US3174856A - Electrolytic recording sheets - Google Patents

Electrolytic recording sheets Download PDF

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Publication number
US3174856A
US3174856A US116092A US11609261A US3174856A US 3174856 A US3174856 A US 3174856A US 116092 A US116092 A US 116092A US 11609261 A US11609261 A US 11609261A US 3174856 A US3174856 A US 3174856A
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Prior art keywords
photoconductive
binder
weight percent
electrically conductive
particles
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US116092A
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English (en)
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Einar D Horne
David A Morgan
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3M Co
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Minnesota Mining and Manufacturing Co
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Publication date
Priority to BE615645D priority Critical patent/BE615645A/xx
Priority to NL276497D priority patent/NL276497A/xx
Application filed by Minnesota Mining and Manufacturing Co filed Critical Minnesota Mining and Manufacturing Co
Priority to US116092A priority patent/US3174856A/en
Priority to DEP1272A priority patent/DE1272124B/de
Priority to ES0274922A priority patent/ES274922A1/es
Priority to FI0647/62A priority patent/FI43263B/fi
Priority to CH362962A priority patent/CH433990A/de
Priority to FR898708A priority patent/FR1332605A/fr
Priority to GB22383/62A priority patent/GB1017114A/en
Application granted granted Critical
Publication of US3174856A publication Critical patent/US3174856A/en
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/05—Organic bonding materials; Methods for coating a substrate with a photoconductive layer; Inert supplements for use in photoconductive layers
    • G03G5/0528—Macromolecular bonding materials
    • G03G5/0532—Macromolecular bonding materials obtained by reactions only involving carbon-to-carbon unsatured bonds
    • G03G5/0535—Polyolefins; Polystyrenes; Waxes
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G17/00—Electrographic processes using patterns other than charge patterns, e.g. an electric conductivity pattern; Processes involving a migration, e.g. photoelectrophoresis, photoelectrosolography; Processes involving a selective transfer, e.g. electrophoto-adhesive processes; Apparatus essentially involving a single such process
    • G03G17/02—Electrographic processes using patterns other than charge patterns, e.g. an electric conductivity pattern; Processes involving a migration, e.g. photoelectrophoresis, photoelectrosolography; Processes involving a selective transfer, e.g. electrophoto-adhesive processes; Apparatus essentially involving a single such process with electrolytic development
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/05—Organic bonding materials; Methods for coating a substrate with a photoconductive layer; Inert supplements for use in photoconductive layers
    • G03G5/0528—Macromolecular bonding materials
    • G03G5/0532—Macromolecular bonding materials obtained by reactions only involving carbon-to-carbon unsatured bonds
    • G03G5/0553—Polymers derived from conjugated double bonds containing monomers, e.g. polybutadiene; Rubbers
    • 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
    • G03G5/08—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being inorganic
    • G03G5/087—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being inorganic and being incorporated in an organic bonding material

Definitions

  • This invention relates to new and useful sheets for the reproduction of visible images.
  • this invention relates to improved image recording sheets which can be developed by electrolytic techniques.
  • this invention relates to a method for the preparation of such sheets and to a method for their use in image reproduction.
  • Photoconductive coatings and sheet materials have been suggested for various purposes, including the reproduction of light images.
  • Electrofax process an ordinary paper base is coated with photoconductive zinc oxide in a resinous binder.
  • the sheet is electrostatically charged, exposed to a light image, and the remaining electrostatic charge developed with a charged powder as in the conventional xerographic process, except that the image is permanently retained on the coated paper, the powder being fused in place.
  • the sensitive papers used in these processes have required that the sheet surface be capable or" retaining a high voltage electrostatic charge under dark conditions, and of permitting such charge to be dissipated when the surface is exposed to light.
  • a recently developed image reproduction process involves electrolytically developing permanent and visible images on suitable photoconductive copysheets after exposure to light images.
  • This method described more fully in United States application Serial Number 575,070, led March 30, 1956, now United States Patent No. 3,010,883, includes the electrolysis of an electrolytic developer and particularly the electrodeposition of a metallic or other visibly distinct coating at the exposed photosensitive surface, usually by electrolytic reduction. No preliminary charging of the copysheet is required, and the copy produced needs no further heating or other processing to render the image permanent.
  • the successful application of the electrolytic method has been found to require, among other things, that the sensitive sheet be strongly photoconductive and have certain other conductivity requirements rather than merely the capacity to hold and dissipate an electrostatic charge.
  • Serial Number 629,529, filed October 28, 1957, now United States Patent No. 3,010,884, generally comprise a photoconductive layer of zinc oxide particles in an insulative organic resinous binder superimposed on a contiguous electrically conductive layer, the combined layers having a conductivity of at least about i-7 mho/cm. on exposure to 1300 footcandles of incident light (i.e., light conductivity) and a dark conductivity not greater than about one-twentieth of the light conductivity.
  • a preferred organic resinous binder is a copolymer of butadiene and styrene (e.g., 30 mol percent butadiene copolymer, Pliolite S-7, Goodyear Tire and Rubber Co.). Copysheets employing photoconductive indium oxide and their preparation are described in US. Serial Number 848,219, filed October 23, 1958.
  • lt is therefore an object of this invention to prepare an improved photoconductive copysheet suitable for use in image reproduction processes, particularly the electrolytic image reproduction process.
  • Still another object of this invention is to provide a photoconductive copysheet having both improved whiteness and greater sensitivity.
  • Yet another object of this invention is to provide a photoconductive copysheet with a greater light conductance to dark conductance ratio and with a higher photoresponse rate.
  • improved photoconductive copysheets contain 'an organic resinous binder having from about 72 mol percent to about 88 mol percent of a vinyl benzene in polymer form and, correspondingly, from about l2 mol percent to about 28 mol percent of a polymerized conjugated diene, such as butadiene, pentadiene, etc. This may be readily achieved by using a single copolymer of the conjugated diene and the vinyl benzene.
  • such improved results may also be achieved by utilizing a binder comprising from about 0.1 to about 70 weight percent, prefer-ably from about 5 to about 65 weight percent, of a vinyl benzene homopolymer and from 30 to about 99.9 weight percent, preferably from about 35 to about 95 weight percent, of a copolymer of butadiene and a vinyl benzene, preferably having from about 20 to about 50 ⁇ mol percent butadiene.
  • a binder comprising from about 0.1 to about 70 weight percent, prefer-ably from about 5 to about 65 weight percent, of a vinyl benzene homopolymer and from 30 to about 99.9 weight percent, preferably from about 35 to about 95 weight percent, of a copolymer of butadiene and a vinyl benzene, preferably having from about 20 to about 50 ⁇ mol percent butadiene.
  • Vinyl benzene as used herein, includes both the unsubstituted vinyl benzene, i.e., styrene, and the substituted vinyl benzene, e.g., alkyl styrenes, alkoxystyrenes, halostyrenes, carboxystyrenes, aminostyrenes, hydroxystyrenes, nitrosytrenes, etc.
  • substituted vinyl benzenes are shown in Vinyl and Related Polymers, by C. E. Schildknecht, chapter III, John Wiley & Sons, NY., 2.
  • binder compositions when employed as matrices for photoconductive particulate materials, such as Zine oxide, cadmium sulfide, indium oxide, etc., increase the light conductance of the resultant copysheets when coated onto an electrically conductive backing, such as clean aluminum foil, as well as increase the difference between the light and dark conductance values.
  • photoconductive particulate materials such as Zine oxide, cadmium sulfide, indium oxide, etc.
  • a whitener or 'a filler such ⁇ as an insulating coloring agent or a white, insulating, non-photoconductive inorganic pigment, eg., titanium dioxide, zinc sulfate, barium sulfate, etc., to be added ⁇ to these coating compositions, preferably up to a maximum of about 30 weight percent of total pigment, i.e., combined whitener and photoconductive pigment. Since the difference between the light and dark conductance values (i.e., photoconductance) is a measure of sensitivity and also of the available contrast, the greater difference is highly desirable for image reproduction, even without added whitener. Usually when titanium dioxide is employed, between 10 and 20 weight percent of TiO2 based on total pigment is preferred.
  • the ratio of total pigment to binder ranges from 2:1 to about 7:1, preferably from about 3.5 :l to about 6: 1. Higher total pigment to binder ratios may be used, although the flexibility of the copysheet and/or the adhesion of the photoconductive layer to the electrically conductive layer are not generally as acceptable for commercial copysheets.
  • the pigment to binder ratio must be at least suticient to provide an electrically conductive path between the exposed surface of the photoconductive layer and the electrically conductive layer.
  • a further advantage realized by this invention is the ability to reduce the coating thickness of the photoconductive layer without adversely affecting the appearance or performance of the resultant copysheet, thereby effecting marked economies in material cost per unit. This is apparently due to the high opacifying power of the whitening agents, particularly titanium dioxide. As used herein,
  • the properties of whitener or whitening agent are relative to the particular photoconductive particles used, particularly zinc oxide.
  • the polymers employed in the binder composition of this invention are insulating materials, no theoretical explanation is known for the marked and unexpected improvements ach-ieved when the composition contains vinyl benzene monomeric units within the abovementioned range.
  • any butadiene-vinyl ,benzene copolymer with at least about 10 mol percent of butadiene may be used in conjunction with a vinyl benzene homopolymer, those copolymers having between about 20 and about 50 mol percent butadiene are more readily available and are moreover preferred, particularly the copolymers with styrene and vinyl toluene.
  • the homopolymer when used, maybe a homopolymer of any of a number of vinyl benzenes, ranging in molecular weight ⁇ from the low molecular weight tetramer to the high molecular weight polymers (i.e., average molecular weights above about 10,000), for example Dow Styron 700, Koppers Type 2, Koppers Type 3, polyvinyltoluene, polystyrene tetramer, etc.
  • the weight ratio of these polymeric substituents is selected to provide an overall vinyl benzene content within the ranges set forth earlier, provided that the resultant binder mixture is essentially non-tacky and is tightly adherent to the electrically conductive material used in the copysheet construction.
  • This can readily be determined by coating the binder mixture onto a test panel, e.g., aluminum, and testing the dry coating by conventional techniques both for tack and for adhesion. Brittleness is generally to be avoided in flexible copysheets and can also be tested by this simple technique.
  • the flexibility of the resultant photoconductive coatings may be enhanced by the incorporation of minor amounts of plasticizing agents, up to about 5 (preferably below l) weight percent of the total polymeric binder.
  • plasticizing agents include tricresyl phosphate, dioctyl phthalate, etc.
  • the lower molecular weight polystyrene polymers also provide a plasticizing effect.
  • the binder compositions herein it is to be understood that the binders consist essentially of the aforementioned polymers with or without such minor amounts of a plasticizer to modify the physical properties of the coating.
  • pigment refers herein to the total of both the photocond-uctive pigment and the non-photoccnductive insulating coloring agent or whitener.
  • Other coloring agents and fillers of an insulating nature, relative to the photoconductive pigment employed, may also be used, particularly if some other sheet color is desired, but whitening agents and especially titanium dioxide are usually preferred because of the greater commercial importance of copysheets having the over-all appearance of a good white bond paper.
  • the techni-ques employed in coating these pigmented compositions onto the electrically conductive backings, such as aluminum foil and plastic which is vapor coated with aluminum are essentially the same as those employed with the photoconductive compositions heretofore utilized (e.g., slurry of the photoconductive pigment in a solution of the polymeric binders in ethyl acetate, methyl ethyl ketone, acetone toluene or benzene), the dry coating weight and thickness generally is less, usually ranging from about l gram per square foot to about 5 grams per square foot preferably from 2 to 3 grams per square foot, permitting considerable economy in materials cost.
  • the dry coating weight and thickness generally is less, usually ranging from about l gram per square foot to about 5 grams per square foot preferably from 2 to 3 grams per square foot, permitting considerable economy in materials cost.
  • FIGURE 1 is a plot of percent reflection from image areas (pure white having percent reflection) versus exposure for various copysheets employing from 0 to 75 weight percent styrene homopolymer (Dow PS-Z,
  • the copysheets were prepared by coating aluminum foil (2.5-3.0 grrr/ft2 dry weight) with a slurry in ethyl acetate of a composition having a 5:1 pigment:binder ratio.
  • the pigment contained zinc oxide and 15 mol percent Ti02.
  • a ten second exposure was made through a standard gray scale transparency With optical density units varying from 0.3 to 1.7.
  • Electrolytic development was made using a constant plating time and 60 volts 11C.
  • the binder compositions containing up to about 70 weight percent styrene homopolymer displayed both significantly greater contrast and speed than those cornpositions containing no styrene homopolymer and those compositions containing above about 70 weight percent styrene homopolymer.
  • FIGURE 2 represents a plot of percent reflection versus exposure for various copysheets.
  • Contrast is measured by the difference between the percent reilection in the image areas compared -to the original percent reflection of the sheet.
  • the data shows the decreased response rate and decreased contrast obtained (with and without 15 Weight percent of TiO2 pigment) when the binder composition contained only Pliolite S-7 butadiene-styrene copolymer.
  • the data further shows the improved response characteristics and sheet whiteness obtained when the resinous binder also included 50 weight percent of styrene homopolymer (Dow 13S-2), even when the composition contained weight percent of titanium dioxide based on total pigment.
  • the amount of polystyrene in the binder approached 100 percent, the contrast dropped markedly and the developed sheet was black even in the background areas under almost all exposure conditions.
  • a further series of illustrative runs will graphically show the improvement in response rate and contrast as related to the weight percent of styrene homopolymer in the binder system. No whitening ⁇ agent was employed for this series of runs, although similar results are obtained with a given amount of whitener incorporated therein.
  • One square inch sample specimens were provided by coating clean aluminum foil with a 0.7 mil dry coating thickness of a zinc oxide/binder mixture (5.5/1 wt. ratio) in suitable solvent. After the coating was dry, the electrically conductive surface of a conductive glass plate (NESA glass, tin oxide coating) was placed in contact with the dry coating surface.
  • a conductive glass plate NESA glass, tin oxide coating
  • FIGURE 3 is a plot of the light conductance at varying weight percent values of styrene homopolymer (Dow 700) in the binder.
  • the copolymer of butadiene and styrene was Pliolite S-7. It was also noted that the increase in light conductance was greater than the increase in dark conductance up to a value of about 70 weight percent of the polystrene.
  • the data set forth in FIGURE 5 illustrates the results achieved in the instant invention, using a wet test technique.
  • the measured conductance values difer somewhat between the wet and dry test methods, perhaps due to the eifect of electrolyte in the wet test.
  • Wet test measurements are generally preferred when such copysheets are to be used in the electrolytic development method discussed earlier.
  • the wet test technique utilized a one square inch test specimen having a 0.7 mil dry thickness coating of zinc oxide-binder mixture (5/1 Weight ratio) on a clean aluminum foil backing.
  • the specimens were exposed for live seconds to 10 footcandles of incident light from a 150 watt tungsten source. With the aluminum foil connected as cathode, the exposed specimen was immersed in a developer bath (1:3 mol ratio silver nitrate-ethylene thiourea in dilute aqueous solution, 0.65 weight percent silver nitrate, 0.75 weight percent acetic acid, 5 weight percent magnesium acetate) and developed for 5 seconds using a 1.5 volt D.C. potential. An anode was immersed in the developer bath. Current flow was measured by a meter in the circuit, and conductance measurements were then calculated. In FIGURE 5 the rapid increase in the dark conductance above about 70 weight percent of vinyl benzene homo-polymer is shown.
  • the vinyl benzene homopolymer was polystyrene (20,000-35,000 molecular weight) and the other polymer was butadiene-styrene copolymer (30:70 mol ratio respectively).
  • Conductance values can, of course, be converted to conductivity values in conventional manner.
  • FIGURE 3 illustrate the improvement in light conductance obtained with about 0.1 to about 70 Weight percent of vinyl benzene homoplymer in admixture with 70:30 mol ratio vinyl-benzene-butadiene copolymer.
  • improvement is related to the mol percent ot vinyl benzene in the overall binder system, and experimental data has indicated that the light conductance of a vinyl benzene homopolymer-vinyl benzene copolymer binder system is generally comparable to a system having a single vinyl benzene-butadiene copolymer with an equivalent mol percent of vinyl benzene in the copolymer.
  • a binder system having vinyl benzene within the abovementioned molar concentrations may be prepared by admixing polybutadiene and polystyrene, although some diiiculty is encountered in the coating techniques when the higher pigment to binder ratios are used.
  • FIGURE 4 is a plot of the response rate (mbo/sec.) at varying weight percent values of styrene homopolymer in the resinous binder, using the same dry test techniques and polymers as described with respect to FIGURE 3.
  • the increased response characteristics, particularly between about 5 and about 70 weight percent of homopolymer in the binder further indicates the greatly improved sensitivity of these copysheets.
  • this response rate decreases somewhat with the incorporation of pigments such as TiO2, though the response rate remains comparatively high.
  • sensitizing dyes in the photosensitive films or coatings of this invention broadens the spectral response of the photoconductor, and small quantities of those dyes, e.g., Phosphine R (Cl 788), Patent Blue (Cl. 672), xylene cyanol (Cl. 715), etc. increase the rate of response and the ratio of light to dark conductors.
  • Phosphine R Cl 788
  • Patent Blue Cl. 672
  • xylene cyanol Cl. 715
  • the increased response rates obtained when the binders of this invention include small amounts of polystyrene tetramer illustrate the advantages of using more than one vinyl benzene homopolymer.
  • the response rates calculated at 1/ 10, 2/ 10 and 3/ 10 seconds exposure under the dry test conditions described earlier (10 footcandles incident light from a tungsten source) were 200, 293 and 387 mho/sec. respectively.
  • the response rates at 1/10, 2/10 and 3/10 seconds were 73.3, and 120 respectively. This represents an approximate threefold increase in the rate of response and hence almost a threefold increase in light conductance for a given exposure time.
  • the homopolymer employed may be of relatively low molecular weight, in which case smaller quantities of homopolymer are generally used to avoid problems of adhesion and tack.
  • Table II illustrates the improved results obtained by adding polystyrene tetramer to a butadiene-styrene copolymer (30:70 mol ratio). A 5.5:1 zinc oxide to binder ratio was employed, and the slurry in toluene was ball milled for 4 hours.
  • Sensitizing dyes 0.05 Weight percent Seto Flavin T and 0.05 weight percent Eosin
  • the light conductance was measured after a 15 second exposure to 10 footcandles of illumination from a watt tungsten source, using the dry test method r described earlier.
  • Pliolite S-7 (28 gm.) 13.3X107- 23.3Xl0-7- 27.8X10-7.
  • Pliolite S-7 (14 gm.) Dow 700 (14 gm.) 66.7X10-1 100 10"7 153 107 Pliolite S-7 (14 gm Dow PS-2 (14 gm 93.3X101 140 107 182 10-1 Pliolite S-7 (14 gm.) Dow PS-3 (14 gm). 10 107 167 107 220x10-7 Table II Response Rate, mbo/sec., alter- Run Wt. percent Wt. percent Light tctramer copolymer Conductance 0.5 99. 500 107 1,183X10-7. 1,727X10-7. 4,500X10"7.
  • Table III illustrate the comparative effect on copysheet whiteness of titanium dioxide and barium sulfate. It is noted from Table III that the titanium dioxide provides better reection than the barium sulfate. The dry test technique was employed.
  • the electrolytic image reproduction process in which the copysheets of this invention are used, has made possible the direct copying of microfilm reproductions of printed pages of books, papers and the like, with the same dimensions as the original and within a period of time of not more than about live or ten seconds from initial inspection of the light image to delivery of the completed print.
  • the improved photoconductive copysheets described herein provide prints of greater contrast which have whiter highlight areas, as Well as the other adv-antages described earlier.
  • the binder composition must contain from about 72 mol percent to .about 88 mol percent of a vinyl benzene in polymer form fand, correspondingly, from about 12 mol percent to about 28 mol percent of butadiene. In a preferred embodiment, this is achieved by admixing appropriate amounts of a vinyl benzene homopolymer with a butadiene-vinyl benzene copolymer, as mentioned earlier.
  • a photoconductive copysheet capable of electrolytic development having :a thin, uniform layer of pigment particles comprising photoconductive particles and up to about 30 weight percent, based on total pigment particles, of 1an insulating, White, non-photoconductive inorganic pigment dispersed in a binder, said layer being -iirmly held to a continuous electrically conductive support, said binder comprising a substantially water-insoluble, non-tacky insulative organic resinous binder consisting essentially of from about 0.1 to labout 70 weight percent of a monovinyl benzene homopolymer Iand between about 30 and about 99.9 weight percent of a butadiene-vinyl benzene copolymer having from about 20 to about 50 mol percent but-adiene, the amount of said photoconductive particles being such that an electrically conductive path is created between the exposed surface of said layer and said electrically conductive support upon irradiation of said layer.
  • organic resinous binder contains from about 3() to about 60 weight percent of said butadiene-styrene copolymer, based on total weight of binder.
  • a photoconductive copysheet capable of electrolytic development having a thin, uniform layer of pigment particles comprising photoconductive particles land up to about weight percent, based on total pigment particles, of an insulating, white non-photoconductive inorganic pigment dispersed in a binder, s-aid layer being firmly held to a continuous electrically conductive support, said binder comprising a substantially water-insoluble, nontacky insulative organic resinous binder consisting essentially of from about 1 to about 70 weight percent of a high molecular weight monovinyl benzene homopolymer and between about 30 and about 99 weight percent of a butadiene-vinyl benzene copolymer having from about 2() to about 50 mol percent butadiene, the amount of said photoconductive particles being such that an electrically conductive path is created between the exposed surface of said layer land said electrically conductive support upon irradiation of said layer.
  • a photoconductive copysheet capable of electrolytic development having a thin, uniform layer of pigment particles comprising photoconductive particles and up to about 30 weight percent, based on total pigment particles, of an insulating, white, non-photoconductive inorganic pigment dispersed in a binder, said layer being rmly held to a continuous electrically conductive support, said binder comprising a substantially water-insoluble, non-tacky insulative organic resinous binder consisting essentially of from about 1 to about 70 weight percent of a low molecular weight monovinyl benzene homopolymer and between about 30 and about 99 weight percent of a butadiene-vinyl benzene copolymer having from Iabout 2O to about mol percent butadiene, the amount of said photoconductive particles being such that an electrically conductive path is created between the exposed surface of said layer and said electrically conductive support upon irradiation of said layer.
  • a photoconductive copysheet suitable for use in the electrolytic image reproduction process and having a thin, uniform, continuous layer of photoconductive particles in a binder adhered to a smooth, continuous electrically conductive surface
  • said binder comprises a substantially water-insoluble, non-tacky, insulative organic resin mixture having between about 0.1 and weight percent of a monvinyl benzene homopolymer and between about 30 and 99.9 weight percent of a butadiene-vinyl benzene copolymer having from about 20 to about 50 mol percent butadiene, said continuous layer also having between about l0 and about 30 weight percent of an insulating, white, non-photoconductive inorganic pigment.

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US116092A 1961-06-09 1961-06-09 Electrolytic recording sheets Expired - Lifetime US3174856A (en)

Priority Applications (9)

Application Number Priority Date Filing Date Title
BE615645D BE615645A (de) 1961-06-09
NL276497D NL276497A (de) 1961-06-09
US116092A US3174856A (en) 1961-06-09 1961-06-09 Electrolytic recording sheets
DEP1272A DE1272124B (de) 1961-06-09 1962-02-19 Elektrophotographisches Aufzeichnungsmaterial
ES0274922A ES274922A1 (es) 1961-06-09 1962-02-24 Mejoras introducidas en la fabricaciën de hojas de copia fotoconductoras
FI0647/62A FI43263B (de) 1961-06-09 1962-03-27
CH362962A CH433990A (de) 1961-06-09 1962-03-27 Photoleitfähiges Kopierblatt
FR898708A FR1332605A (fr) 1961-06-09 1962-05-25 Feuilles pour la reproduction électrolytique d'images
GB22383/62A GB1017114A (en) 1961-06-09 1962-06-08 Photo-conductive copy-sheets

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US116092A US3174856A (en) 1961-06-09 1961-06-09 Electrolytic recording sheets

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BE (1) BE615645A (de)
CH (1) CH433990A (de)
DE (1) DE1272124B (de)
ES (1) ES274922A1 (de)
FI (1) FI43263B (de)
GB (1) GB1017114A (de)
NL (1) NL276497A (de)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3581661A (en) * 1968-04-03 1971-06-01 Sperry Rand Corp Electrostatically imaged lithographic plate
US3864127A (en) * 1971-08-12 1975-02-04 Fuji Photo Film Co Ltd Method for preparing ZnO-TiO{HD 2 {B bichargeable electrophotographic material
US3865587A (en) * 1971-07-20 1975-02-11 Agfa Gevaert Nv Electrophographic bichargeable materials and process

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2574439A (en) * 1945-06-11 1951-11-06 Monsanto Chemicals Plasticized polystyrene composition
US2727878A (en) * 1952-09-09 1955-12-20 Monsanto Chemicals Polyblends
US2955938A (en) * 1955-08-01 1960-10-11 Haloid Xerox Inc Xerography
US2990279A (en) * 1956-09-25 1961-06-27 Rca Corp Electrostatic printing
US3010884A (en) * 1957-10-28 1961-11-28 Minnesota Mining & Mfg Electrophotosensitive copy-sheet
US3041168A (en) * 1959-09-18 1962-06-26 Rca Corp Electrostatic printing

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US2990279A (en) * 1956-09-25 1961-06-27 Rca Corp Electrostatic printing
US3010884A (en) * 1957-10-28 1961-11-28 Minnesota Mining & Mfg Electrophotosensitive copy-sheet
US3041168A (en) * 1959-09-18 1962-06-26 Rca Corp Electrostatic printing

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* Cited by examiner, † Cited by third party
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US3581661A (en) * 1968-04-03 1971-06-01 Sperry Rand Corp Electrostatically imaged lithographic plate
US3865587A (en) * 1971-07-20 1975-02-11 Agfa Gevaert Nv Electrophographic bichargeable materials and process
US3864127A (en) * 1971-08-12 1975-02-04 Fuji Photo Film Co Ltd Method for preparing ZnO-TiO{HD 2 {B bichargeable electrophotographic material

Also Published As

Publication number Publication date
DE1272124B (de) 1968-07-04
NL276497A (de)
FI43263B (de) 1970-11-02
ES274922A1 (es) 1962-05-16
CH433990A (de) 1967-04-15
BE615645A (de)
GB1017114A (en) 1966-01-19

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