US3139338A - Electrophotographic material and process - Google Patents

Electrophotographic material and process Download PDF

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Publication number
US3139338A
US3139338A US14210A US1421060A US3139338A US 3139338 A US3139338 A US 3139338A US 14210 A US14210 A US 14210A US 1421060 A US1421060 A US 1421060A US 3139338 A US3139338 A US 3139338A
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United States
Prior art keywords
formula
photoconductive
layer
compound
resins
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Expired - Lifetime
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US14210A
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English (en)
Inventor
Schlesinger Heinz
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Azoplate Corp
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Azoplate Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D257/00—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms
    • C07D257/02—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
    • G03G5/0622—Heterocyclic compounds
    • G03G5/0624—Heterocyclic compounds containing one hetero ring
    • G03G5/0642—Heterocyclic compounds containing one hetero ring being more than six-membered
    • 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
    • G03G5/0644—Heterocyclic compounds containing two or more hetero rings
    • G03G5/0661—Heterocyclic compounds containing two or more hetero rings in different ring systems, each system containing at least one hetero ring

Definitions

  • This dry reproduction process is becoming of particular interest in certain fields, for example, office duplicating, and it consists of the application to a material, consisting of'a support and a photoconductive insulating layer adherent thereto, of an electrostatic charge which imparts to the insulating layer the property of light-sensitivity.
  • a material consisting of'a support and a photoconductive insulating layer adherent thereto, of an electrostatic charge which imparts to the insulating layer the property of light-sensitivity.
  • Such light-sensitive material can be used for the production of images by electrophotographic means; it is exposed to light beneath a master, so that the electrostatic charge is leaked away in the parts of the layer struck by light.
  • the invisible electrostatic image thereby produced is made visible (developed) by powdering over with finely divided, colored, synthetic resin and then made permanent (fixed) by the application to the support of heat.
  • Material known for the preparation of the photoconductive insulating layers required for the aforedescribed process include selenium, sulphur, zinc oxide, and also organic substances, such as anthracene or anthraquinone. Consideration has also been given to a method of preparation of the photoconductive insulating layers whereby the photoconductive substances, in association with binders, are dispersed in solvents and the resultant dispersions are applied to electrically conductive supports,
  • the photoelectrically sensitizable material thus obtained has not yet satisfied the extensive demands made upon modern duplicating material as regards range of use, reliability, simplicity in handling and, not least in importance, 1ightsensitivity and storageability qualities.
  • the present invention can be prepared by condensing dihydrazones of aromatics or heterocyclic 1,2-diketones With equimolecular quantities of such 1,2- diketones, either by fusing the reactants with each other at temperatures ranging above 100 C. using, if desired, higher pressure, or by heating the reactants with each other in a dissolved state.
  • All the other 1,2,5,6- tetraaza-cyclooctatetraenes-(2,4,6,8) to be used according to thepresent invention can be prepared by analogous methods, if need be with slight changes in the conditions employed during reaction.
  • benzil. 12 4-methoxy-benzil 229-230 D0. 13 2,2-dihydr0Xy-5,5- 279-280 D0.
  • the compounds to be used in accordance with the invention have very good light-sensitivity and are particularly suitable for the production of homogeneous layers with unlimited shelf life.
  • solvents there may be used organic solvents such as chloroform, benzene, acetone, methylene chloride, ethyleneglycol monomethylether, and others, or mixtures of such solvents.
  • organic solvents such as chloroform, benzene, acetone, methylene chloride, ethyleneglycol monomethylether, and others, or mixtures of such solvents.
  • the compounds to be used according to the present invention can also be used in admixture with each other or with other organic photoconductive substances.
  • water-insoluble natural and synthetic resins e.g., balsam resins, phenol resins modified with colophony, and other resins of which colophony constitutes the major part, coumarone resins and indene resins and the substances covered by the collective term synthetic lacquer resins, which according to the Kunststoffstofiftaschenbuch (Plastics Pocket Book) published by Saechtling-Zebrowski (11th edition, 1955, page 212 at seq.) include processed natural substances such as cellulose ether; polymers such as polyvinyl chlorides, polyvinyl acetate, polyvinyl acetals, polyvinyl ethers, polyacrylic and polymethacrylic esters, as also polystyrene and isobutylene;
  • the proportion of resin to photoconductive substance can vary very greatly.
  • the use of mixtures of approximately equal parts of resin and l,2,5,6-tetraaza-cyclooctatetraene-(2,4,6,8) compound has been found advantageous. If such mixtures of approximately equal parts of resin and tetraene compound are used, their solution in most cases gives, on drying, transparent layers which are regarded as solid solutions.
  • the base materials used as electroconductive supports may be any that satisfy the requirements of xerography,
  • pretreatment of the paper against penetration of the coating solution is advisable, e.g., with methyl cellulose in aqueous solution or polyvinyl alcohol in aqueous solution or with a solution 111 acetone and methylethylketone of a copolymer of acrylic acid methyl ester and acrylonitrile or with solutions of polyamides in aqueous alcohols.
  • Aqueous dispersions of substances suitable for thepretreatment of the paper surface may also be used.
  • the layers After the layers have beenpositively or negatively charged, by means of, for example, a corona discharge, they are light-sensitive and canbe used advantageously with long-Wave UV. light of 36004200 A. for electrophotographic image production. Very short exposure under a master to a high pressure mercury lamp will give good images. a
  • sensitizers dyestuifs inparticular are suitable, for the readier identification of which the number is given under which they are listed in Schultz Farbstofftabellen (7th edition, 1st vol., 1931).
  • triarylmethane dyestuffs such as Brillant Green (No. 760, p. 31 4), Victoria Blue B (No. 822, p. 347), Methyl Violet (No. 783, p. 327), Crystal Violet (No. 785, p. 329), Acid Violet 6B (N0. 831, p.
  • xanthene dyestutfs namely rhodamines, such as Rhodamine B (No. 864, p. 365), Rhodamine 66 (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.
  • rhodamines such as Rhodamine B (No. 864, p. 365), Rhodamine 66 (No. 866, p. 366), Rhodamine G Extra (No. 865, p. 366), Sulphor
  • the production of images by electrophotographic means is performed as follows: when the photoconductive layer has been charged by means of, for example, a corona discharge with a charging apparatus maintained at 6000- 7000 volts, the support, e.g., paper or aluminum foil or plastic film, with the sensitized coating, is exposed to light under a master or by episcopic or diascopic projection and is then dusted over in known manner With a resin powder colored with carbon black.
  • the image that now becomes visible can be easily wiped oif. It therefore must be fixed; it can, for example, be briefly heated to about 120 C. or, according to the fusion temperature of the developer used, it can be exposed to infrared radiation. The temperature required is less if the heat treatment is effected in the presence of vapors of solvents such as trichloroethylene, carbon tetrachloride or ethyl alcohol.
  • the fixing of the powder image can also be accomplished by steam treatment. From positive masters, positive images, characterized by good contrast, are produced.
  • the electro-photographic images can also be used as masters for the production of additional copies on any type of light-sensitive sheet.
  • the photoconductive compounds to be used as provided by the invention are superiorto the substances used hitherto, such as selenium or zinc oxide, inasmuch-as the latter produce only cloudy layers not readily capable of further reproduction, because solid solutions can not be produced with these materials, and only suspensions are possible.
  • the production of a reflex copy also constitutes an advance over the known art.
  • the photoconductive layers prepared in accordance with the invention have a further important advantage in that they can be charged positively as well as negatively. With positive charging the images are particularly good and evolution of ozone, which with negative charging is very copious and, because it is injurious to health calls for the adoption of special measures, such as the installation-of fans, is scarcely to be detected.
  • Example 1 0.5 g. of 3,4-di-(4rphenoxy-phenyl)-7,8-diphenyl-1,2, 5,6-tetraaza-cyclooctatetraene-(2,4,6,8) corresponding to Formula 4, and 0.5 g. of a ketone resin, e.g., the product commercially'available under the designation Kunststoffharz EM, are dissolved in 15 ml. of chloroform and the solution is coated onto paper, the surface of which had been pretreated to, prevent the penetration of organic solvents, and dried. By means of the thus coated paper, a direct image is produced in an electrophotographic process.
  • a ketone resin e.g., the product commercially'available under the designation Kunststoffharz EM
  • the coated dried layer With a corona discharge produced by means of a charging apparatus maintained at about 6000 volts, the coated dried layer is provided with a negative electric charge, then exposed under a positive original using a high pressure mercury lamp, and then dusted over in known manner with a developer powder.
  • the developer used consists of small glass balls and a very finely divided resin-carbon black mixture.
  • the black colored resin adheres to those parts of the layer which were not struck by light during exposure and, thus, a positive image of the original becomes visible, which is fixed by heating.
  • the developer used consists of g. of glass balls of .a particle size from 300 to 400 and 2.5 g. of a toner having a particle size from 20 to 50
  • the toner is produced by meltlng together, grinding and sitting:
  • resin-modified maleic acid resin e.g., the prod uct commercially available under the registered trademark Beckacite K105, and L 3 g. of carbon black, e.g., the product commercially available under the designation Peerless Black Russ 552.
  • Example 2 Paper is coated as described in Example 1 and the layer thus produced is positively charged by means of a corona discharge. After exposure under an original, the
  • the solution thus obtained is coated onto an aluminum foil and dried to form a layer which adheres firmly to the support.
  • An electrophotographic image is produced on this material in known manner.
  • Example 4 The process described in Example 1 is followed with the modification that for coating the base paper a solution is used containing 0.5 g. of 3,4-di-(4'-methoxy-phenyl)- 7,8 diphenyl-l,2,5,6-tetraaza-cyclooctatetraene-(2,4,6,8) corresponding to Formula 2, and 0.5 g. of Zinc resin, e.g., of the product commercially available under the designation Erkazit Zinkharz 165, in 15 ml. of chloroform.
  • Zinc resin e.g., of the product commercially available under the designation Erkazit Zinkharz 165
  • Example 6 0.5 g. of 3,4-di-pyridyl-(2')-7,8-diphenyl-1,2,5,6-tetraaza-cyclooctatetraene-(2,4,6,8 corresponding to Formula 5, and 0.5 g. of a ketone-aldehyde condensation resin, e.g., the product commercially available under the designation Kunststoffharz AP are dissolved in 3 ml. of chloroform and the solution is coated onto a superficially roughened aluminum surface. After evaporation of the solvent, a layer remains'which adheres firmly to the surface of the aluminum foil. The thus coated foil is treated as described in Example 1 whereby after fixing the powder image, a positive image is produced on the aluminum surface.
  • a ketone-aldehyde condensation resin e.g., the product commercially available under the designation Kunststoffharz AP
  • Example 7 0.5 g. of 3,4,7,8-tetraphenyl-1,2,5,6-tetraaza-cyclooctatetraene-(2,4,6,8), corresponding to Formula 1, and 0.5 g. of polyvinylacetate, e.g., the product commercially available under the registered trademark Mowilith 50, and 0.5 mg. of Rhodamine B-extra (Schultz, Farbstoiftabellen, 7th edition, vol. 1, No. 864), dissolved in 0 .1 ml. of methanol, are dissolved in 7 ml. of chloroform and an aluminum foil is coated with this solution. After drying, an electrophotographic image is produced as described in Example 1, but instead of a high pressure mercury lamp, a 100 watt incandescent lamp is used for exposure.
  • Rhodamine B-extra Schoultz, Farbstoiftabellen, 7th edition, vol. 1, No. 864
  • An electrophotographic material comprising ductive support layer and a photoconductive insulating mula layer, the latter" comprising a compound having the formula in which R R R and R are selected from the group consisting of aryl groups and heterocyclic groups of aromatic nature.
  • An electrophotographic material comprising a conductive support layer and a photoconductive insulating layer, the latter comprising a compound having the formula 5.
  • An electrophotographic material comprising a conductive support layer and a photoconductive insulating layer, the latter comprising a compound having the for- 6.
  • An electrophotographic material comprising a conductive support layer and a photoconductive insulating layer, the latter comprising a compound having the formula 7.
  • An electrophotographic material comprising a conductive support layer and a photoconductive insulating layer, the latter comprising a compound having the formula 9.
  • An electrophotographic material comprising a conductive support layer and a photoconductive insulating layer, the latter comprising a compound having the for 10.
  • An electrophotographic material comprising a conductive support layer and a photoconductive insulating layer, the latter comprising a compound having the formula 11.
  • An electrophotographic material comprising a conductive support layer 'and a photoconductive insulating layer, the latter comprising a compound having the formula CHaO- CHzO- 12.
  • An electrophotographic material comprising a conductive support layer and a photoconductive insulating layer, the latter comprising a compound having the formula ffCgLiHi 13.
  • An electrophotographic material comprising a conductive support layer and a photoconductive insulating layer, the latter comprising a compound having the formula 14.
  • An electrophotographic material comprising a conductive support layer and a photoconductive insulating layer, the latter comprising a compound having the formula 15.
  • An electrophotographic material comprising a conductive support layer and a photoconductive insulating in layer, the latter comprising a compound having the formula 16.
  • a photographic reproduction process which comprises electrically charging a supported photoconductive insulating layer, exposing it to light under a master, and developing the resulting image, the photoconductive layer comprising a compound having the formula 20.
  • a photographic reproduction process which c0m prises electrically charging a supported photoconductive insulating layer, exposing it to light under a master, and
  • a photographic reproduction process which comprises electrically charging a supported photoconductive insulating layer, exposing it to light under a master, and developing the resulting image, the photoconductive layer comprising a compound having the formula N- '22.
  • a photographic reproduction process which comprises electrically charging a supported photoconductive insulating layer, exposing it to light under a master, and
  • a photographic reproduction process which com- 29.
  • a photographic reproduction process which comprises electrically charging a supported photoconductive prises electrically charging a supported photoconductive insulaung layer, exposing it-to light under a master, and insulating layer, exposing it to light under a master, and develop ng the resulting image, the photoconductive layer developing the resulting image, the photoconductive layer compnsing a compound having the formula 5 comprising a compound having the formula N N l /N-N ⁇ OH: Q Q N i l CH;
  • a photograph1c reproduction process which co n 24 A Photographic reproduction process which prises electrically charging a supported photoconductive prises electrically charging a supported photoconductive msulatlqg layer 6x13951115 It to hght under and insulating layer exposing it to light under a master, and develop ng the resulting image, the photoconductive layer developing the resulting image, the photoconductive layer compnsmg a compound havmg the formula comprising a compound having the formula 25.
  • a photographic reproduction process whichcomprises electrically charging a supported photoconductive An electrophomgraphlc matenal comPnslPg f insulating layer, exposing it to light under a master, and 0 ducnve Support layer a photoconductlve mulalmg developing the resulting image, the photoconductive layer layer the latter compnsmg a Compound havmg the comprising a compound having the formula formula N OH can a A :3, 3 i 3 3 26.
  • a photographic reproduction process which com- 4O ⁇ O prises electrically charging a supported photoconductive insulating layer, exposing it to light under a master, and developing the resulting image, the photoconductive layer comprising a compound having the formula I r 32.
  • a photographic reproduction PI'OCGSS'WhlCh comprises electrically charging a supported photoconductive I-I:OC C -'OC2H5 insulating layer, exposing it to light under a master, and l I developing the resulting image, the photoconductive layer 02m comprising a compound having the formula N-N OH 27.
  • a photographic reproduction process which comprises electrically charging a supported photoconductive 1 C insulating layer, exposing it to light under a master, and 7 developing the resulting image, the photoconductive layer O C comprising a compound having the formula i B 3 I l References Cited in the file of this patent f UNITED STATES PATENTS 28.
  • a photographic reproduction process which com- 2,663,636 Middleton Dec. 22,5195?
  • Baines The Science of Photography, Fountain Press (1958), pages 104-105.,TR200. B3.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Photoreceptors In Electrophotography (AREA)
  • Press-Shaping Or Shaping Using Conveyers (AREA)
  • Paints Or Removers (AREA)
US14210A 1959-03-18 1960-03-11 Electrophotographic material and process Expired - Lifetime US3139338A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEK37258A DE1110007B (de) 1959-03-18 1959-03-18 Material fuer elektrophotographische Reproduktion

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US3139338A true US3139338A (en) 1964-06-30

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US (1) US3139338A (enrdf_load_stackoverflow)
DE (2) DE1110007B (enrdf_load_stackoverflow)
GB (1) GB937496A (enrdf_load_stackoverflow)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE960348C (de) * 1953-10-14 1957-03-21 Dorstener Eisengiesserei U Mas Drehtischpresse mit Lochdornen
US3542546A (en) * 1966-11-29 1970-11-24 Eastman Kodak Co Organic photoconductors containing the >n-n< nucleus

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2663636A (en) * 1949-05-25 1953-12-22 Haloid Co Electrophotographic plate and method of producing same
US2859211A (en) * 1956-08-02 1958-11-04 Geigy Chem Corp 1, 2-diaryl-1, 2-diaza cyclobutanone-3-carboxylic acid derivatives
US2878245A (en) * 1958-01-15 1959-03-17 Parke Davis & Co Norleucine derivatives and process for producing same
US2937944A (en) * 1957-11-20 1960-05-24 Haloid Xerox Inc Xerographic light-sensitive member and process therefor
US2940848A (en) * 1959-03-11 1960-06-14 Gen Aniline & Film Corp Photoconductive layer for recording element and method of producing same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2663636A (en) * 1949-05-25 1953-12-22 Haloid Co Electrophotographic plate and method of producing same
US2859211A (en) * 1956-08-02 1958-11-04 Geigy Chem Corp 1, 2-diaryl-1, 2-diaza cyclobutanone-3-carboxylic acid derivatives
US2937944A (en) * 1957-11-20 1960-05-24 Haloid Xerox Inc Xerographic light-sensitive member and process therefor
US2878245A (en) * 1958-01-15 1959-03-17 Parke Davis & Co Norleucine derivatives and process for producing same
US2940848A (en) * 1959-03-11 1960-06-14 Gen Aniline & Film Corp Photoconductive layer for recording element and method of producing same

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DE1110007B (de) 1961-06-29
DE111007C (enrdf_load_stackoverflow)
GB937496A (en) 1963-09-25

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