US3138547A - Electrosensitive recording sheets - Google Patents

Electrosensitive recording sheets Download PDF

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Publication number
US3138547A
US3138547A US848393A US84839359A US3138547A US 3138547 A US3138547 A US 3138547A US 848393 A US848393 A US 848393A US 84839359 A US84839359 A US 84839359A US 3138547 A US3138547 A US 3138547A
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US
United States
Prior art keywords
tin plate
electrosensitive
metal compound
sheet
electrolyte
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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US848393A
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English (en)
Inventor
Bryce L Clark
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
3M Co
Original Assignee
Minnesota Mining and Manufacturing Co
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Filing date
Publication date
Application filed by Minnesota Mining and Manufacturing Co filed Critical Minnesota Mining and Manufacturing Co
Priority to US848393A priority Critical patent/US3138547A/en
Priority to GB36228/60A priority patent/GB892807A/en
Priority to DE19601446655 priority patent/DE1446655B2/de
Application granted granted Critical
Publication of US3138547A publication Critical patent/US3138547A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/20—Duplicating or marking methods; Sheet materials for use therein using electric current

Definitions

  • This invention relates to an electrosensitive recording sheet.
  • this invention relates to an electrosensitive recording paper for facsimile signals and the like.
  • One of the most Widely used types of electronsensitive paper consists of a carbon impregnated conductive paper bearing, on one surface, a metallic paint layer and, on v the other surface, a powdery light gray coating.
  • the light gray coating is at least partially displaced or removed by the passage of current from the stylus through the paper.
  • Such sheets are difficult to handle because of the readily smeared, readily pressure marked surface.
  • the current flow tends not only to alter the character of the light gray coating but also to disrupt the bonding or adhesion of the light gray masking coating to the adjacent carbon impregnated paper and to provide thereby a readily removable image.
  • An additional object of this invention is to produce an electrosensitive facsimile sheet capable of reproducing an image with substantially no dusting, flaking or smoking.
  • Another object of this invention is to provide a method for making an electrosensitive paper with the above properties.
  • Still another object of this invention is to provide an image bearing sheet which can be further developed by electrolytic means.
  • FIGURE 1 is a cross-sectional view of an electrosensitive sheet according to this invention.
  • FIGURE 2 is a schematic diagram of a facsimile recording system embodying an electrosensitive copysheet according to this invention.
  • the electrosensitive sheets of this invention comprise a continuous electrically conductive layer and a contiguous layer comprising at least one water-insoluble, heat stable, light insensitive, particulate metal compound capable of being electrically reduced in situ to the corresponding free metal, in a matrix of a binder having a lower electrical conductivity than said metal compound, said contiguous layer being essentially nondisplaceable under the conditions of electrical reduction.
  • the electrically conductive layer may be any conductive material, including metal foil, paper or fabric impregnated with conductive particles, such as aluminum flakes, conductive glass, conductive plastics, etc.
  • Flexible sheets are generally used, particularly when the electrosensitive sheet is wrapped around a rotatable roll or drum during the receipt of electrical facsimile signals and reproduction of the image.
  • a carbon'irnpregnated matrix such as carbon impregnated paper, as the electrically conductive layer, this is not preferred because of other generally less desirable properties of carbon impregnated matrices, for example, relatively low tear strength, etc.
  • the electrosensitive layer or topcoating contains a binder having a low electrical conductivity in which is uniformly distributed or dispersed 'at least one water-insoluble, heat stable, particulate metal compound which can be reduced to the corresponding free metal by the passage of electrical current, e.g. by means of a stylus.
  • This current passage results in reduction of the particulate metal compound in the dry state.
  • the free metal thereby produced in those areas contacted by a stylus provides a visible reproduction of the electrical impulses or currents, the dark colored free metal varying in intensity with the current passed. In this manner, it is possible to produce varying tonal gradations in the image areas as the stylus scans the electrosensitive layer with which it makes electrical contact.
  • Example 1 Since it has now been found that a variety of diverse metallic compounds can be electrically reduced in this manner, selection depends on such factors as the color contrast desired, cost, toxicity, desired electrical requirements for reduction, etc.
  • the following laboratory test procedure (Example 1) may be used to determine the utility of a given metallic compound in the electrosensitive sheets of this invention and will be used to define such electrically reducible metal compounds within the scope of this invention.
  • EXAMPLE 1 To a wide mouth pint jar 80 grams of the particulate material to be evaluated is charged along with grams of a :70 mol ratio copolymer of butadiene and styrene and 100 grams of toluene. One-half pint of 0.5 in. diameter glass or porcelain balls are added and the mixture is milled until an 8.5 or better fineness of grind, as measured on the Hegman fineness of grind gauge, is attained (usually about 8 hours of milling). With a 0.001" aluminum foil backing sheet positioned in a fiat bed, notched bar knife coater, the knife was adjusted to provide a Wet coating thickness of 3 mils. The above milled mixture is placed on the backing sheet behind the knife, and the backing sheet is thereafter pulled through the orifice to provide a uniform 3 mil thick wet coating. The coated sheet is thereafter allowed to dry at room temperature.
  • the dry coated sheet is then wrapped around a 3 inch diameter aluminum roll connected as anode to a variable D.C. source and is held securely in position by means of spring clips.
  • a 10 mil diameter tungsten stylus actuated by means of a screw drive lightly contacts the coated surface of the sheet and is moved progressively along an axis parallel to the axis of the metal roll.
  • the stylus is connected as cathode to the variable D.C. source.
  • Meters are provided to measure the voltage and current in the circuit.
  • the metal roll is rotated at a peripheral speed of 100 inches/ second and the stylus is advanced at a rate of 75 lines per inch. The voltage is slowly increased until a current flow is noted or to a maximum of 500 volts when no current flow is detected.
  • the voltage is held constant to observe the effect of the voltage and current on the coated sheet.
  • the voltage is increased in increments with similar observation until an image or darkening of the surface under the stylus is observed.
  • Those sheets on which are produced a dark image area in this manner are then analyzed to ascertain the presence of a free metal image.
  • the metal compounds are considered non-electrically reducible for purposes of this invention and can be employed as inert fillers.
  • the following table illustrates the results obtained in this test using illustrative materials. This test can also be run with the stylus connected as anode and the aluminum roll connected as cathode. In ordinary facsimile machines, such atures below about 200 C., preferably below about 250 C. Both organic and inorganic electrically reducible metal compounds are contemplated within the scope of this in- Vention.
  • the electrically reducible metal compound employed is preferably light in color, usually white or olf-white.
  • light colored metal compounds include, for example, zinc oxide, lead monoxide, basic lead carbonate, stannic oxide, barium sulfate, etc.
  • electrically reducible metal compounds which are colored are particularly desirable.
  • the lighter colored metal compounds such as vanadium pentoxide, silver oxide, cadmium sulfide, ceric oxide, zirconium oxide, antimony pentasulfide, cadmium oxide, etc.
  • the lighter colored metal compounds such as vanadium pentoxide, silver oxide, cadmium sulfide, ceric oxide, zirconium oxide, antimony pentasulfide, cadmium oxide, etc.
  • the lighter colored metal compounds such as vanadium pentoxide, silver oxide, cadmium sulfide, ceric oxide, zirconium oxide, antimony pentasulfide, cadmium oxide, etc.
  • light colored non-reducible pigments or fillers such as titanium dioxide, magnesium oxide, etc.
  • an immediately visible image is not necessary.
  • the ratio of filler to the electrically reducible metal compound may be varied widely, depending on the desired definition, the desired color contrast and the resistivity required for efficient reduction of the electrically reducible metal compound in the
  • the binder which is incorporated into the electrosensitive layer serves to firmly affix the particulate material onto the electrically conductive substrate and to maintain the continuity or integral nature of the layer.
  • the current passing through the electrosensitive sheet tends to blast or disrupt the continuity of the particulate material if insuificient binder is employed.
  • the particulate material to binder weight ratio is maintained below 10:1, preferably below 8:1 and above about 1:2.
  • the finely divided particulate material i.e. the electrically reducible metal compound and filler, if used, is uniformly distributed throughout the binder matrix.
  • Suitable insulating binders include various organic materials such as cellulose acetate, cellulose nitrate, ethyl cellulose, polystyrene, polyvinyl acetate, polyvinyl chloride, chlorinated rubbers, butadiene-styrene copolymer (e.g. 30:70 mol ratio), polyisobutylene, poly-. methacrylates, etc.
  • decomposition of the binder is to be minimized and preferably precluded.
  • the resistance characteristics of the entire electrosensitive layer may be adjusted either by controlling the resistance or proportion of the binder and of the particulate material, or by controlling the thickness of the electrosensitive layer. It is also possible to control the resistance by controlling the fineness of the particulate particles. This resistance is regulated in such fashion as to impress sufiicient electrical potential across said layer stable, i.e. which is not decomposed at sustained temperto effect eificient reduction of the metal compound in the image areas and to permit disruption of the continuity of the electrosensitive layer.
  • the layer thickness should be maintained at a substantially constant value throughout the useful area of the sheet.
  • Layer thicknesses above about 0.5 mil, generally above about 1 mil, are usually employed. Ordinarily, the thickness need not exceed about 3 mils.
  • the electrosensitive sheets of this invention When .the electrosensitive sheets of this invention are used to reproduce an image transmitted by a facsimile process, as in FIGURE 2, the passage of electrical current from the scanning stylus (l), in contact with the electrosensitive surfaceof the copysheet (2), through the sheet to the metal drum (3) rotatable about axis (4), reduces the metallic compound in the image areas to a lower valence state, in which state the conductivity and other electrical properties of the image areas is sufiiciently diiferent from the equivalent properties of the background areas to afford a unique means not only for visual recording but also for the storage and reuse of reduction with essentially no 6 the recorded information.
  • Such recorded information can then be reused both by optical or visual sensing means and potentially by electronic sensing means relying on the diiferential pattern of electrical properties. No satisfactory information storage sheets or tapes of this character have heretofore been found that possess this combination of potentially .valuable properties.
  • Electrolytic processes in which the electrically conductive backing sheet is connected as the cathode and the electrosensitive layer is contacted by a suitable electrolyte, such as aqueous nickel chloride, an aqueous solution of a silver salt and thiourea, etc., can be used for further development of the image, if desired.
  • a suitable electrolyte such as aqueous nickel chloride, an aqueous solution of a silver salt and thiourea, etc.
  • Example 2 Using the preparative techniques described in Example 1, the electrosensitive sheets in Table II were prepared. Images were obtained by using these sheets on the standard Western Union Intrafax facsimile machine.
  • the electrically conductive material of the backing was aluminum in all runs except for Example 28, in which a carbon impregnated paper (2000 ohms per square) :was employed. All percents are percent by weight.
  • P/B represents the weight ratio of particulate material to binder.
  • Pliolite S7 is 0 mole ratio butadiene-styrene copolymer supplied by Goodyear Tire & Rubber Co.
  • ZnO(USP) is lead free, acicular French process zinc oxide supplied by New Jersey Zinc Co.
  • 5 aran F120 is polyvinyl chloride resin supplied by Dow Chemical Co.
  • Co Dow 70Q is polystyrene resin supplied by Dow Chemical All of the image containing clectroscnsitive sheets of Table II were resistant to smudging and pressure marking.
  • An electrosens'itive non-electrolytic recording sheet which comprises a continuous electrically conductive layer and a contiguous layer thereon comprising at least one water-insoluble, heat stable, light insensitive particulate metal compound capable of electrical reduction in situ to the corresponding free metal, said metal compound being uniformly dispersed in an inorganic matrix having a lower electrical conductivity than said metal compound, said contiguous layer being essentially nondisplaceable under conditions required for said electrical reduction.
  • ucite 42 is polyethylmethacrylate supplied by E. I. du Pont de Nemours and Co.
  • Dow V9 is polystyrene supplied by Dow Chemical Co. as a viscous, low viscosity liquid.
  • An electrosensitive non-electrolytic recording sheet which comprises a non-carbonaceous electrically conductive layer and a contiguous layer thereon consisting esscntially of at least one water-insoluble, heat stable, light insensitive particulate metal compound capable of elec-' trical reduction in situ to the corresponding free metal, said metal compound being uniformly dispersed in an organic matrix having a lower electrical conductivity than said metal compound, said contiguous layer being essentially nondisplaceable under conditions required for said electrical reduction.

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  • Heat Sensitive Colour Forming Recording (AREA)
  • Cosmetics (AREA)
US848393A 1959-10-23 1959-10-23 Electrosensitive recording sheets Expired - Lifetime US3138547A (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US848393A US3138547A (en) 1959-10-23 1959-10-23 Electrosensitive recording sheets
GB36228/60A GB892807A (en) 1959-10-23 1960-10-21 Electrosensitive recording sheet material
DE19601446655 DE1446655B2 (de) 1959-10-23 1960-10-22 Elektroempfindliches registrierblatt

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US848393A US3138547A (en) 1959-10-23 1959-10-23 Electrosensitive recording sheets

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US3138547A true US3138547A (en) 1964-06-23

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US (1) US3138547A (enrdf_load_stackoverflow)
DE (1) DE1446655B2 (enrdf_load_stackoverflow)
GB (1) GB892807A (enrdf_load_stackoverflow)

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3256523A (en) * 1963-10-23 1966-06-14 Medical Electronics And Res Co Recording instrument
US3335423A (en) * 1965-03-24 1967-08-08 Denki Onkyo Co Ltd Medium for treating information
US3516911A (en) * 1967-12-01 1970-06-23 Nashua Corp Electrosensitive recording material
DE1671571B1 (de) * 1966-09-15 1971-07-08 Phonocopy Inc Elektrothermographisches aufzeichnungsverfahren und dabei verwendeter schichttraeger
US3691105A (en) * 1970-05-12 1972-09-12 Kiyoshi Juna Compositions for electrosensitive recording material
US3713996A (en) * 1971-01-06 1973-01-30 Bausch & Lomb Electrosensitive recording media
US3864684A (en) * 1974-03-22 1975-02-04 Mitsubishi Paper Mills Ltd Multicolor electrothermic recording sheet
US3898672A (en) * 1972-01-28 1975-08-05 Ricoh Kk Electrosensitive recording member
DE2533688A1 (de) * 1974-07-29 1976-02-19 Eastman Kodak Co Elektrographisches verfahren sowie vorrichtung zur durchfuehrung desselben
US4067780A (en) * 1974-07-27 1978-01-10 Canon Kabushiki Kaisha Image recording member
FR2435100A1 (fr) * 1978-08-29 1980-03-28 Antzan Paul Procede electroyltique d'inscription
US4263105A (en) * 1979-08-21 1981-04-21 Issec Sa Electrosensitive recording material and process
US4296422A (en) * 1978-02-08 1981-10-20 Fuji Photo Film Co., Ltd. Image recording material and image recording method using the same
US4324622A (en) * 1974-09-26 1982-04-13 American Cyanamid Company Multilayered electroplatographic element comprising ion conductive and electrochromic layers
US4550061A (en) * 1984-04-13 1985-10-29 International Business Machines Corporation Electroerosion printing media using depolymerizable polymer coatings
US5109771A (en) * 1988-08-19 1992-05-05 Presstek, Inc. Spark-discharge lithography plates containing image-support pigments

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH149268A (de) * 1930-03-22 1931-08-31 Bausch Viktor Verfahren zur Herstellung von Jodid enthaltendem Empfangspapier für elektrische Aufzeichnungsgeräte.
GB464112A (en) * 1934-10-13 1937-04-12 Fritz Goldmann Photographic process
US2281013A (en) * 1939-02-25 1942-04-28 Radio Inventions Inc Electrolytic recording paper
US2319765A (en) * 1939-12-14 1943-05-18 Radio Inventions Inc Electrolytic recording
US2554017A (en) * 1946-11-14 1951-05-22 Timefax Corp Electroresponsive recording blank
DE962661C (de) * 1951-06-25 1957-04-25 Int Standard Electric Corp Verfahren zur Herstellung von Aufzeichnungspapier

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH149268A (de) * 1930-03-22 1931-08-31 Bausch Viktor Verfahren zur Herstellung von Jodid enthaltendem Empfangspapier für elektrische Aufzeichnungsgeräte.
GB464112A (en) * 1934-10-13 1937-04-12 Fritz Goldmann Photographic process
US2281013A (en) * 1939-02-25 1942-04-28 Radio Inventions Inc Electrolytic recording paper
US2319765A (en) * 1939-12-14 1943-05-18 Radio Inventions Inc Electrolytic recording
US2554017A (en) * 1946-11-14 1951-05-22 Timefax Corp Electroresponsive recording blank
DE962661C (de) * 1951-06-25 1957-04-25 Int Standard Electric Corp Verfahren zur Herstellung von Aufzeichnungspapier

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3256523A (en) * 1963-10-23 1966-06-14 Medical Electronics And Res Co Recording instrument
US3335423A (en) * 1965-03-24 1967-08-08 Denki Onkyo Co Ltd Medium for treating information
DE1671571B1 (de) * 1966-09-15 1971-07-08 Phonocopy Inc Elektrothermographisches aufzeichnungsverfahren und dabei verwendeter schichttraeger
US3516911A (en) * 1967-12-01 1970-06-23 Nashua Corp Electrosensitive recording material
US3691105A (en) * 1970-05-12 1972-09-12 Kiyoshi Juna Compositions for electrosensitive recording material
US3713996A (en) * 1971-01-06 1973-01-30 Bausch & Lomb Electrosensitive recording media
US3898672A (en) * 1972-01-28 1975-08-05 Ricoh Kk Electrosensitive recording member
US3864684A (en) * 1974-03-22 1975-02-04 Mitsubishi Paper Mills Ltd Multicolor electrothermic recording sheet
US4067780A (en) * 1974-07-27 1978-01-10 Canon Kabushiki Kaisha Image recording member
DE2533688A1 (de) * 1974-07-29 1976-02-19 Eastman Kodak Co Elektrographisches verfahren sowie vorrichtung zur durchfuehrung desselben
US4324622A (en) * 1974-09-26 1982-04-13 American Cyanamid Company Multilayered electroplatographic element comprising ion conductive and electrochromic layers
US4296422A (en) * 1978-02-08 1981-10-20 Fuji Photo Film Co., Ltd. Image recording material and image recording method using the same
FR2435100A1 (fr) * 1978-08-29 1980-03-28 Antzan Paul Procede electroyltique d'inscription
US4261799A (en) * 1978-08-29 1981-04-14 Paul Anizan Electrolytic process for generating erasable pictures on a solid substrate
US4263105A (en) * 1979-08-21 1981-04-21 Issec Sa Electrosensitive recording material and process
US4550061A (en) * 1984-04-13 1985-10-29 International Business Machines Corporation Electroerosion printing media using depolymerizable polymer coatings
US5109771A (en) * 1988-08-19 1992-05-05 Presstek, Inc. Spark-discharge lithography plates containing image-support pigments

Also Published As

Publication number Publication date
DE1446655C3 (enrdf_load_stackoverflow) 1975-08-07
DE1446655A1 (de) 1969-03-20
DE1446655B2 (de) 1973-07-12
GB892807A (en) 1962-03-28

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