US3767394A - Color copying and sheet material therefor - Google Patents

Color copying and sheet material therefor Download PDF

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US3767394A
US3767394A US00111981A US3767394DA US3767394A US 3767394 A US3767394 A US 3767394A US 00111981 A US00111981 A US 00111981A US 3767394D A US3767394D A US 3767394DA US 3767394 A US3767394 A US 3767394A
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sheet
dye
photosensitive
image
heat
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US00111981A
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J Wiese
Dyke Tiers G Van
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3M Co
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Minnesota Mining and Manufacturing Co
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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
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • B41M5/48—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • 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
    • 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
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/22—Subtractive cinematographic processes; Materials therefor; Preparing or processing such materials
    • G03C7/24—Subtractive cinematographic processes; Materials therefor; Preparing or processing such materials combined with sound-recording
    • 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
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/26—Silver halide emulsions for subtractive colour processes

Definitions

  • ABSTRACT A stabilized photosensitive heat-developable sheet material or assembly of sheet materials for making color prints or transparencies by a method involving exposure, heat development, and thermographic transfer.
  • This invention relates generally to the recording of light-images on light-sensitive heat-developable dry silver sheet materials.
  • the invention relates to modified dry silver sheet materials and to a method of using the same in making colored prints of colored light-images.
  • the invention relates to dry silver sheet materials in tri-pack form and to their application in making multi-color prints by a method involving but a single exposure, e.g. through a color negative.
  • Dry silver sheet materials have been described, in U.S. Pat. No. 3,457,075, as consisting essentially of (a) photosensitive silver halide catalyst-forming means and (b) heat-sensitive reactant image-forming means including an organic silver salt oxidizing agent and a reducing agent for silver ion, the oxidation-reduction reaction of which to produce a visible change is accelerated by said catalyst.
  • thermographically induced transfer of volatilizable dyes has been described, e.g., in.U.S. Pat. No. 3,280,735, in terms of briefly exposing to intense infrared radiation a printed original, whereby to produce a corresponding heat pattern for volatilizing the dye from a source sheet onto a receptor sheet.
  • the heat pattern is subject to lateral diffusion.
  • the combination of intense light and high temperature has been found in many cases to cause image blurring of imaged dry silver sheet materials under thermographic copying conditions. 1
  • FIGURE of the drawing represents in cross-section a portion of a pack of modified dry silver sheets prepared in accordance with the principles of the invention and useful in making full-color prints.
  • Sheet comprises a transparent film support 11 having on one surface a modified dry silver coating 12 and on the .other surface a volatilizable dye 13.
  • sheet 14 comprises film 15, dry silver coating 16 and dye coat 17, and sheet 18 comprises film 19, dry silver coating-20 and dye coating 21.
  • the threesheets, assembled as shown, comprise a tripack 22.
  • the,tripack 22 is first exposed to a light-image from the upper surface as seen in the drawing. After exposure .the three sheets are heated briefly to develop in each-a dense image corresponding to a portion of the light-image, and the three are then successively placed in registry against a receptor sheet and the composite is briefly exposed to intense infrared radiation, e.g., in a thermographic copying machine.
  • the heat patterns induced in the image areas cause transfer of dye to corresponding areas of the receptor sheet, with production of a colored image.
  • the separate dye images are transferred to separate transparent film receptor sheets which are then placed in registry to form a full-color transparency.
  • the exposed sheets are developed in a manner to produce a positive rather than a negative image.
  • the resulting dye images obtained by thermographic transfer from the thus imaged films then represent a direct rather than a color reversed record of the initial colored light pattern.
  • the dry silver coatings 12, 16 and 20 are respectively sensitized to blue, green and red light, as indicated in the drawing by the letters B, G and R.
  • the dye coatings l3, l7 and 21 analogously contain yellow, magenta and cyan dyes respectively, indicated as Y, M and C.
  • the transparent carrier film is marked T in each instance.
  • the dye layers assist inabsorbing light other than that to which the lower layer or layers of dry silver material have been sensitized, so that a sharp separation of color is accomplished and a true showing of both white and black as well as color is accomplished in the final print or print assembly.
  • the lower dye layers also serve as antihalation layers and assist in providing sharply defined images.
  • both direct and reverse light patterns may be reproduced as direct color prints.
  • the light pattern may be obtained either by direct reflection from a colored subject or colored original, or by projection through a colored transparency which may be either a positive or a negative photographic color transparency.
  • An important feature of the invention resides in the stabilizing of the imaged dry silver layer against further darkening of the background, or lateral spreading of the image areas, under continued heating or exposure to infra-red. It has been found that various halogencontaining organic oxidizing agents may be incorpo rated in the dry silver coatings without altering the initial light-sensitivity thereof, and'that such compounds effectively stabilize the imaged sheet.
  • Aibengoylethylerrediamine are representative.
  • This compound also known as N,N-dichloro-l,Z-ethyleri bisbenzamide, is a presently preferred stabilizer material.
  • the stabilizer may be incorporated in a compositioncontaining all of the required components for preparing the photosensitive heat-developable dry silver coating.
  • the more active stabilizers are preferably added in a second coating, the photosensitive components being applied in a separate first coating, to avoid any tendency toward desensitization of the photosensitive materials prior to heat development.
  • Red Sensitizer add 6 ml. of a .05% solution in methanol.
  • the second coating is likewise applied at a wet thickness of 3 mils and dried.
  • the reverse surfaces of the three coated films are then separately coated with the appropriate dyes, the coating solutions in each instance consisting of 326 mgm. of dye in 10 gms. ofa 16.7% solution of acrylonitrile:vinylidene copolymer (Saran F-220) in methylethyl ketone.
  • the yellow dye is Sudan Yellow GR Concentrate, Color Index 21240.
  • the magenta-dye is 4;
  • the cyan dye is DuPont Oil Blue A, Color Index Solvent Blue 36.
  • Other useful volatilizable dyes include Sudan Yellow RRA, Sudan Yellow GGA, Special Red S Conc., and Smoke Green No. l.
  • the three coated films are combined in a tri-pack in the relationship shown in the drawing, and the pack is exposed to a reverse color light-image by contact printing through a photographic color negative.
  • the three films are separately briefly heated to form on each a dense visisble image at the light-struck areas.
  • the films are then laid against transparent polymeric receptor films, in this case consisting of thin transparent Mylar polyester film lightly coated with a mixture of 1.5 grams of nickel acetate tetrahydrate and 10 grams of polyvinyl alcohol applied from solution in grams of water, and are briefly exposed to intense infra-red radiation in a'thermographic copying machine to form on each receptor a monocolor partial negative image.
  • the three imaged receptor films are placed together in registry to provide a full color positive transparency.
  • Another tripack assembly is first exposed to a direct color light-image by contact printing through a photographic color positive serving as an original, and the three films are separately subjected to minimum heat required to produce maximum useful density at unexposed areas. By such continued heating the initially darkened light-struck areas are transparentized while the initially transparent non-light-struck areas progressively darken to a maximum.
  • the three films are then successively placed against a receptor sheet consisting of white paper lightly coated with a mixture of four parts by weight of calcium stearate, two parts of nickel stearate, four parts of calcium carbonate, and ten parts of polyvinyl alcohol, applied in 90 parts of water.
  • the composite is in each case passed through the thermographic copying machine, the imaged film in each case being placed in registry with the position of any preceding imaged film or films. A direct full-color reproduction of the colored original is obtained.
  • a photosensitive sheet material comprising a transparent thin carrier having over one surface a photosensitive heat developable dry silver layer comprising (a) photosensitive silver halide catalyst-forming means, (b) heat-sensitive reactant image-forming means including an organic silver salt oxidizing agent and a reducing agent for silver ion, the oxidation-reduction reaction of which to produce a visible change is accelerated by said catalyst, and (c) N,N-dichloro-l ,2-
  • said carrier having over the other surface a layer comprising, in a polymeric binder, a dye which is volatilizable therefrom at temperatures obtained under thermographic copying conditions.
  • a pack of sheet material useful in making fullcolor prints comprised of three sheets of photosensitive sheet material each comprising a transparent thin carrier having over one surface a heat-stabilized photosensitive heat developable dry silver layer comprising (a) photosensitive silver halide catalyst-forming means and (b) heat-sensitive reactant image-forming means including an organic silver salt oxidizing agent and a reducing agent for silver ion, the oxidation-reduction re action of which to produce a visible change is accelerated by said catalyst, and (c) a spectral sensitizer for sensitizing said sheet to a primary color, and said carrier having over the other surface a layer comprising, in a polymeric binder, a dye which is volatilizable therefrom at temperatures obtainable under thermographic copying conditions, and wherein the first of said three sheets carries a cyan dye and is sensitized to red, the second carries a magenta dye and is sensitized to green, and the third carries a yellow dye and is sensitized to blue.
  • Method of making a multicolor print comprising:
  • the receptor sheet includes a surface coating comprising a nickel salt of an organic acid in a water-soluble binder.
  • Method of making a color print comprising: exposing to a light-image a photosensitive sheet material comprising a transparent thin carrier having over one surface a photosensitive heat developable dry silverlayer comprising (a) photosensitive silver halide catalyst-forming means, (b) heat-sensitive reactant imageforming means including an organic silver salt oxidizing agent and a reducing agent for silver ion, the oxidationreduction reaction of which to produce a visible change l c r siby qsa a mtaadl lNfi q o 1,2-ethylenebisbenzamide or N-bromosuccinimide,
  • said carrier having over the other surface a layer comprising, in a polymeric binder, a dye which is volatilizable therefrom at temperatures obtained under thermographic copying conditions; heating the exposed sheet to develop a visible image; and briefly exposing the imaged surface to intense infrared radiation while maintaining the dye-carrying surface against a receptor sheet.

Abstract

A stabilized photosensitive heat-developable sheet material or assembly of sheet materials for making color prints or transparencies by a method involving exposure, heat development, and thermographic transfer.

Description

United States Patent 1 Wiese, Jr. et al.
[ Oct. 23, 1973 COLOR COPYING AND SHEET MATERIAL THEREFOR [75] Inventors: Joseph A. Wiese, Jr.; George Van Dyke Tiers, both of St. Paul, Minn.
[73] Assignee: Minnesota Mining and Manufacturing Company, St. Paul, Minn.
[22] Filed: Feb. 2, 1971 [21] Appl. No.2 111,981
[56] References Cited UNITED STATES PATENTS 2,396,726 Trimble 96/11 3,280,735 10/1966 Clark 250/65 T 3,301,697 1/1967 Russell 250/65 T 3,370,170 2/1968 Gold 350/65 T 3,392,020 7/1968 Yutzy.... 250/65 T 3,418,468 12/1968 Marx..... 250/65 T 3,457,075 7/1969 Morgan. 96/1 14.1 3,502,871 3/1970 Marx 117/36.8
3,520,691 7/1970 Scheler 117/36.8 3,531,286 9/1970 Renfrew 117/36.8
Primary ExaminerNorman G. Torchin Assistant Examiner-Richard L. Schilling AttorneyAlexander, Sell, Steldt & Delahunt [57] ABSTRACT A stabilized photosensitive heat-developable sheet material or assembly of sheet materials for making color prints or transparencies by a method involving exposure, heat development, and thermographic transfer.
7 Claims, 1 Drawing Figure COLOR COPYING AND SHEET MATERIAL THEREFOR This invention relates generally to the recording of light-images on light-sensitive heat-developable dry silver sheet materials. In one aspect the invention relates to modified dry silver sheet materials and to a method of using the same in making colored prints of colored light-images. In a particular aspect the invention relates to dry silver sheet materials in tri-pack form and to their application in making multi-color prints by a method involving but a single exposure, e.g. through a color negative.
Dry silver sheet materials have been described, in U.S. Pat. No. 3,457,075, as consisting essentially of (a) photosensitive silver halide catalyst-forming means and (b) heat-sensitive reactant image-forming means including an organic silver salt oxidizing agent and a reducing agent for silver ion, the oxidation-reduction reaction of which to produce a visible change is accelerated by said catalyst.
The thermographically induced transfer of volatilizable dyes has been described, e.g., in.U.S. Pat. No. 3,280,735, in terms of briefly exposing to intense infrared radiation a printed original, whereby to produce a corresponding heat pattern for volatilizing the dye from a source sheet onto a receptor sheet. The heat pattern is subject to lateral diffusion. The combination of intense light and high temperature has been found in many cases to cause image blurring of imaged dry silver sheet materials under thermographic copying conditions. 1
It has nowbeen found possible to provide a modified dry silver sheet or coating with which the'rmographically stable imaged sheets may be produced. It has also been found possible to employ such sheet materials in a thermographic image transfer process whereby to produce sharply defined monocolor or multicolor prints of colored light images, all as will hereinafter be set forth.
The single FIGURE of the drawing represents in cross-section a portion of a pack of modified dry silver sheets prepared in accordance with the principles of the invention and useful in making full-color prints.
Sheet comprises a transparent film support 11 having on one surface a modified dry silver coating 12 and on the .other surface a volatilizable dye 13. Similarly, sheet 14 comprises film 15, dry silver coating 16 and dye coat 17, and sheet 18 comprises film 19, dry silver coating-20 and dye coating 21. The threesheets, assembled as shown, comprise a tripack 22.
In making a print, the,tripack 22 is first exposed to a light-image from the upper surface as seen in the drawing. After exposure .the three sheets are heated briefly to develop in each-a dense image corresponding to a portion of the light-image, and the three are then successively placed in registry against a receptor sheet and the composite is briefly exposed to intense infrared radiation, e.g., in a thermographic copying machine. The heat patterns induced in the image areas cause transfer of dye to corresponding areas of the receptor sheet, with production of a colored image. Alternatively, the separate dye images are transferred to separate transparent film receptor sheets which are then placed in registry to form a full-color transparency.
In a modification of the method just described, and using a dry silver composition which under appropriate development conditions has a negative D log E slope, the exposed sheets are developed in a manner to produce a positive rather than a negative image. The resulting dye images obtained by thermographic transfer from the thus imaged films then represent a direct rather than a color reversed record of the initial colored light pattern.
The dry silver coatings 12, 16 and 20 are respectively sensitized to blue, green and red light, as indicated in the drawing by the letters B, G and R. The dye coatings l3, l7 and 21 analogously contain yellow, magenta and cyan dyes respectively, indicated as Y, M and C. The transparent carrier film is marked T in each instance. The dye layers assist inabsorbing light other than that to which the lower layer or layers of dry silver material have been sensitized, so that a sharp separation of color is accomplished and a true showing of both white and black as well as color is accomplished in the final print or print assembly. The lower dye layers also serve as antihalation layers and assist in providing sharply defined images.
As above indicated, both direct and reverse light patterns may be reproduced as direct color prints. Thus the light pattern may be obtained either by direct reflection from a colored subject or colored original, or by projection through a colored transparency which may be either a positive or a negative photographic color transparency.
An important feature of the invention resides in the stabilizing of the imaged dry silver layer against further darkening of the background, or lateral spreading of the image areas, under continued heating or exposure to infra-red. It has been found that various halogencontaining organic oxidizing agents may be incorpo rated in the dry silver coatings without altering the initial light-sensitivity thereof, and'that such compounds effectively stabilize the imaged sheet.
Compounds in which a positive halogen is attached directly to nitrogen represent a particularly effective class of stabilizers. Compounds such as N- bromosuccinimide and N,N'-dichloro-N,N-
Aibengoylethylerrediamine are representative. This compound also known as N,N-dichloro-l,Z-ethyleri bisbenzamide, is a presently preferred stabilizer material. The stabilizer may be incorporated in a compositioncontaining all of the required components for preparing the photosensitive heat-developable dry silver coating. The more active stabilizers are preferably added in a second coating, the photosensitive components being applied in a separate first coating, to avoid any tendency toward desensitization of the photosensitive materials prior to heat development. I
The following specific Example will serve as a further illustration of. the principles of the invention.
EXAMPLE A first composition is prepared by first dispersing 20 parts by weight of silver behenate full soap in a mixture of 37.5 parts methylethyl ketone and 42.5 parts toluene, pre fe11bl y byprolonged ballmillingig 50 gms. of the dispersion is added 40 ml. of methyl isobutyl ketone, 10 ml. of a 2% solution of mercuric bromide in methyl alcohol, and 22 gms. of a 15% solution of polyvinylbutyral resin in ethyl alcohol, all operations beginning with addition of mercuric bromide being conducted under darkroom conditions. To such mixtures are then added various spectral sensitizer materi- (3:0 S /o= zs N Et I Green Sensitizer: add 3 ml. of a .05% solution in acetone.
Red Sensitizer: add 6 ml. of a .05% solution in methanol.
I CHiCHi-C Over the above coatings is then supplied a further coating consisting of the following:
3% solution of cellulose acetate butyrate in methylethyl ketone75 ml. 20% solution of 'polymethylmethacrylate in ethyl acetateml.
phthalazinonel gm.
2,2'-methylenebis-(4-methyl-G-tertiarybutylplie n'oli l gm.
2% solution of phthalic acid in methanoll.5 ml.
N ,N'-dichloro l ,2-ethylene bisbenzamide 2.75 gm.
The second coating is likewise applied at a wet thickness of 3 mils and dried.
The reverse surfaces of the three coated films are then separately coated with the appropriate dyes, the coating solutions in each instance consisting of 326 mgm. of dye in 10 gms. ofa 16.7% solution of acrylonitrile:vinylidene copolymer (Saran F-220) in methylethyl ketone. The yellow dye is Sudan Yellow GR Concentrate, Color Index 21240. The magenta-dye is 4;
tricyanovinyl-N,N-di-n-butylaniline. The cyan dye is DuPont Oil Blue A, Color Index Solvent Blue 36. Other useful volatilizable dyes include Sudan Yellow RRA, Sudan Yellow GGA, Special Red S Conc., and Smoke Green No. l.
- The three coated films are combined in a tri-pack in the relationship shown in the drawing, and the pack is exposed to a reverse color light-image by contact printing through a photographic color negative. The three films are separately briefly heated to form on each a dense visisble image at the light-struck areas. The films are then laid against transparent polymeric receptor films, in this case consisting of thin transparent Mylar polyester film lightly coated with a mixture of 1.5 grams of nickel acetate tetrahydrate and 10 grams of polyvinyl alcohol applied from solution in grams of water, and are briefly exposed to intense infra-red radiation in a'thermographic copying machine to form on each receptor a monocolor partial negative image. The three imaged receptor films are placed together in registry to provide a full color positive transparency.
Another tripack assembly is first exposed to a direct color light-image by contact printing through a photographic color positive serving as an original, and the three films are separately subjected to minimum heat required to produce maximum useful density at unexposed areas. By such continued heating the initially darkened light-struck areas are transparentized while the initially transparent non-light-struck areas progressively darken to a maximum. The three films are then successively placed against a receptor sheet consisting of white paper lightly coated with a mixture of four parts by weight of calcium stearate, two parts of nickel stearate, four parts of calcium carbonate, and ten parts of polyvinyl alcohol, applied in 90 parts of water. The composite is in each case passed through the thermographic copying machine, the imaged film in each case being placed in registry with the position of any preceding imaged film or films. A direct full-color reproduction of the colored original is obtained.
In the foregoing Example, exposure is typically between 3 and 6 seconds using as the light source a 650 watt FAB tungsten filament quartz iodine lamp at a distance of 3 feet, and development is achieved by heating at temperatures between about and C. With other formulations and conditions it may be found necessary to modify these values, but the necessary modifications are readily determined by simple preliminary sensitometric test procedures well within the skill of the art.
What is claimed is as follows:
1. A photosensitive sheet material comprising a transparent thin carrier having over one surface a photosensitive heat developable dry silver layer comprising (a) photosensitive silver halide catalyst-forming means, (b) heat-sensitive reactant image-forming means including an organic silver salt oxidizing agent and a reducing agent for silver ion, the oxidation-reduction reaction of which to produce a visible change is accelerated by said catalyst, and (c) N,N-dichloro-l ,2-
ethylenebisbenzamide or N-bromosuccinimide, and
said carrier having over the other surface a layer comprising, in a polymeric binder, a dye which is volatilizable therefrom at temperatures obtained under thermographic copying conditions.
2. Sheet material of claim 1 wherein said dry silver layer contains a spectral'sensitizer for sensitizing said sheet to a primary color.
3. A pack of sheet material useful in making fullcolor prints and comprised of three sheets of photosensitive sheet material each comprising a transparent thin carrier having over one surface a heat-stabilized photosensitive heat developable dry silver layer comprising (a) photosensitive silver halide catalyst-forming means and (b) heat-sensitive reactant image-forming means including an organic silver salt oxidizing agent and a reducing agent for silver ion, the oxidation-reduction re action of which to produce a visible change is accelerated by said catalyst, and (c) a spectral sensitizer for sensitizing said sheet to a primary color, and said carrier having over the other surface a layer comprising, in a polymeric binder, a dye which is volatilizable therefrom at temperatures obtainable under thermographic copying conditions, and wherein the first of said three sheets carries a cyan dye and is sensitized to red, the second carries a magenta dye and is sensitized to green, and the third carries a yellow dye and is sensitized to blue.
4. A pack ofsheets according to cl ai m {wherein tl e dry silver layers each contain N,N-dichloro-l,2 ethylene-bisbenzamide or N-bromosuccinimide.
5. Method of making a multicolor print comprising:
(l) exposing to a light-image a pack of three sheets of I photosensitive sheet material each comprising a transparent thin carrier having over one surface a heatstabilized photosensitive heat developable dry silver layer comprising (a) photosensitive silver halide catalyst-forming means and (b) heat-sensitive reactant image-forming means including an organic silver salt oxidizing agent and a reducing agent for silver ion, the oxidation-reduction reaction of which to produce a visible change is accelerated by said catalyst, and (c) a spectral sensitizer for sensitizing said sheet to a primary color, and said carrier having over the other surface a layer comprising, in a polymeric binder, a dye which is volatilizable therefrom at temperatures obtainable under thermographic copying conditions, and wherein the first of said three sheets carries a cyan dye and is sensitized to red, the second carries a magenta dye and is sensitized to green, and the third carries a yellow dye and is sensitized to blue, with said light-image being incident on said third sheet; (2) separating the three sheets and heating each one independently to develop a visible image; and (3) separately briefly exposing each sheet to intense infra-red radiation while maintaining the dye layer against a common receptor sheet and with each sheet in registry with the position of the preceding sheet or sheets.
6. Method of claim 5 wherein the receptor sheet includes a surface coating comprising a nickel salt of an organic acid in a water-soluble binder. I
7. Method of making a color print comprising: exposing to a light-image a photosensitive sheet material comprising a transparent thin carrier having over one surface a photosensitive heat developable dry silverlayer comprising (a) photosensitive silver halide catalyst-forming means, (b) heat-sensitive reactant imageforming means including an organic silver salt oxidizing agent and a reducing agent for silver ion, the oxidationreduction reaction of which to produce a visible change l c r siby qsa a mtaadl lNfi q o 1,2-ethylenebisbenzamide or N-bromosuccinimide,
and said carrier having over the other surface a layer comprising, in a polymeric binder, a dye which is volatilizable therefrom at temperatures obtained under thermographic copying conditions; heating the exposed sheet to develop a visible image; and briefly exposing the imaged surface to intense infrared radiation while maintaining the dye-carrying surface against a receptor sheet.
UNITED STATES PATENT 0mm: CERTIFICATE OF CORRECTION Patent: No- 3,767,394 Dated Oct. 23, 1973 Inventor) Joseph A. Wiese, Jr. and George Van Dyke Tiers It is certified that error appears in the above-identified-patent .and that said Letters Patent are hereby corrected as shown below:
Column 3, lines 21-30 The structural formula of the green sensitizer should be:.
Signed and sealed this 9th day of April 1971;.
(SEA-L) v Attest:
. EDWARD II.FLETCHER,JR. C. MARSHALL DANN Commissioner of Patents FORM PC4050 (10-697

Claims (6)

  1. 2. Sheet material of claim 1 wherein said dry silver layer contains a spectral sensitizer for sensitizing said sheet to a primary color.
  2. 3. A pack of sheet material useful in making full-color prints and comprised of three sheets of photosensitive sheet material each comprising a transparent thin carrier having over one surface a heat-stabilized photosensitive heat developable dry silver layer comprising (a) photosensitive silver halide catalyst-forming means and (b) heat-sensitive reactant image-forming means including an organic silver salt oxidizing agent and a reducing agent for silver ion, the oxidation-reduction reaction of which to produce a visible change is accelerated by said catalyst, and (c) a spectral sensitizer for sensitizing said sheet to a primary color, and said carrier having over the other surface a layer comprising, in a polymeric binder, a dye which is volatilizable therefrom at temperatures obtainable under thermographic copying conditions, and wherein the first of said three sheets carries a cyan dye and is sensitized to red, the second carries a magenta dye and is sensitized to green, and the third carries a yellow dye and is sensitized to blue.
  3. 4. A pack of sheets according to claim 3 wherein the dry silver layers each contain N,N''-dichloro-1,2-ethylene-bisbenzamide or N-bromosuccinimide.
  4. 5. Method of making a multicolor print comprising: (1) exposing to a light-image a pack of three sheets of photosensitive sheet material each comprising a transparent thin carrier having over one surface a heat-stabilized photosensitive heat developable dry silver layer comprising (a) photosensitive silver halide catalyst-forming means and (b) heat-sensitive reactant image-forming means including an organic silver salt oxidizing agent and a reducing agent for silver ion, the oxidation-reduction reaction of which to produce a visible change is accelerated by said catalyst, and (c) a spectral sensitizer for sensitizing said sheet to a primary color, and said carrier having over the other surface a layer comprising, in a polymeric binder, a dye which is volatilizable therefrom at temperatures obtainable under thermographic copying conditions, and wherein the first of said three sheets carries a cyan dye and is sensitized to red, the second carries a magenta dye and is sensitized to green, and the third carries a yellow dye and is sensitized to blue, with said light-image being incident on said third sheet; (2) separating the three sheets and heating each one independently to develop a visible image; and (3) separately briefly exposing each sheet to intense infra-red radiation while maintaining the dye layer against a common receptor sheet and with each sheet in registry with the position of the preceding sheet or sheets.
  5. 6. Method of claim 5 wherein the receptor sheet includes a surface coating comprising a nickel salt of an organic acid in a water-soluble binder.
  6. 7. Method of making a color print comprising: exposing to a light-image a photosensitive sheet material comprising a transparent thin carrier having over one surface a photosensitive heat developable dRy silver layer comprising (a) photosensitive silver halide catalyst-forming means, (b) heat-sensitive reactant image-forming means including an organic silver salt oxidizing agent and a reducing agent for silver ion, the oxidation-reduction reaction of which to produce a visible change is accelerated by said catalyst, and (c) N,N''-dichloro-1,2-ethylenebisbenzamide or N-bromosuccinimide, and said carrier having over the other surface a layer comprising, in a polymeric binder, a dye which is volatilizable therefrom at temperatures obtained under thermographic copying conditions; heating the exposed sheet to develop a visible image; and briefly exposing the imaged surface to intense infrared radiation while maintaining the dye-carrying surface against a receptor sheet.
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Publication number Priority date Publication date Assignee Title
US3859094A (en) * 1973-01-05 1975-01-07 Minnesota Mining & Mfg Sheet material useful in image transfer techniques
DE2634893A1 (en) * 1975-08-04 1977-02-17 Minnesota Mining & Mfg STABILIZED TRANSPARENT RECEIVING MATERIAL FOR THERMOGRAPHIC IMAGE RECORDING
EP0867762A1 (en) * 1997-03-28 1998-09-30 Brother Kogyo Kabushiki Kaisha Method for manufacturing pattern sheet for plate-making
US6528894B1 (en) 1996-09-20 2003-03-04 Micron Technology, Inc. Use of nitrides for flip-chip encapsulation

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US2396726A (en) * 1942-02-23 1946-03-19 Lyne S Trimble Process for producing color prints and products
US3280735A (en) * 1964-04-13 1966-10-25 Minnesota Mining & Mfg Heat-copying process
US3301697A (en) * 1960-12-02 1967-01-31 Robert B Russell Thermographic transfer sheet having a support of a paper and plastic coating and the method of use
US3370170A (en) * 1964-10-02 1968-02-20 Keuffel & Esser Co Article and method for forming a thermographic reproduction on a sheet of polyethylene terephthalate
US3392020A (en) * 1956-05-14 1968-07-09 Eastman Kodak Co Photo-thermographic process and element
US3418468A (en) * 1963-08-01 1968-12-24 Printing Arts Res Lab Inc Process for the production of projection transparencies
US3457075A (en) * 1964-04-27 1969-07-22 Minnesota Mining & Mfg Sensitized sheet containing an organic silver salt,a reducing agent and a catalytic proportion of silver halide
US3520691A (en) * 1966-03-19 1970-07-14 Keuffel & Esser Co Heat-developable diazotype material
US3531286A (en) * 1966-10-31 1970-09-29 Minnesota Mining & Mfg Light-sensitive,heat developable copy-sheets for producing color images

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US2396726A (en) * 1942-02-23 1946-03-19 Lyne S Trimble Process for producing color prints and products
US3392020A (en) * 1956-05-14 1968-07-09 Eastman Kodak Co Photo-thermographic process and element
US3301697A (en) * 1960-12-02 1967-01-31 Robert B Russell Thermographic transfer sheet having a support of a paper and plastic coating and the method of use
US3418468A (en) * 1963-08-01 1968-12-24 Printing Arts Res Lab Inc Process for the production of projection transparencies
US3502871A (en) * 1963-08-01 1970-03-24 Printing Arts Research Lab Inc Process for making a projection transparency by exposing a sublimeable material to a pattern of infrared radiation
US3280735A (en) * 1964-04-13 1966-10-25 Minnesota Mining & Mfg Heat-copying process
US3457075A (en) * 1964-04-27 1969-07-22 Minnesota Mining & Mfg Sensitized sheet containing an organic silver salt,a reducing agent and a catalytic proportion of silver halide
US3370170A (en) * 1964-10-02 1968-02-20 Keuffel & Esser Co Article and method for forming a thermographic reproduction on a sheet of polyethylene terephthalate
US3520691A (en) * 1966-03-19 1970-07-14 Keuffel & Esser Co Heat-developable diazotype material
US3531286A (en) * 1966-10-31 1970-09-29 Minnesota Mining & Mfg Light-sensitive,heat developable copy-sheets for producing color images

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3859094A (en) * 1973-01-05 1975-01-07 Minnesota Mining & Mfg Sheet material useful in image transfer techniques
DE2634893A1 (en) * 1975-08-04 1977-02-17 Minnesota Mining & Mfg STABILIZED TRANSPARENT RECEIVING MATERIAL FOR THERMOGRAPHIC IMAGE RECORDING
US6528894B1 (en) 1996-09-20 2003-03-04 Micron Technology, Inc. Use of nitrides for flip-chip encapsulation
EP0867762A1 (en) * 1997-03-28 1998-09-30 Brother Kogyo Kabushiki Kaisha Method for manufacturing pattern sheet for plate-making
US6030743A (en) * 1997-03-28 2000-02-29 Brother Kogyo Kabushiki Kaisha Method for manufacturing pattern sheet for plate-making

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