EP0177328B1 - Photothermograhic accelerators for leuco diazine, oxazine, and thiazine dyes - Google Patents

Photothermograhic accelerators for leuco diazine, oxazine, and thiazine dyes Download PDF

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Publication number
EP0177328B1
EP0177328B1 EP19850306999 EP85306999A EP0177328B1 EP 0177328 B1 EP0177328 B1 EP 0177328B1 EP 19850306999 EP19850306999 EP 19850306999 EP 85306999 A EP85306999 A EP 85306999A EP 0177328 B1 EP0177328 B1 EP 0177328B1
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EP
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Prior art keywords
silver
color
acid
leuco
alkyl
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EP19850306999
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German (de)
English (en)
French (fr)
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EP0177328A2 (en
EP0177328A3 (en
Inventor
Peter A. Minnesota Mining And Bellus
Robert A. Minnesota Mining And Frenchik
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3M Co
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Minnesota Mining and Manufacturing Co
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/494—Silver salt compositions other than silver halide emulsions; Photothermographic systems ; Thermographic systems using noble metal compounds
    • G03C1/498—Photothermographic systems, e.g. dry silver
    • G03C1/49836—Additives
    • G03C1/49845—Active additives, e.g. toners, stabilisers, sensitisers
    • G03C1/49854—Dyes or precursors of dyes
    • 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

  • the present invention relates to photothermographic color constructions.
  • the invention also relates to two- or three-color separation photothermographic recording systems utilizing such constructions.
  • Photothermographic imaging systems are those imaging materials which, upon first being exposed to light in an imagewise fashion, produce an image when subsequently heated.
  • the exposure to light or other radiation photoactivates or photodeactivates a component in the imageable element and subsequent heating causes an image forming reaction to differentially occur in exposed and unexposed regions.
  • Silver halide photothermographic imaging materials often referred to as "dry silver” compositions because no liquid development is necessary to produce the final image, have been known in the art for many years. These imaging materials basically comprise a light-insensitive, reducible silver source, a light-sensitive material which generates silver when irradiated, and a reducing agent for silver ion in the silver source.
  • the light-sensitive material is generally photographic silver halide which must be in catalytic proximity to the light-insensitive silver source. Catalytic proximity is an intimate physical association of these two materials which enables catalysis of the reduction of the silver source by silver specks formed on the silver halide. Exposure of the silver halide to light produces small clusters of silver atoms.
  • the imagewise distribution of these clusters is known in the art as the latent image.
  • This latent image generally is not visible by ordinary means and the light-sensitive article must be further processed in order to produce a visual image.
  • the visual image is produced by the catalytic reduction of silver ions which, as already noted, are in catalytic proximity to the specks of the latent image.
  • the silver source used in this area of technology is a material which contains a reducible source of silver ions.
  • the earliest and still preferred source comprises silver salts of long chain carboxylic acids, usually of from 10 to 30 carbon atoms.
  • the silver salt of behenic acid or mixtures of acids of like molecular weight have been primarily used. Salts of other organic acids or other organic materials such as silver imidazolates have been proposed, and U.S. Patent No. 4,260,677 discloses the use of complexes of inorganic or organic silver salts as image source materials.
  • Color-forming, "dry silver” imaging systems are known in the photographic art. Color-formation is based on the oxidation/reduction reaction between the light-exposed silver salt of a fatty acid which has been halidized and dye-sensitized to a specific wavelength and is used with a chromogenic developer in the presence of elevated temperature.
  • U.S. Patent No. 3,531,286 teaches the inclusion of color coupler components such as a p-phenylenediamine developer and a phenolic or active methylene coupler in close proximity to the light-sensitive emulsion. J. W. Carpenter and P. W. Lauf, Research Disclosure No. 17029, issued June 1978, review prior art relating to photothermographic silver halide systems which include color formation.
  • US Patent No. 4,021,240 discloses the use of sulfonamidophenol reducing agents and four equivalent photographic color couplers in thermographic and photothermographic emulsions to produce dye images including multicolor images.
  • US Patent No. 3,985,565 discloses the use of certain class of phenolic type photographic color couplers in photothermographic emulsions to provide a color image.
  • US Patent No. 4,021,250 discloses the use of 0.0025 percent leuco thiazine dye as a shelf life extender in a photothermographic system for generating a black and white image, the system comprising an organic silver salt, a catalytic amount of a photosensitive silver halide, a reducing agent, and a binder.
  • a photothermographic system for generating a black and white image
  • the system comprising an organic silver salt, a catalytic amount of a photosensitive silver halide, a reducing agent, and a binder.
  • One example discloses 1.87 percent chlorothymol and 0.126 percent phthalazinone as the image producing reactants.
  • the leuco thiazine dye can be used in combination with other acid stabilizers.
  • Leuco methylene blue a thiazine dye
  • US Patent No. 2,646,367 discloses a carbonless copy system using, for example, benzoyl leuco methylene blue as the color forming agent.
  • US Patent No. 3,447,944 discloses a thermographic copy system utilizing leuco methylene blue and its derivatives as color former.
  • US Patent No. 4,309,255 relates to leuco methylene blue in electrochromic recording paper.
  • Japanese laid-open patent document 59-5239 discloses a 2-sheet, positive-acting, light-sensitive, heat-developable, diffusion, image transfer construction.
  • the present invention comprises a single-sheet, negative-acting photothermographic construction comprising at least one light-sensitive, color-forming element on a support base, the element comprising a light-sensitive and non light-sensitive silver source, a binder, an oxidizable leuco phenazine, phenoxazine, or phenothiazine dye as the sole reducing agent for said silver sources, and as development accelerator a carboxylic acid, Lewis acid or Bronsted acid, wherein the image color is provided by the oxidized form of said leuco dye.
  • Any oxidizable leuco phenazine, phenoxazine, or phenothiazine dye known in the art is useful in the present invention.
  • the light-sensitive element may optionally include a silver halide.
  • the oxidized forms can have colors ranging from turquoise to yellow.
  • the photothermographic portion of the element can be any imageable layer or layers which are photosensitive and developable by being heated (e.g., on a heated drum roll or by exposure to infrared radiation), preferably in the temperature range of approximately 65 to 180°C (150 to 350°F).
  • Particularly important are silver halide photothermographic systems comprising silver halide, a silver source material in catalytic proximity to the silver halide, and a reducing agent for silver ion in a binder, these systems being commonly known as "dry silver" construction. These systems may be in a single layer or in a plurality of layers as is well known in the art.
  • the color-forming element of the present invention can be useful in a two or three color separation photothermographic recording system. In such a system it may be required to provide in a topcoat layer a "barrier polymer" which is impervious to an upper adjacent color layer.
  • a "barrier polymer" which is impervious to an upper adjacent color layer.
  • association with means in the same layer or in a layer contiguous thereto.
  • the location of the photosensitive silver halide in the photothermographic element or composition of the invention is such that will enable catalytic action.
  • the described photosensitive silver halide can accordingly be in the same layer as or in a layer contiguous to the described oxidation-reduction image- forming combination (i.e., the silver salt oxidizing agent such as silver behenate or silver stearate and the reducing agent and development modifier of the present invention).
  • a preferred embodiment of the present invention comprises a single-sheet, negative-acting, photothermographic element on a support base, said element comprising a silver source, optionally silver halide, a leuco dye as the sole reducing agent for silver ion, a binder, and a development accelerator, wherein
  • the above-defined leuco dyes can have a molecular weight up to 2000, preferably up to 700, and the carboxylic acids can have a molecular weight up to 500, preferably up to 400.
  • the preferred photothermographic construction of the present invention is of the "dry silver" type.
  • the color-forming element which can provide an image ranging from cyan to yellow, including, magenta, red, violet, purple or blue can be of unitary construction or the light-sensitive layer may be in association with the leuco dye, i.e., in a bilayer construction.
  • Single layer constructions must contain the silver source material, the silver halide, the developer, and the development accelerator in the same layer.
  • the light-sensitive layer has a topcoat layer which comprises the leuco dye and acid material.
  • Dry silver bilayer constructions must contain the silver source and silver halide in one emulsion layer (usually the layer adjacent the substrate).
  • the other ingredients can be in the same layer, a second layer, or both layers.
  • Optional additional materials include toners, coating aids, and other adjuvants.
  • Photothermographic color constructions of the present invention incorporate at least one spectrally- sensitized color-forming element according to the present invention to produce a single or multi-color photothermographic color recording system.
  • the spectral sensitization may be to a pair of colors such as two of black, yellow, red, green, blue, and purple provided that each color-forming element is sensitized to a portion of the spectrum at least 60 nm different from the other color-forming element(s), and each color-forming layer forms a visible dye having a maximum absorbance at least 60 nm different from that of the dye formed in the other color-forming element(s).
  • Preferred pairs of colors to which the construction may be sensitized are yellow-cyan, yellowmagenta, and cyan-magenta.
  • a barrier polymer which is impervious to the solvent system of a color construction above it is coated between each pair of color-forming layers.
  • Such a barrier polymer or barrier polymers are essential for the production of good color separation.
  • the test for determining if a barrier polymer is impermeable to the solvent of the next layer can be simply performed. Such a test is described in U.S. Patent No. 4,452,883.
  • the photothermographic color construction may comprise three different monocolor-forming layers to provide a 3-color forming system.
  • the oxazine and thiazine leuco dyes and dyes of the invention can be prepared as is known in the art by acylation of an unsubstituted phenoxazine or phenothiazine compound to provide an N-acylated phenoxazine or phenothiazine compound. Nitration, in acetic acid, as is known in the art provides, after recrystallization, the 3,7-dinitro phenoxazine or phenothiazine compound. Hydrogenation catalyzed by platinum metal gives the corresponding diamino compounds.
  • a phenylene diamine compound e.g., N,N-dimethyl p-phenylenediamine and an aniline compound, e.g., N,N-dimethylaniline are combined in a solvent, preferably water, in a reaction vessel and stirred, preferably at room temperature. It is preferred that the reaction be conducted in an aqueous acidic environment.
  • a second aniline compound e.g., 4-methylaniline is then added to the mixture.
  • the resulting mixture is then stirred and heated for a sufficient period of time to bring about formation of the dye product in free form.
  • an ionizable halide salt e.g., KI, NaCI
  • the solution is then cooled, and the dye collected by filtration and dried in air.
  • Reduction in water in the presence of a water-soluble reducing agent, e.g., sodium dithionite provides a hydrogen leuco dye.
  • Extraction in a non-reactive water-insoluble solvent e.g., methylene dichloride
  • a reactive halide compound e.g., benzoyl chloride
  • the silver source material may be any material which contains a reducible source of silver ions.
  • Silver salts of organic acids, particularly long chain (10 to 30, preferably 15 to 28, carbon atoms) fatty carboxylic acids are preferred.
  • Complexes of organic or inorganic silver salts wherein the ligand has a gross stability constant for silver ion of between 4.0 and 10.0 are also desirable.
  • the silver source material should constitute from about 5 to 70 and preferably from 7 to 30 percent by weight of the imaging layer. The second layer in a two-layer construction would not affect the percentage of the silver source material desired in the single imaging layer.
  • the silver halide may be any photosensitive silver halide such as silver bromide, silver iodide, silver chloride, silver bromoiodide, silver chlorobromoiodide, silver chlorobromide, etc., and may be added to the emulsion layer in any fashion which places it in catalytic proximity to the silver source.
  • the silver halide is generally present as 0.75 to 15 percent by weight of the imaging layer, although larger amounts up to 20 or 25 percent are useful. It is preferred to use from 1 to 10 percent by weight silver halide in the imaging layer and most preferred to use from 1.5 to 7.0 percent.
  • the dyes formed from the leuco dyes in the various color-forming layers should of course be different. A difference of at least 60 nm in reflective or transmissive maximum absorbance is required. Preferably the absorbance maximum of dyes formed will differ at least 80 or 100 nm. When three dyes are to be formed, two should differ by at least these minimums, and the third should differ from at least one of the other dyes by at least 150 nm and preferably at least 200 or even at least 250 nm. This will provide a good, full color range for the final image.
  • the sole reducing agent (developer) for silver ion is the leuco phenazine, phenoxazine, or phenothiazine dye defined above which will reduce silver ion to metallic silver and produce a colored dye.
  • the reducing agent should be present as 0.1 to 10 percent by weight of the imaging layer. In a two-layer construction, if the reducing agent is in the second layer, slightly higher proportions, of from about 2 to 15 percent, tend to be more desirable.
  • Toners such as phthalazinone and phthalazine and others known in the art are not essential to the construction, but may be desirable. These materials may be present, for example, in amounts of from 0.001 to 1 percent by weight.
  • the binder for the silver coating is selected from well-known natural and synthetic resins such as gelatin, polyvinyl acetals, polyvinyl chloride, polyvinyl acetate, cellulose acetate, ethyl cellulose, polyolefins, polyesters, polystyrene, polyacrylonitrile, polycarbonates, methacrylate copolymers, maleic anhydride ester copolymers, and butadiene-styrene copolymers, for example.
  • the binder is selected to coordinate with the solvent used. Copolymers and terpolymers which include the above-stated binders are of course included in these definitions.
  • the preferred photothermographic silver containing binder is polyvinyl butyral.
  • the binders are generally used in a range of from 20 to 75 percent by weight of each layer, and preferably about 30 to 55 percent by weight.
  • the acid chosen for a particular light-sensitive element depends on the activity of the leuco diazine, oxazine, or thiazine dye, i.e., upon its tendency to become oxidized to a colored form. More reactive leuco dyes require less acidic materials than to less readily oxidized leuco dyes. For example, Pergascript Turquoise" (a more reactive leuco dye) requires phthalic acid whereas Copikem WM (a less reactive leuco dye) requires a more reactive acid such as 4-nitrophthalic acid.
  • Representative and preferred development modifiers include aromatic carboxylic acids and their anhydrides such as phthalic acid, benzoic acid, chlorinated and nitro- substituted benzoic acids, 1,2,4-benzenetricarboxylic acid, 2,3-naphthalene dicarboxylic acid, tetrachlorophthalic acid, 4-methyl phthalic acid, homophthalic acid, 4-nitrophthalic acid, o-phenylacetic acid, naphthoic acid, naphthalic acid, phthalic anhydride, naphthalic anhydride, tetrachlorophthalic anhydride, 3-nitrophthalic acid; aliphatic carboxylic acids such as malic acid, chloracetic acid, itaconic acid, tartaric acid, benzoylformic acid, and thiodiacetic acid; Bronsted acids, e.g., sulfonic acids such as p-toluene sulfonic acid, phosphonic and phosphinic acids, phenols such
  • Sensitizing dyes useful in the present invention include many compounds known in the art, as well as 454 (prepared as in US Patent No. 2,493,748)
  • the support base or substrate is a transparent or opaque polymeric film.
  • it is made of such materials as polyester [e.g., poly(ethyleneterephthalate)], cellulose ester (e.g., cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate), polyolefins, polyvinyl resins, and the like.
  • the coatings can either be made as single layers, as for example by knife-coating or extruding, and dried before the next layer is applied or each monocolor can be dual coated, as for example by dual slide- coating or dual extrusion, i.e., each of the sensitized silver layers with its respective topcoat, which may contain a barrier resin, can be coated together to reduce the number of passes through the coater.
  • a halide sensitized silver soap solution was prepared using the example 2A silver soap homogenate as follows:
  • a topcoat master solution was made as follows: Run using Pergascript Turquoise
  • TABLES IV and V demonstrate the usefulness of various acids as development accelerators with oxazine, thiazine, and diazine leuco dyes in a silver halide-containing photothermographic system.
  • a silver behenate half soap dispersion was prepared by dispersing 300 grams in 2696 ml of ethanol and 347 ml of toluene by rapid mixing. This dispersion was then homogenized on a Manton-Gaulin Model 15M 8TBA SND homogenizer (Manton-Gaulin CO.) using two passes at 550 kg/cm 2 (8000 psi) and 225 kg/cm 2 (4000 psi). Then 389.8 grams of this material were diluted with 113 ml of ethanol. Mixing in 34.7 grams of polyvinyl butyral polymer (Butvar-B76) for 1 hour finished this premix.
  • the 4-nitrophthalic acid was re-evaluated with the addition of 0.4 ml of 0.57 g of mercuric chloride per 100 ml of ethanol and the same repeated with the addition of 3.0 ml of 5 g of tonoxTM (R) 201 antioxidant (Shell Chemical Company) to the test solution formulation. These solutions were coated and tested in the same manner as previous samples. The results are listed in TABLE VII below.
  • TABLE VII show that mercuric chloride can be used as a Lewis acid type development accelerator and as an antifoggant in the present invention with or without an antioxidant.
  • a silver behenate premix was prepared to use in evaluating use of metal nitrate with oxazine and thiazine leuco dyes in a dye sensitized, silver halide containing silver behenate half soap system.
  • the silver behenate homogenate 3A was used.
  • the solution premix 4A was halidized and dye sensitized to green light using the following formula:
  • This solution was coated at 0.0508 mm onto 0.0508 mm thick titanium oxide filled polyester (3M) and dried for 3 minutes at 77°C (170°F). This was used to evaluate the metal nitrates used in a topcoat containing the leuco dye, phthalic acid, and a polymer.
  • topcoat master solution containing Pergascript Turquoise for Lewis acid (nitrate) evaluation was prepared using the following: Topcoat Solution 4E
  • nitrate salts were predissolved in methanol at a concentration of 1 gram per 100 ml. These were added to topcoat master solution 4D to give an equivalent concentration of 2.34 x 10- 5 moles of metal nitrate per 30 grams of solution. The nitrates which were evaluated are shown in TABLE X with the amounts used in milligrams.
  • topcoat solutions were individually coated on top of silver behenate coatings 4B and 4C at an orifice setting of 0.1016 mm and dried for 5 minutes at 77°C (170°F). They were exposed for 10- 3 seconds to Xenon flash (EG&G sensitometer) through a continuous tone wedge, then heat developed for 20 seconds at 124°C (255°F) on 3M Model 70 Heat Blanket Processor. The resulting wedges were measured on a computer densitometer using a red filter. The results are shown in TABLES Xl and XII below.
  • the solution premix 4A prepared in EXAMPLE 4 was halidized and dye sensitized to green light using the following formulation:
  • This solution was coated at 0.0508 mm onto 0.508 mm thick titanium oxide filled polyester and dried for 3 minutes at 77°C (170°F).
  • a topcoat master solution containing Copikem-II for metal nitrate evaluation was prepared using the following formulation: Nickel Nitrate Evaluation
  • Nickel nitrate and phthalic acid were individually predissolved in methanol at a concentration of 1 gram per 100 mi. Then 0.5 ml of these solutions were added to individual 22.354 gram portions of topcoat master solution 5B. These topcoat solutions were coated over a sensitized silver behenate coating 5A at an orifice setting of 0.1016 mm and dried for 5 minutes at 77°C (170°F). They were exposed, processed, and tested as in EXAMPLE 4. The results are shown in TABLE XIII below: The data demonstrate the effectiveness of a nitrate salt as development accelerator.
  • a topcoat master solution containing 4-nitrophthalic acid and leuco crystal violet was made to evaluate the effect of combining the oxazine and thiazine leuco dyes with nickel nitrate.
  • the following formulation was used:
  • phthalazine was evaluated using the following formulation 7A and 7B: These solutions were coated 0.1016 mm thick onto Silver Behenate Coating 4C and dried for 5 minutes at 77°C (170°F). They were exposed, processed, and tested as in Example 4. The results are shown in TABLE XV below. The samples were aged for two hours using 2152 milliphots (2000 foot candles), 27°C (80°F), and 60 percent relative humidity. The changes in Dmin are shown in TABLE XV.
  • Cyan Silver Coating 8A (below) was prepared and coated at 3.6 g/m 2 (0.32 grams per square foot) onto 0.076 mm thick polyester film MELINEXTM TYPE 329 (ICI) using a laboratory hand knife coater.
  • Various acids were used in the construction with the leuco oxazine dye, Pergascript Turquoise 5-2G. 0.064 mm (2.5 mil) orifice; dried 5 min at 82°C (180°F)
  • topcoat was coated at a 0.076 mm orifice and dried for 5 minutes at 82°C (180°F). The material was then exposed for 10- 3 seconds to an EG&G xenon flash sensitometer. No filter was used. The samples were processed at 124°C (255°F) on a 3M Model 70 heated blanket processor. The dwell times, Dmin and Dmax, are noted with the acid tested in TABLE XX below.
  • TABLE XX show the usefulness of various acids as development accelerator with Pergascript Turquoise S ⁇ 2G in color constructions.
  • a dispersion of a silver behenate half soap was made at 10% by weight in a solvent mixture of 90% toluene and 10% ethanol using two passes with a Manton-Gaulin homogenizer, Model 15M, at 550 kg/cm 2 and 225 kg/cm 2 (8000 and 4000 psi).
  • This silver soap dispersion is then prepared for coating by the addition of dilution solvents, halide, polymer and sensitizing dye in a selected sequence of time and mixing.
  • EXAMPLE 1 90 grams were dye sensitized with 2.7 ml of a #534 dye (green light sensitizer) solution with a concentration of 0.013 g dye/50 ml methanol. This solution was coated on top of a 0.05 mm (2 mil) thick titanium dioxide filled polyester film (3M) using a 0.076 mm (3 mil) orifice on a laboratory hand knife coater. This coating was dried at 81°C (177°F) for 5 minutes.
  • #534 dye green light sensitizer
  • the following topcoat solution was prepared to coat on top of Magenta Silver Coating 9A.
  • This solution was coated on top of coating 9A using a 0.076 mm (3 mil) orifice and drying at 81°C (177°F) for 5 minutes.
  • a different dispersion of a silver behenate half soap was made similar to 9A, except that a solvent mixture of 90% ethanol and 10% toluene was used. This silver soap dispersion was used in preparing a red light sensitive coating for the cyan color system which was to be coated on top of the pre-coated magenta color forming system.
  • Cyan Silver Premix 9C solution 50 grams were dye sensitized with 1.2 ml of MSD 563 dye (red light sensitizer) solution having a concentration of 0.017 grams/50 ml methanol. This was coated on top of the precoated 9A and 9B layers at an orifice of 0.05 mm (2 mils). The coating was dried at 81°C (177°F) for 5 minutes.
  • topcoat solution was prepared to coat on top of Cyan Silver premix 9C to finish the magenta/cyan color bipack.
  • This material was exposed to an EG&G (EG&G, Electrooptics Div., Salem, MA) xenon flash sensitometer using the proper light filtration to generate the mono-magenta and mono-cyan colors. A Wratten Number 58 and a Wratten Number 25 were used. The exposed material was then processed at 124°C (255°F) for 20 seconds.
  • EG&G Electrooptics Div., Salem, MA
  • This solution was prepared by adding 1.5 ml of a #454 dye (blue sensitizer) solution having a concentration of 0.032 grams per 50 cc of methanol to 40 grams of Magenta Silver Coating 9A. This was coated at a 0.1016 mm (4 mil) orifice using a laboratory hand knife coater onto a 0.0508 mm thick (2 mil) titanium dioxide filled polyester film (3M). The coating was dried for 5 minutes at 81°C (177°F).
  • a #454 dye blue sensitizer
  • Charges B through F were predissolved in charge A before addition of charge G. This solution was coated on top of precoated Yellow Silver Coating 9A at a 0.076 (3 mil) orifice and dried for 5 minutes at 79°C (175°C).
  • Example 8 The magenta color forming systems 9A and 9B described in Example 8 were coated on top of the yellow color forming system described above. The resulting material was exposed and processed using the procedure of Example 9. A Wratten Number 47B (blue light) was used for the yellow color.
  • the cyan color forming system utilizing Cyan Silver premix 9C and Cyan Silver Coating 9D was coated on top of the yellow/magenta bipack.
  • the sensitometry for the yellow, magenta, and cyan were obtained by the same methods just described. The results showed a good three color separation for copying in color.
  • the sensitometry for the yellow did not change from the bipack and the magenta and cyan were the same as disclosed in the magenta/cyan bipack.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
EP19850306999 1984-10-01 1985-10-01 Photothermograhic accelerators for leuco diazine, oxazine, and thiazine dyes Expired EP0177328B1 (en)

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US65669084A 1984-10-01 1984-10-01
US656690 1984-10-01

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EP0177328A3 EP0177328A3 (en) 1988-01-07
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JP (1) JPS6188254A (enrdf_load_stackoverflow)
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US4782010A (en) * 1986-12-29 1988-11-01 Minnesota Mining And Manufacturing Company Photohermographic emulsions having stable color forming developers
GB8815829D0 (en) * 1988-07-04 1988-08-10 Minnesota Mining & Mfg Photothermographic elements
GB9404805D0 (en) * 1994-03-11 1994-04-27 Minnesota Mining & Mfg Novel developing agents for (photo)thermographic systems
GB9404806D0 (en) * 1994-03-11 1994-04-27 Minnesota Mining & Mfg Monoaminophenzaine leuco dyes and photothermographic materials
JP5330854B2 (ja) * 2009-02-19 2013-10-30 国立大学法人埼玉大学 カラーフォーマー、オルガノゲルおよび放射線検出材料

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JPS5415211B2 (enrdf_load_stackoverflow) * 1973-10-01 1979-06-13
JPS5813365B2 (ja) * 1977-07-07 1983-03-14 オ−ツタイヤ株式会社 車輪
US4386154A (en) * 1981-03-26 1983-05-31 Minnesota Mining And Manufacturing Company Visible light sensitive, thermally developable imaging systems
US4374921A (en) * 1981-06-08 1983-02-22 Minnesota Mining And Manufacturing Company Image enhancement of photothermographic elements
JPS58107534A (ja) * 1981-12-21 1983-06-27 Oriental Shashin Kogyo Kk 熱現像性感光材料
US4452883A (en) * 1983-05-17 1984-06-05 Minnesota Mining And Manufacturing Company Barrier resin for photothermographic color separation

Also Published As

Publication number Publication date
EP0177328A2 (en) 1986-04-09
EP0177328A3 (en) 1988-01-07
JPS6188254A (ja) 1986-05-06
DE3577008D1 (de) 1990-05-10
JPH052215B2 (enrdf_load_stackoverflow) 1993-01-12

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