US3287115A - Process for the sensitization of photoconductors - Google Patents

Process for the sensitization of photoconductors Download PDF

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US3287115A
US3287115A US426364A US42636465A US3287115A US 3287115 A US3287115 A US 3287115A US 426364 A US426364 A US 426364A US 42636465 A US42636465 A US 42636465A US 3287115 A US3287115 A US 3287115A
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photoconductor
acid
electron
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Hoegl Helmut
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Azoplate Corp
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Azoplate Corp
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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
    • G03G5/0601—Acyclic or carbocyclic compounds
    • G03G5/0612—Acyclic or carbocyclic compounds containing 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
    • 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
    • G03G5/0605—Carbocyclic compounds
    • 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
    • G03G5/0609—Acyclic or carbocyclic compounds containing oxygen
    • 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
    • G03G5/0614—Amines
    • 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
    • G03G5/0627—Heterocyclic compounds containing one hetero ring being five-membered
    • G03G5/0629—Heterocyclic compounds containing one hetero ring being five-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
    • G03G5/0627—Heterocyclic compounds containing one hetero ring being five-membered
    • G03G5/0631—Heterocyclic compounds containing one hetero ring being five-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
    • G03G5/0622—Heterocyclic compounds
    • G03G5/0624—Heterocyclic compounds containing one hetero ring
    • G03G5/0627—Heterocyclic compounds containing one hetero ring being five-membered
    • G03G5/0633—Heterocyclic compounds containing one hetero ring being five-membered containing three 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
    • G03G5/0622—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
    • G03G5/0698—Compounds of unspecified structure characterised by a substituent only
    • 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
    • G03G5/07—Polymeric photoconductive materials
    • G03G5/071—Polymeric photoconductive materials obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • G03G5/072—Polymeric photoconductive materials obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising pending monoamine groups
    • G03G5/073—Polymeric photoconductive materials obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising pending monoamine groups comprising pending carbazole groups
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/001—Electric or magnetic imagery, e.g., xerography, electrography, magnetography, etc. Process, composition, or product
    • Y10S430/10—Donor-acceptor complex photoconductor

Definitions

  • Electrophotographic material normally consists of a support on which there is a photoconductive substance, this coating being provided in the absence of light with an electrostatic charge. Then, the material is exposed to light behind a master, or an episcopic image is projected thereon, so that an electrostatic image is formed which corresponds to the master. This image is developed by being briefly contacted with a resin powder, whereupon a visible image is formed which is fixed by heating or by the action of solvents. In this way, an image of the master which is resistant to abrasion is obtained electrophotographically.
  • the absorption maxima of the organic photoconductors are mostly in the ultra-violet region of the spectrum.
  • the addition of these dyestuff sensitizers achieves the result that the photoconductors become sensitive to visible light.
  • the dyestuff sensitizers cause a displacement of the available sensitivity from the ultraviolet region to the visible region.
  • With increased addition of dyestufi sensitizer the sensitivity to visible light at first increases rapidly, but further additions give an increase in sensitivity which is much less than would be expected, and still further additions finally give no appreciable increase in sensitivity.
  • the dyestulf sensitizers have the disadvantage that they color the coating considerably.
  • the maximum achievable increase in sensitivity can seldom be utilized because then the photoconductor coatings have an intensity of color that is undesirable.
  • Colorless or practically colorless photoconductor coatings are desired, since colored material can be employed only in special cases. If additions of dyestutf sensitizers are such as not to adversely alfect the coloring of the coating for practical purposes, the sensi tizing effect often does not meet the demands of general usage. Further, the dyestufi sensitizers have the disadvantage that they bleach out relatively quickly so that their sensitizing action tends to be lost during the storage of the electrophotographic material.
  • a process for the sensitization of photoconductor coatings has now been found in which organic substances, containing polarizing residues and being capable of serving as electron-acceptors in a molecule complex, having low molecular weight, i.e. being non-resinous, being colorless or of palecolor and having a melting point above room temperature, are added to the photoconductor coatings.
  • Substances which are primarily of interest as photoconductor coatings in accordance with the present process are those which can serve as electron donors in mole- Patented Nov. 22, 1966 cule complexes of the donor/acceptor type (known as 1r-complex) and contain at least one aromatic or heterocyclic ring, which may be substituted.
  • Such photoconductors include aromatic hydrocarbons such as naphthalene, anthracene, benzanthrene, chrysene, p -diphenylbenzene, diphenyl anthracene, p-terphenyl, p-quaterphenyl, sexiphenyl; heterocycles such as N-alkyl carbazole, thiodiphenylamine, oxadiazoles, e.g., 2,5-bis-(p-aminophenyl)-1,3,4-oxadiazole and its N-alkyl and N-acyl derivatives; triazoles such as 2,5 bis-(p-aminophenyl)- 1,3,4-triazole and its N-alkyl and N-acyl derivatives; imidazolones and imidazolthiones, e.g., 1,3,4,5-tetraphenyl-imidazolone-Z and 1,3,4,5-tetraphenyl
  • 1,3,5-triphenyl-pyrazoline 1,3,5-triphenyl-pyrazoline; hydrated imidazoles, e.g., 1,3- diphenyl-tetrahydroimidazole; oxazole derivates such as 2,5-diphenyloxazole-2- p-dimethylamino-4,5-diphenyloxazole; thiazole derivatives such as 2-p-dia1kylaminophenyl-methyl-benzthiazole; as also the following:
  • Molecule complexes are defined in H. A. Staabs Einbowung in die theoretician organische Chemie (Introduction to Theoretical Organic Chemistry), Verlag Chemie, 1959, pp. 694-707, and by L. I. Andrews, Chemical Review, vol. 54, 1954, pp. 713-777.
  • the donor/ acceptor complex (w-complexes) charge-transfer complexes which are formed from an electron-acceptor and an electron-donor are included.
  • the photoconductors are the electrondonors and the substances here called activators-to distinguish them from the dyestuff sensitizers-are the electron-acceptors.
  • the electron-donors have a low ionization energy and have a tendency to give up electrons. They are bases in the sense of the definition of acids and bases given by G. N. Lewis (H. A. Staab, as above, p. 600).
  • the electron-donors primarily concerned in the present case are the photoconductors described above. These photoconductors consist of aromatic or heterocyclic systems containing a plurality of fused rings, or, alternatively, single rings having substituents which facilitate further electrophilic substitution of the aromatic ring, socalled electron-repellent substituents, as described by L. F. and M. Fieser, Lehrbuch der organischen Chemie (Textbook of Organic Chemistry), Verlag Chemie, 1954, p. 651, Table I.
  • saturated groups e.g., alkyl groups such as methyl, ethyl, and propyl; alkoxy groups such as methoxy, ethoxy and propoxy; carbalkoxy groups such as carbmethoxy, carbethoxy and carbpropoxy; hydroxyl groups, amino groups and 1 and dialkylamino groups such as dimethylamino, diethylamino and dipropylamino.
  • the activators in accordance with the invention are compounds with a high elec-' tron-afiinity, and have a tendency to take up electrons. They are acids in the sense of Lewis definition. Such properties are possessed by substances having strongly polarizing residues or groupings such as cyano and nitro groups, halogens such as fluorine, chlorine, bromine and iodine; ketone groups, ester groups, acid anhydride groups, acid groups such as carboxyl groups or the quinone grouping. Strongly polarizing electron-attracting groups of this type are described by L. F. and M. Fieser in the Lehrbuch der organischen Chemie, Verlag Chemie, 1954, p. 651, Table I.
  • the activator substances in accordance with the present process should be of lower molecular weight, i.e. between about 50 and 5000, preferably between about 100 and 1000, because with activators of lower molecular weight it is possible for reproducible results to. be obtained insofar as sensitivity is concerned. Also, the sensitivity remains constant over rather long periods, since substances of lower molecular weight, unlike those of high molecular weight, undergo hardly any change during storage.
  • o-Chloronitrobenzene Chloracetophenone. 2-chlorocinnamic acid.
  • Mucochloric acid Mucobromic acid. Styrenedibroruide. Tetrabromo xylene.
  • Triphenylchloromethane Tetrachlcrophthalic acid. Tetrabromophthalic acid. Tetraicdophthalic acid. Tetrachlorophthalic anhydride. Tetrabromophthalic anhydride. 'letralodophthalic anhydride. Tetrachlorophthalic acid monoethylester. Tetrabromophthalic acid monoethylester. Tettraiodophthalic acid mono- Tetracyanethylene. s-Tricyano-benzene.
  • 2,4-dinitro-l-ehloronaphthalene 1,4-dinitro-naphthalene. 1,5-dinitro-naphthalene.
  • S-nitrobenzoie acid 4-nitrobenzoic acid. 3-nitro-4-ethoxy-benzoie acid. 3-nitro-2-creso1-5-sulphonic acid. -nitrobarbituric acid.
  • Picryl chloride 2,4,7-trinitro-fiuorenone. s-Trinitro-beuzene.
  • Thymoquinone The quantity of the solid, non-resinous, substantially colorless electron-acceptors (activators) which is best incorporated in the photoconductive coating to be sensitized is easily established by simple experiments.
  • photoconductive coating containing at least one photo-1 conductor and at least one solid, non-resinous, substan-' tially colorless, electron-acceptor should contain the photoconductor and electron-acceptor in proportions rang.- ing from substantially less than equal amounts to a substantial excess of the photoconductor with respect to the electron-acceptor.
  • the optimum of the proportions varies somewhat according to the substance used. Generally, minor amounts are used, i.e. from about.0.1 to
  • a further increase in the photoconductivity may be obtained by the addition of dye-. stuff sensitizers in the same amounts as in the photoconductor-activator mixtures in which the photoconductor is present in a major amount.
  • the coatings are treated in other respects in accordance with the known processes of electrophotography, i.e. the photoconductor substances are used in the form of thin, coherent homogeneous coatings on a supporting material.
  • the materials used as supports are primarily metals, such as aluminum, zinc, and copper; cellulose products, such as paper and cellulose hydrate; plastics, such as polyvinyl alcohol, polyamides, and polyurethanes.
  • materials are suitable the specific resistance of which is less than ohm-cm, preferably less than 10 ohm-cm.
  • paper is used as the supporting material, it is preferably pretreated against the penetration of coating solutions, e.g., it can be treated with a solution of methyl cellulose or polyvinyl alcohol in water or with a solution of an interpolymer of acrylic acid methyl ester and acrylonitrile in a mixture of acetone and methylethyl ketone, or with solutions of polyamides in aqueous alcohols or with dispersions of such substances.
  • coating solutions e.g., it can be treated with a solution of methyl cellulose or polyvinyl alcohol in water or with a solution of an interpolymer of acrylic acid methyl ester and acrylonitrile in a mixture of acetone and methylethyl ketone, or with solutions of polyamides in aqueous alcohols or with dispersions of such substances.
  • the photoconductive compounds are preferably dissolved in organic solvents such as benzene, acetone, methylene chloride or ethyleneglycol monomethylether or other organic solvents or in mixtures of such solvents, and resins and the activators and possibly also the dyestuff sensitizersare advantageously added thereto.
  • organic solvents such as benzene, acetone, methylene chloride or ethyleneglycol monomethylether or other organic solvents or in mixtures of such solvents, and resins and the activators and possibly also the dyestuff sensitizersare advantageously added thereto.
  • organic solvents such as benzene, acetone, methylene chloride or ethyleneglycol monomethylether or other organic solvents or in mixtures of such solvents
  • resins and the activators and possibly also the dyestuff sensitizersare advantageously added thereto are coated upon the supporting material in the normal manner, e.g., by immersion processes, painting or roller application or by spraying. The material is then heated so that
  • a number of the compounds in question can be applied together to the supporting material or the compounds can be applied in association with other photoconductive substances.
  • the photoconductor substances may be applied to the supporting material in association with one or more binders, e.g., resins.
  • binders e.g., resins.
  • Resins primarily of interest as additions to the photoconductor coatings include natural resins such as balsam resins, colophony and shellac, synthetic resins such as coumarone resins 'and indene resins, processed natural substances such as cellulose ethers; polymers such as vinyl polymers, e. g.
  • polyvinyl chloride polyvinylidene chloride, polyvinyl acetate, polyvinyl acetals, polyvinyl alcohol, polyvinyl ethers, polyacrylic and polymethacrylic acid esters, isobutylene and chlorinated rubber.
  • the proportion of resin to photoconductor substance can vary very greatly. Mixtures of from two parts of resin and one part of photoconductor substance to two parts of photoconductor substance and one part of resin are to be preferred. Mixtures of the two substances in equal parts by weight are particularly favorable.
  • dyestulf sensitizers can be used in addition to the activators. Even very small additions of sensitizer, e.g., less than 0.01 percent, give good results. In general, however, 0.01 to 5 percent, and preferably 0.1 to 3 percent of dyestuff sensitizer is added to the photoconductor coatings. The addition of larger quantities is possible but in general is not accompanied by any considerable increase in sensitivity.
  • Triarylmethane dyestuffs such as Brilliant Green (No. 760, p. 314), Victoria Blue B (No. 822, p. 347), Methyl Violet (No. 783, p. 327), Crystal Violet (No. 785, p. 329), Acid Violet 6B (No. 831, p. 351); xanthene dyestuffs, namely rhodamines, such as Rhod'amine B (No.
  • thiazine dyestuffs such as Methylene Blue (No. 1038, p. 449); acridine dyestuffs such as Acridine Yellow (No. 901, p. 383), Acridine Orange (No. 908, p. 387) and Trypaflavine (No. 906, p. 386); quinoline dyestuffs such as Pinacyanol (No. 924, p. 396) and Cryptocyanine (No. 927, p. 397); cyanine dyestuffs, e.g., Cyanine (No. 921, p. 394) and chlorophyll.
  • Methylene Blue No. 1038, p. 449
  • acridine dyestuffs such as Acridine Yellow (No. 901, p. 383), Acridine Orange (No. 908, p. 387) and Trypaflavine (No. 906, p. 386)
  • quinoline dyestuffs such as Pinacyan
  • the photoconductive coating is charged by means of, for example, a corona discharge with a charging apparatus maintained at 60004000 volts.
  • the electro-copying material is then exposed to light in contact with a master.
  • an episcopic or diascopic image is projected thereon.
  • An electrostatic image corresponding to the master is thus produced on the material.
  • This invisible image is developed by contact with a developer consisting of carrier and toner.
  • the carriers used may be, for example, tiny glass balls, iron powder or tiny plastic balls.
  • the toner consists of a resin-carbon black mixture or a pigmented resin.
  • the toner is used in a grain size of 1 to g.
  • the developer may also consist of a resin or pigment suspended in a non-conductive liquid in which resins may be dissolved.
  • the image that is made visible by development is then fixed, e.g., bv heating with an infra-red radiator to 100-170 0., preferably -150 C. or by treatment with solvents such as trichloroethylene, carbon tetrachloride or ethyl alcohol, or steam. Images corresponding to the master characterized by ood contrast effect are obtained.
  • the electrophotographic images can also be used as masters for the production of further copies on any type of light-sensitive sheets.
  • reflex images can be produced also.
  • the application of the activators in accordance with the present process is not restricted to electrophotographic coatings, but can extend to other devices containing photoconductors, e.g., photoelectric cells, photoresistances, sensing heads or camera tubes and electroluminescent apparatus.
  • EXAMPLE 1 A solution containing 26 parts by weight of polyvinyl acetate (e.g., Mowilith 50), 25.6 parts by weight of naphthalene, 0.0415 part by weight of 2,3,7-trinitrofiuorenone and 800 parts by volume of toluene is applied by means of a coating device to an aluminum foil. After the coating has dried, direct images are produced thereon by the electrophotographic process in the following manner: the coated foil is given a negative electric charge by corona discharge, exposed behind a master to the light of a high-pressure mercury vapor lamp watts, at a distance of 30 cm.) for about 10 seconds and then dusted over with a developer.
  • polyvinyl acetate e.g., Mowilith 50
  • naphthalene e.g., naphthalene
  • 2,3,7-trinitrofiuorenone e.g., 2,3,7-trinitrofiuorenone
  • the developer consists of tiny glass balls and a mixture of resin and carbon black which has been melted together and then finely divided.
  • a developer of this sort con-- sists of, e.g., 100 parts by weight of tiny glass balls (grain size: 100-400 approx.) and a toner (grain size: 20-50 approx.).
  • the toner is prepared by melting together 30 parts by weight of Polystyrol LG, 30 parts by weight of modified maleic acid resin (Beckacite K 105) and 3 parts by Weight of Peerless Black Russ 552. The melt is then ground and screened.
  • the finely divided resin ad heresto the parts of the coating not struck by light during the exposure and a positive image of the master becomes visible. It is slightly heated and thereby fixed.
  • EXAMPLE 2 26 parts by weight of polyvinyl acetate, 16.6 parts by weight of fluorene and 0.3602 part by weight of tetranitrofiuorenone are dissolved in 800 parts by volume of toluene. This solution is applied to an aluminum foil and further procedure is as described in Example 1. Exposure time, if a 125-watt high-pressure mercury vapor lamp is used, is seconds.
  • the images obtained even after an exposure of two minutes are not free of background, i.e., the exposed parts are not fully discharged and therefore retain a certain amount of developer.
  • EXAMPLE 3 A solution of 26 parts by weight of polyvinyl acetate, 17.8 parts by weight of anthracene and 0.3357 part "by weight of hexabromonaphthalic anhydride in 800 parts by volume of toluene is applied to aluminum and further procedure is as described in Example 1. With a 125-watt high-pressure mercury vapor lamp, the exposure time is 4 seconds.
  • EXAMPLE 4 A solution containing 18 parts by weight of polyvinyl acetate, 18.2 parts by Weight of 2,4-bis-(4'-diethylaminophenyl)-1,3,4-triazole and 0.130 part by weight of tetrachlorophthalic anhydride to 500 parts by volume of toluene is applied to an aluminum foil and further procedure is as described in Example 1. The exposure time with a 100-watt incandescent lamp is 2 seconds. 7 7
  • the polyvinyl acetate used was the product commercially available under the registered trademark M-owilith C.
  • the maleic acid resin used was the product commercially available under the designation Alrosat.
  • naphthalene 26 2,-1.5,7-tetranitrofiuorenone l,5-dinit'r0naphthalene 1,4-benzoquinone- Chlorarlil 21.6 1,5-diethoxynaphthalene.
  • the increase in sensibility obtained by the addition of activating substances may be taken from a comparison of the degrees of blackening obtained with the activated photoconductive layer and with the unactivated photoconductive layer, under the same customary step wedge (e.g. Kodak No. 2 density strip with color patches).
  • EXAMPLE 8 A solution containing 20 parts by weight of afterchlorinated polyvinyl chloride with a content of chlorine from 61.7 to 62.3 percent and K-value from 59 to 62, 18.01 parts by weight of 2,4,5,7-tetranitrofluorenone and 0.216 part by weight of 1,5-diethoxynaphthalene dissolved in a mixture of 450 parts by volume toluene and parts by volume butanone is applied to an aluminum foil.
  • the subsequent procedure is that described in Example 1.
  • the exposure time, with a 100 watt incandescent lamp at a distance of 30 centimeters is 2 seconds.
  • the exposure time is about 40 seconds.
  • Exposure time A solution of 12 parts by weight of chlorinated rubber (Pergut 8-40), 5.04 parts by weight of 1,3-dinitrobenzene and 0.106 part by weight of anthracene in 150 parts by volume of toluene is applied to a paper foil and the material is further processed as described in Example 1.
  • the exposure time 125 watt high pressure mercury vapor lamp
  • the exposure time is 20 seconds. Without the anthracene addition, even after an exposure time of 80 seconds, only traces of an image were obtained. This means that the exposed parts of the coating were not discharged and therefore still attracted developer.
  • Exposure time Photoconductors (parts by weight): (seconds) 12 2,2'-dinaphthylamine, the exposure time is about 10 seconds.
  • EXAMPLE 12 To a solution containing 28.6 parts by weight of tetrachlorophthalic acid anhydride and20 parts by weight of afterchlorinated polyvinyl chloride in a mixture of 150 parts by volume of butanone and 450 parts by volume.
  • Exposure time Photoconductors (parts by weight): (seconds) 2,2'-dinaphthylamine (0.540) 20 2,5-bis-(4'-diethylamino-phenyl) 1,3,4 oxdiazole (0.730) V 5 Poly-N-vinylcarbazole (0.390) 30 EXAMPLE 11 A solution containing 6.2 parts by Weight of afterchlorinated polyvinyl chloride, 3.94 parts by weight of 1,5-dichloronaphthalene and 0.145 part by weight of 2,5-bis- (4-diethylaminophenyl)-1,3,4-oxdiazole in a mixture of 135 parts by volume of toluene and 45 parts by volume of butanone is applied to a paper base and is further processed as described in Example 1.
  • the exposure time (125 watt high pressure mercury vapor lamp at a distance of 30 centimeters) is 10 seconds. Without the addition of the oxdiazole compound, even after an exposure time of 40 seconds, no image could be obtained.
  • the oxdiazole compound is replaced by 0.120 part'by weight of EXAMPLE 13
  • a solution is prepared, containing 57.2 parts by weight of tetrachlorophthalic acid anhydride and parts by weight of afterchlorinated polyvinyl chloride in 700 parts i by volume toluene and suflicient butanone is added to make up 1000 parts by volume.
  • one of the photoconduc tors listed below is added, and the solution is applied to an aluminum foil and further processed as described in Example 1. In the following table, the added photoconductors are indicated, and the corresponding exposure times are given.
  • As the light source a l25-watthigh pressure mercury vapor lamp in a distance of about 30 centimeters from the exposed material was used in all instances.
  • Exposure time (seconds) EXAMPLE 15 29.62 parts by weight of phthalic acid anhydride and 33 parts by weight of afterchlorinated polyvinyl chloride are dissolved in 670 parts by volume of toluene and 330 parts by volume of butanone. To 50 parts by volume of the resulting stock solution, one of the photoconductors listed in the following table is added; these coating solutions are applied to an aluminum foil, and further processed as described in Example 1. The light source and the distance of the light sourcewere the same as in Example 13.
  • Exposure time Photoconductor (parts by weight): (seconds) None 1 60 N-ethylcarbazole (0.10) 5 Anthracene (0.09) Chrysene (0.114) Pyrene (0.10) 10 2,2'-dinaphthylamine (0.134) 10 2,3,5-triphenylpyrrole (0.153) 10 1 No image obtained.
  • EXAMPLE 16 49.2 parts by weight of chloranil and 56 parts by weight of afterchlorinated polyvinyl chloride are dissolved in a mixture of 1170 parts by volume of toluene and parts by volume of butanone. The resulting solution is filled up to 2000 parts by volume with chlorobenzene. To 100 parts by volume of this stock solution, one of the photoconductors listed in the following table is added; the coating solution is applied to an aluminum foil and further processed as described in Example 1. The light source and the distance of the light source were the same as in Example 13.
  • Exposure time Photoconductor (parts by weight): (seconds) None 180 Naphthalene (0.064) ca. Hydroquinonedimethyl ether (0.070) 30' N-ethylcarbazole (0.097) 10 Anthracene (0.090) 5 Chrysene (0.114) 15 Pyrene (0.10) 10 o-Dianisidine (0.122) 5 2,6-dimethyl-naphthalene (0.078) 30 Hexamethylbenzene (0.081) 120 2,2'-dinaphthylamine (0.134) 1-2 2,5 -bis- (4-diethyl aminophenyl 1, 3,4-oxdiazole (0.182) 1 2,3,5-tiiphenylpyrrole (0.153) 4 EXAMPLE 17 10.6 parts by weight of 2-acetyl fluorene and 12 parts by weight of afterchlorinated polyvinyl chloride are dissolved in parts of toluene and sufi'icient butanol
  • Exposure time Photoconductor (parts by weight): (seconds) None 1 180 o-Dianisidine (0.120) 30 2,5 -bis- 4'-diethylaminophenyl) -1,3 ,4-oxdiazole 1 No image obtained,
  • EXAMPLE 18 44 parts by weight of 9 acetyl-anthracene and 48 parts by Weight of afterchlorinated polyvinyl chloride are dissolved in 700 parts by volume of solution. To 50 parts by volume of the resulting stock solution, one of the photoconductors of the following table is added. This solution is applied to an aluminum foil and further processed as described in Example 1. The light source and the distance thereof was the same as in Example 13.
  • Exposure time Photoconduc-tor (parts by weight): (seconds) None 1 180 Hydroquinonedimethyl ether (0.069) 30 N-ethyl carbazole (0.097) 60 Anthracene (0.089) 60 Hexamethylbenzene (0.081) 30 1 Image with heavy background.
  • EXAMPLE 19 46.2 parts by weight of pyrene-3-aldehyde and 50 parts by weight of afterchlorinated polyvinyl chloride are dissolved in 670 parts by volume of toluene and suflicient butanol to make up 1000 parts by volume of solution. To 5 0 parts by volume of the resulting stock solution one of the photoconductors of the following table is added. The solution is applied to an aluminum foil and further processed as described in Example 1. The light source 15 and the distance of the light source were the same as'in Example 13.
  • Exposure time Photoconductor (parts by weight): (seconds) None 30 Naphthalenev (0.064) 20 Hydroquinonedimethyl ether (0.070) 20 N-ethylcarbazole (0.10) 10 Anthracene (0.090) 20 Chrysene' (0.114) 20 Pyrene (0.10) 20 Hexamethylbenzene (0.080) 20 2,2'-dinaphthylamine (0.135) 15 2,5 -bis- (4-diethylaminophenyl) -l ,3 ,4-oxdiazole (0.180) 2,3,5-triphenylpyrrole (0.
  • EXAMPLE 20 13.1 parts by weight of '1,4,5-trinitronaphthalene and 15 parts by weight of afterchlorinated polyvinyl chloride were dissolved in 180 parts by volume of toluene and sufiicient butanone to make up 250 parts by volume. To 50 parts of the resulting stock solution, one of the photoconductors of the following table is added in the amount indicated. This solution is applied to an aluminum foil and further processed as described in Example 1.. The light source and the distance thereof were the same as in Example 13.
  • Exposure time Photoconductor (parts by weight): (seconds) None 1 180 N-ethylcarbazole (0.10) 30 Anthracene (0.09) 30 o-Dianisidine (0.12)
  • R stands for a residue selected from the group consisting of hydrogen, aryl, alkenyl, alkyl, and hetero cyclic groups
  • R stands for a residue selected from the group consisting of hydrogen, alkyl, alkylated aminoaryl and aryl groups
  • R stands tfor a residue selected from the gruop consisting of hydrogen and an aryl group, the compound containing at least two aryl groups.
  • a sensitized photoconductive layer comprising at least one solid, non-resinous, substantially colorless electron-acceptor, and a compound having the formula in which R stands for a residue selected (from the group consisting of hydrogen, aryl, alkenyl, alkyl, and heterocyclic groups, R stands for a residue selected from the group consisting of hydrogen, alkyl, alkylated aminoaryl and aryl groups, and R stands for a residue selected from the group consisting of hydrogen and an aryl "group, the compound containing at least two aryl groups; the layer containing the photoconductor and the electronaoceptor in proportions ranging from substantially less than equal amounts to a substantial excess of the photoconductor with repect to the electron-acceptor and from substantially less than equal amounts to a substantial excess of the electron-acceptor with respect to the photoconductor.
  • a sensitized photoconductiye layer comprising at least one solid, non-resinous, substantially colorless electron acceptor, and a compound having the formula in which R stands for a residue selected from the group consisting of hydrogen, aryl, alkenyl, alkyl, and heterocyclic groups, R stands for a residue selected fromthe group consisting of hydrogen, alkyl, alk-ylated aminoaryl and aryl groups, and R stands for a residue selected from the group consisting of hydrogen and an aryl group,
  • proportions ranging from about 0.1 to about 300 moles of the electron-acceptor per. 1000 moles of photoconductor.
  • a sensitized photoconductive layer comprising at least one solid, non-resinous, substantially colorless electron-acceptor, and a compound having the formula in which R stands for a residue selected from the group consisting of hydrogen, aryl, alken-yl, alkyl, and heterocyclic groups, R stands for a residue selected from the group consisting of hydrogen,-alkyl, alkylated aminoaryl and aryl groups, and R stands for a residue selected from the group consisting of hydrogen and an aryl group, the compound containing at least two aryl groups; in proportions ranging from about 0.1 to about 300 moles of the photoconductor per 1000'moles of the electron-;
  • a sensitized photoconductive layer comprising at least one solid, non-resinous, substantially colorless electron-acceptor, and a compound having the formula in which R stands for a residue selected from the group in which R stands for a residue selected from the group consisting of hydrogen, aryl, alkenyl, alkyl, and heterocyclic groups, R stands for a residue selected from the group consisting of hydrogen, alkyl, alkylated aminoaryl and aryl groups, and R stands for a residue selected 17 from the group consisting of hydrogen and an aryl group, the compound containing at least two aryl groups; in proportions rang'gm-g from about 1 to about 50 moles of the photoconductor per 1000 moles of the electron-acceptor.
  • a layer according to claim 1 in which the electronacceptor is 2,4,7-tninitrofluorenone.
  • a layer according to claim 1 in which the electronacceptor is tetrachlo rophthal-ic anhydride.
  • a layer according to claim 1 in which the electroacceptor is diblromomaleic anhyd-ride.
  • a layer according to claim 1 including a dyestufi sensitizer.
  • a photographic reproduction process which comprises exposing an electrostatically charged, supported photoconductive insulating layer to light under a master and developing the resulting image with an electroscopic material, the photoconductive layer comprising at least one solid, non-resinous, substantially colorless electronacceptor, and a compound having the formula in which R stands for a residue selected from the group consisting of hydrogen, aryl, alkenyl, alkyl, and heterocyclic groups, R stands for a residue selected from the group consisting of hydrogen, alkyl, alkylated aminoaryl and aryl groups, and R stands for a [residue selected firom the group consisting of hydrogen and an aryl group, the compound containing :at least two aryl groups.
  • a photographic reproduction process which comprises exposing an electrostatically charged, supported photoconductive insulating layer to light under a master and developing the resulting image with an electroscopic material, the photoconductive layer comprising at least one solid, non-resinous, substantially colorless electronacceptor, and a compound having the formula in which R stands for a residue selected from the group consisting of hydrogen, aryl, alkenyl, alkyl, and heterocyclic groups, R stands for a residue selected from the group consisting of hydrogen, alkyl, alkylated aminoaryl and aryl groups, and R stands for a residue selected from the group consisting of hydrogen and an aryl group, the compound containing at least two aryl groups; the layer containing the photoconductor and the electron-acceptor in proportions ranging from substantially less than equal amounts to a substantial excess of the photoconductor with respect to the electron-acceptor and from substantially less than equal amounts to a substantial excess of the electron-acceptor with respect to the photoconductor.
  • a photographic reproduction process which comprises exposing an electrostatically charged, supported photoconductive insulating layer to light under a master and developing the resulting image with an electroscopic material, the photoconductive layer comprising at least one solid, non-resinous, substantially colorless electronacceptor and a compound having the formula in which R stands for a residueselected from the group consisting of hydrogen, aryl, alkenyl, alkyl, and heterocyclic groups, R stands for a residue selected from the group consisting of hydrogen, alkyl, alkylated aminoaryl and aryl groups, and R stands for -a residue selected from the groupconsisting of hydrogen and an aryl group, the compound containing at least two aryl groups; in proportions ranging from about 0.1 to about 300 moles of the electron-acceptor per 1000 moles of photoconductor.
  • a photographic reproduction process which comprises exposing an electrostatically charged, supported photoconductive insulating layer to light under a master and developing the resulting image with an electroscopic material, the photoconductive layer comprising at least one solid, non-resinous, substantially colorless electronacceptor and a compound 'having the formula are N in which R stands for a residue selected from the group consisting of hydrogen, aryl, alkenyl, alkyl, and heterocyclic groups, R stands for a residue selected from the group consisting of hydrogen, alkyl, alkylated aminoaryl and aryl groups, and R stands fora residue selected from the group consisting of hydrogen and an aryl group,
  • R stands for a residue selected from the group consisting of hydrogen, aryl, alkenyl, alkyl, and heterocyclic groups
  • R stands for a residue selected from the group consisting of hydrogen, alkyl, alkylated aminoaryl and :aryl groups
  • R stands for a residue selected from the group consisting of hydrogen and an aryl group, the compound containing at least two aryl groups; in proportions ranging from about 1 to about 50 moles of the electron-acceptor per 1000 moles of the photoconductor.
  • a photographic reproduction process which comprises exposing an electrostatically charged, supported photoconductive insulating layer to light under a master and developing the resulting image with an electroscopic material, the photoconductive layer comprising at least one solid, non-resinous, substantially colorless electronacceptor and a compound having the formula Bi

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Description

United States Patent M 3,287,115 PROCESS FOR THE SENSITIZATION 0F PHOTOCONDUCTORS Helmut Hoegl, Geneva, Switzerland, assignor, by
34 Claims. (:L 96-1) This application is a division of copending application Serial No. 125,984, filed July 24, 1961, now abandoned, which, in turn, is a continuation-in-part of application Serial No. 30,752, filed May 23, 1960, and also now abandoned.
Electrophotographic material normally consists of a support on which there is a photoconductive substance, this coating being provided in the absence of light with an electrostatic charge. Then, the material is exposed to light behind a master, or an episcopic image is projected thereon, so that an electrostatic image is formed which corresponds to the master. This image is developed by being briefly contacted with a resin powder, whereupon a visible image is formed which is fixed by heating or by the action of solvents. In this way, an image of the master which is resistant to abrasion is obtained electrophotographically.
In the electrophotographic process as described an increase in the sensitivity of the photoconductive coatings has already been attempted by the addition of organic dyestuffs, e.g. tn'phenylmethane, xanthene, phthalein, thiazine and acridine dyestulfs, to the photoconductors.
The absorption maxima of the organic photoconductors are mostly in the ultra-violet region of the spectrum. The addition of these dyestuff sensitizers achieves the result that the photoconductors become sensitive to visible light. Generally, the dyestuff sensitizers cause a displacement of the available sensitivity from the ultraviolet region to the visible region. With increased addition of dyestufi sensitizer, the sensitivity to visible light at first increases rapidly, but further additions give an increase in sensitivity which is much less than would be expected, and still further additions finally give no appreciable increase in sensitivity. The dyestulf sensitizers have the disadvantage that they color the coating considerably. In practice, the maximum achievable increase in sensitivity can seldom be utilized because then the photoconductor coatings have an intensity of color that is undesirable. Colorless or practically colorless photoconductor coatings are desired, since colored material can be employed only in special cases. If additions of dyestutf sensitizers are such as not to adversely alfect the coloring of the coating for practical purposes, the sensi tizing effect often does not meet the demands of general usage. Further, the dyestufi sensitizers have the disadvantage that they bleach out relatively quickly so that their sensitizing action tends to be lost during the storage of the electrophotographic material.
A process for the sensitization of photoconductor coatings has now been found in which organic substances, containing polarizing residues and being capable of serving as electron-acceptors in a molecule complex, having low molecular weight, i.e. being non-resinous, being colorless or of palecolor and having a melting point above room temperature, are added to the photoconductor coatings.
Substances which are primarily of interest as photoconductor coatings in accordance with the present process are those which can serve as electron donors in mole- Patented Nov. 22, 1966 cule complexes of the donor/acceptor type (known as 1r-complex) and contain at least one aromatic or heterocyclic ring, which may be substituted. Such photoconductors include aromatic hydrocarbons such as naphthalene, anthracene, benzanthrene, chrysene, p -diphenylbenzene, diphenyl anthracene, p-terphenyl, p-quaterphenyl, sexiphenyl; heterocycles such as N-alkyl carbazole, thiodiphenylamine, oxadiazoles, e.g., 2,5-bis-(p-aminophenyl)-1,3,4-oxadiazole and its N-alkyl and N-acyl derivatives; triazoles such as 2,5 bis-(p-aminophenyl)- 1,3,4-triazole and its N-alkyl and N-acyl derivatives; imidazolones and imidazolthiones, e.g., 1,3,4,5-tetraphenyl-imidazolone-Z and 1,3,4,5-tetraphenyl-imidazolthione-2; N-aryl-pyrazolines, e.g. 1,3,5-triphenyl-pyrazoline; hydrated imidazoles, e.g., 1,3- diphenyl-tetrahydroimidazole; oxazole derivates such as 2,5-diphenyloxazole-2- p-dimethylamino-4,5-diphenyloxazole; thiazole derivatives such as 2-p-dia1kylaminophenyl-methyl-benzthiazole; as also the following:
Triphenylamines described in German patent application K 37,436 IVa/57b, filed Apr. 9, 1959. 1 Furans, thiophenes and pyrroles described in Germ patent application K 37,423 IVa/ 5 7b, filed Apr. 8, 1959. Amino compounds with multinuclear heterocyclic and multinuclear aromatic ring system described in Gerrligasn patent application K 37,437 lVa/ 57b, filed Apr. 9,
9. Azomethines described in German patent application K 29,270 Iva/57b, filed July 4, 1956.
Molecule complexes are defined in H. A. Staabs Einfuhrung in die theoretische organische Chemie (Introduction to Theoretical Organic Chemistry), Verlag Chemie, 1959, pp. 694-707, and by L. I. Andrews, Chemical Review, vol. 54, 1954, pp. 713-777. In particular, the donor/ acceptor complex (w-complexes) charge-transfer complexes which are formed from an electron-acceptor and an electron-donor are included. In the present case, the photoconductors are the electrondonors and the substances here called activators-to distinguish them from the dyestuff sensitizers-are the electron-acceptors. The electron-donors have a low ionization energy and have a tendency to give up electrons. They are bases in the sense of the definition of acids and bases given by G. N. Lewis (H. A. Staab, as above, p. 600). The electron-donors primarily concerned in the present case are the photoconductors described above. These photoconductors consist of aromatic or heterocyclic systems containing a plurality of fused rings, or, alternatively, single rings having substituents which facilitate further electrophilic substitution of the aromatic ring, socalled electron-repellent substituents, as described by L. F. and M. Fieser, Lehrbuch der organischen Chemie (Textbook of Organic Chemistry), Verlag Chemie, 1954, p. 651, Table I. These are, in particular, saturated groups, e.g., alkyl groups such as methyl, ethyl, and propyl; alkoxy groups such as methoxy, ethoxy and propoxy; carbalkoxy groups such as carbmethoxy, carbethoxy and carbpropoxy; hydroxyl groups, amino groups and 1 and dialkylamino groups such as dimethylamino, diethylamino and dipropylamino.
The activators in accordance with the invention, which are electron-acceptors, are compounds with a high elec-' tron-afiinity, and have a tendency to take up electrons. They are acids in the sense of Lewis definition. Such properties are possessed by substances having strongly polarizing residues or groupings such as cyano and nitro groups, halogens such as fluorine, chlorine, bromine and iodine; ketone groups, ester groups, acid anhydride groups, acid groups such as carboxyl groups or the quinone grouping. Strongly polarizing electron-attracting groups of this type are described by L. F. and M. Fieser in the Lehrbuch der organischen Chemie, Verlag Chemie, 1954, p. 651, Table I. Of these substances with a melting point above room temperature (25 C.) are preferable, i.e. solid substances, because these impart a particularly long shelf life to the photoconductive coatings as a result of their low vapor pressure. Substances which are rather deeply colored such as quinones can be used, but those that are colorless or only weak in color are preferable. Their absorption maximum should preferably be in the ultra-violet region of the spectrum, i.e. below 4,500. A. Further, the activator substances in accordance with the present process should be of lower molecular weight, i.e. between about 50 and 5000, preferably between about 100 and 1000, because with activators of lower molecular weight it is possible for reproducible results to. be obtained insofar as sensitivity is concerned. Also, the sensitivity remains constant over rather long periods, since substances of lower molecular weight, unlike those of high molecular weight, undergo hardly any change during storage. The
following are examples of such substances:
2,4dich1oro-benzisatin 2,6-dicl1loro-benzaldehyde Hexabrcmonaphthalic anhydridebz-1-cyano-benzanthrone Cyan acetic acid 2-cyanocinnam1c acid- 1,5-dicyanonaphthalene 3,5-dinitrobenzoic acid 3,5-dinitrosalicylic ac 2,4-dinitro-1-benzoic aci 2,4-dinitro-1-toluene-6-sul 2,ddilitro-l-phenol-rsulphonic a 1,3-dinitro-benzene 4,4-dinitro-bipheny 3-nitro-4-mcth0xy-ben 4-nitro-1-rnethyl-benzoic acid 6-nitro-4-methyl-1-phenol-2-sul phonic acid. Q-nitrohenzenesulphmic acid. 3-nitro-2-hydroxyl-1-henzoic act 2-nitro-l-phenol-Lsulphonic acid 3-nitro-N-butyl-carbazole 4-nitrobiphenyl Tetranitrofluorenone- 2,4,6-trinitro-anisole. Anthraquinone Anthraquinone-2-carboxylic Anthraquinone-Z-aldehyde Anthraquinone-Z-sulphonic acid anilide. Anthraquinone-2,7-disulphonic acid.
o-Chloronitrobenzene. Chloracetophenone. 2-chlorocinnamic acid.
2-chloro-4-nitro-1-benzoic acid. 2-chloro-5-nitro-1-benzoic acid. 3-ehlor0-6-nitro-1-benzoic acid.
Mucochloric acid. Mucobromic acid. Styrenedibroruide. Tetrabromo xylene.
fl-Trichlorolactic acid nitrile.
Triphenylchloromethane. Tetrachlcrophthalic acid. Tetrabromophthalic acid. Tetraicdophthalic acid. Tetrachlorophthalic anhydride. Tetrabromophthalic anhydride. 'letralodophthalic anhydride. Tetrachlorophthalic acid monoethylester. Tetrabromophthalic acid monoethylester. Tettraiodophthalic acid mono- Tetracyanethylene. s-Tricyano-benzene.
2,4-dinitro-l-ehloronaphthalene. 1,4-dinitro-naphthalene. 1,5-dinitro-naphthalene.
1,8-dinitro-naphthalene.
2-nitrobenzoic acid.
S-nitrobenzoie acid. 4-nitrobenzoic acid. 3-nitro-4-ethoxy-benzoie acid. 3-nitro-2-creso1-5-sulphonic acid. -nitrobarbituric acid.
knitroacenaphthene. t-nitro-benzaldehyde. 4nitro-pheuol.
Picryl chloride. 2,4,7-trinitro-fiuorenone. s-Trinitro-beuzene.
l-chioro-Z-methyl-anthraquinone. Duroquinone. 2,6-dich1oroquinone. 1,5-diphenoxy-anthraquinone.
2,7-dinitro-anthraquinonc.
1,5-dichloro-anthraquinone.
1,4dimethyl-anthraquinone.
2,5-dichloro-benzoquinqne. 2,3-dichlor0-naphthoqu1none-1,4.
l,5-dichloro-anthraquinone. l-methyli-chloro-anthraqumone. Picric acid. 2-methyianthraquinona. Naphthoquinone-i ,2. Naphthoquiuone-1,4. Penteceuequinone. Tetracene-7,12-quinone.
1,4-toluquinone.
Chrysenequinone-.-
2,5,7,IO-tetrachloropyrenequinone.
Thymoquinone The quantity of the solid, non-resinous, substantially colorless electron-acceptors (activators) which is best incorporated in the photoconductive coating to be sensitized is easily established by simple experiments. The
photoconductive coating containing at least one photo-1 conductor and at least one solid, non-resinous, substan-' tially colorless, electron-acceptor, should contain the photoconductor and electron-acceptor in proportions rang.- ing from substantially less than equal amounts to a substantial excess of the photoconductor with respect to the electron-acceptor. The optimum of the proportions varies somewhat according to the substance used. Generally, minor amounts are used, i.e. from about.0.1 to
about 300 moles, preferably from about 1 to about 50 moles of electron-acceptor per 1000 moles of photoconductor. Alternatively, it has also been found that in the. photoconductive coatings containing at least one photo-. conductor and at least one solid, non-resinous, substantially colorless electron-acceptor, it is also very useful to have present the photoconductor and the electron-acr ceptor in proportions ranging from substantially less-than equal amounts to a substantial excess of. the electron-- acceptor with respect to the photoconductor. These proportions in which minor amounts of the photoconductor are added to the activator vary according to the substance used; however, in general, amounts from about i 0.1 to about 300 moles, preferably from about 1 to about 50 moles photoconductor per 1000 moles activator are used. In some cases, it is also possible to use more than 300 moles photoconductor or activator per 1000 moles activator or photoconductor, respectively, but by exceeding the above range the dark decay of the mixture, usually increases, and in such cases coatings made therefrom are inferior.
Mixtures of several photoconductors and activator sub-. stances mayalso be used. Moreover, in addition to these substances, sensitizing dyestufis may be added.
By means of the present process, photoconductor coatings can be prepared which have a high degree of light- A sensitivity, particularly in the ultra-violet region, and
which are practically colorless. There is the further possibility of the photoconductor coatings being thereby strongly activated in the ultra-violet region and afterwards being invested with a high degree of sensitivity to visible light by a very small addition of dyestutf' sensitizer without it being necessary for so much dyestutf to be added that the coating takes on a deep color. Also, it is possible, by means of activators, for photoconduc-' tors such as naphthalene, whose initial sensitivity is very slight, tobe given adequate sensitivity for the production of satisfactory images by electrophotographic processes.
Furthermore, by addition of minor amounts of photos conductors to activators, photoconductive mixtures are obtained which have photoconductivity much higher than could be expected from the amount of the photoconduc:
tor added to the activator. A further increase in the photoconductivity may be obtained by the addition of dye-. stuff sensitizers in the same amounts as in the photoconductor-activator mixtures in which the photoconductor is present in a major amount.
The coatings are treated in other respects in accordance with the known processes of electrophotography, i.e. the photoconductor substances are used in the form of thin, coherent homogeneous coatings on a supporting material. The materials used as supports are primarily metals, such as aluminum, zinc, and copper; cellulose products, such as paper and cellulose hydrate; plastics, such as polyvinyl alcohol, polyamides, and polyurethanes. Other plastics, such as cellulose acetate and cellulose butyrate, especially in a partially saponified form, polyesters, polycarbonates, and polyolefins, if they are covered with an electroconductive layer or if they are converted into materials which have the above-mentioned specific conductivity, e. g. by chemical treatment or by introduction of materials which render them electrically conductive, can also be used, as well as glass plates. In general, materials are suitable the specific resistance of which is less than ohm-cm, preferably less than 10 ohm-cm.
If paper is used as the supporting material, it is preferably pretreated against the penetration of coating solutions, e.g., it can be treated with a solution of methyl cellulose or polyvinyl alcohol in water or with a solution of an interpolymer of acrylic acid methyl ester and acrylonitrile in a mixture of acetone and methylethyl ketone, or with solutions of polyamides in aqueous alcohols or with dispersions of such substances.
For the preparation of the electrophotognaphic material, the photoconductive compounds are preferably dissolved in organic solvents such as benzene, acetone, methylene chloride or ethyleneglycol monomethylether or other organic solvents or in mixtures of such solvents, and resins and the activators and possibly also the dyestuff sensitizersare advantageously added thereto. These solutions are coated upon the supporting material in the normal manner, e.g., by immersion processes, painting or roller application or by spraying. The material is then heated so that the solvent will be removed.
A number of the compounds in question can be applied together to the supporting material or the compounds can be applied in association with other photoconductive substances.
Further, it is often advantageous for the photoconductor substances to be applied to the supporting material in association with one or more binders, e.g., resins. Resins primarily of interest as additions to the photoconductor coatings include natural resins such as balsam resins, colophony and shellac, synthetic resins such as coumarone resins 'and indene resins, processed natural substances such as cellulose ethers; polymers such as vinyl polymers, e. g. polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, polyvinyl acetals, polyvinyl alcohol, polyvinyl ethers, polyacrylic and polymethacrylic acid esters, isobutylene and chlorinated rubber.
If the photoconductive compounds in accordance with the invention are used in association with the resins described above, the proportion of resin to photoconductor substance can vary very greatly. Mixtures of from two parts of resin and one part of photoconductor substance to two parts of photoconductor substance and one part of resin are to be preferred. Mixtures of the two substances in equal parts by weight are particularly favorable.
For the displacement of sensitivity from the ultra-violet to the visible range of the spectrum, dyestulf sensitizers can be used in addition to the activators. Even very small additions of sensitizer, e.g., less than 0.01 percent, give good results. In general, however, 0.01 to 5 percent, and preferably 0.1 to 3 percent of dyestuff sensitizer is added to the photoconductor coatings. The addition of larger quantities is possible but in general is not accompanied by any considerable increase in sensitivity.
Some examples are given below of dyestuif sensitizers which may be used with good results, and some with very good results. They are taken from Schultz Farbstotftabellen (7th edition, 1931, 1st vol.):
6 Triarylmethane dyestuffs such as Brilliant Green (No. 760, p. 314), Victoria Blue B (No. 822, p. 347), Methyl Violet (No. 783, p. 327), Crystal Violet (No. 785, p. 329), Acid Violet 6B (No. 831, p. 351); xanthene dyestuffs, namely rhodamines, such as Rhod'amine B (No.
864, p. 365), Rhodamine 6G (No. 866, p. 366), Rhodamine G Extra (No. 865, p. 366), Sulphorhodamine B (No. 863, p. 364) and Fast Acid Eosin G (No. 870, p. 368), as also phthaleins such as Eosin S (No. 883, p. 375), Eosin A (No. 881, p. 374), Erythrosin (No. 886, p. 376), Phloxin (No. 890, p. 378), Bengal Rose (No. 889, p. 378), and Fluorescein (No. 880, p. 373); thiazine dyestuffs such as Methylene Blue (No. 1038, p. 449); acridine dyestuffs such as Acridine Yellow (No. 901, p. 383), Acridine Orange (No. 908, p. 387) and Trypaflavine (No. 906, p. 386); quinoline dyestuffs such as Pinacyanol (No. 924, p. 396) and Cryptocyanine (No. 927, p. 397); cyanine dyestuffs, e.g., Cyanine (No. 921, p. 394) and chlorophyll.
For the production of copies with the electrocopying material, the photoconductive coating is charged by means of, for example, a corona discharge with a charging apparatus maintained at 60004000 volts. The electro-copying material is then exposed to light in contact with a master. Alternatively, an episcopic or diascopic image is projected thereon. An electrostatic image corresponding to the master is thus produced on the material. This invisible image is developed by contact with a developer consisting of carrier and toner. The carriers used may be, for example, tiny glass balls, iron powder or tiny plastic balls. The toner consists of a resin-carbon black mixture or a pigmented resin. The toner is used in a grain size of 1 to g. The developer may also consist of a resin or pigment suspended in a non-conductive liquid in which resins may be dissolved. The image that is made visible by development is then fixed, e.g., bv heating with an infra-red radiator to 100-170 0., preferably -150 C. or by treatment with solvents such as trichloroethylene, carbon tetrachloride or ethyl alcohol, or steam. Images corresponding to the master characterized by ood contrast effect are obtained.
If transparent supporting material is used, the electrophotographic images can also be used as masters for the production of further copies on any type of light-sensitive sheets.
If translucent supports are used for photoconductive layers such as are provided by the invention, reflex images can be produced also.
The application of the activators in accordance with the present process is not restricted to electrophotographic coatings, but can extend to other devices containing photoconductors, e.g., photoelectric cells, photoresistances, sensing heads or camera tubes and electroluminescent apparatus.
The invention will be further illustrated by reference to the following specific examples:
EXAMPLE 1 A solution containing 26 parts by weight of polyvinyl acetate (e.g., Mowilith 50), 25.6 parts by weight of naphthalene, 0.0415 part by weight of 2,3,7-trinitrofiuorenone and 800 parts by volume of toluene is applied by means of a coating device to an aluminum foil. After the coating has dried, direct images are produced thereon by the electrophotographic process in the following manner: the coated foil is given a negative electric charge by corona discharge, exposed behind a master to the light of a high-pressure mercury vapor lamp watts, at a distance of 30 cm.) for about 10 seconds and then dusted over with a developer. I
The developer consists of tiny glass balls and a mixture of resin and carbon black which has been melted together and then finely divided. A developer of this sort con-- sists of, e.g., 100 parts by weight of tiny glass balls (grain size: 100-400 approx.) and a toner (grain size: 20-50 approx.). The toner is prepared by melting together 30 parts by weight of Polystyrol LG, 30 parts by weight of modified maleic acid resin (Beckacite K 105) and 3 parts by Weight of Peerless Black Russ 552. The melt is then ground and screened. The finely divided resin ad heresto the parts of the coating not struck by light during the exposure and a positive image of the master becomes visible. It is slightly heated and thereby fixed.
, If 2,4,7-trinitrofluorenone is not added to the coatings described above, even an exposure of two minutes will not produce an electrophotographic image.
EXAMPLE 2 26 parts by weight of polyvinyl acetate, 16.6 parts by weight of fluorene and 0.3602 part by weight of tetranitrofiuorenone are dissolved in 800 parts by volume of toluene. This solution is applied to an aluminum foil and further procedure is as described in Example 1. Exposure time, if a 125-watt high-pressure mercury vapor lamp is used, is seconds.
Without the .tetranitrofiuorenone addition, the images obtained even after an exposure of two minutes are not free of background, i.e., the exposed parts are not fully discharged and therefore retain a certain amount of developer.
EXAMPLE 3 A solution of 26 parts by weight of polyvinyl acetate, 17.8 parts by weight of anthracene and 0.3357 part "by weight of hexabromonaphthalic anhydride in 800 parts by volume of toluene is applied to aluminum and further procedure is as described in Example 1. With a 125-watt high-pressure mercury vapor lamp, the exposure time is 4 seconds.
8 EXAMPLE 5 A solution of 26 parts by weight of polyvinyl acetate, 21.6 parts by weight of 1,5-diethoxynaphthalene and 0.258 part by weight of 1,2-benzanthraquinone in 800 parts by volume of toluene is applied to paper and the material is further processed as described in Example 1. The exposure time (125-watt high-pressure mercury vapor lamp) is 20 seconds.
Without the 1,2-benzanthraquinone addition, the copy still has considerable background after an exposure of 80 seconds.
7 EXAMPLE 6 26 parts by weight of polyvinyl acetate, 17.8 parts by Weight of phenanthrene and 0.245 part by weight of chloranil are dissolved together in 800 parts by volume- EXAMPLE 7 A solution containing 26 parts by weight of polyvinyl acetate, 24.4 parts by Weight of o-dianisidine and 0.0256
part by Weight of dibromomaleic anhydride in 800 parts by volume of toluene is applied to an aluminum foil and the material is further processed as described in Example 1. The exposure time (l25-watt high-pressure mercury vapor lamp) is 2 seconds. Without the dibromomaleic anhydride addition, it is 10 seconds.
TABLE A N o. A B C D E Polyvinylacetate, 10 parts (1) 8 1 0 see. (b) (ca.). rln 8 Anthraquinone, 0.08 30 see. (b). rln 8 Anthraquinone, 0.17 20 see. (b). dn 8 Anthraquinone, 0.25 20 see. (b). dn 8 0. 001 sec. (b). rin 8 0. 005 60 see. (b). dn 8 0. 010 60 sec. (b). do 8 0. 030 90 see. (1)). do 8 0.050 90 see. (b). dn 8 Anthraquiuone, 0.17. 0. 001 20 sec. (b). dn 8 do 0.010 20 sec. (b). dn 8 do 0.50 20sec. (b). dn 8 240 see. (a). (ln 8 Anthraqumone, 0 180 see. (a). Cyclized rubber, 10 parts (2) 8 0 sec. (a). (]n 8 Anthraquinone, 0.25 30 see. (a).
Aiterchlorinated polyvinylchloride, 7 parts (3)- 8 10 see. (a).
Polyvinylehloride, afterchlorinated, 7 parts (3). 8 3 sec. (a). Maleic acid resin, 10 parts (4) 8 240 see. (a).
do 8 60 see. (a). Chlorinated rubber, 10 parts (5) 8 20 sec. (a). dn 8 Anthraquinone, 0.25 part- 10 see. (a). Chlorinated rubber, 10 parts (6) 8 M 0 5 0- (a). d 8 Anthraquinone, 0.25 10 see. (a).
S l,2benzanthraquinone, 0.31 part 1-l.5 see. (a). 8 Hexabromonaphthalie anhydride, 0 pa 11.5 see. (a). 8 2,4,5,7-tetranitroiluorenone, 0.43 part"--- 1.5 see. (a). 8 Dibromornalelc anhydride, 0.30 part 4-6 see. (a). 8 Nitroi'terephthalie acid-dimethylester, 0.28 6-8 see. (a).
par 8 Tetracyano ethylene, 015 part 4-6 see. (a). 8 1,3,5-trinitrobenzene, 0.25 part; 1.5-2 see. (a).
Without the hexabromonaphthalic anhydride addition, an exposure of as much as 30 seconds gives an image which contains background.
EXAMPLE 4 A solution containing 18 parts by weight of polyvinyl acetate, 18.2 parts by Weight of 2,4-bis-(4'-diethylaminophenyl)-1,3,4-triazole and 0.130 part by weight of tetrachlorophthalic anhydride to 500 parts by volume of toluene is applied to an aluminum foil and further procedure is as described in Example 1. The exposure time with a 100-watt incandescent lamp is 2 seconds. 7 7
Without the tetrachlorophthalic anhydride addition, the image obtained after an exposure of 1 minute is not free of background.
Explanations on Table A volume of toluene.
Column B: Quantity of the photoeonductor.
examples, the same amount of pyrene was used. Column C: Quantity of theactivator used.
damine B extra).
Column E: Time of exposure, using:
(a) a 250 watt photographic lamp (Philips Photocrescenta Column D: Quantity of dyestuif sensitizer used (Rho- (b) a customary watt incandescent lamp.
In all The tests were carried through under the same experimental conditions, with the exception of the variations stated in the table.
(1) The polyvinyl acetate used was the product commercially available under the registered trademark M-owilith C.
(2) The cyclized rubber used was the product commercially available under the registered trademark Pliolite S-SD.
(3) The afterchlorinated polyvinylchloride used was the product commercially available under the registered trademark Rhenoflex.
(4) The maleic acid resin used was the product commercially available under the designation Alrosat.
(5) The chlorinated rubber used in Table A, col. A, under N0. 21 (5) was the product commercially available under the registered trademark Parlon S-5 cps.
(6) The chlorinated rubber used in Table A, col. A, under N0. 23 (6) was a product commercially available under the registered trademark Pergut 8-40.
' The following Table B shows further examples of various photoconductors which were activated, and the reduction in exposure time caused by the activators:
TABLE B 26 Chloranil Hexabromonaphthalic anh dride.
2,4,5,7-tetranitrofiuorenone Hexabromonaphthalic anhydride 13.6 hydroquinonedimethylether.
25.6 naphthalene 26 2,-1.5,7-tetranitrofiuorenone l,5-dinit'r0naphthalene 1,4-benzoquinone- Chlorarlil 21.6 1,5-diethoxynaphthalene.
Tetrachlorophthalic anhydri Hexabromonaphthalic anhydride Picrylchloride 2,4,5.7-tetranitrofluorenone 15.4 acenaphthene 26 1,2-benzanthraquinone- Dibromomaleic anhydrid Hexabromonaphthalic anhydn e- Picrylchloride 2,4,5.7-tetranitrofluorenone Chloranjl Hexabrornonaphthalic anhydnde. 2,4,5,7-tetranitrofluorenone 15.2 acenaphtbylene- 26 15.4 diphenyl 18 1,2-benzanthraquiuone Tetrachlorophthalic anhydride Picrylchloride 16.6 fiuorene 26 17.8 anthmcene 26 22.8 chrysene 52 16.9 diphenylamine 26 2,4,5,7-tetranitrofluorenoue 1 ,4-benzo quinoue ChlorauiL 3,5-dinitrosalicylic acid 1,2-benzanthraquinone Dibromomaleic acid anhydride- Tetrachlorophthalic anhydridefil. Hexabromonaphthalic anhydride Picrylchloride 2,4,5,7-tetranitrofluorenone. LZ-benzanthraquinone- Dibromomaleic anhydride Tetrachlorophthalic anhydn'de.--. Hexabromonaphthalic anhydride Picrylchloride 2,4,5,7-tetranitrofluorenone 26.9 2,2'-dinaphthylamine 17.8 phenanthrene 26 :sxsssamzsssxsxxxxm:
TABLE BContinued A B C D 19.3 Z-phenyl-indole 26 Chlorauil $4 1,2-benzanthraquinone. 54 Dibromomaleic anhydride- 54 Tetrachlorophthalic auhydrid $4 Hexabromonaphthalic anhydr Picrylchloride 2,4,5,7-tetranitrofluoreno 96 16.7 carbazole 26 Chloranil ,4 1,2-benzauthraquinone. M 3,5-dinitrosalicy1ic acid $6 Dibromomaleic anhydri M Tetrachlorophthalic auhydn 96 Hexabromonaphthalic anhydride Ho Picrylchloride 2,4,5,7-tetranitrofiuorenoue. Mo 19.9 thiodiphenylamine 26 1,2-benzanthraquinone. 31% 25.48 2,4-bis-(4-diethyl- 26 2,4,5,7-tetranitrofiuorcnone- 9&0 amiuopheny1)-1,3,4- 1,2-benzanthraquinone--- Mo oxadiazole. 2,4-dichlorobenzoic acid- Mo Tetrachlorophthalic acidlo 18.2 2,4-bis-(4-diethyl- 18 3,5dinitrosalicy1icacid Mo aminophenyl)-1,3,4- 1,2-benzanthraquinone. l triazole. Dibromomaleic anhydri $6 Hexabroruonaphthalic anhydrl el-to Picrylchloride Mu 2,4,5,7-tetranitrofluorenone 3&0
Explanations on Table B The table describes a series of experiments carried through for improving the photoconductivity of organic substances by adding activators.
In Column A the quantity and nature of the substance used is stated. The substances marked with a yielded .no electrophotographic images even after an exposure time of several minutes. I
In Column B the quantity of the binder used is stated. In all of the cases, polyvinyl acetate having a K-value of 50 was used. Binder, photoconductive substance, and activator were dissolved in toluene, coated onto an aluminum foil, and dried.
In Column C the substance used as activator is stated. In all of the cases 1 mol of the activator stated under C was used per 100 moles of the substance stated under A.
In Column D the reduced time of exposure is stated which is required to produce images equal in quality to those produced without the addition of an activator. In
those cases where a prolonged exposure of the ph0tocon-- ductor yielded not even a Weak image (marked with a the calculation of the reduced time of exposure was based on the longest exposure used for the unactivated photoconductor substance.
Alternatively, the increase in sensibility obtained by the addition of activating substances may be taken from a comparison of the degrees of blackening obtained with the activated photoconductive layer and with the unactivated photoconductive layer, under the same customary step wedge (e.g. Kodak No. 2 density strip with color patches).
EXAMPLE 8 A solution containing 20 parts by weight of afterchlorinated polyvinyl chloride with a content of chlorine from 61.7 to 62.3 percent and K-value from 59 to 62, 18.01 parts by weight of 2,4,5,7-tetranitrofluorenone and 0.216 part by weight of 1,5-diethoxynaphthalene dissolved in a mixture of 450 parts by volume toluene and parts by volume butanone is applied to an aluminum foil. The subsequent procedure is that described in Example 1. The exposure time, with a 100 watt incandescent lamp at a distance of 30 centimeters is 2 seconds.
Without the addition of 1,5-diethoxynaphthalene the exposure time is about 40 seconds.
11 In the following table, the exposure times are given, which were obtained when using other photoconductors instead of the 1,5-diethoxynaphthalene.
Exposure time A solution of 12 parts by weight of chlorinated rubber (Pergut 8-40), 5.04 parts by weight of 1,3-dinitrobenzene and 0.106 part by weight of anthracene in 150 parts by volume of toluene is applied to a paper foil and the material is further processed as described in Example 1. The exposure time (125 watt high pressure mercury vapor lamp) is 20 seconds. Without the anthracene addition, even after an exposure time of 80 seconds, only traces of an image were obtained. This means that the exposed parts of the coating were not discharged and therefore still attracted developer.
In the following table the exposure times are given, which were obtained, when using other photoconductors instead of the 1,3-dinitrobenzene.
Exposure time Photoconductors (parts by weight): (seconds) 12 2,2'-dinaphthylamine, the exposure time is about 10 seconds.
EXAMPLE 12 To a solution containing 28.6 parts by weight of tetrachlorophthalic acid anhydride and20 parts by weight of afterchlorinated polyvinyl chloride in a mixture of 150 parts by volume of butanone and 450 parts by volume.
of toluene, X parts by weight of photoconductor and Y parts by weight of dyestutf sensitizer are added. In the followingptable, the amounts of the photoconductor and sensitizer are given together with the corresponding exposure times. It is advantageous to dissolve the dyestuff sensitizer in a small amount of ethyleneglycol monomethyl ether before adding it to the solution. The latter is applied to a paper base, material and further processed as described in Example 1. The light source used throughout was a 125-watt high pressure mercury vapor lamp and the distance between this lamp and the material exposed was about 30 centimeters.
Photoconductor X parts Dyestufi sensitizer Y Exposure by weight Parts by weight Time (Seconds) None None ca. 200 0.39 N-ethylcarbazole do 9 Do 0.30 Rhodamine B extra 2-3 0.54 2,2-dinaphthylamine None 4-5 Do 0.30 Rhodamine B extra"-.- 2 0.73 2,5-bis- (4'-diethylan1ino- None 4 phenyl)-1,3,4-oxdiazole.
Do 0.30 Rhodamine B extra..-" 1-2 0.025 Basischreinblau 3 G-.- 2 0.015 Brillantgreen extra 3 0.015 Kristallviolet--- 2 Do 0.015 Methylenblue 0. 5 0.39 poly-N-vinylcarbazole 0.30 Rhodamine B extra 9 Do None 20 2,2'-dinaphthylamine (0.180) 2,5-bis-(4'-diethylaminophenyl)-1,3,4 oxdiazole EXAMPLE 10 A solution containing 20 parts by Weight of the afterchlorinated polyvinyl chloride mentioned in Example 8, 21.02 parts by weight of benzile and 0.370 part by weight of benzidine in a mixture of 450 parts by volume of to1 none and 150 parts by volume of butanone is applied to an aluminum foil and the material is further processed as described in Example 1. The exposure time (125 watt high pressure mercury vapor lamp at a distance of 30 centimeters) is 10 seconds. Without the addition of the benzidine activator, even after an exposure time of 4 minutes, no electrophotographic image could be obtained.
In the following table, the exposure times are given which were obtained when using photoconductors other than benzidine.
Exposure time Photoconductors (parts by weight): (seconds) 2,2'-dinaphthylamine (0.540) 20 2,5-bis-(4'-diethylamino-phenyl) 1,3,4 oxdiazole (0.730) V 5 Poly-N-vinylcarbazole (0.390) 30 EXAMPLE 11 A solution containing 6.2 parts by Weight of afterchlorinated polyvinyl chloride, 3.94 parts by weight of 1,5-dichloronaphthalene and 0.145 part by weight of 2,5-bis- (4-diethylaminophenyl)-1,3,4-oxdiazole in a mixture of 135 parts by volume of toluene and 45 parts by volume of butanone is applied to a paper base and is further processed as described in Example 1. The exposure time (125 watt high pressure mercury vapor lamp at a distance of 30 centimeters) is 10 seconds. Without the addition of the oxdiazole compound, even after an exposure time of 40 seconds, no image could be obtained. When the oxdiazole compound is replaced by 0.120 part'by weight of EXAMPLE 13 A solution is prepared, containing 57.2 parts by weight of tetrachlorophthalic acid anhydride and parts by weight of afterchlorinated polyvinyl chloride in 700 parts i by volume toluene and suflicient butanone is added to make up 1000 parts by volume. of the resulting stock solution, one of the photoconduc tors listed below is added, and the solution is applied to an aluminum foil and further processed as described in Example 1. In the following table, the added photoconductors are indicated, and the corresponding exposure times are given. As the light source, a l25-watthigh pressure mercury vapor lamp in a distance of about 30 centimeters from the exposed material was used in all instances.
Exposure time 1 Image with heavy background,
To 50 parts by volume 13 Photoconductor (parts by weight) Exposure time Continued (seconds) Phenanthrene (0.089) Phenoxathin (0.100) 10 Stilbene (0.090) 30 2,3,5-triphenylpyrrole (0.153) 10 l,l'-dinaphthylamine (0.134) 30 l,2'-dinaphthylamine (0.134) 30 4-tolyl-l-naphthylamine (0.116) 60 2-phenylindole (0.096) 60 Acenaphthene (0.077) 60 Diphenyl (0.077) 120 N-methyldiphenylamine (0.091) 30 4-hydroxy-diphenylamine (0.092) 30 Phlorglucinediethyl ether (0.091) 120 EXAMPLE 14 57.2 parts by weight of tetrachlorophthalic acid anhydride and 65 parts by weight of polyvinyl acetate are dissolved in suflicient toluene to make up 1000 parts by volume. To 50 parts by volume of this stock solution, one of the photoconductors listed below is added and the coating solution is applied to an aluminum foil and further processed as described in Example 1. The light source and the distance of the light source from the exposed material were the same as in the foregoing example.
Exposure time (seconds) EXAMPLE 15 29.62 parts by weight of phthalic acid anhydride and 33 parts by weight of afterchlorinated polyvinyl chloride are dissolved in 670 parts by volume of toluene and 330 parts by volume of butanone. To 50 parts by volume of the resulting stock solution, one of the photoconductors listed in the following table is added; these coating solutions are applied to an aluminum foil, and further processed as described in Example 1. The light source and the distance of the light sourcewere the same as in Example 13.
Exposure time Photoconductor (parts by weight): (seconds) None 1 60 N-ethylcarbazole (0.10) 5 Anthracene (0.09) Chrysene (0.114) Pyrene (0.10) 10 2,2'-dinaphthylamine (0.134) 10 2,3,5-triphenylpyrrole (0.153) 10 1 No image obtained.
EXAMPLE 16 49.2 parts by weight of chloranil and 56 parts by weight of afterchlorinated polyvinyl chloride are dissolved in a mixture of 1170 parts by volume of toluene and parts by volume of butanone. The resulting solution is filled up to 2000 parts by volume with chlorobenzene. To 100 parts by volume of this stock solution, one of the photoconductors listed in the following table is added; the coating solution is applied to an aluminum foil and further processed as described in Example 1. The light source and the distance of the light source were the same as in Example 13.
Exposure time Photoconductor (parts by weight): (seconds) None 180 Naphthalene (0.064) ca. Hydroquinonedimethyl ether (0.070) 30' N-ethylcarbazole (0.097) 10 Anthracene (0.090) 5 Chrysene (0.114) 15 Pyrene (0.10) 10 o-Dianisidine (0.122) 5 2,6-dimethyl-naphthalene (0.078) 30 Hexamethylbenzene (0.081) 120 2,2'-dinaphthylamine (0.134) 1-2 2,5 -bis- (4-diethyl aminophenyl 1, 3,4-oxdiazole (0.182) 1 2,3,5-tiiphenylpyrrole (0.153) 4 EXAMPLE 17 10.6 parts by weight of 2-acetyl fluorene and 12 parts by weight of afterchlorinated polyvinyl chloride are dissolved in parts of toluene and sufi'icient butanol to make up 250 parts by volume of solution. To 50 parts by volume of this stock solution, one of the photoconductors of the following table is added. The solution is applied to an aluminum foil and further processed as described in Example 1. The light source and the distance of the light source were the same as in Example 13.
Exposure time Photoconductor (parts by weight): (seconds) None 1 180 o-Dianisidine (0.120) 30 2,5 -bis- 4'-diethylaminophenyl) -1,3 ,4-oxdiazole 1 No image obtained,
EXAMPLE 18 44 parts by weight of 9 acetyl-anthracene and 48 parts by Weight of afterchlorinated polyvinyl chloride are dissolved in 700 parts by volume of solution. To 50 parts by volume of the resulting stock solution, one of the photoconductors of the following table is added. This solution is applied to an aluminum foil and further processed as described in Example 1. The light source and the distance thereof was the same as in Example 13.
Exposure time Photoconduc-tor (parts by weight): (seconds) None 1 180 Hydroquinonedimethyl ether (0.069) 30 N-ethyl carbazole (0.097) 60 Anthracene (0.089) 60 Hexamethylbenzene (0.081) 30 1 Image with heavy background.
EXAMPLE 19 46.2 parts by weight of pyrene-3-aldehyde and 50 parts by weight of afterchlorinated polyvinyl chloride are dissolved in 670 parts by volume of toluene and suflicient butanol to make up 1000 parts by volume of solution. To 5 0 parts by volume of the resulting stock solution one of the photoconductors of the following table is added. The solution is applied to an aluminum foil and further processed as described in Example 1. The light source 15 and the distance of the light source were the same as'in Example 13.
Exposure time Photoconductor (parts by weight): (seconds) None 30 Naphthalenev (0.064) 20 Hydroquinonedimethyl ether (0.070) 20 N-ethylcarbazole (0.10) 10 Anthracene (0.090) 20 Chrysene' (0.114) 20 Pyrene (0.10) 20 Hexamethylbenzene (0.080) 20 2,2'-dinaphthylamine (0.135) 15 2,5 -bis- (4-diethylaminophenyl) -l ,3 ,4-oxdiazole (0.180) 2,3,5-triphenylpyrrole (0. 150) 20 EXAMPLE 20 13.1 parts by weight of '1,4,5-trinitronaphthalene and 15 parts by weight of afterchlorinated polyvinyl chloride were dissolved in 180 parts by volume of toluene and sufiicient butanone to make up 250 parts by volume. To 50 parts of the resulting stock solution, one of the photoconductors of the following table is added in the amount indicated. This solution is applied to an aluminum foil and further processed as described in Example 1.. The light source and the distance thereof were the same as in Example 13.
Exposure time Photoconductor (parts by weight): (seconds) None 1 180 N-ethylcarbazole (0.10) 30 Anthracene (0.09) 30 o-Dianisidine (0.12)
2,5-bis-(4'-diethylaminophenyl)-l,3,4-oxdiazole 1 Image with heavy background.
in which R stands for a residue selected from the group consisting of hydrogen, aryl, alkenyl, alkyl, and hetero cyclic groups, R stands for a residue selected from the group consisting of hydrogen, alkyl, alkylated aminoaryl and aryl groups, and R stands tfor a residue selected from the gruop consisting of hydrogen and an aryl group, the compound containing at least two aryl groups.
2. A sensitized photoconductive layer according to claim 1 in which the photoconductor is 2,5-diphenyloxazole.
3. A sensitized photocond-uctive layer according to claim 1 in which the photoconductor is 2-p-dimethylamino-'4,S-diphenyloxazole.
4.. A sensitized photoconductive layer comprising at least one solid, non-resinous, substantially colorless electron-acceptor, and a compound having the formula in which R stands for a residue selected (from the group consisting of hydrogen, aryl, alkenyl, alkyl, and heterocyclic groups, R stands for a residue selected from the group consisting of hydrogen, alkyl, alkylated aminoaryl and aryl groups, and R stands for a residue selected from the group consisting of hydrogen and an aryl "group, the compound containing at least two aryl groups; the layer containing the photoconductor and the electronaoceptor in proportions ranging from substantially less than equal amounts to a substantial excess of the photoconductor with repect to the electron-acceptor and from substantially less than equal amounts to a substantial excess of the electron-acceptor with respect to the photoconductor.
5. A sensitized photoconductiye layer comprising at least one solid, non-resinous, substantially colorless electron acceptor, and a compound having the formula in which R stands for a residue selected from the group consisting of hydrogen, aryl, alkenyl, alkyl, and heterocyclic groups, R stands for a residue selected fromthe group consisting of hydrogen, alkyl, alk-ylated aminoaryl and aryl groups, and R stands for a residue selected from the group consisting of hydrogen and an aryl group,
the compound containing at least two aryl groups; in.
proportions ranging from about 0.1 to about 300 moles of the electron-acceptor per. 1000 moles of photoconductor.
6. A sensitized photoconductive layer comprising at least one solid, non-resinous, substantially colorless electron-acceptor, and a compound having the formula in which R stands for a residue selected from the group consisting of hydrogen, aryl, alken-yl, alkyl, and heterocyclic groups, R stands for a residue selected from the group consisting of hydrogen,-alkyl, alkylated aminoaryl and aryl groups, and R stands for a residue selected from the group consisting of hydrogen and an aryl group, the compound containing at least two aryl groups; in proportions ranging from about 0.1 to about 300 moles of the photoconductor per 1000'moles of the electron-;
acceptor.
7. A sensitized photoconductive layer comprising at least one solid, non-resinous, substantially colorless electron-acceptor, and a compound having the formula in which R stands for a residue selected from the group in which R stands for a residue selected from the group consisting of hydrogen, aryl, alkenyl, alkyl, and heterocyclic groups, R stands for a residue selected from the group consisting of hydrogen, alkyl, alkylated aminoaryl and aryl groups, and R stands for a residue selected 17 from the group consisting of hydrogen and an aryl group, the compound containing at least two aryl groups; in proportions rang'gm-g from about 1 to about 50 moles of the photoconductor per 1000 moles of the electron-acceptor.
9. A layer according to claim 1 in which the electronacceptor is 2,4,7-tninitrofluorenone.
10. A layer according to claim -1 in which the electron-acceptor is tetnanitrofluorenone.
11. A layer according toclaim 1 in which the electro-acceptor is hexabromonaphthalic anhydn'de.
12. A layer according to claim 1 in which the electronacceptor is tetrachlo rophthal-ic anhydride.
13. A layer according to claim 1 in which the electronacceptor is 1,2-benzanthraquinone.
14. A layer according to claim 1 in which the electroacceptor is chloranil.
15. A layer according to claim 1 in which the electroacceptor is diblromomaleic anhyd-ride.
16. A layer according to claim 1 including a resin.
17. A layer according to claim 1 including a dyestufi sensitizer.
18. A photographic reproduction process which comprises exposing an electrostatically charged, supported photoconductive insulating layer to light under a master and developing the resulting image with an electroscopic material, the photoconductive layer comprising at least one solid, non-resinous, substantially colorless electronacceptor, and a compound having the formula in which R stands for a residue selected from the group consisting of hydrogen, aryl, alkenyl, alkyl, and heterocyclic groups, R stands for a residue selected from the group consisting of hydrogen, alkyl, alkylated aminoaryl and aryl groups, and R stands for a [residue selected firom the group consisting of hydrogen and an aryl group, the compound containing :at least two aryl groups.
19. A process according to claim 18 in which the photoconductor is 2,5-diphenyloxazole.
20. A process according to claim 18 in which the photoconductor is 2-p-dimethylamino-4,S-diphenyloxazole.
21. A photographic reproduction process which comprises exposing an electrostatically charged, supported photoconductive insulating layer to light under a master and developing the resulting image with an electroscopic material, the photoconductive layer comprising at least one solid, non-resinous, substantially colorless electronacceptor, and a compound having the formula in which R stands for a residue selected from the group consisting of hydrogen, aryl, alkenyl, alkyl, and heterocyclic groups, R stands for a residue selected from the group consisting of hydrogen, alkyl, alkylated aminoaryl and aryl groups, and R stands for a residue selected from the group consisting of hydrogen and an aryl group, the compound containing at least two aryl groups; the layer containing the photoconductor and the electron-acceptor in proportions ranging from substantially less than equal amounts to a substantial excess of the photoconductor with respect to the electron-acceptor and from substantially less than equal amounts to a substantial excess of the electron-acceptor with respect to the photoconductor.
22. A photographic reproduction process which comprises exposing an electrostatically charged, supported photoconductive insulating layer to light under a master and developing the resulting image with an electroscopic material, the photoconductive layer comprising at least one solid, non-resinous, substantially colorless electronacceptor and a compound having the formula in which R stands for a residueselected from the group consisting of hydrogen, aryl, alkenyl, alkyl, and heterocyclic groups, R stands for a residue selected from the group consisting of hydrogen, alkyl, alkylated aminoaryl and aryl groups, and R stands for -a residue selected from the groupconsisting of hydrogen and an aryl group, the compound containing at least two aryl groups; in proportions ranging from about 0.1 to about 300 moles of the electron-acceptor per 1000 moles of photoconductor. r
23. A photographic reproduction process which comprises exposing an electrostatically charged, supported photoconductive insulating layer to light under a master and developing the resulting image with an electroscopic material, the photoconductive layer comprising at least one solid, non-resinous, substantially colorless electronacceptor and a compound 'having the formula are N in which R stands for a residue selected from the group consisting of hydrogen, aryl, alkenyl, alkyl, and heterocyclic groups, R stands for a residue selected from the group consisting of hydrogen, alkyl, alkylated aminoaryl and aryl groups, and R stands fora residue selected from the group consisting of hydrogen and an aryl group,
t i Rr-C l-R in which R stands for a residue selected from the group consisting of hydrogen, aryl, alkenyl, alkyl, and heterocyclic groups, R stands for a residue selected from the group consisting of hydrogen, alkyl, alkylated aminoaryl and :aryl groups, and R stands for a residue selected from the group consisting of hydrogen and an aryl group, the compound containing at least two aryl groups; in proportions ranging from about 1 to about 50 moles of the electron-acceptor per 1000 moles of the photoconductor.
25. A photographic reproduction process which comprises exposing an electrostatically charged, supported photoconductive insulating layer to light under a master and developing the resulting image with an electroscopic material, the photoconductive layer comprising at least one solid, non-resinous, substantially colorless electronacceptor and a compound having the formula Bi |T i 2C C-R in which R stands for a residue selected from the group consisting of hydrogen, aryl, alkenyl, alkyl, and heterocyclic groups, R stands for a residue selected from the group consisting of hydrogen, alkyl, alkylated aminoaryl and aryl groups, and R stands for a residue selected from the group consisting of hydrogen and an aryl group, the
28. A process according to'claim 21 in which the electron-acceptor is hexabromonaphthalic anhydride.
29. A process according to claim 21 in which the electron-acceptor is tetrachlorophthalic anhydridc.
30. A process according to claim 21 in which the electron-acceptor is 1,2-benzanthraquinone.
31. A process according to claim 21 in which the elec- .tronacceptr is chloranil.
32. A process according to claim 21 in which the electron-acceptor is dibromomaleic anhydride.
33. A process according to claim 21 in which the layer includes a resin.
34. A process according to claim 21 in which the layer includes a dyestuff sensitizer.
References Cited By the Examiner UNITED STATES PATENTS 3,037,861 6/1962 Hoegl et a1. -96-11 73,113,022 12/1963 Cassiersetal. 961, 3,155,503 11/1964 Cassiers et a1. '96 1 OTHER REFERENCES Czekalla et al.: Chemical Abstracts, 52:4317h (1957). Schneider and Compton et al.: Journal of Chemical Physics, vol. 358, 1075-1076 (1956 NORMAN G. TORCHIN, Primary Examiner. C. E. VAN HORN, Assistant Examiner.
Andrews, Chemical Reviews, 54: 713-777, October

Claims (1)

1. A SENSITIZED PHOTOCONDUCTIVE LAYER COMPRISING AT LEAST ONE SOLID, NON-RESINOUS, SUBSTANTIALLY COLORLESS ELECTRON-ACCEPTOR AND A COMPOUND HAVING THE FORMULA
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4006017A (en) * 1974-03-25 1977-02-01 Xerox Corporation Photoconductive composition, article and process
US4018602A (en) * 1975-04-17 1977-04-19 Xerox Corporation Method for in situ fabrication of photoconductive composite
US4105447A (en) * 1975-07-14 1978-08-08 Eastman Kodak Company Photoconductive insulating compositions including polyaryl hydrocarbon photoconductors
US4201591A (en) * 1977-12-08 1980-05-06 Eastman Kodak Company Electrically activated recording material and process
US4201583A (en) * 1977-12-08 1980-05-06 Eastman Kodak Company Electrically activated recording material and process

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3037861A (en) * 1957-09-07 1962-06-05 Kalle Ag Electrophotographic reproduction material
US3113022A (en) * 1959-02-26 1963-12-03 Gevaert Photo Prod Nv Electrophotographic process
US3155503A (en) * 1959-02-26 1964-11-03 Gevaert Photo Prod Nv Electrophotographic material

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3037861A (en) * 1957-09-07 1962-06-05 Kalle Ag Electrophotographic reproduction material
US3113022A (en) * 1959-02-26 1963-12-03 Gevaert Photo Prod Nv Electrophotographic process
US3155503A (en) * 1959-02-26 1964-11-03 Gevaert Photo Prod Nv Electrophotographic material

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4006017A (en) * 1974-03-25 1977-02-01 Xerox Corporation Photoconductive composition, article and process
US4018602A (en) * 1975-04-17 1977-04-19 Xerox Corporation Method for in situ fabrication of photoconductive composite
US4105447A (en) * 1975-07-14 1978-08-08 Eastman Kodak Company Photoconductive insulating compositions including polyaryl hydrocarbon photoconductors
US4201591A (en) * 1977-12-08 1980-05-06 Eastman Kodak Company Electrically activated recording material and process
US4201583A (en) * 1977-12-08 1980-05-06 Eastman Kodak Company Electrically activated recording material and process

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