9:1-Mischung Tetrahydrofuran und Toluol und Trocknen unter Ausbildung eines mehrschichtigen elektrophotographischen Aufzeichnungsmaterials. Bei einer Prüfung wie in Beispiel 1 ergab sich, daß 1,40 µJ/cm2 Lichtenergie erforderlich waren, um das Aufzeichnungsmaterial von einer Spannung im Dunkeln von -870 V auf -150 V bei einer Ansprechzeit auf Belichtung von 146 ms zu entladen.In a manner similar to that given in Example 1, hydroxysquarylium in an amount of 1 g is dissolved in a mixed solvent of 1 ml of ethylenediamine, 5 ml of propylamine and 24 ml of tetrahydrofuran and applied to an aluminized polyester base by a meniscus coating method and dried to obtain a layer generating charge carriers. A charge carrier transport layer in accordance with the present invention was prepared by meniscus coating the carrier-coated layer with a solution of 8.12 g of a polycarbonate resin and 8.12 g of p-diethylaminobenzaldehyde (diphenylhydrazone) in a 9: 1 mixture of tetrahydrofuran and toluene and drying to form a multilayer electrophotographic recording material. During an exam As in Example 1, it was found that 1.40 µJ / cm 2 of light energy was required to discharge the recording material from a voltage in the dark from -870 V to -150 V with a response time to exposure of 146 ms.

Beispiel 14Example 14

Ein mehrschichtiges elektrophotographisches Aufzeichnungsmaterial, das dem in Beispiel 13 ähnlich ist, wurde hergestellt mit der Ausnahme, daß o-Äthoxy-p-diäthylaminobenzaldehyd-(diphenylhydrazon) in der Lösung der Ladungsträgertransportschicht verwendet wurde. Bei einer Prüfung wie in Beispiel 1 ergab sich, daß 1,02 µJ/cm2 Lichtenergie erforderlich waren, um das Aufzeichnungsmaterial von einer Spannung im Dunkeln von -870 V auf -150 V bei einer Ansprechzeit auf Belichtung von 146 ms zu entladen.A multilayer electrophotographic recording material similar to that in Example 13 was made except that o-ethoxy-p-diethylaminobenzaldehyde (diphenylhydrazone) was used in the charge transport layer solution. When tested as in Example 1, it was found that 1.02 µJ / cm 2 of light energy was required to discharge the recording material from a voltage in the dark from -870 V to -150 V with a response time to exposure of 146 ms.

Beispiel 15Example 15

Es wurde ein nehrschichtiges elektrophotographisches Aufzeichnungsmaterial, das dem in Beispiel 13 ähnlich ist, hergestellt mit der Ausnahme, daß die Lösung der Ladungsträger erzeugenden Sch:.cht 0,85 g Hydroxysquarylium und 0,15 g Methylsquarylium enunielt. Bei einer Prüfung wie in Beispiel 1 ergab sich, laß 0,86 µJ/cm2 Lichtenergie erforderlich waren, um das Atfzeichnungsmaterial von einer Spannung im Dunkeln von -870 auf -150 V bei einer Ansprechzeit auf Belichtung von 116 ms zu entladen.A multi-layer electrophotographic recording material similar to that in Example 13 was prepared except that the charge generation solution contained 0.85 g of hydroxysquarylium and 0.15 g of methylsquarylium. When tested as in Example 1, it was found that 0.86 µJ / cm 2 of light energy was required to discharge the recording material from a voltage in the dark from -870 to -150 V with a response time to exposure of 116 ms.

Beispiel 16Example 16

Ein mehrschichtiges erektrophotographisches Aufzeichnungsmaterial, das dem in eispiel 13 ähnlich war, wurde hergestellt mit der Ausnahre, daß die Lösung der Ladungsträger erzeugenden Schicht 0,15 g Hydroxysquarylium und 0,15 g Methylsquarylium und die Lösung der Ladungsträgertransportschicht 8,12 g Polycarbonatharz und 5,42 g p-Diäthylaminobenzaldehyd-(diphenylhydrazon) enthielt. Bei einer Prüfung wie in Beispiel 1 ergab sich, daß 1,10 µJ/cm2 Lichtenergie erforderlich waren, um das Aufzeichnungsmaterial von einer Spannung im Dunkeln von -870 V auf -150 V bei einer Ansprechzeit auf Belichtung von 146 ms zu entladen.A multilayered electrophotographic recording material similar to that in Example 13 was prepared except that the carrier generation layer solution was 0.15 g of hydroxysquarylium and 0.15 g Methylsquarylium and the solution of the charge carrier transport layer contained 8.12 g of polycarbonate resin and 5.42 g of p-diethylaminobenzaldehyde (diphenylhydrazone). When tested as in Example 1, it was found that 1.10 µJ / cm 2 of light energy was required to discharge the recording material from a voltage in the dark from -870 V to -150 V with a response time to exposure of 146 ms.

Beispiel 17Example 17

Ein mehrschichtiges elektrophotographisches Aufzeichnungsmaterial wurde hergestellt, indem auf eine Ladungsträger erzeugende Schicht, welche durch Vakuumabscheidung von Selen und Tellur hergestellt worden war, eine Ladungsträgertransportschicht aus einer Lösung von 6,75 g Polyesterharz, 6,75 g Polycarbonatharz und 13,5 g p-Diäthylaminobeazalde- hyd-(diphenylhydrazon) aufgetragen wurde. Bei einer Prüfung wie in Beispiel 1 ergab sich, daß 2,0 µJ/cm2 Lichtrnergie erforderlich waren, um das Aufzeichnungsmaterial vcn einer Spannung im Dunkeln von -800 V auf -300 V bei eine: Ansprechzeit auf Belichtung von 454 ms zu entladen.A multilayer electrophotographic recording material was prepared by adding a charge transport layer composed of a solution of 6.75 g polyester resin, 6.75 g polycarbonate resin and 13.5 g p-diethylaminobeazalde to a charge-generating layer which was produced by vacuum deposition of selenium and tellurium - hyd (diphenylhydrazone) was applied. When tested as in Example 1, it was found that 2.0 µJ / cm 2 of light energy was required to discharge the recording material from a voltage in the dark from -800 V to -300 V with a response time to exposure of 454 ms.

Aus den zuvor angegebenen Beispielen ist ersichtlich, daß die Ladungsträgertransportschicht vom p-Typ gemäß der vorliegenden Erfindung mit verschiedenen Typen von Hatzbindemitteln wie auch einer Vielzahl von Hydrazonverbiniungen des angegebenen Typs hergestellt werden kann. Sowchl organische wie auch anorganische Ladungsträger erzeugende Schichten sind mit der Ladungsträgertransportschich gemäß der vorliegenden Erfindung verwendbar, und an sich bekannte verschiedene Kombinationen von Lösungsmitreln, polymeren Bindemitteln und dergleichen können ve vendet werden. Bestimmte Hydrazonverbindungen zeigen, wenn sie in relativ hohen Konzentrationen verwendet werdei, eine Tendenz zur Kristallisation, wodurch ihre Ladungsträgertransportfunktion abnimmt. Wenn jedoch geringere Mengen verwendet werden, werden brauchbare Ergebnisse erhalten. Eine Auswahl in dieser Richtung kann durch den Fachmann getroffen werden. Die elektrophotographischen Aufzeichnungsmaterialien mit der erfindungsgemäßen Ladungsträgertransportschicht zeigen ein ausgezeichnetes Verhältnis von Empfindlichkeit, insbesondere bei niedrigen Temperaturen, Adhäsior. zu benachbarten Schichten und Widerstandsfähigkeit gegen Aechanische Abnutzung wiederum bei verschiedenen Temperaturen. Die Aufzeichnungsmaterialien zeigen auch hinsichtli.h der Alterung ausgezeichnete Eigenschaften und weisin eine beträchtliche Widerstandsfähigkeit gegen Tonerf.Imbildung auf.From the examples given above it can be seen that the p-type charge carrier transport layer according to the present invention can be produced with various types of scavengers as well as a large number of hydrazone compounds of the specified type. Both organic and inorganic charge generation layers can be used with the charge transport layer according to the present invention, and various combinations of solvents, polymeric binders, and the like, known per se, can be used. Certain hydrazone compounds, when used in relatively high concentrations, tend to crystallize, thereby reducing their charge carriers transport function decreases. However, if smaller amounts are used, useful results will be obtained. A selection in this direction can be made by a person skilled in the art. The electrophotographic recording materials with the charge carrier transport layer according to the invention show an excellent ratio of sensitivity, especially at low temperatures, to adhesive. to neighboring layers and resistance to mechanical wear at different temperatures. The recording materials also show excellent properties with regard to aging and have a considerable resistance to toner formation.

Claims (12)

1. Elektrophotographisches Aufzeichnungsmaterial bestehend aus einem elektrisch leitenden Schichtträger, einer Ladungsträger erzeugenden Schicht und einer Ladungsträgertransportschicht, dadurch gekennzeichnet, daß die Ladungsträgertransportschicht als Ladungen transportierende Verbindung ein Hydrazon der allgemeinen Formel
Figure imgb0026
in der die Reste R1 = -O(CH2)yCH3; y = 0,1
Figure imgb0027
Figure imgb0028
; x = 0, 1 , 2, 3
Figure imgb0029
-H R 2 = -OC2H5; -CH3; -C2H5; -H R3 = -H; -OC 2 H5 R4 = -H; -CH3; -C 2 H 5 R5 = -H; -CH3 R 6 = -C6H5; -CH2-C6H5; -CH3; n-C4H9 R7 = -C6H5; -CH3
Figure imgb0030
bedeuten, und ein polymeres Bindemittel enthält. 1. Electrophotographic recording material consisting of an electrically conductive support, a charge-generating layer and a charge transport layer, characterized in that the charge transport layer as a charge-transporting compound is a hydrazone of the general formula
Figure imgb0026
 in which the leftovers R 1 = -O (CH 2 ) y CH 3 ; y = 0.1
Figure imgb0027
Figure imgb0028
 ; x = 0, 1, 2, 3
Figure imgb0029
 -H R 2 = -OC 2 H 5 ; -CH 3 ; -C 2 H 5 ; -H R 3 = -H; -O C 2 H 5 R4 = -H; -CH 3 ; - C 2 H 5 R 5 = - H; -C H 3 R 6 = -C 6 H 5 ; -CH 2 -C 6 H 5 ; -CH 3 ; nC 4 H 9 R 7 = -C 6 H 5 ; -CH 3rd
Figure imgb0030
 mean, and contains a polymeric binder. 2. Elektrophotographisches Aufzeichnungsmaterial nach Anspruch 1, dadurch gekennzeichnet, daß die Ladungsträgertransportschicht Hydrazone aus der Gruppe von p-Diäthylaminobenzaldehyd-(diphenylhydrazon), o-Äthoxy-p-diäthylaminobenzaldehyd-(diphenylhydrazon), o-Methyl-p-diäthylaminobenzaldehyd-(diphenylhydrazon), o-Methyl-p-dimethylaminobenzaldehyd-(diphenylhydrazon), p-Dipropylaminobenzaldehyd-(diphenyihydrazon), p-Diäthylaminobenzaldehyd-(benzylphenylhydrazon), p-Dibutyl- aminobenzaldehyd-(diphenylhydrazon) und p-Dimethylamino- benzaldehyd-(diphenylhydrazon) enthält.2. Electrophotographic recording material according to claim 1, characterized in that the charge carrier transport layer hydrazone from the group of p-diethylaminobenzaldehyde (diphenylhydrazone), o-ethoxy-p-diethylaminobenzaldehyde (diphenylhydrazone), o- Methyl-p-diethylaminobenzaldehyde- (diphenylhydrazone), o-methyl-p-dimethylaminobenzaldehyde- (diphenylhydrazone), p-dipropylaminobenzaldehyde- (diphenyihydrazone), p-diethylaminobenzaldehyde- (benzylphenylhydrazone), p-dibutyl- (diphenyl) aminobenzene Dimethylamino-benzaldehyde (diphenylhydrazone) contains. 3. Elektrophotographisches Aufzeichnungsmaterial nach Anspruch 1, dadurch gekennzeichnet, daß die Ladungsträgertransportschicht als polymeres Bindemittel ein Polycarbonatharz, ein Polyesterharz oder ein Acrylharz, oder Mischungen derselben enthält.3. Electrophotographic recording material according to claim 1, characterized in that the charge carrier transport layer contains as a polymeric binder a polycarbonate resin, a polyester resin or an acrylic resin, or mixtures thereof. 4. Elektrophotographisches Aufzeichnungsmaterial nach den Ansprüchen 1, 2 und 3, dadurch gekennzeichnet, daß die Ladungsträgertransportschicht p-Diäthylaminobenzaldehyd-(diphenylhydrazon) und ein Polycarbonat-, Polyester-oder Acrylharz, oder Mischungen derselben enthält.4. Electrophotographic recording material according to claims 1, 2 and 3, characterized in that the charge carrier transport layer contains p-diethylaminobenzaldehyde (diphenylhydrazone) and a polycarbonate, polyester or acrylic resin, or mixtures thereof. 5. Elektrophotographisches Aufzeichnungsmaterial nach den Ansprüchen 1 und 4, dadurch gekennzeichnet, daß die Ladungsträgertransportschicht eine Dicke zwischen 7 und 35 µm aufweist.5. Electrophotographic recording material according to claims 1 and 4, characterized in that the charge carrier transport layer has a thickness between 7 and 35 microns. 6. Elektrophotographisches Aufzeichnungsmaterial nach den Ansprüchen 1 bis 5, dadurch gekennzeichnet, daß die Ladungsträgertransportschicht vom p-Typ ist.6. Electrophotographic recording material according to claims 1 to 5, characterized in that the charge carrier transport layer is of the p-type. 7. Elektrophotographisches Aufzeichnungsmaterial nach Anspruch 1, dadurch gekennzeichnet, daß die Ladungsträgertransportschicht auf der Ladungsträger erzeusenden Schicht oder zwischen derselben und dem elektrisch leitenden Schichtträger angeordnet ist.7. Electrophotographic recording material according to claim 1, characterized in that the charge carrier transport layer is arranged on the charge carrier generating layer or between the same and the electrically conductive layer carrier. 8. Elektrophotographisches Aufzeichnungsmaterial nach. Anspruch 1, dadurch gekennzeichnet, daß die Ladungsträger erzeugende Schicht einen Photoleiter aus der Gruppe von Selen, Tellur oder deren Legierungen; Verbindungen von Elementen der Gruppe II b mit denen der Gruppe VI a des periodischen Systems; von Cyanin-, Disazo-, Phthalocyaninverbindungen und Methinfarbstoffen, die sich von der Quadratsäure ableiten, enthält.8. Electrophotographic recording material after. Claim 1, characterized in that the charge generating layer is a photoconductor from the group of selenium, tellurium or their alloys; Connections of elements of group II b with those of group VI a of the periodic system; of cyanine, disazo, phthalocyanine compounds and methine dyes derived from squaric acid. 9. Elektrophotographisches Aufzeichnungsmaterial nach Anspruch 8, dadurch gekennzeichnet, daß die Ladungsträger erzeugende Schicht Chlordianblau, Methylsquarylium und/oder Hydroxysquarylium enthält.9. Electrophotographic recording material according to claim 8, characterized in that the charge-generating layer contains chlorodian blue, methylsquarylium and / or hydroxysquarylium. 10. Elektrophotographisches Aufzeichnungsmaterial nach einem oder mehreren der Ansprüche 1 bis 9, dadurch gekennzeichnet, daß die Ladungsträger erzeugende Schicht eine Dicke zwischen 0,05 und 0,2 µm und die Ladungsträgertransportschicht eine Dicke von mindestens 5 µm aufweisen.10. Electrophotographic recording material according to one or more of claims 1 to 9, characterized in that the charge carrier generating layer has a thickness between 0.05 and 0.2 µm and the charge carrier transport layer has a thickness of at least 5 µm. 11. Elektrophotographisches Aufzeichnungsmaterial nach den Ansprüchen 1 und 8, dadurch gekennzeichnet, daß die Ladungsträger erzeugende Schicht gegenüber aktinischer Strahlung mit einer Wellenlänge größer 390 nm empfindlich und die Ladungsträgertransportschicht für diese Strahlung durchlässig ist.11. Electrophotographic recording material according to claims 1 and 8, characterized in that the charge carrier generating layer is sensitive to actinic radiation with a wavelength greater than 390 nm and the charge carrier transport layer is transparent to this radiation. 12. Verwendung des elektrophotographischen Aufzeichnungsmaterials nach den Ansprüchen 1 bis 11 in einem elektrophotographischen Kopierverfahren.12. Use of the electrophotographic recording material according to claims 1 to 11 in an electrophotographic copying process.
EP78101087A 1977-10-17 1978-10-06 Electrophotographic recording material and its application in a copying process Expired EP0001599B1 (en)

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FR2471625A1 (en) * 1979-12-08 1981-06-19 Ricoh Kk ELECTROPHOTOGRAPHIC ELEMENT COMPRISING A CONDUCTIVE SUBSTRATE AND A PHOTOSENSITIVE LAYER CONTAINING A HYDRAZONE DERIVATIVE
DE3046240A1 (en) * 1979-12-08 1981-09-17 Ricoh Co., Ltd., Tokyo ELECTROPHOTOGRAPHIC ELEMENT
DE3124396A1 (en) * 1980-06-24 1982-07-22 Fuji Photo Film Co., Ltd., Minami-Ashigara, Kanagawa ELECTROPHOTOGRAPHIC PHOTO RECEPTOR
US4410615A (en) * 1980-10-23 1983-10-18 Konishiroku Photo Industry Co., Ltd. Layered electrophotographic photosensitive element having hydrazone charge transport layer
DE3150068A1 (en) * 1980-12-17 1982-07-22 Canon K.K., Tokyo Light-sensitive element for electrophotographic purposes
DE3150265A1 (en) * 1980-12-19 1982-08-26 Fuji Photo Film Co., Ltd., Minami-Ashigara, Kanagawa ELECTROPHOTOGRAPHICALLY SENSITIVE MATERIALS
US4415640A (en) * 1981-02-19 1983-11-15 Konishiroku Photo Industry Co., Ltd. Electrophotographic element with fluorenylidene hydrazone compounds
EP0069397B1 (en) * 1981-07-07 1985-02-20 Mitsubishi Kasei Corporation Electrophotographic plate
DE3245637A1 (en) * 1981-12-09 1983-06-16 Canon K.K., Tokyo LIGHT SENSITIVE ELEMENT FOR ELECTROPHOTOGRAPHIC PURPOSES
DE3245637C2 (en) * 1981-12-09 1990-02-01 Canon K.K., Tokio/Tokyo, Jp
DE3245637C3 (en) * 1981-12-09 1998-07-09 Canon Kk Electrophotographic recording material
EP0084147A2 (en) * 1982-01-16 1983-07-27 BASF Aktiengesellschaft Phenyl hydrazones and their use
EP0084147A3 (en) * 1982-01-16 1984-09-05 Basf Aktiengesellschaft Phenyl hydrazones and their use
EP0366308A2 (en) * 1988-10-28 1990-05-02 Lexmark International, Inc. Organic photoconductors with reduced fatigue
EP0366308A3 (en) * 1988-10-28 1991-04-03 Lexmark International, Inc. Organic photoconductors with reduced fatigue
FR2647563A1 (en) * 1989-05-27 1990-11-30 Japat Ltd ELECTROPHOTOGRAPHIC PHOTORECEPTOR, AND COMPOUNDS AND COMPOSITION COMPRISING THE SAME
US8268457B2 (en) 2006-06-05 2012-09-18 Idemitsu Kosan Co., Ltd. Organic electroluminescent device and material for organic electroluminescent device

Also Published As

Publication number Publication date
JPS5459143A (en) 1979-05-12
CA1108914A (en) 1981-09-15
EP0001599B1 (en) 1981-10-21
AR222158A1 (en) 1981-04-30
AU3719478A (en) 1979-12-20
JPS5542380B2 (en) 1980-10-30
US4150987A (en) 1979-04-24
AU520312B2 (en) 1982-01-28
DE2861209D1 (en) 1981-12-24

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