US3767394A - Color copying and sheet material therefor - Google Patents
Color copying and sheet material therefor Download PDFInfo
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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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- 239000000463 material Substances 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000000975 dye Substances 0.000 claims description 34
- 229910052709 silver Inorganic materials 0.000 claims description 34
- 239000004332 silver Substances 0.000 claims description 34
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 26
- 238000000576 coating method Methods 0.000 claims description 16
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 12
- 239000007800 oxidant agent Substances 0.000 claims description 9
- -1 silver halide Chemical class 0.000 claims description 9
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims description 8
- 230000008859 change Effects 0.000 claims description 8
- 239000003638 chemical reducing agent Substances 0.000 claims description 8
- 239000000376 reactant Substances 0.000 claims description 8
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 230000005855 radiation Effects 0.000 claims description 7
- 238000006479 redox reaction Methods 0.000 claims description 7
- 230000003595 spectral effect Effects 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 230000001235 sensitizing effect Effects 0.000 claims description 6
- AJDUTMFFZHIJEM-UHFFFAOYSA-N n-(9,10-dioxoanthracen-1-yl)-4-[4-[[4-[4-[(9,10-dioxoanthracen-1-yl)carbamoyl]phenyl]phenyl]diazenyl]phenyl]benzamide Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2NC(=O)C(C=C1)=CC=C1C(C=C1)=CC=C1N=NC(C=C1)=CC=C1C(C=C1)=CC=C1C(=O)NC1=CC=CC2=C1C(=O)C1=CC=CC=C1C2=O AJDUTMFFZHIJEM-UHFFFAOYSA-N 0.000 claims description 5
- 239000001043 yellow dye Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 150000002815 nickel Chemical class 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 239000003232 water-soluble binding agent Substances 0.000 claims description 2
- 238000012546 transfer Methods 0.000 abstract description 6
- 238000011161 development Methods 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- MWMVYHASHGWSDG-UHFFFAOYSA-N 2-[2-(2-carbamoylphenyl)ethyl]benzamide Chemical compound NC(=O)C1=CC=CC=C1CCC1=CC=CC=C1C(N)=O MWMVYHASHGWSDG-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000002508 contact lithography Methods 0.000 description 2
- NGYIMTKLQULBOO-UHFFFAOYSA-L mercury dibromide Chemical compound Br[Hg]Br NGYIMTKLQULBOO-UHFFFAOYSA-L 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NMZURKQNORVXSV-UHFFFAOYSA-N 6-methyl-2-phenylquinoline Chemical compound C1=CC2=CC(C)=CC=C2N=C1C1=CC=CC=C1 NMZURKQNORVXSV-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 239000005041 Mylar™ Substances 0.000 description 1
- 206010034960 Photophobia Diseases 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000000586 desensitisation Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 208000013469 light sensitivity Diseases 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 229940078487 nickel acetate tetrahydrate Drugs 0.000 description 1
- OINIXPNQKAZCRL-UHFFFAOYSA-L nickel(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O OINIXPNQKAZCRL-UHFFFAOYSA-L 0.000 description 1
- JMWUYEFBFUCSAK-UHFFFAOYSA-L nickel(2+);octadecanoate Chemical compound [Ni+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O JMWUYEFBFUCSAK-UHFFFAOYSA-L 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- AQRYNYUOKMNDDV-UHFFFAOYSA-M silver behenate Chemical compound [Ag+].CCCCCCCCCCCCCCCCCCCCCC([O-])=O AQRYNYUOKMNDDV-UHFFFAOYSA-M 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Images
Classifications
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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.
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
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)
- 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 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.
- 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.
- 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.
- 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.
- 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.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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US11198171A | 1971-02-02 | 1971-02-02 |
Publications (1)
Publication Number | Publication Date |
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US3767394A true US3767394A (en) | 1973-10-23 |
Family
ID=22341480
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US00111981A Expired - Lifetime US3767394A (en) | 1971-02-02 | 1971-02-02 | Color copying and sheet material therefor |
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Cited By (4)
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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 |
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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 |
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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 |
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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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