US3094620A - Copy-sheet and method - Google Patents

Copy-sheet and method Download PDF

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Publication number
US3094620A
US3094620A US79991A US7999161A US3094620A US 3094620 A US3094620 A US 3094620A US 79991 A US79991 A US 79991A US 7999161 A US7999161 A US 7999161A US 3094620 A US3094620 A US 3094620A
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Prior art keywords
copy
sheet
dithiooxamide
film
bis
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US79991A
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John L Reitter
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3M Co
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Minnesota Mining and Manufacturing Co
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Priority to NL273128D priority Critical patent/NL273128A/xx
Priority to BE612242D priority patent/BE612242A/xx
Application filed by Minnesota Mining and Manufacturing Co filed Critical Minnesota Mining and Manufacturing Co
Priority to US79991A priority patent/US3094620A/en
Priority to US79990A priority patent/US3094619A/en
Priority to SE13164/61A priority patent/SE313248B/xx
Priority to ES0273372A priority patent/ES273372A1/en
Priority to DEM51374A priority patent/DE1200846B/en
Priority to GB300/62A priority patent/GB997361A/en
Priority to FR883772A priority patent/FR1311591A/en
Priority to GB10700/65A priority patent/GB997362A/en
Priority to CH5362A priority patent/CH419198A/en
Priority to FI0008/62A priority patent/FI43136B/fi
Application granted granted Critical
Publication of US3094620A publication Critical patent/US3094620A/en
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/494—Silver salt compositions other than silver halide emulsions; Photothermographic systems ; Thermographic systems using noble metal compounds
    • G03C1/498—Photothermographic systems, e.g. dry silver
    • G03C1/4989—Photothermographic systems, e.g. dry silver characterised by a thermal imaging step, with or without exposure to light, e.g. with a thermal head, using a laser
    • 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
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/32—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers one component being a heavy metal compound, e.g. lead or iron

Definitions

  • thermographic reproduction One well-known for copying typewritten ofiice correspondence and other graphic originals having difierentially radiation-absorptive image and background areas is known as thermographic reproduction. It involves the brief irradiation of the original, while sensitive copy-sheet, with high-intensity radiation. Preferential absorption of the radiation in the absorptive image areas then results in localized heating of the copy-sheet, producing a visible direct copy of the original. The background areas of the copy-sheet remain heat-sensitive.
  • Another commercial 'oifice copying system requires preliminary exposure of a photosensitive sheet material to actinic radiation in a pattern determined by an original having radiation-transmissive background areas. Irradiated areas are thereby rendered non-reactive. The unexposed image areas may in some instances be rendered visible by heating, but for images of effective color density the sheet mustbe treated with a further reagent or activator in liquid or vapor form.
  • Apparatus for carrying out the required sequence of operations is available under the designation Copy-Flex Model 100 copying machine. In this apparatus the composite of copy-sheet and transparency is passed over a rotating glass cylinder containing a mercury vapor lamp.
  • Heat-sensitive copy-sheets have been described in which the visible change produced on localized brief heating is caused to occur by the inter-reaction ofa metal'saltand an organic chelating agent. The reaction produces a strongly colored permanent image. As previously described, however, these copy-sheets have been found to remain visibly heat-sensitive after, exposure to actinic radiation at speed in the Copy-Flex copying machine.
  • the present invention provides a heat-sensitive copysheet having a visibly heat-sensitive layer containing, in physically distinct and chemically inter-reactive relationship, a metal salt and an organic chelating agent capable of reacting together, in the thermographic copying process or on momentarily heating the sheet to a conversion temperature in the range of about 90 C. to about 150 C., with the formation of a visibly distinct reaction product, the reactants being rendered incapable of undergoing such reaction on exposure to actinic radiation as provided in the Copy-Flex copying machine.
  • the invention therefore makes possible the preparation of permanent, heatstable, high image density reproductions of graphic originals by procedures involving only irradiation and without any necessity of treatment with solutions, fumes, vapors, powders or other adjuvants.
  • the composite of copy-sheet and original is first briefly irradiated with intense radiation rich in infrared and in accordance with known thermographic copying procedures.
  • the thus imaged copy-sheet is next passed through the Copy-Flex copying machine under maximum exposure to the nearultraviolet radiation from the mer- 3,094,620 Ce Patented June 18, '1963 2 cury vapor arc.
  • the resulting copy is stable against further heating to conversion temperature at the undarkened background areas.
  • Copies may alternatively be prepared by first exposing the copy-sheet to the near-ultraviolet through a transparency, for example a ribbon or carbon copy of a typeand commercially important method in heat-conductive contact with a heatbacking,
  • Dithiooxamide is known to be reactive with metal salts such as nickel stearate in the tom of heat-sensitive copy-sheets; but such products are found to remain heatsensitive under exposureto near-ultraviolet as just described.
  • substituted dithiooxarnide such as N,N'-bis furfuryl dithioox-amide are equally elfectively, reactive with nickel stearate in copy-sheet formulations at conversion temperatures, while at the same time making possible the complete desensitization of the copy-sheet against such reaction by a single pass through the Copy-Flex machine.
  • the substituted dithiooxamide and metal salt may be intimately dispersed in a thin film of a resinous or polymeric film-forming binder, either in self-sustaining film form or as a coating on a paper, film or other paper-like providing a unitary heat-sensitive copy-sheet in a single coating and drying operation.
  • the two reactants may separately be dispersed or dissolved together with appropriate binders, and applied to a paper-like backing in separate coatings withintermediate drying, or to In the latter case the two sheets when held in face-to-face contact permit interfaci-al reaction at conversion temperature.
  • the relative amounts of the two reactants are not critical, particularly in structures wherein the image-forming reaction occurs at an interface, the only requirement being that sutlicient of each reactant be present to ensure a readily visible change on reaction. It is desirable to employ a minimum amount of the substituted dithiooxamide and to maintain'this material in position for maximum exposure to the actinic radiation.
  • Various additives are useful in providing copy-sheets of improved appearance, handling characteristics, or other properties. Pigments, fillers, plasticizers, dyes, waxes, resins and other additives may be incorporated. H I Thefollowing specific examples will further illustrate but not limit the invention. Proportions are given in parts by weight.
  • the image areas are equally readily developed by replacing the transparency with a sheet of radiation-absorbent black paper prior to irradiating the composite with infra-red, or by placing the copy-sheet in contact with a heated metal platen or roller or in an oven heated to about 150 C.
  • N,N'-bis fu-rfuryl dithiooxamide and nickel stearate as the reactant materials, a purple image color is obtained.
  • Nickel stearate with N,N'-bis carboxyamyl dithiooxarnide provides a pink image.
  • Other salts of nickel, such for example as nickel behenate, produce similar results. Salts of cobalt and copper are also useful.
  • Other non-inventive variations will be apparent in view of the foregoing disclosures.
  • a heat-sensitive copysheet capable of undergoing permanent visible change on being momentarily heated to a conversion temperature within the range of about 90 C. to about 150 C. and of becoming insensitive to said heating on moderate exposure .to near-ultraviolet radiation, said copy-sheet including a visibly heat-sensilive layer containing, in physically distinct and chemically inter-reactive relationship, chemically inter-reactant consisting essentially of nickel stearate and N,N-bis furfuryl dithiooxamide.
  • a unitary heat-sensitive copy-sheet capable of undergoing permanent visible change on being momentarily heated to a conversion temperature within the range of about 90 C. to about 150 C. and of becoming inseni sitive to said heating on moderate exposure to near-ultraviolet radiation, said copy-sheet comprising a thin paperlike backing and a coating comprising a film-forming binder and, in physically distinct and chemically interreactive relationship, chemically inter-reactant components consisting essentially of nickel stearate and N,N'-'
  • Method of copying comprising placing in surface contact and in position for irradiation a graphic original having ditierentially inf-rared absorptive image and back- 7 ground areas and a heat-sensitive copyisheet having a visibly heat-sensitive layer containing nickel stearate and N,N-bis furfiuryl dithiooxamide in physically distinct and chemically inter-reactive relationship, momentarily irradiating said graphic original with intense radiation rich in infra-red for causing visible inter-reaction in said i the near-ultraviolet wavelength region and in localized background-defining areas sufiicient to render said areas selectively insensitive to heat, and then heating at least the image-defining areas of said layer to provide a visible image.
  • a radiation-desensitizable intermediate sheet product suitable for use in the reproduction of a graphic original by a process involving heating said sheet product, while in face-to-face contact with a separate receptor sheet consisting essentially of a paper-like backing and a surface layer of nickel stearate, at areas corresponding to image-forming areas of said original; the said intermediate sheet product consisting essentially of a paperlike backing and a surface layer of N,N'-bis furfuryl dithiooxamide.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Optics & Photonics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)

Abstract

997, 362. Thermographic copying material and process. MINNESOTA MINING & MANUFACTURING CO. Jan. 3,1962 [Jan. 3,1961], No. 10700/65. Divided out of 997,361. Heading G2C. A copy sheet or copysheet combination, which forms a visible image when heated but can be desensitized by exposure to ultra-violet radiation, contains (1) a normally solid organic salt of nickel, cobalt or copper and (2) N, N<SP>1</SP>-bis-furfuryl-dithiooxamide or N, N<SP>1</SP>-bis-carboxyamyl-dithiooxamide. Copies may be made by placing an original in contact with the copy sheet or combination, irradiating with infra-red while in contact, and subsequently desensitizing the copy by exposure to ultraviolet, or by exposing a copy sheet to ultra-violet through a transparent original bearing opaque markings, and subsequently heating to develop colour in the areas not so desensitized. The two reagents may be disposed in a single layer, in separate layers on a single carrier, or in separate layers on separate carriers. The reagent (1) may be nickel stearate or behenate. The reagents may be dispersed in a thin film of a resinous or polymeric film-forming binder in the form of a self-sustaining film, or as a coating on a backing of film, paper or the like. The Specification includes a list of suitable binders. The sheets may also include pigments, fillers, plasticizers, dyes, waxes and resins.

Description

United States Patent 3,094,620 COPY-SHEET AND METHOD John Reitter, St. Paul, Minn., assignor to Minnesota Mining and Manufacturing Company, St. Paul, Minn., a corporation of Delaware No Drawing. Filed Jan. 3, 1961, Ser. No. 79,991 5 Claims. (Cl. 250-65) This invention relates to heat-sensitive copy-sheets and methods of making and using the same.
One well-known for copying typewritten ofiice correspondence and other graphic originals having difierentially radiation-absorptive image and background areas is known as thermographic reproduction. It involves the brief irradiation of the original, while sensitive copy-sheet, with high-intensity radiation. Preferential absorption of the radiation in the absorptive image areas then results in localized heating of the copy-sheet, producing a visible direct copy of the original. The background areas of the copy-sheet remain heat-sensitive.
Another commercial 'oifice copying system requires preliminary exposure of a photosensitive sheet material to actinic radiation in a pattern determined by an original having radiation-transmissive background areas. Irradiated areas are thereby rendered non-reactive. The unexposed image areas may in some instances be rendered visible by heating, but for images of effective color density the sheet mustbe treated with a further reagent or activator in liquid or vapor form. Apparatus for carrying out the required sequence of operations is available under the designation Copy-Flex Model 100 copying machine. In this apparatus the composite of copy-sheet and transparency is passed over a rotating glass cylinder containing a mercury vapor lamp. Typically, a ,600 watt UA-20 side of the axis of a glass cylinder having a 12 inch cir-' cumference, and the composite, in contact with the outer surface of the rotating cylinder, is exposed over an arcuate path of 6 inches at a minimum speed ofone inch in 5 seconds. Y
. Heat-sensitive copy-sheets have been described in which the visible change produced on localized brief heating is caused to occur by the inter-reaction ofa metal'saltand an organic chelating agent. The reaction produces a strongly colored permanent image. As previously described, however, these copy-sheets have been found to remain visibly heat-sensitive after, exposure to actinic radiation at speed in the Copy-Flex copying machine.
The present invention provides a heat-sensitive copysheet having a visibly heat-sensitive layer containing, in physically distinct and chemically inter-reactive relationship, a metal salt and an organic chelating agent capable of reacting together, in the thermographic copying process or on momentarily heating the sheet to a conversion temperature in the range of about 90 C. to about 150 C., with the formation of a visibly distinct reaction product, the reactants being rendered incapable of undergoing such reaction on exposure to actinic radiation as provided in the Copy-Flex copying machine. The invention therefore makes possible the preparation of permanent, heatstable, high image density reproductions of graphic originals by procedures involving only irradiation and without any necessity of treatment with solutions, fumes, vapors, powders or other adjuvants.
Typically, the composite of copy-sheet and original is first briefly irradiated with intense radiation rich in infrared and in accordance with known thermographic copying procedures. The thus imaged copy-sheet is next passed through the Copy-Flex copying machine under maximum exposure to the nearultraviolet radiation from the mer- 3,094,620 Ce Patented June 18, '1963 2 cury vapor arc. The resulting copy is stable against further heating to conversion temperature at the undarkened background areas.
Copies may alternatively be prepared by first exposing the copy-sheet to the near-ultraviolet through a transparency, for example a ribbon or carbon copy of a typeand commercially important method in heat-conductive contact with a heatbacking,
separate backings.
Written document on thin semi-transparent paper, and then heating the entire copy-sheet to conversion temperature, for example on a heated roller or platen or in an oven.
Dithiooxamide is known to be reactive with metal salts such as nickel stearate in the tom of heat-sensitive copy-sheets; but such products are found to remain heatsensitive under exposureto near-ultraviolet as just described. Surprisingly, it has now been found that substituted dithiooxarnide such as N,N'-bis furfuryl dithioox-amide are equally elfectively, reactive with nickel stearate in copy-sheet formulations at conversion temperatures, while at the same time making possible the complete desensitization of the copy-sheet against such reaction by a single pass through the Copy-Flex machine.
The substituted dithiooxamide and metal salt may be intimately dispersed in a thin film of a resinous or polymeric film-forming binder, either in self-sustaining film form or as a coating on a paper, film or other paper-like providing a unitary heat-sensitive copy-sheet in a single coating and drying operation. The two reactants may separately be dispersed or dissolved together with appropriate binders, and applied to a paper-like backing in separate coatings withintermediate drying, or to In the latter case the two sheets when held in face-to-face contact permit interfaci-al reaction at conversion temperature. The relative amounts of the two reactants are not critical, particularly in structures wherein the image-forming reaction occurs at an interface, the only requirement being that sutlicient of each reactant be present to ensure a readily visible change on reaction. It is desirable to employa minimum amount of the substituted dithiooxamide and to maintain'this material in position for maximum exposure to the actinic radiation. Various additives are useful in providing copy-sheets of improved appearance, handling characteristics, or other properties. Pigments, fillers, plasticizers, dyes, waxes, resins and other additives may be incorporated. H I Thefollowing specific examples will further illustrate but not limit the invention. Proportions are given in parts by weight.
EXAMPLEl Mixture A is prepared by prolonged milling in a ball mill, and is then coated in a thin uniform layer on map overlay tracing paper and dried. Mixture B is prepared by mixing the components together until solution is effected. The solution is then applied as a thin uniform coating over the previous coating and the sheet is again dried. There is obtained a heat-sensitive copy-sheet having a neutral color. Local heating, as by momentary contact of the sheet with a metal test bar at C., causes intense darkening.
A portion of the copy-sheet is placed beneath a graphic original prepared by typing on thin paper and the composite is irradiated in accordance with thermographic copying procedure. A sharp and clear reproduction of the typed characters is obtained. The copy is then exposed for approximately 30 seconds to intense near-ultraviolet radiation bypassing it through the Copy-Flex copying machine at speed. The dark image areas remain unchanged. The background areas no longer darken when placed in momentary contact with the heated test bar. I
A separate portion of the copy-sheet is placed beneath a printed transparency prepared by typing on thin semitransparent paper, and the composite is exposed to nearultraviolet radiation by passing it through the Copy-Flex copying machine as before. With the copy-sheet and transparency maintained in register, the composite is next briefly irradiated as for thermographic copying. The resulting copy has sharply defined dark image areas on a neutral background and is stable against further heating at 150 C.
The image areas are equally readily developed by replacing the transparency with a sheet of radiation-absorbent black paper prior to irradiating the composite with infra-red, or by placing the copy-sheet in contact with a heated metal platen or roller or in an oven heated to about 150 C.
With N,N'-bis fu-rfuryl dithiooxamide and nickel stearate as the reactant materials, a purple image color is obtained. Nickel stearate with N,N'-bis carboxyamyl dithiooxarnide provides a pink image. Other salts of nickel, such for example as nickel behenate, produce similar results. Salts of cobalt and copper are also useful. Other non-inventive variations will be apparent in view of the foregoing disclosures.
The compound N,N-bis (furfuryl)dithiooxamide having the structural formula HOCH HCCH Hii ii-oHPNH-o-o-NH-oHr-ii iii;
is similarly prepared using .dithiooxamide and aminocaproic acid.
What is claimed is as follows:
1. A heat-sensitive copysheet capable of undergoing permanent visible change on being momentarily heated to a conversion temperature within the range of about 90 C. to about 150 C. and of becoming insensitive to said heating on moderate exposure .to near-ultraviolet radiation, said copy-sheet including a visibly heat-sensilive layer containing, in physically distinct and chemically inter-reactive relationship, chemically inter-reactant consisting essentially of nickel stearate and N,N-bis furfuryl dithiooxamide.
2. A unitary heat-sensitive copy-sheet capable of undergoing permanent visible change on being momentarily heated to a conversion temperature within the range of about 90 C. to about 150 C. and of becoming inseni sitive to said heating on moderate exposure to near-ultraviolet radiation, said copy-sheet comprising a thin paperlike backing and a coating comprising a film-forming binder and, in physically distinct and chemically interreactive relationship, chemically inter-reactant components consisting essentially of nickel stearate and N,N'-'
bis furfuryl dithiooxamide.
3. Method of copying comprising placing in surface contact and in position for irradiation a graphic original having ditierentially inf-rared absorptive image and back- 7 ground areas and a heat-sensitive copyisheet having a visibly heat-sensitive layer containing nickel stearate and N,N-bis furfiuryl dithiooxamide in physically distinct and chemically inter-reactive relationship, momentarily irradiating said graphic original with intense radiation rich in infra-red for causing visible inter-reaction in said i the near-ultraviolet wavelength region and in localized background-defining areas sufiicient to render said areas selectively insensitive to heat, and then heating at least the image-defining areas of said layer to provide a visible image.
5. A radiation-desensitizable intermediate sheet product suitable for use in the reproduction of a graphic original by a process involving heating said sheet product, while in face-to-face contact with a separate receptor sheet consisting essentially of a paper-like backing and a surface layer of nickel stearate, at areas corresponding to image-forming areas of said original; the said intermediate sheet product consisting essentially of a paperlike backing and a surface layer of N,N'-bis furfuryl dithiooxamide.
References Cited in the file of this patent UNITED STATES PATENTS 2,482,815 Urbach Sept. 27, 1949 2,813,042 Gordon et a1 Nov. 12, 1957 2,910,377 Owen Oct. 27, 1959 2,936,276 Chalkley May 10, 1960 2,950,987 Howard Aug. 30, .1960 2,967,785 Allen et a1. Jan. 10, 1961

Claims (1)

  1. 5. A RADIATION-DESENSITIZABLE INTERMEDIATE SHEET PRODUCT SUITABLE FOR USE IN THE REPRODUCTION OF A GRAPHIC ORIGINAL BY A PORCESS INVOLVING HEATING SAID SHEET PRODUCT, WHILE A FACE-TO-FACE CONTACT WITH A SEPARATE RECEPTOR SHEET CONSISTING ESSENTIALLY OF A PAPER-LIKE BACKING AND A SURFACE LAYER OF NICKEL STEARATE, AT AREAS CORRESPONDING TO IMAGE-FORMING AREAS OF SAID ORIGINAL; THE SAID INTERMEDIATE SHEET PRODUCT CONSISTING ESSENTIALLY OF A PAPERLIKE BACKING AND A SURFACE LAYER OF N,N''-BIS-FURFURYL DITHIOOXAMIDE.
US79991A 1961-01-03 1961-01-03 Copy-sheet and method Expired - Lifetime US3094620A (en)

Priority Applications (12)

Application Number Priority Date Filing Date Title
NL273128D NL273128A (en) 1961-01-03
BE612242D BE612242A (en) 1961-01-03
US79991A US3094620A (en) 1961-01-03 1961-01-03 Copy-sheet and method
US79990A US3094619A (en) 1961-01-03 1961-01-03 Ultra-violet radiation-desensitizable thermographic copy-sheet and method
SE13164/61A SE313248B (en) 1961-01-03 1961-12-30
DEM51374A DE1200846B (en) 1961-01-03 1962-01-02 Thermographic copier material and method for making heat-resistant copies hereby
ES0273372A ES273372A1 (en) 1961-01-03 1962-01-02 Ultra-violet radiation-desensitizable thermographic copy-sheet and method
GB300/62A GB997361A (en) 1961-01-03 1962-01-03 Heat-sensitive copy sheets
FR883772A FR1311591A (en) 1961-01-03 1962-01-03 Thermographic reproduction sheet and its manufacturing process
GB10700/65A GB997362A (en) 1961-01-03 1962-01-03 Heat-sensitive copy-sheets
CH5362A CH419198A (en) 1961-01-03 1962-01-03 Heat-sensitive copying material and how to use it
FI0008/62A FI43136B (en) 1961-01-03 1962-01-03

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Application Number Priority Date Filing Date Title
US79991A US3094620A (en) 1961-01-03 1961-01-03 Copy-sheet and method
US79990A US3094619A (en) 1961-01-03 1961-01-03 Ultra-violet radiation-desensitizable thermographic copy-sheet and method

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US3094620A true US3094620A (en) 1963-06-18

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US79990A Expired - Lifetime US3094619A (en) 1961-01-03 1961-01-03 Ultra-violet radiation-desensitizable thermographic copy-sheet and method

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US79990A Expired - Lifetime US3094619A (en) 1961-01-03 1961-01-03 Ultra-violet radiation-desensitizable thermographic copy-sheet and method

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BE (1) BE612242A (en)
CH (1) CH419198A (en)
DE (1) DE1200846B (en)
ES (1) ES273372A1 (en)
FI (1) FI43136B (en)
FR (1) FR1311591A (en)
GB (2) GB997361A (en)
NL (1) NL273128A (en)
SE (1) SE313248B (en)

Cited By (10)

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US3157526A (en) * 1962-04-17 1964-11-17 Bemis Bro Bag Co Thermo-sensitive copy sheet and method of making
US3219470A (en) * 1962-02-13 1965-11-23 Agfa Ag Heat sensitive copying layers
US3241996A (en) * 1962-10-10 1966-03-22 Polaroid Corp Heat-sensitive copy sheet system and process of copying
US3715267A (en) * 1969-10-08 1973-02-06 Ricoh Kk Heat-sensitive stencil sheet
US3906138A (en) * 1968-05-10 1975-09-16 Minnesota Mining & Mfg Print sheet
US4808565A (en) * 1986-08-14 1989-02-28 Minnesota Mining And Manufacturing Company Thermal imaging material
US4829046A (en) * 1987-10-15 1989-05-09 Minnesota Mining And Manufacturing Company Positive-acting thermographic materials
US4902668A (en) * 1988-08-25 1990-02-20 Minnesota Mining And Manufacturing Company Pressure sensitive carbonless imaging system incorporating uncolored ferric organophosphates and colored chelates
US4902667A (en) * 1988-08-25 1990-02-20 Minnesota Mining And Manufacturing Company Pressure sensitive carbonless imaging system incorporating uncolored ferric organophosphates and uncolored chelates
US4910186A (en) * 1987-10-15 1990-03-20 Minnesota Mining And Manufacturing Company Positive-acting thermographic materials

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BE611269A (en) * 1960-12-10
US3446617A (en) * 1962-04-20 1969-05-27 Minnesota Mining & Mfg Thermographic copying process
BE638254A (en) * 1962-10-05
US3218168A (en) * 1962-10-15 1965-11-16 Minnesota Mining & Mfg Heat and photosensitive copy sheet
DE1250842B (en) * 1962-11-23 1967-09-28 Minnesota Mining and Manufacturing Company, Saint Paul, Minn. (V. St. A.) Heat sensitive copying material
US3291600A (en) * 1963-01-14 1966-12-13 Rca Corp Electrophotographic recording element and method of making
US3409438A (en) * 1963-08-26 1968-11-05 Minnesota Mining & Mfg Photosensitive heat developable copysheet
US3446648A (en) * 1965-09-27 1969-05-27 Minnesota Mining & Mfg Reactive copying sheet and method of using
US3460946A (en) * 1966-02-03 1969-08-12 Minnesota Mining & Mfg Image receptor sheets containing organic silver salts and metal ion image
US3559578A (en) * 1968-09-19 1971-02-02 Minnesota Mining & Mfg Lithographic duplicating method and lithoplate master therefor
US3708304A (en) * 1970-06-03 1973-01-02 Eastman Kodak Co Use of divalent metal salt image amplifiers in photosensitive and thermosensitive elements
JPS5129819B2 (en) * 1972-03-27 1976-08-27
US3924049A (en) * 1973-07-30 1975-12-02 Texas Instruments Inc Multicolor thermosensitive paper
JP2538043B2 (en) * 1989-04-05 1996-09-25 松下電器産業株式会社 Pattern forming material and method of manufacturing pattern forming substrate using the same
EP0704318A1 (en) * 1994-09-27 1996-04-03 Minnesota Mining And Manufacturing Company Imaging method for thermal-sensitive material
EP0730196B1 (en) * 1995-03-02 2000-10-25 Agfa-Gevaert N.V. Heat-sensitive recording material having image-stabilization properties
DE69610725T2 (en) * 1995-03-02 2001-05-10 Agfa-Gevaert N.V., Mortsel Heat sensitive recording material with image stabilizing properties

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US2813042A (en) * 1952-10-02 1957-11-12 Dick Co Ab Method of preparing a sensitized thermographic copy sheet and resultant sheet
US2910377A (en) * 1956-06-28 1959-10-27 Minnesota Mining & Mfg Heat-sensitive copying-paper
US2936276A (en) * 1957-06-25 1960-05-10 Chalkley Lyman Photochemical compositions and processes utilizing salts of para-amino triphenylacetonitriles
US2950987A (en) * 1958-10-28 1960-08-30 Du Pont Thermally-sensitive recording elements
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US3219470A (en) * 1962-02-13 1965-11-23 Agfa Ag Heat sensitive copying layers
US3157526A (en) * 1962-04-17 1964-11-17 Bemis Bro Bag Co Thermo-sensitive copy sheet and method of making
US3241996A (en) * 1962-10-10 1966-03-22 Polaroid Corp Heat-sensitive copy sheet system and process of copying
US3906138A (en) * 1968-05-10 1975-09-16 Minnesota Mining & Mfg Print sheet
US3715267A (en) * 1969-10-08 1973-02-06 Ricoh Kk Heat-sensitive stencil sheet
US4808565A (en) * 1986-08-14 1989-02-28 Minnesota Mining And Manufacturing Company Thermal imaging material
US4829046A (en) * 1987-10-15 1989-05-09 Minnesota Mining And Manufacturing Company Positive-acting thermographic materials
US4910186A (en) * 1987-10-15 1990-03-20 Minnesota Mining And Manufacturing Company Positive-acting thermographic materials
US4902668A (en) * 1988-08-25 1990-02-20 Minnesota Mining And Manufacturing Company Pressure sensitive carbonless imaging system incorporating uncolored ferric organophosphates and colored chelates
US4902667A (en) * 1988-08-25 1990-02-20 Minnesota Mining And Manufacturing Company Pressure sensitive carbonless imaging system incorporating uncolored ferric organophosphates and uncolored chelates

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GB997362A (en) 1965-07-07
DE1200846B (en) 1965-09-16
SE313248B (en) 1969-08-04
FR1311591A (en) 1962-12-07
ES273372A1 (en) 1962-07-01
GB997361A (en) 1965-07-07
NL273128A (en)
BE612242A (en)
US3094619A (en) 1963-06-18
CH419198A (en) 1966-08-31
FI43136B (en) 1970-10-01

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