US3531286A - Light-sensitive,heat developable copy-sheets for producing color images - Google Patents
Light-sensitive,heat developable copy-sheets for producing color images Download PDFInfo
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- US3531286A US3531286A US590551A US3531286DA US3531286A US 3531286 A US3531286 A US 3531286A US 590551 A US590551 A US 590551A US 3531286D A US3531286D A US 3531286DA US 3531286 A US3531286 A US 3531286A
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- light
- color
- silver
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- image
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Links
- 229910052709 silver Inorganic materials 0.000 description 22
- 239000004332 silver Substances 0.000 description 22
- -1 silver halide Chemical class 0.000 description 21
- 238000000576 coating method Methods 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 11
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 8
- 239000003638 chemical reducing agent Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000000344 soap Substances 0.000 description 7
- 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 description 7
- 239000000243 solution Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 5
- 235000021357 Behenic acid Nutrition 0.000 description 5
- 229940116226 behenic acid Drugs 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000000975 dye Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 150000007524 organic acids Chemical class 0.000 description 4
- AQRYNYUOKMNDDV-UHFFFAOYSA-M silver behenate Chemical compound [Ag+].CCCCCCCCCCCCCCCCCCCCCC([O-])=O AQRYNYUOKMNDDV-UHFFFAOYSA-M 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000008199 coating composition Substances 0.000 description 3
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 230000033458 reproduction Effects 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- HVLJEMXDXOTWLV-UHFFFAOYSA-N 2,4-dichloronaphthalen-1-ol Chemical compound C1=CC=C2C(O)=C(Cl)C=C(Cl)C2=C1 HVLJEMXDXOTWLV-UHFFFAOYSA-N 0.000 description 2
- GCABLKFGYPIVFC-UHFFFAOYSA-N 3-(1-benzofuran-2-yl)-3-oxopropanenitrile Chemical compound C1=CC=C2OC(C(CC#N)=O)=CC2=C1 GCABLKFGYPIVFC-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229910000039 hydrogen halide Inorganic materials 0.000 description 2
- 239000012433 hydrogen halide Substances 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 150000004668 long chain fatty acids Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- KYYRTDXOHQYZPO-UHFFFAOYSA-N n-(2-methoxyphenyl)-3-oxobutanamide Chemical compound COC1=CC=CC=C1NC(=O)CC(C)=O KYYRTDXOHQYZPO-UHFFFAOYSA-N 0.000 description 2
- 150000004989 p-phenylenediamines Chemical class 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- MMLCSDNEYQRUDM-UHFFFAOYSA-M silver;docosanoate;docosanoic acid Chemical compound [Ag+].CCCCCCCCCCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCCCCCCCCCC([O-])=O MMLCSDNEYQRUDM-UHFFFAOYSA-M 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- PXJHVKRLFWZUNV-UHFFFAOYSA-N 1-n,4-n-dimethylbenzene-1,4-diamine;hydron;dichloride Chemical compound Cl.Cl.CNC1=CC=C(NC)C=C1 PXJHVKRLFWZUNV-UHFFFAOYSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- GHJUWGHWJYULLK-UHFFFAOYSA-N 2,6-dibromonaphthalene-1,5-diol Chemical compound BrC1=CC=C2C(O)=C(Br)C=CC2=C1O GHJUWGHWJYULLK-UHFFFAOYSA-N 0.000 description 1
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 1
- QNGVNLMMEQUVQK-UHFFFAOYSA-N 4-n,4-n-diethylbenzene-1,4-diamine Chemical compound CCN(CC)C1=CC=C(N)C=C1 QNGVNLMMEQUVQK-UHFFFAOYSA-N 0.000 description 1
- VVYWUQOTMZEJRJ-UHFFFAOYSA-N 4-n-methylbenzene-1,4-diamine Chemical compound CNC1=CC=C(N)C=C1 VVYWUQOTMZEJRJ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 206010073306 Exposure to radiation Diseases 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical class OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 229910021612 Silver iodide Inorganic materials 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- KTWNIUBGGFBRKH-UHFFFAOYSA-N [4-(dimethylamino)phenyl]azanium;chloride Chemical compound Cl.CN(C)C1=CC=C(N)C=C1 KTWNIUBGGFBRKH-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002508 contact lithography Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 235000021588 free fatty acids Nutrition 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 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 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- 229940045105 silver iodide Drugs 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000001043 yellow dye Substances 0.000 description 1
Classifications
-
- 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
- G03C1/49836—Additives
- G03C1/49845—Active additives, e.g. toners, stabilisers, sensitisers
- G03C1/49854—Dyes or precursors of dyes
Definitions
- This invention relates to the recording of light-images, and has particular reference to sheet materials which, when merely exposed to a light-image and then uniformly briefly heated, display a colored corresponding visible image.
- sheet materials formulated in accordance with the principles of the invention are useful in preparing full-color reproductions of multi-colored originals, e.g. vfrom color separation negative transparencies thereof.
- a light pattern from each negative is impressed on a transparent copy-sheet capable of being developed to a corresponding color; the sheets are heated to develop the colored reproduction; and the several sheets, either before or after heating, are laid up in registry. Treatment with aqueous solutions or chemical vapors is avoided, the color images being rapidly developed by simple brief heating of the exposed integral sheet.
- Light-sensitive copy-sheets which are heat-developable have previously been described, for example in Belgian Pat. No. 663,112 of Oct. 27, 1965.
- the sheet contains small amounts of light-sensitive silver halide catalytically associated with much larger amounts of a silver soap and a reducing agent. Exposure to a light-pattern followed by moderate over-all heating results in a black image.
- Color-forming systems are known in the photographic art in which light-struck silver halide is reacted with a mild reducing agent, e.g. a p-phenylenediamine developer, to form an oxidized intermediate which when the n reacted with a coupler yields a colored dye.
- a mild reducing agent e.g. a p-phenylenediamine developer
- the reducing agent is introduced as a component of an aqueous alkaline developer solution at a high pH; the coupler components may also form a part of the solution. Diffusion of the several components into and out of the gelatin-silver halide stratum is a major problem in such systems.
- a first coating composition is prepared, by prolonged mixing in a ball mill, of
- the treated surface is exposed to a light-image from a projection lamp, for example from five to 20 seconds, and then heated uniformly for a few seconds at C. A somewhat muddy magenta image pattern appears at the light-struck areas.
- Coupler Image color 4-(p-toluenesullonamldo)-benzoylacetanilide Yellow.
- the first coating composition contains three parts by weight of 2,4-dichloro-1-naphthol in place of the two parts of M-3l, being otherwise prepared and applied as in Example 1.
- the second coating applied by swabbing, consists of methanol containing approximately .4 percent of N ,N -dimethyl-p-phenylenediamine hydrochloride.
- the initially white coating is converted to a dull cyan at exposed areas by exposure to light followed by brief over-- all heating at 110 C.
- Coupler Image color 3-methyl-l-phenylpyrazolone Magenta. l0 Acetoacet-o-anisidide Yellow.
- EXAMPLE 11 the precipitated silver, for example by brief washing with a solvent for the silver.
- magenta image areas of the copy formed as described under Example 1 are clarified and brightened by soaking of the imaged sheet for a short time in a five-percent solution of potassium cyanide in water, followed by washing and drying.
- the background areas are at the same time rendered essentially white or clear.
- a binder component must be selected which permits effective washing without being itself dissolved or otherwise rendered ineffective.
- the addition of inert fillers or pigments is sometimes helpful for these or other purposes.
- the clarity of the colored image may also be improved by holding the silver soap content of the coating to a minimum, by selecting particular combinations of substituted p-phenylenediamine developer components and active methylene or phenolic coupler components capable of producing dyes of maximum tint intensity, and by otherwise compounding and proportioning to cause the reduction and precipitation of minimal amounts of silver and in as nearly colloidal state as possible.
- Silver salts of other high molecular weight organic acids, and particularly the silver soaps of other long chain fatty acids, e.g. stearic acid, are also useful for the purposes of the invention.
- Commercial behenic acid from which the silver behenate-behenic acid mixture is prepared is itself a mixture of long chain fatty acids of which not more than about three-fourths is behenic acid.
- the presence of free fatty acid increases the opacity and water-resistance of the coating, but free acid is not essential and may be omitted where a transparent coating is desired.
- EXAMPLE 12 A mixture of 240 grams of silver behenate-behenic acid, 88 grams of polyvinylbutyral resinous binder, 508 grams of toluene and 753 grams of methylethyl ketone is homogenized by milling in a ball mill. To 15 grams of the mixture is added a solution of one-half gram of the color coupler 1-(p-phenylsulfonylphenyl)-3-(2 phenoxymyristoylamido)-2-pyrazolin-5-0ne in 5 ml. of methylethylketone. The composition is thoroughly mixed and is smoothly coated on transparent polyester film. After drying, the residual coating is microns thick.
- a second layer is then applied and dried, to a dry thickness of 6 microns; the solution as applied contains 0.5 gram of N ,N -diethyl-pphenylenediamine hydrobromide and 2.5 grams of polyvinylpyrrolidone in grams of methanol.
- the sheet is maintained under darkroom conditions during and following application of the second coating.
- the second coating composition may then consist of one-half gram of color coupler, one-half gram of N ,N diethyl-p-phenylenediamine hydrobromide, 2.5 grams of polyvinylpyrrolidone, 5 ml. of acetone, and 39 ml. of methanol.
- color couplers of equal effectiveness include 3- (p-(p-nonylphenoxyacetamido) *benzamido)-1-phenyl-2- pyrazolin-S-one and 2 (p-(p-benzoylacetamidobenzenesulfonamido) phenyl) 1 stearylbenzimidazole-S-sulfonic acid giving magenta and yellow images respectively in the composition of Example 12.
- Example 8 the dimethyl-p-phenylenediamine hydrochloride serves as a source of chloride ions; in Example 1 there is additionally included a source of iodide ions.
- the procedure employed makes certain that full catalytic effectiveness is achieved at the light-struck areas during subsequent reduction of the silver behenate.
- the amount of silver halide which must be formed to yield adequate photosensitivity is surprisingly small due to its essentially catalytic function, and substantially all of the oxidation of substituted p-phenylenediamine occurring at the image is by reaction with silver behenate rather than with silver halide.
- halide ion may equally well be introduced in other ways, for example by subjecting the coated silver soap to the action of hydrogen halide vapors, or by pre-reaction of the silver soap particles with halide ion.
- Organic as well as inorganic sources of halide ion are useful. Mixtures of halides may be used.
- Silver iodide is itself sensitive mainly to blue light. Where exposure to radiations of other restricted wavelength ranges and for minimum time is contemplated, the use of silver bromide in conjunction with various sensitizing dyes is indicated.
- Images of any desired color may be produced, as already noted in conjunction with the illustrative examples, by selection of appropriate color couplers.
- acylacetanilides as color formers or couplers results in yellow images
- couplers such as 3-methyl-1- phenylpyrazolone and 2-cyanoacetylcoumarone give magenta images
- cyan images are obtained with phenolic and naphtholic couplers.
- Combinations of these classes of color-forming components may also be used; a particularly effective formulation includes a blend of appropriate members from all three classes to produce a black image, thereby adding to the density of the silver image and permitting an economically attractive reduc tion in the total amount of both silver soap and reducing agent for a desired image density.
- Multi-color products may also be provided using the principles of this invention.
- the combination in registry of a plurality of different monocolor transparencies has already been indicated.
- Multiple color layers in an integral sheet are also contemplated, the structure typically including, on a transparent film base and in the order named, a first layer sensitized to red light and containing a coupler and developer combination suitable for producing a cyan dye, a second layer sensitized to green light and producing a magenta dye, a filter layer for preventing the passage of blue and ultraviolet, and an outer layer sensitive to blue light and producing a yellow dye.
- the three color-sensitive and color-producing coatings are applied as separate side-by-side microscopic dot areas, together with appropriate filters where necessary. Exposure of either structure to a color image, as from a multi-color transparency either by contact printing or through suitable projection apparatus, followed by simple overall heating, is suflicient in either case to provide a multicolor reproduction.
- Method of making a record in color of a lightpattern comprising: exposing to said light-pattern a sheet material including a photosensitive layer comprising photosensitive silver halide catalytically associated with light-stable high molecular weight organic acid silver salt oxidizing agent, p-phenylenediamine developer as reducing agent for said silver salt, and phenolic or active-methylene color-forming coupler, to form an invisible latent image; and briefly uniformly heating said layer in the absence of water to produce a visible colored image at areas corresponding to said light-pattern.
Description
United States Patent C ABSTRACT OF THE DISCLOSURE Color images are formed by dry photography using a sheet or film containing a phenolic or acive methylene color coupler component in conjunction with a photosensitive silver halide catalyst progenitor in catalytic proximity with major amounts of a catalyzable heat-sensitive light-stable silver salt and a p-phenylenediamine reducing agent.
This invention relates to the recording of light-images, and has particular reference to sheet materials which, when merely exposed to a light-image and then uniformly briefly heated, display a colored corresponding visible image.
Among other applications, sheet materials formulated in accordance with the principles of the invention are useful in preparing full-color reproductions of multi-colored originals, e.g. vfrom color separation negative transparencies thereof. A light pattern from each negative is impressed on a transparent copy-sheet capable of being developed to a corresponding color; the sheets are heated to develop the colored reproduction; and the several sheets, either before or after heating, are laid up in registry. Treatment with aqueous solutions or chemical vapors is avoided, the color images being rapidly developed by simple brief heating of the exposed integral sheet.
Light-sensitive copy-sheets which are heat-developable have previously been described, for example in Belgian Pat. No. 663,112 of Oct. 27, 1965. The sheet contains small amounts of light-sensitive silver halide catalytically associated with much larger amounts of a silver soap and a reducing agent. Exposure to a light-pattern followed by moderate over-all heating results in a black image.
Color-forming systems are known in the photographic art in which light-struck silver halide is reacted with a mild reducing agent, e.g. a p-phenylenediamine developer, to form an oxidized intermediate which when the n reacted with a coupler yields a colored dye. The process is described in Mees, Theory of the Photographic Process, 3rd ed., p .384 et seq. The reducing agent is introduced as a component of an aqueous alkaline developer solution at a high pH; the coupler components may also form a part of the solution. Diffusion of the several components into and out of the gelatin-silver halide stratum is a major problem in such systems.
It has now been found possible to produce colored image patterns in sensitive sheet materials in the absence of water and merely open exposure to a light-image followed by moderate heating, by incorporating in the copysheet a catalytically small amount of photosensitive silver halide in close catalytic association with much larger amounts of a light-stable silver salt and in conjunction with both a p-phenylenediamine developer and a phenolic or active methylene coupler, preferably in the presence of a film-forming polymeric binder.
The following specific examples, in which all proportions are in parts by weight unless otherwise indicated, will serve further to illustrate but not to limit the invention.
ice
EXAMPLE 1 A first coating composition is prepared, by prolonged mixing in a ball mill, of
Parts Silver behenate:behenic acid (equimolar mixture) 94 Ethyl cellulose 13 2-cyanoacetylcoumarone (M-31 coupler) 2 Toluene 404 The mixture is coated onto transparent polyester film using a knife coater at an orifice of 2 mils (.002 inch) and permitted to dry. Over the dry coating is then applied, by lightly swabbing with a saturated cotton pledget and undar darkroom conditions, a solution containing Parts N N -diethyl 3 methyl-p-phenylene diamine hydrochloride (CD-2 color developing agent) 2 Aqueous hydriodic acid 2 Methanol 600' and the sheet is again dried, the increase in weight being within the range of about .01.04 gram per square foot.
The treated surface is exposed to a light-image from a projection lamp, for example from five to 20 seconds, and then heated uniformly for a few seconds at C. A somewhat muddy magenta image pattern appears at the light-struck areas.
The incorporation of another source of halide ion, such as the hydriodic acid employed here, permits the substitution of a soluble non-halide salt of the developer, such for example as the oxalic acid salt, for the hydrogen halide salt if desired.
In a series of further examples, other specific couplers are substituted in equal weight proportions for the M 31. The composition and procedure is otherwise identical. The image color is as indicated.
Ex. Coupler Image color 4-(p-toluenesullonamldo)-benzoylacetanilide Yellow.
2,6-dibromo1,5-dihydroxynaphthalene Cyan.
Acetoacet-o-anisidide 2,4-dichloro-l-naphthol 3-Inethyl1-phenylpyrazolone 2,4-dibromo-1-naphtl1ol EXAMPLE 8 The first coating composition contains three parts by weight of 2,4-dichloro-1-naphthol in place of the two parts of M-3l, being otherwise prepared and applied as in Example 1. The second coating, applied by swabbing, consists of methanol containing approximately .4 percent of N ,N -dimethyl-p-phenylenediamine hydrochloride. The initially white coating is converted to a dull cyan at exposed areas by exposure to light followed by brief over-- all heating at 110 C.
Additional examples are prepared in the same manner but with substitution of other coupler components for the naphthol, with results as tabulated.
Ex. Coupler Image color 9. 3-methyl-l-phenylpyrazolone Magenta. l0 Acetoacet-o-anisidide Yellow.
EXAMPLE 11 the precipitated silver, for example by brief washing with a solvent for the silver. As an illustration, the magenta image areas of the copy formed as described under Example 1 are clarified and brightened by soaking of the imaged sheet for a short time in a five-percent solution of potassium cyanide in water, followed by washing and drying. The background areas are at the same time rendered essentially white or clear. Where a washing step is contemplated, a binder component must be selected Which permits effective washing without being itself dissolved or otherwise rendered ineffective. The addition of inert fillers or pigments is sometimes helpful for these or other purposes.
The clarity of the colored image may also be improved by holding the silver soap content of the coating to a minimum, by selecting particular combinations of substituted p-phenylenediamine developer components and active methylene or phenolic coupler components capable of producing dyes of maximum tint intensity, and by otherwise compounding and proportioning to cause the reduction and precipitation of minimal amounts of silver and in as nearly colloidal state as possible.
The formation of colored images by the simple procedures and with the simple coatings hereinbefore described is particularly surprising in view of the presence of the relatively large proportions of free behenic acid, since color coupling by conventional photographic techniques ordinarily requires an alkaline medium. Even in the ab sence of free behenic acid in the original coating, it might be supposed that any chemical reducing action on the silver soap would liberate the acid and thus prevent the color coupling reaction. Nevertheless the reaction in either case proceeds smoothly upon mere heating of the exposed area, with formation of a colored image as already described.
Silver salts of other high molecular weight organic acids, and particularly the silver soaps of other long chain fatty acids, e.g. stearic acid, are also useful for the purposes of the invention. Commercial behenic acid from which the silver behenate-behenic acid mixture is prepared is itself a mixture of long chain fatty acids of which not more than about three-fourths is behenic acid. The presence of free fatty acid increases the opacity and water-resistance of the coating, but free acid is not essential and may be omitted where a transparent coating is desired.
EXAMPLE 12 A mixture of 240 grams of silver behenate-behenic acid, 88 grams of polyvinylbutyral resinous binder, 508 grams of toluene and 753 grams of methylethyl ketone is homogenized by milling in a ball mill. To 15 grams of the mixture is added a solution of one-half gram of the color coupler 1-(p-phenylsulfonylphenyl)-3-(2 phenoxymyristoylamido)-2-pyrazolin-5-0ne in 5 ml. of methylethylketone. The composition is thoroughly mixed and is smoothly coated on transparent polyester film. After drying, the residual coating is microns thick. A second layer is then applied and dried, to a dry thickness of 6 microns; the solution as applied contains 0.5 gram of N ,N -diethyl-pphenylenediamine hydrobromide and 2.5 grams of polyvinylpyrrolidone in grams of methanol. The sheet is maintained under darkroom conditions during and following application of the second coating.
Exposure of the sheet through a photographic negative transparency followed by contact for about one second with a smooth metal plate at a temperature of 100 C. results in a magenta image conforming to the light-struck areas.
Substitution of the same amount of dodecyl 4-(benzoylacetamido)-benzoate for the 1-(p-phenylsulfonylphenyl)- 3-(2 phenoxymyristoylamido)-2-pyrazolin-5-one gives a yellow image. 2,4-dichloro 6 (p-nonylphenoxyacetamido)-m-cresol similarly gives a cyan image.
Essentially the same results are obtained by adding the color coupler compound with the second coating rather than with the first coating, using a slightly different solvent mixture to assure complete solution of all components. The second coating composition may then consist of one-half gram of color coupler, one-half gram of N ,N diethyl-p-phenylenediamine hydrobromide, 2.5 grams of polyvinylpyrrolidone, 5 ml. of acetone, and 39 ml. of methanol.
Other color couplers of equal effectiveness include 3- (p-(p-nonylphenoxyacetamido) *benzamido)-1-phenyl-2- pyrazolin-S-one and 2 (p-(p-benzoylacetamidobenzenesulfonamido) phenyl) 1 stearylbenzimidazole-S-sulfonic acid giving magenta and yellow images respectively in the composition of Example 12.
In each of the several examples the formation of photosensitive silver halide occurs by reaction between the silver behenate and the source of halide ions present in the second coating. Thus in Example 8 the dimethyl-p-phenylenediamine hydrochloride serves as a source of chloride ions; in Example 1 there is additionally included a source of iodide ions. The procedure employed makes certain that full catalytic effectiveness is achieved at the light-struck areas during subsequent reduction of the silver behenate. The amount of silver halide which must be formed to yield adequate photosensitivity is surprisingly small due to its essentially catalytic function, and substantially all of the oxidation of substituted p-phenylenediamine occurring at the image is by reaction with silver behenate rather than with silver halide.
The halide ion may equally well be introduced in other ways, for example by subjecting the coated silver soap to the action of hydrogen halide vapors, or by pre-reaction of the silver soap particles with halide ion. Organic as well as inorganic sources of halide ion are useful. Mixtures of halides may be used.
Silver iodide is itself sensitive mainly to blue light. Where exposure to radiations of other restricted wavelength ranges and for minimum time is contemplated, the use of silver bromide in conjunction with various sensitizing dyes is indicated.
Images of any desired color may be produced, as already noted in conjunction with the illustrative examples, by selection of appropriate color couplers. Thus the use of acylacetanilides as color formers or couplers results in yellow images; couplers such as 3-methyl-1- phenylpyrazolone and 2-cyanoacetylcoumarone give magenta images; and cyan images are obtained with phenolic and naphtholic couplers. Combinations of these classes of color-forming components may also be used; a particularly effective formulation includes a blend of appropriate members from all three classes to produce a black image, thereby adding to the density of the silver image and permitting an economically attractive reduc tion in the total amount of both silver soap and reducing agent for a desired image density.
Multi-color products may also be provided using the principles of this invention. The combination in registry of a plurality of different monocolor transparencies has already been indicated. Multiple color layers in an integral sheet are also contemplated, the structure typically including, on a transparent film base and in the order named, a first layer sensitized to red light and containing a coupler and developer combination suitable for producing a cyan dye, a second layer sensitized to green light and producing a magenta dye, a filter layer for preventing the passage of blue and ultraviolet, and an outer layer sensitive to blue light and producing a yellow dye. In another multi-color structure the three color-sensitive and color-producing coatings are applied as separate side-by-side microscopic dot areas, together with appropriate filters where necessary. Exposure of either structure to a color image, as from a multi-color transparency either by contact printing or through suitable projection apparatus, followed by simple overall heating, is suflicient in either case to provide a multicolor reproduction.
What is claimed is as follows:
1. Method of making a record in color of a lightpattern, comprising: exposing to said light-pattern a sheet material including a photosensitive layer comprising photosensitive silver halide catalytically associated with light-stable high molecular weight organic acid silver salt oxidizing agent, p-phenylenediamine developer as reducing agent for said silver salt, and phenolic or active-methylene color-forming coupler, to form an invisible latent image; and briefly uniformly heating said layer in the absence of water to produce a visible colored image at areas corresponding to said light-pattern.
2. Sheet material useful in making a record by the method defined in claim 1 and including a photosensitive layer comprising photosensitive silver halide catalytically associated with light-stable high molecular weight organic acid silver salt oxidizing agent, a p-phenylenediamine developer as reducing agent for said silver salt, and at least one phenolic or active-methylene color-forming coupler.
3. In the method of making a photosensitive colorforming sheet material having photosensitive silver halide in catalytic association with light-stable high molecular Weight organic acid silver salt oxidizing agent and in- UNITED STATES PATENTS 3,457,075 7/1969 Morgan et al. 96l02 3,409,457 11/1968 MenZel 1l736.8
FOREIGN PATENTS 663,112 1 0/1965 Belgium.
J. TRAVIS BROWN, Primary Examiner
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US59055166A | 1966-10-31 | 1966-10-31 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3531286A true US3531286A (en) | 1970-09-29 |
Family
ID=24362683
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US590551A Expired - Lifetime US3531286A (en) | 1966-10-31 | 1966-10-31 | Light-sensitive,heat developable copy-sheets for producing color images |
Country Status (4)
Country | Link |
---|---|
US (1) | US3531286A (en) |
BE (1) | BE705872A (en) |
DE (1) | DE1597633A1 (en) |
GB (1) | GB1201785A (en) |
Cited By (49)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3767394A (en) * | 1971-02-02 | 1973-10-23 | Minnesota Mining & Mfg | Color copying and sheet material therefor |
US3770448A (en) * | 1970-04-29 | 1973-11-06 | Agfa Gevaert Ag | Lightsensitive photographic material |
US4021250A (en) * | 1973-10-01 | 1977-05-03 | Fuji Photo Film Co., Ltd. | Thermally developable photosensitive material |
US4021240A (en) * | 1975-12-22 | 1977-05-03 | Eastman Kodak Company | Photothermographic and thermographic compositions and uses therefor containing sulfonamidophenol reducing agents and four equivalent color couplers |
US4022617A (en) * | 1974-07-25 | 1977-05-10 | Eastman Kodak Company | Photothermographic element, composition and process for producing a color image from leuco dye |
US4069759A (en) * | 1974-07-27 | 1978-01-24 | Canon Kabushiki Kaisha | Light and heat formation of conductive image printing plate |
US4137079A (en) * | 1978-04-03 | 1979-01-30 | Eastman Kodak Company | Antifoggants in heat developable photographic materials |
US4187108A (en) * | 1977-02-07 | 1980-02-05 | Eastman Kodak Company | Heat developable material and process |
US4283477A (en) * | 1978-11-02 | 1981-08-11 | Eastman Kodak Company | Photothermographic material and process |
JPS57186744A (en) * | 1981-05-12 | 1982-11-17 | Fuji Photo Film Co Ltd | Heat developable color photosensitive material |
JPS57207250A (en) * | 1981-06-17 | 1982-12-18 | Fuji Photo Film Co Ltd | Heat developing color photosensitive material |
EP0071488A1 (en) * | 1981-07-31 | 1983-02-09 | Konica Corporation | A method of forming an image by means of heat development |
US4374921A (en) * | 1981-06-08 | 1983-02-22 | Minnesota Mining And Manufacturing Company | Image enhancement of photothermographic elements |
JPS5879247A (en) * | 1981-11-05 | 1983-05-13 | Fuji Photo Film Co Ltd | Color photosensitive material developable by heating |
US4426441A (en) | 1982-12-03 | 1984-01-17 | Eastman Kodak Company | Dye-forming developers in an imaging material and process |
US4452883A (en) * | 1983-05-17 | 1984-06-05 | Minnesota Mining And Manufacturing Company | Barrier resin for photothermographic color separation |
US4455363A (en) * | 1982-03-02 | 1984-06-19 | Fuji Photo Film Co., Ltd. | Heat-developable color photographic material with polymeric color coupler |
EP0119102A2 (en) * | 1983-03-15 | 1984-09-19 | Minnesota Mining And Manufacturing Company | Image enhancement of photothermographic elements |
US4504568A (en) * | 1983-02-08 | 1985-03-12 | Eastman Kodak Company | Sensitive silver halide photothermographic materials for producing dye images |
EP0143424A2 (en) | 1983-11-25 | 1985-06-05 | Fuji Photo Film Co., Ltd. | Heat-developable light-sensitive materials |
US4594307A (en) * | 1985-04-25 | 1986-06-10 | Minnesota Mining And Manufacturing Company | Color thermal diffusion-transfer with leuco dye reducing agent |
EP0200216A2 (en) | 1985-04-30 | 1986-11-05 | Fuji Photo Film Co., Ltd. | Heat-developable light-sensitive material |
EP0210660A2 (en) | 1985-07-31 | 1987-02-04 | Fuji Photo Film Co., Ltd. | Image forming process |
US4670374A (en) * | 1984-10-01 | 1987-06-02 | Minnesota Mining And Manufacturing Company | Photothermographic accelerators for leuco diazine, oxazine, and thiazine dyes |
USH456H (en) | 1984-02-01 | 1988-04-05 | Fuji Photo Film Co., Ltd. | Thermodevelopable silver halide photographic material and process for producing images therewith |
US5032499A (en) * | 1986-08-08 | 1991-07-16 | Konishiroku Photo Industry Co., Ltd. | Thermal light-sensitive material with combination of fog restrainers |
US5185231A (en) * | 1991-08-26 | 1993-02-09 | Minnesota Mining And Manufacturing Company | Dry silver systems with fluoran leuco dyes |
US5206112A (en) * | 1991-06-27 | 1993-04-27 | Minnesota Mining And Manufacturing Company | Positive imaging diffusion - transfer dry silver system |
US5264321A (en) * | 1992-07-16 | 1993-11-23 | Minnesota Mining And Manufacturing Company | Photothermographic elements with novel layer structures |
US5270145A (en) * | 1991-12-06 | 1993-12-14 | Eastman Kodak Company | Heat image separation system |
US5281515A (en) * | 1991-09-18 | 1994-01-25 | Minnesota Mining And Manufacturing Company | Thermally developable photographic elements |
US5350669A (en) * | 1994-01-19 | 1994-09-27 | Minnesota Mining And Manufacturing Company | Silver-carboxylate/1,2-diazine compounds as silver sources in photothermographic and thermographic elements |
US5358843A (en) * | 1993-08-20 | 1994-10-25 | Minnesota Mining And Manufacturing Company | Photothermographic elements containing silyl blocking groups |
US5369000A (en) * | 1993-04-29 | 1994-11-29 | Minnesota Mining And Manufacturing Company | Post-processing stabilizers for photothermographic articles |
US5380644A (en) * | 1993-08-10 | 1995-01-10 | Minnesota Mining And Manufacturing Company | Additive for the reduction of mottle in photothermographic and thermographic elements |
US5382504A (en) * | 1994-02-22 | 1995-01-17 | Minnesota Mining And Manufacturing Company | Photothermographic element with core-shell-type silver halide grains |
US5415993A (en) * | 1993-04-26 | 1995-05-16 | Minnesota Mining And Manufacturing Company | Thermoreversible organogels for photothermographic elements |
US5424183A (en) * | 1993-03-15 | 1995-06-13 | Minnesota Mining And Manufacturing Company | Ballasted leuco dyes and photothermographic element containing same |
US5432041A (en) * | 1993-03-18 | 1995-07-11 | Minnesota Mining And Manufacturing Company | Yellow and magenta chromogenic leuco dyes for photothermographic elements |
US5439790A (en) * | 1994-06-24 | 1995-08-08 | Minnesota Mining And Manufacturing Company | Phthalimide blocked post-processing stabilizers for photothermography |
US5492804A (en) * | 1994-06-30 | 1996-02-20 | Minnesota Mining And Manufacturing Company | Chromogenic leuco redox-dye-releasing compounds for photothermographic elements |
US5492805A (en) * | 1994-06-30 | 1996-02-20 | Minnesota Mining And Manufacturing Company | Blocked leuco dyes for photothermographic elements |
US5492803A (en) * | 1995-01-06 | 1996-02-20 | Minnesota Mining And Manufacturing Company | Hydrazide redox-dye-releasing compounds for photothermographic elements |
US5547810A (en) * | 1994-09-16 | 1996-08-20 | Konica Corporation | Image forming method with alkali precursor |
US5583255A (en) * | 1993-12-03 | 1996-12-10 | Imation Corp. | Yellow and magenta chromogenic leuco dyes for photothermographic elements |
EP0757287A1 (en) | 1995-07-19 | 1997-02-05 | Fuji Photo Film Co., Ltd. | Image formation method |
US6280913B1 (en) | 2000-06-13 | 2001-08-28 | Eastman Kodak Company | Photographic element comprising an ion exchanged photographically useful compound |
EP1624337A2 (en) | 2004-08-02 | 2006-02-08 | Fuji Photo Film Co., Ltd. | Silver halide holographic sensitive material and system for taking holographic images by using the same |
EP1691237A2 (en) | 2005-02-15 | 2006-08-16 | Fuji Photo Film Co., Ltd. | Holographic recording material and holographic recording method |
Citations (2)
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BE663112A (en) * | 1964-04-27 | 1965-10-27 | ||
US3409457A (en) * | 1964-01-11 | 1968-11-05 | Agfa Ag | Thermographic copying sheet |
-
1966
- 1966-10-31 US US590551A patent/US3531286A/en not_active Expired - Lifetime
-
1967
- 1967-10-30 BE BE705872D patent/BE705872A/xx unknown
- 1967-10-30 DE DE19671597633 patent/DE1597633A1/en active Pending
- 1967-10-30 GB GB49205/67A patent/GB1201785A/en not_active Expired
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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US3409457A (en) * | 1964-01-11 | 1968-11-05 | Agfa Ag | Thermographic copying sheet |
BE663112A (en) * | 1964-04-27 | 1965-10-27 | ||
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 |
Cited By (64)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3770448A (en) * | 1970-04-29 | 1973-11-06 | Agfa Gevaert Ag | Lightsensitive photographic material |
US3767394A (en) * | 1971-02-02 | 1973-10-23 | Minnesota Mining & Mfg | Color copying and sheet material therefor |
US4021250A (en) * | 1973-10-01 | 1977-05-03 | Fuji Photo Film Co., Ltd. | Thermally developable photosensitive material |
US4022617A (en) * | 1974-07-25 | 1977-05-10 | Eastman Kodak Company | Photothermographic element, composition and process for producing a color image from leuco dye |
US4069759A (en) * | 1974-07-27 | 1978-01-24 | Canon Kabushiki Kaisha | Light and heat formation of conductive image printing plate |
US4021240A (en) * | 1975-12-22 | 1977-05-03 | Eastman Kodak Company | Photothermographic and thermographic compositions and uses therefor containing sulfonamidophenol reducing agents and four equivalent color couplers |
US4187108A (en) * | 1977-02-07 | 1980-02-05 | Eastman Kodak Company | Heat developable material and process |
US4137079A (en) * | 1978-04-03 | 1979-01-30 | Eastman Kodak Company | Antifoggants in heat developable photographic materials |
US4283477A (en) * | 1978-11-02 | 1981-08-11 | Eastman Kodak Company | Photothermographic material and process |
JPS57186744A (en) * | 1981-05-12 | 1982-11-17 | Fuji Photo Film Co Ltd | Heat developable color photosensitive material |
JPS6214822B2 (en) * | 1981-05-12 | 1987-04-03 | Fuji Photo Film Co Ltd | |
US4474867A (en) * | 1981-05-12 | 1984-10-02 | Fuji Photo Film Co., Ltd. | Heat-developable color photographic material |
US4374921A (en) * | 1981-06-08 | 1983-02-22 | Minnesota Mining And Manufacturing Company | Image enhancement of photothermographic elements |
JPS57207250A (en) * | 1981-06-17 | 1982-12-18 | Fuji Photo Film Co Ltd | Heat developing color photosensitive material |
JPS6215852B2 (en) * | 1981-06-17 | 1987-04-09 | Fuji Photo Film Co Ltd | |
US4507380A (en) * | 1981-06-17 | 1985-03-26 | Fuji Photo Film Co., Ltd. | Heat-developable color photographic material containing dye releasing couplers |
EP0071488A1 (en) * | 1981-07-31 | 1983-02-09 | Konica Corporation | A method of forming an image by means of heat development |
JPS5879247A (en) * | 1981-11-05 | 1983-05-13 | Fuji Photo Film Co Ltd | Color photosensitive material developable by heating |
JPS6229786B2 (en) * | 1981-11-05 | 1987-06-29 | Fuji Photo Film Co Ltd | |
US4483914A (en) * | 1981-11-05 | 1984-11-20 | Fuji Photo Film Co., Ltd. | Heat-developable color photographic material |
US4455363A (en) * | 1982-03-02 | 1984-06-19 | Fuji Photo Film Co., Ltd. | Heat-developable color photographic material with polymeric color coupler |
US4426441A (en) | 1982-12-03 | 1984-01-17 | Eastman Kodak Company | Dye-forming developers in an imaging material and process |
US4504568A (en) * | 1983-02-08 | 1985-03-12 | Eastman Kodak Company | Sensitive silver halide photothermographic materials for producing dye images |
EP0119102A3 (en) * | 1983-03-15 | 1985-07-03 | Minnesota Mining And Manufacturing Company | Image enhancement of photothermographic elements |
EP0119102A2 (en) * | 1983-03-15 | 1984-09-19 | Minnesota Mining And Manufacturing Company | Image enhancement of photothermographic elements |
EP0126588A3 (en) * | 1983-05-17 | 1985-06-19 | Minnesota Mining And Manufacturing Company | Barrier resin for photothermographic color separation |
EP0126588A2 (en) * | 1983-05-17 | 1984-11-28 | Minnesota Mining And Manufacturing Company | Barrier resin for photothermographic color separation |
US4452883A (en) * | 1983-05-17 | 1984-06-05 | Minnesota Mining And Manufacturing Company | Barrier resin for photothermographic color separation |
EP0143424A2 (en) | 1983-11-25 | 1985-06-05 | Fuji Photo Film Co., Ltd. | Heat-developable light-sensitive materials |
USH456H (en) | 1984-02-01 | 1988-04-05 | Fuji Photo Film Co., Ltd. | Thermodevelopable silver halide photographic material and process for producing images therewith |
US4670374A (en) * | 1984-10-01 | 1987-06-02 | Minnesota Mining And Manufacturing Company | Photothermographic accelerators for leuco diazine, oxazine, and thiazine dyes |
US4594307A (en) * | 1985-04-25 | 1986-06-10 | Minnesota Mining And Manufacturing Company | Color thermal diffusion-transfer with leuco dye reducing agent |
EP0200216A2 (en) | 1985-04-30 | 1986-11-05 | Fuji Photo Film Co., Ltd. | Heat-developable light-sensitive material |
EP0210660A2 (en) | 1985-07-31 | 1987-02-04 | Fuji Photo Film Co., Ltd. | Image forming process |
US5032499A (en) * | 1986-08-08 | 1991-07-16 | Konishiroku Photo Industry Co., Ltd. | Thermal light-sensitive material with combination of fog restrainers |
US5278024A (en) * | 1991-06-27 | 1994-01-11 | Minnesota Mining And Manufacturing Company | Positive imaging diffusion-transfer dry silver system using formazan dye |
US5206112A (en) * | 1991-06-27 | 1993-04-27 | Minnesota Mining And Manufacturing Company | Positive imaging diffusion - transfer dry silver system |
US5185231A (en) * | 1991-08-26 | 1993-02-09 | Minnesota Mining And Manufacturing Company | Dry silver systems with fluoran leuco dyes |
US5281515A (en) * | 1991-09-18 | 1994-01-25 | Minnesota Mining And Manufacturing Company | Thermally developable photographic elements |
US5270145A (en) * | 1991-12-06 | 1993-12-14 | Eastman Kodak Company | Heat image separation system |
US5364733A (en) * | 1992-07-16 | 1994-11-15 | Minnesota Mining And Manufacturing Company | Photothermographic elements with novel layer structures, each of which contains a thermally-diffusible oxidizable leuco dye and process for producing a color image from leuco dye |
US5264321A (en) * | 1992-07-16 | 1993-11-23 | Minnesota Mining And Manufacturing Company | Photothermographic elements with novel layer structures |
US5424183A (en) * | 1993-03-15 | 1995-06-13 | Minnesota Mining And Manufacturing Company | Ballasted leuco dyes and photothermographic element containing same |
US5432041A (en) * | 1993-03-18 | 1995-07-11 | Minnesota Mining And Manufacturing Company | Yellow and magenta chromogenic leuco dyes for photothermographic elements |
US5415993A (en) * | 1993-04-26 | 1995-05-16 | Minnesota Mining And Manufacturing Company | Thermoreversible organogels for photothermographic elements |
US5464737A (en) * | 1993-04-29 | 1995-11-07 | Minnesota Mining And Manufacturing Company | Post-processing stabilizers for photothermographic articles |
US5369000A (en) * | 1993-04-29 | 1994-11-29 | Minnesota Mining And Manufacturing Company | Post-processing stabilizers for photothermographic articles |
US5380644A (en) * | 1993-08-10 | 1995-01-10 | Minnesota Mining And Manufacturing Company | Additive for the reduction of mottle in photothermographic and thermographic elements |
US5358843A (en) * | 1993-08-20 | 1994-10-25 | Minnesota Mining And Manufacturing Company | Photothermographic elements containing silyl blocking groups |
US5583255A (en) * | 1993-12-03 | 1996-12-10 | Imation Corp. | Yellow and magenta chromogenic leuco dyes for photothermographic elements |
US5350669A (en) * | 1994-01-19 | 1994-09-27 | Minnesota Mining And Manufacturing Company | Silver-carboxylate/1,2-diazine compounds as silver sources in photothermographic and thermographic elements |
US5466804A (en) * | 1994-01-19 | 1995-11-14 | Minnesota Mining And Manufacturing | Silver-carboxylate/1,2-diazine compounds as silver sources in photothermographic and thermographic elements |
US5382504A (en) * | 1994-02-22 | 1995-01-17 | Minnesota Mining And Manufacturing Company | Photothermographic element with core-shell-type silver halide grains |
US5439790A (en) * | 1994-06-24 | 1995-08-08 | Minnesota Mining And Manufacturing Company | Phthalimide blocked post-processing stabilizers for photothermography |
US5492804A (en) * | 1994-06-30 | 1996-02-20 | Minnesota Mining And Manufacturing Company | Chromogenic leuco redox-dye-releasing compounds for photothermographic elements |
US5492805A (en) * | 1994-06-30 | 1996-02-20 | Minnesota Mining And Manufacturing Company | Blocked leuco dyes for photothermographic elements |
US5696289A (en) * | 1994-06-30 | 1997-12-09 | Minnesota Mining And Manufacturing Company | Blocked leuco dyes for photothermographic elements |
US5705676A (en) * | 1994-06-30 | 1998-01-06 | Minnesota Mining And Manufacturing Company | Chromogenic leuco redox-dye-releasing compounds for photothermographic elements |
US5547810A (en) * | 1994-09-16 | 1996-08-20 | Konica Corporation | Image forming method with alkali precursor |
US5492803A (en) * | 1995-01-06 | 1996-02-20 | Minnesota Mining And Manufacturing Company | Hydrazide redox-dye-releasing compounds for photothermographic elements |
EP0757287A1 (en) | 1995-07-19 | 1997-02-05 | Fuji Photo Film Co., Ltd. | Image formation method |
US6280913B1 (en) | 2000-06-13 | 2001-08-28 | Eastman Kodak Company | Photographic element comprising an ion exchanged photographically useful compound |
EP1624337A2 (en) | 2004-08-02 | 2006-02-08 | Fuji Photo Film Co., Ltd. | Silver halide holographic sensitive material and system for taking holographic images by using the same |
EP1691237A2 (en) | 2005-02-15 | 2006-08-16 | Fuji Photo Film Co., Ltd. | Holographic recording material and holographic recording method |
Also Published As
Publication number | Publication date |
---|---|
GB1201785A (en) | 1970-08-12 |
DE1597633A1 (en) | 1970-06-25 |
BE705872A (en) | 1968-04-30 |
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