EP0559228B1 - Eléments photothermographiques - Google Patents

Eléments photothermographiques Download PDF

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Publication number
EP0559228B1
EP0559228B1 EP93103608A EP93103608A EP0559228B1 EP 0559228 B1 EP0559228 B1 EP 0559228B1 EP 93103608 A EP93103608 A EP 93103608A EP 93103608 A EP93103608 A EP 93103608A EP 0559228 B1 EP0559228 B1 EP 0559228B1
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EP
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Prior art keywords
silver
emulsion
pat
compounds
silver halide
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EP93103608A
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German (de)
English (en)
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EP0559228A1 (fr
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James B. Jr. C/O Minnesota Mining And Philip
Gary L. C/O Minnesota Mining And Featherstone
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Eastman Kodak 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
    • 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
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/28—Sensitivity-increasing substances together with supersensitising substances
    • 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
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/16—X-ray, infrared, or ultraviolet ray processes
    • G03C5/164—Infra-red processes

Definitions

  • the present invention relates to materials which produce an increase in infrared sensitivity when added to infrared sensitized photothermographic imaging elements.
  • These elements comprise a photosensitive silver halide, silver salt oxidizing agent, infrared sensitizing dye, and reducing agent for silver ion in a binder.
  • the infrared supersensitizers used in the present invention comprise mercapto substituted heteroaromatic compounds.
  • 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 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 so that when silver specks or nuclei are generated by the irradiation or light exposure of the photographic silver halide, those nuclei are able to catalyze the reduction of the silver source by the reducing agent.
  • silver is a catalyst for the reduction of silver ions and the silver-generating light sensitive silver halide catalyst progenitor may be placed into catalytic proximity with the silver source in a number of different fashions, such as partial metathesis of the silver source with a halogen-containing source (e.g., U.S. Pat. No. 3,457,075), coprecipitation of the silver halide and silver source material (e.g., U.S. Pat. No. 3,839,049), and any other method which intimately associates the silver halide and the silver source.
  • a halogen-containing source e.g., U.S. Pat. No. 3,457,075
  • coprecipitation of the silver halide and silver source material e.g., U.S. Pat. No. 3,839,049
  • Silver halide photothermographic imaging materials can undergo spectral sensitization which enables the silver halide grains to benefit from radiation in regions of the electromagnetic spectrum where the silver halide would ordinarily not absorb.
  • Dyes which absorb radiation and can transfer energy to the grains to help in the photoreduction of silver ions to clusters of silver metal are conventionally used to effect spectral sensitization.
  • Infrared absorbing dyes are required to sensitize silver halide into the infrared region (750 nm to 1300 nm) and are described by Mees in The Theory of the Photographic Process, third edition (MacMillan, 1966), pages 198-201.
  • Supersensitization has developed as a method to improve the efficiency and often the stability of infrared sensitization.
  • the supersensitizers are used in combination with the infrared sensitizing dye.
  • the addition of the supersensitizer frequently in quantities ranging from an equivalent molar rate to a 100 fold molar excess of supersensitizer to dye, can increase the spectrally sensitized speed of the emulsion by more than an order of magnitude.
  • Some supersensitizers are dyes themselves, but many others do not absorb radiation in significant amounts in the visible portion of the electromagnetic spectrum.
  • the effect of the supersensitizers on spectral sensitization is not clearly dependent on the ability of compounds to absorb radiation in the visible or infrared portion of the spectrum.
  • Certain supersensitizers are sometimes more effective with one sensitizing dye class versus a second dye class. Due to supersensitizer-dye specificity and the large sensitivity increases generated by supersensitizers, an expanded selection of supersensitizers is desired.
  • Supersensitization has been used effectively in silver halide photographic systems to minimize the inefficiency of infrared sensitizing dyes.
  • the supersensitizers have included diazenyl and triazenyl stilbenes as described in U.S. Pat. No. 2,875,058 and Great England Patent No. 2,140,928, benzotriazoles as described in U.S. Pat. No. 4,030,927 and 4,105,454, thioureas as described in U.S. Pat. No. 4,607,006, U.S. Pat. No. 3,458,318 and U.S. Pat. No. 3,954,481, thiatriazoles as described in U.S. Pat No. 4,780,404 and 4,914,015, tetraazaindenes as described in U.S. Pat. No. 3,695,888 and certain heterocyclic salts as described in U.S. Pat. No. 4,596,767.
  • Mercapto aromatic compounds have also been used in silver halide photographic elements as infrared supersensitizers and include mercapto-substituted oxazine, oxazole, thiazole, thiadiazole, imidazole or tetrazole as described in U.S. Pat. No. 3,457,078 and mercapto substituted triazoles as described in U.S. Pat. No. 4,910,129.
  • the photothermographic, infrared supersensitizers of the present invention are aromatic, heterocyclic mercapto or disulphide compounds. These compounds have been used extensively in photothermographic elements. Mercapto heterocycles have appeared as antifoggants and development restrainers in U.S. Pat. Nos. 4,639,408; 4,451,561; 3,961,963; 4,678,735 and 4,837,141 as post print stabilizers in U.S. Pat. Nos. 3,617,289 and 3,997,346 in the preparation of silver soaps as in U.S. Pat. Nos. 4,138,265; 4,728,600 and 4,859,580 as toners in U.S. Pat. No. 4,201,582 and as speed enhancers in U.S. Pat. No. 3,359,105 for an N-vinyl carbazole and an organic halogen dye-forming, thermal imaging system.
  • U.S. Patent No. 4,968,597 describes the use of mercapto substituted heteroaromatic compounds in a blue sensitive silver halide layer of a color, heat-developable material. No supersensitization was observed in systems similar to those of the present invention which had been spectrally sensitized to the blue, green, or red. Only in infrared sensitive systems was supersensitization noted.
  • U.S. Patent No. 4,245,033 describes the use of a number of classes of sulfur compounds in heat developable photosensitive compositions. That system varies from the present invention in that thioethers and nonaromatic thiols work as well as aromatic thiols. In addition, there are no infrared sensitized examples.
  • U.S. Patent No. 4,105,451 describes the use of mercapto-aromatic compounds in combination with a silver salt of a heterocyclic thione in a photothermographic material incorporating very high levels of silver iodide. No infrared sensitizing dyes are shown.
  • Photothermographic emulsions which have been spectrally sensitized to the infrared and near infrared regions of the electromagnetic spectrum are supersensitized by the addition of mercapto substituted heteroaromatic compounds.
  • Silver halide crystals have an inherent photosensitivity only in the ultraviolet and blue regions of the electromagnetic spectrum.
  • dyes are used in order to provide the crystals with sensitivity to other portions of the electromagnetic spectrum. These dyes which extend the range of sensitivity of the silver halide are generally referred to as spectral sensitizing dyes. As noted above, supersensitizers increase the efficiency of these spectral sensitizing dyes.
  • heteroaromatic mercapto compounds (I) or heteroaromatic disulfide compounds (II) are effective supersensitizers for photothermographic emulsions spectrally sensitized to wavelengths longer than 750 nm (e.g. 750-1300 nm, preferably 750 to 950 nm).
  • Ar-SM Ar-S-S-Ar wherein M represents a hydrogen atom or an alkali metal atom, Ar represents an aromatic ring or fused aromatic ring containing one or more of nitrogen, sulfur, oxygen, selenium or tellurium atoms.
  • the heteroaromatic ring is benzimidazole, naphthimidazole, benzothiazole, naphthothiazole, benzoxazole, naphthoxazole, benzoselenazole, benzotellurazole, imidazole, oxazole, pyrazole, triazole, thiadiazole, tetrazole, triazine, pyrimidine, pyridazine, pyrazine, pyridine, purine, quinoline or quinazolinone.
  • other heteroaromatic rings are envisioned under the breadth of this invention.
  • the heteroaromatic ring may also carry substituents with examples of preferred substituents being selected from the class consisting of halogen (e.g. Br and Cl), hydroxy, amino, carboxy, alkyl (e.g. of 1 or more carbon atoms, preferably 1 to 4 carbon atoms) and alkoxy (e.g. of 1 or more carbon atoms, preferably of 1 to 4 carbon atoms).
  • substituents being selected from the class consisting of halogen (e.g. Br and Cl), hydroxy, amino, carboxy, alkyl (e.g. of 1 or more carbon atoms, preferably 1 to 4 carbon atoms) and alkoxy (e.g. of 1 or more carbon atoms, preferably of 1 to 4 carbon atoms).
  • the supersensitizers are used in an amount of between 0.001 and 1.0 moles of the compound per mole of silver and preferably between 0.01 and 0.3 moles of compound per mole of silver.
  • infrared sensitized photothermographic elements by mercapto substituted heteroaromatic compounds has been shown to be effective with a broad range of infrared sensitizing dyes.
  • the preferred infrared dyes are tricarbocyanine dyes described in U.S. Pat. No. 4,536,473 and rigidized tricarbocyanine dyes described in U.S. Pat. No. 4,515,888 and 4,959,294.
  • Other effective classes of infrared dyes are 4-quinoline pentamethine dyes described in U.S. Pat. No. 4,536,473, merocyanine infrared dyes and trinuclear dyes.
  • photothermographic chemistry is used as the photothermographic chemistry in the system of the present invention.
  • Such chemistry is well described in U.S. Patents 3,457,075; 3,839,049; 3,985,565; 4,022,617 and 4,460,681.
  • black-and-white chemistry is used.
  • Either in situ halidization (e.g., 3,457,075) or preformed silver halide sources (e.g., 3,839,049) may be used.
  • Any of the various photothermographic media such as full soaps, partial soaps, full salts, and the like may be used in the photothermographic chemistry.
  • Conventional photothermographic chemistry comprises a photosensitive silver halide catalyst, an essentially light-insensitive silver compound capable of being reduced to form a metallic silver image (e.g., silver salts, both organic or inorganic, and silver complexes, usually light sensitive silver materials), a developing agent for silver ion (a mild reducing agent for silver ion), and a binder.
  • a photosensitive silver halide catalyst an essentially light-insensitive silver compound capable of being reduced to form a metallic silver image
  • a developing agent for silver ion a mild reducing agent for silver ion
  • a binder e.g., a mild reducing agent for silver ion
  • Conventional photothermographic chemistry is usually constructed as one or two layers on a substrate.
  • Single layer constructions must contain the silver source material, the silver halide, the developer and binder as well as optional additional materials such as toners, coating aids and other adjuvants.
  • Two-layer constructions must contain silver source and silver halide in one emulsion layer (usually the layer adjacent to the substrate) and the other ingredients in the second layer or both layers. In the present invention it is preferred to use two layer chemistry.
  • the silver source material ordinarily may be any material which contains a reducible source of silver ions.
  • Silver salts or organic acids, particularly long chain (10 to 30, preferably 15 to 28 carbon atoms) fatty carboxylic acids are preferred in the practice of the present invention.
  • Complexes of organic or inorganic silver salts wherein the ligand has a gross stability constant between 4.0 and 10.0 are also useful in the present invention.
  • the silver source material should constitute from about 20 to 70 percent by weight of the imaging layer. Preferably it is present as 30 to 55 percent by weight.
  • Preferred examples of the silver salts of aromatic carboxylic acid and other carboxyl group-containing compounds include silver benzoate, a silver substituted benzoate such as silver 3,5-dihydroxybenzoate, silver o-methylbenzoate, silver m-methylbenzoate, silver p-methylbenzoate, silver 2,4-dichlorobenzoate, silver acetamidobenzoate or silver p-phenylbenzoate, silver gallate, silver tannate, silver phthalate, silver terephthalate, silver salicylate, silver phenylacetate, silver pyromellitate, a silver salt of 3-carboxymethyl-4-methyl-4-thiazoline-2-thione or the like as described in U.S. Pat. No. 3,785,830, and silver salt of an aliphatic carboxylic acid containing a thioether group as described in U.S. Pat. No. 3,330,633.
  • Silver salts of compounds containing mercapto or thione groups and derivatives thereof can be used.
  • Preferred examples of these compounds include a silver salt of 3-mercapto-4-phenyl-1,2,4-triazole, a silver salt of 2-mercaptobenzimidazole, a silver salt of 2-mercapto-5-aminothiadiazole, a silver salt of 2-(S-ethylglycolamido) benzothiazole, a silver salt of thioglycolic acid such as a silver salt of a S-alkyl thioglycolic acid (wherein the alkyl group has from 12 to 22 carbon atoms) as described in Japanese patent application No.
  • a silver salt of a dithiocarboxylic acid such as a silver salt of dithioacetic acid, a silver salt of thioamide, a silver salt of 5-carboxylic-1-methyl-2-phenyl-4-thiopyridine, a silver salt of mercaptotriazine, a silver salt of 2-mercaptobenzoxazole, a silver salt as described in U.S. Pat. No.
  • a silver salt of a 1,2,4-mercaptothiazole derivative such as a silver salt of 3-amino-5-benzylthio-1,2,4-thiazole
  • a silver salt of a thione compound such as a silver salt of 3-(2-carboxyethyl)-4-methyl-4-thiazoline-2-thione as disclosed in U.S. Pat. No. 3,301,678.
  • the light sensitive silver halide used in the present invention can be employed in a range of 0.0005 mole to 5 mole and, preferably, from 0.005 mole to 1.0 mole per mole of organic silver salt.
  • the silver halide may be any photosensitive silver halide such as silver bromide, silver iodide, silver chloride, silver bromoiodide, silver chlorobromoiodide, silver chlorobromide, etc.
  • the silver halide may be added to the emulsion layer in any fashion which places it in catalytic proximity to the silver source.
  • preformed silver halide emulsions of this invention can be unwashed or washed to remove soluble salts.
  • the soluble salts can be removed by chill-setting and leaching or the emulsion can be coagulation washed, e.g., by the procedures described in Hewitson, et al., U.S. Pat. No. 2,618,556; Yutzy et al., U.S. Pat. No. 2,614,928; Yackel, U.S. Pat. No. 2,565,418; Hart et al., U.S. Pat. No. 3,241,969; and Waller et al., U.S. Pat. No. 2,489,341.
  • the silver halide grains may have any crystalline habit including, but not limited to cubic, tetrahedral, orthorhombic, tabular, laminar or platelet.
  • Photothermographic emulsions containing preformed silver halide in accordance with this invention can be sensitized with chemical sensitizers, such as with reduction agents; sulfur, selenium or tellurium compounds; gold, platinum or palladium compounds, or combinations of these.
  • chemical sensitizers such as with reduction agents; sulfur, selenium or tellurium compounds; gold, platinum or palladium compounds, or combinations of these.
  • Suitable chemical sensitation procedures are described in Shepard, U.S. Pat. No. 1,623,499; Waller, U.S. Pat. No. 2,399,083; McVeigh, U.S. Pat. No. 3,297,447; and Dunn, U.S. Pat. No. 3,297,446.
  • the reducing agent for silver ion may be any material, preferably organic material, which will reduce silver ion to metallic silver.
  • Conventional photographic developers such as phenidone, hydroquinones, and catechol are useful but hindered phenol reducing agents are preferred.
  • the reducing agent should be present as 1 to 20 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 20 percent tend to be more desirable.
  • amidoximes such as phenylamidoxime, 2-thienylamidoxime and p-phenoxy-phenylamidoxime, azines, e.g., 4-hydroxy-3,5-dimethoxybenzaldehyde azine; a combination of aliphatic carboxylic acid aryl hydrazides and ascorbic acid, such as 2,2'-bis(hydroxymethyl)propionyl-beta-phenyl hydrazide in combination with ascorbic acid; a combination of polyhydroxybenzene and hydroxylamine, a reductone and/or a hydrazine, e.g., a combination of hydroquinone and bis(ethoxyethyl)hydroxylamine, piperidinohexose reductone or formyl-4-methylphenyl hydrazine, hydroxamic acids such as phenylhydroxamic acid, p-hydroxyphenylhydro
  • Toners additives or "toners", which improve the image. Toner materials may be present, for example, in amounts from 0.1 to 10 percent by weight of all silver bearing components. Toners are well known materials in the photothermographic art as shown in U.S. Pat. Nos. 3,080,254, 3,847,612 and 4,123,282.
  • Silver halide emulsions containing the supersensitizers of this invention can be protected further against the additional production of fog and can be stabilized against loss of sensitivity during keeping.
  • Suitable antifoggants and stabilizers which can be used alone or in combination, include the thiazolium salts described in Staud, U.S. Pat. No. 2,131,038 and Allen U.S. Pat. No. 2,694,716; the azaindenes described in Piper, U.S. Pat. No. 2,886,437 and Heimbach, U.S. Pat. No. 2,444,605; the mercury salts described in Allen, U.S. Pat. No. 2,728,663; the urazoles described in Anderson, U.S. Pat. No.
  • Supersensitized emulsions of the invention can contain plasticizers and lubricants such as polyalcohols, e.g., glycerin and diols of the type described in Milton, U.S. Pat. No. 2,960,404; fatty acids or esters such as those described in Robins, U.S. Pat. No. 2,588,765 and Duane, U.S. Pat. No. 3,121,060; and silicone resins such as those described in DuPont British Patent No. 955,061.
  • plasticizers and lubricants such as polyalcohols, e.g., glycerin and diols of the type described in Milton, U.S. Pat. No. 2,960,404; fatty acids or esters such as those described in Robins, U.S. Pat. No. 2,588,765 and Duane, U.S. Pat. No. 3,121,060; and silicone resins such as those described in DuPont British Patent No. 955,
  • the photothermographic elements can include image dye stabilizers.
  • image dye stabilizers are illustrated by U.K. Patent No. 1,326,889; Lestina et al. U.S. Pat. Nos. 3,432,300 and 3,698,909; Stern et al. U.S. Pat. No. 3,573,050; Arai et al. U.S. Pat. No. 3,764,337 and Smith et al. U.S. Pat. No. 4,042,394.
  • Photothermographic elements containing emulsion layers supersensitized according to the present invention can be used in photographic elements which contain light absorbing materials and filter dyes such as those described in Sawdey, U.S. Pat. No. 3,253,921; Gaspar U.S. Pat. No. 2,274,782; Carroll et al., U.S. Pat. No. 2,527,583 and Van Campen, U.S. Pat. No. 2,956,879.
  • the dyes can be mordanted, for example, as described in Milton and Jones, U.S. Pat. No. 3,282,699.
  • Photothermographic elements containing emulsion layers supersensitized as described herein can contain matting agents such as starch, titanium dioxide, zinc oxide, silica, polymeric beads including beads of the type described in Jelley et al., U.S. Pat. No. 2,992,101 and Lynn, U.S. Pat. No. 2,701,245.
  • matting agents such as starch, titanium dioxide, zinc oxide, silica, polymeric beads including beads of the type described in Jelley et al., U.S. Pat. No. 2,992,101 and Lynn, U.S. Pat. No. 2,701,245.
  • Emulsions supersensitized in accordance with this invention can be used in photothermographic elements which contain antistatic or conducting layers, such as layers that comprise soluble salts, e.g., chlorides, nitrates, etc., evaporated metal layers, ionic polymers such as those described in Minsk, U.S. Pat. Nos. 2,861,056, and 3,206,312 or insoluble inorganic salts such as those described in Trevoy, U.S. Pat. No. 3,428,451.
  • antistatic or conducting layers such as layers that comprise soluble salts, e.g., chlorides, nitrates, etc., evaporated metal layers, ionic polymers such as those described in Minsk, U.S. Pat. Nos. 2,861,056, and 3,206,312 or insoluble inorganic salts such as those described in Trevoy, U.S. Pat. No. 3,428,451.
  • the binder may be selected from any of the well-known natural or synthetic resins such as gelatin, polyvinyl acetals, polyvinyl chloride, polyvinyl acetate, cellulose acetate, polyolefins, polyesters, polystyrene, polyacrylonitrile, polycarbonates, and the like. Copolymers and terpolymers are of course included in these definitions.
  • the preferred photothermographic silver containing polymer is polyvinyl butyral, but ethyl cellulose, methacrylate copolymers, maleic anhydride ester copolymers, polystyrene, and butadiene-styrene copolymers are also useful.
  • these polymers may be used in combination of two or more thereof.
  • Such a polymer is used in an amount sufficient to carry the components dispersed therein, that is, within the effective range of the action as the binder.
  • the effective range can be appropriately determined by one skilled in the art.
  • a preferred ratio of the binder to the organic silver salt ranges from 15:1 to 1:2, and particularly from 8:1 to 1:1.
  • Photothermographic emulsions containing the supersensitizer to be used in the invention can be coated on a wide variety of supports.
  • Typical supports include polyester film, subbed polyester film, poly(ethylene terephthalate)film, cellulose nitrate film, cellulose ester film, poly(vinyl acetal) film, polycarbonate film and related or resinous materials, as well as glass, paper metal and the like.
  • a flexible support is employed, especially a paper support, which can be partially acetylated or coated with baryta and/or an alphaolefin polymer, particularly a polymer of an alpha-olefin containing 2 to 10 carbon atoms such as polyethylene, polypropylene, ethylene-butene copolymers and the like.
  • the substrate with a backside resistive heating layer may also be used in photothermographic imaging systems such as shown in U.S. Pat. No. 4,460,681 and 4,374,921.
  • Photothermographic emulsions of this invention can be coated by various coating procedures including dip coating, air knife coating, curtain coating, or extrusion coating using hoppers of the type described in Benguin, U.S. Pat. No. 2,681,294. If desired, two or more layers may be coated simultaneously by the procedures described in Russell, U.S. Pat. No. 2,761,791 and Wynn, British Patent No. 837,095.
  • a silver halide-silver behenate dry soap was prepared by the procedures described in U.S. Pat. No. 3,839,049.
  • the silver halide totalled 9% of the total silver while silver behenate comprised 91% of the total silver.
  • the silver halide was a 50/50 mixture of preformed silver halide grains. Both had a composition of 2% iodide and 98% bromide and were monodispersed.
  • the two silver bromoiodide emulsions had grain sizes of 0.055 and 0.07 microns.
  • a photothermographic emulsion was prepared by homogenizing 300 g of the silver halide-silver behenate dry soap described above with 525 g toluene, 1675 g 2-butanone and 50 g poly(vinylbutyral) (B-76, Monsanto).
  • the photothermographic emulsion was divided into 40 g portions. The control was coated at this stage without additional additives. The remaining aliquots were treated with 3 levels of heteroaromatic mercapto compounds added as 1% solutions in methanol (w/v). The results are reported in Table 1 for the levels of heteroaromatic mercapto compound listed as dry weight per 40 g aliquots giving the best balance of low fog and high speed.
  • the silver photothermographic emulsions were coated and clear 3 mil (0.76 x 10 -4 m) polyester by means of a knife coater and dried at 79.4°C (175°F) for four minutes.
  • the dry coating weight was 23 g/m 2 .
  • An active, protective topcoat solution was prepared with the following ingredients: 256 g acetone 123 g 2-butanone 50 g methanol 20.2 g cellulose acetate 2.89 g phthalazine 2.02 g 4-methylphthalic acid 0.69 g tetrachlorophthalic acid 0.90 g tetrabromophthalic anhydride 1.50 g tetrachlorophthalic anhydride 0.45 g 4-tribromomethylpyrimidine
  • the topcoat solution was coated over the silver layer at a dry weight of 3.0 g/m 2 . The layer was dried at 165°F for four minutes.
  • Table 2 contains a list of sulfur compounds and silver halide, infrared supersensitizers tested in the formula described for Examples 1-13. The compounds were tested at the three levels described in Examples 1-13 with the best level listed in Table 2. The results show that thioethers, thioureas and thiones do not supersensitize the infrared photothermographic system. The thioureas and also benzotriazole and Leucophor BCF (Sandoz, sulfonated triazenyl stilbene) did not supersensitize the photothermographic system although they are used extensively as silver halide, infrared supersensitizers.
  • a photothermograhpic emulsion was prepared by combining 206 g of a silver behenate full soap dispersion (converted to 26t silver by weight) with the following ingredients, each added in its listed order with mixing: 40 g 2-butanone 0.54 g N-methylpyrrolidone 5.4 ml of ZnBr 2 solution (10 g ZnBr 2 and 100 ml of methanol) The mixture was held for 4 hours before adding the following: 3.6 g poly(vinylbutyral) B-76 2.6 ml of pyridine solution (3.6 g pyridine and 71 g 2-butanone) 27.5 g poly(vinylbutyral) B-76 4.6 ml NBS solution (0.67 g N-bromosuccinimide and 40 g 2-butanone) The mixture was held overnight before adding the following: 6.3 g 2,2
  • the resulting composition was divided into 40 g portions.
  • the control was coated without additional additives while M-1(2-mercaptobenzimidazole) was added to a second aliquot.
  • the results are compiled in Table 6.
  • the silver photothermographic emulsions were coated on clear 3 mil (0.76 x 10 -4 m) polyester by means of a knife coater and dried at 85°C (185°F) for three minutes. The dry coating weight was 17 g/m 2 .
  • An active, protective topcoat solution was prepared with the following ingredients: 224 g 2-butanone 33.3 g acetone 13.8 g methanol 20.7 g cellulose acetate 2.64 g phthalazine 1.86 g 4-methylphthalic acid 1.23 g tetrachlorophthalic anhydride 0.57 g tetrachlorophthalic acid 1.80 g 2-(tribromomethylsulfone)benzothiazole
  • the topcoat solution was coated at 2.7 g/m 2 over the silver coating and dried at 85°C (185°F) for three minutes. The coated material was exposed on a laser sensitometer with a 780 nm laser diode and then processed at 126.7°C (260°F) for ten seconds.
  • the following coatings show that a combination of mercapto heteroaromatic compounds may give improved results as infrared supersensitizers for photothermographic systems.
  • the same silver and topcoat formulas were used in these examples as those given in Examples 14-26 except that a higher infrared dye level was used (50% more IR dye, D-1) and a change was made in the tribromo antifoggant.
  • Examples 14-26 had 0.45 g of 4-tribromomethylpyrimidine in the topcoat solution whereas Examples 35-40 contained 2.25 g of 2-(tribromomethylsulfone)benzothiazole in the same quantity of topcoat solution.
  • the examples were again run as 40 g aliquots.
  • the coated film strips were exposed with a laser sensitometer incorporating a 780 nm laser diode. After exposure, the film strips were processed at 126.7°C (260°F) for ten seconds. The results are compiled in Table 7.

Claims (7)

  1. Emulsion photothermographique utilisant une chimie en noir et blanc, comprenant un liant, un sel d'argent non-photosensible, un agent réducteur de l'ion argent, et un halogénure d'argent, ledit halogénure d'argent ayant subi une sensibilisation spectrale à une radiation de 750 à 1300 nm, et ladite émulsion contenant un composé sursensibilisateur choisi parmi les composés mercapto hétéroaromatiques ou les disulfures hétéroaromatiques, en une quantité de 10-3 à 1 mole dudit composé par mole d'argent dans ladite émulsion.
  2. Emulsion selon la revendication 1, comprenant un composé sursensibilisateur choisi parmi l'une ou l'autre des formules suivantes : Ar-SM et Ar-S-S-Ar où M est un atome d'hydrogène ou un métal alcalin, et Ar est un groupe cyclique hétéroaromatique.
  3. Emulsion selon l'une quelconque des revendications 1 ou 2, dans laquelle ledit halogénure d'argent ayant subi une sensibilisation spectrale comprend un halogénure d'argent et un colorant de cyanine, un colorant de carbocyanine ou un colorant de tricarbocyanine.
  4. Emulsion selon l'une quelconque des revendications 2 ou 3, dans laquelle Ar est choisi parmi le benzimidazole, le naphtimidazole, le benzothiazole, le naphtothiazole, le benzoxazole, le naphtoxazole, le benzosélénazole, le benzotellurazole, l'imidazole, l'oxazole, le pyrazole, le triazole, le thiadiazole, le tétrazole, la triazine, la pyrimidine, la pyridazine, la pyrazine, la pyridine, la purine, la quinoléine et la quinazolinone.
  5. Emulsion selon l'une quelconque des revendications 1 à 4, dans laquelle ledit sel d'argent non-photosensible comprend un sel d'argent d'un acide organique.
  6. Emulsion selon la revendication 5, dans laquelle ledit acide organique comprend un acide carboxylique gras.
  7. Emulsion selon l'une quelconque des revendications 1 à 6, comprenant au moins deux composés différents parmi lesdits composés sursensibilisateurs.
EP93103608A 1992-03-06 1993-03-05 Eléments photothermographiques Expired - Lifetime EP0559228B1 (fr)

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US846919 1992-03-06

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US6737227B1 (en) 2003-03-07 2004-05-18 Eastman Kodak Company Thermally developable emulsions and materials containing heterocyclic disulfide compounds
US6849392B2 (en) 2003-01-14 2005-02-01 Eastman Kodak Company Thermally developable emulsions and materials containing triazine-thione compounds
WO2017123444A1 (fr) 2016-01-15 2017-07-20 Carestream Health, Inc. Procédé de préparation de savons de carboxylate d'argent

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US6316179B1 (en) 1993-06-04 2001-11-13 Eastman Kodak Company Infrared sensitized, photothermographic article
JP3616130B2 (ja) * 1993-06-04 2005-02-02 イーストマン コダック カンパニー 感赤外線性光熱写真ハロゲン化銀要素及び画像形成性媒体の露光方法
JP3980636B2 (ja) 1994-11-16 2007-09-26 イーストマン コダック カンパニー 木目干渉パターンを低減した光熱写真成分
US5541054B1 (en) * 1995-04-20 1998-11-17 Imation Corp Spectral sensitizing dyes for photothermographic elements
US6245499B1 (en) 1996-04-30 2001-06-12 Fuji Photo Film Co., Ltd. Photothermographic material
EP0821271B1 (fr) * 1996-07-24 2006-04-19 Agfa-Gevaert Procédé pour la production d'un produit photothermographique sensible à l'infra-rouge comprenant un sensibilisateur spectral et un supersensibilisateur à base de stilbene et procédé d'enregistrement.
US5876915A (en) * 1996-07-24 1999-03-02 Agfa-Gevaert Photothermographic recording material comprising sensitizing dyes and a recording process therefor
EP0821272B1 (fr) * 1996-07-24 2006-01-04 Agfa-Gevaert Procédé de préparation d'un produit d'enregistrement, photothermographique comprenant des colorants sensibilisateurs de l'infra-rouge
US6074814A (en) * 1996-07-24 2000-06-13 Agfa-Gevaert Photothermographic material comprising an infra-red sensitizer
US5851755A (en) * 1996-07-24 1998-12-22 Agfa-Gevaert Photothermographic material comprising at least one dye absorbing electromagnetic radiation in the wavelength range 700 to 1100NM
US5958667A (en) * 1996-07-24 1999-09-28 Agfa-Gevaert Photothermographic recording material comprising IR-sensitizing dyes
JPH10120928A (ja) * 1996-10-22 1998-05-12 Fuji Photo Film Co Ltd 熱現像感光材料、新規な２，３−ジヒドロチアゾール誘導体およびハロゲン化銀写真感光材料
JP4031077B2 (ja) * 1996-12-26 2008-01-09 富士フイルム株式会社 熱現像感光材料
US5939249A (en) * 1997-06-24 1999-08-17 Imation Corp. Photothermographic element with iridium and copper doped silver halide grains
EP0890875B1 (fr) * 1997-07-10 2001-11-14 Agfa-Gevaert N.V. Matériau photographique multicouche à l'halogénure d'argent et méthode de formation d'image pour applications à des fins de test non-destructif en radiographie industrielle
US6153372A (en) * 1997-10-03 2000-11-28 Fuji Photo Film Co., Ltd. Photothermographic element
JPH11282128A (ja) * 1998-03-26 1999-10-15 Fuji Photo Film Co Ltd 熱現像感光材料
US6214533B1 (en) 1998-04-10 2001-04-10 Konica Corporation Thermally developable photosensitive material
EP1422551B1 (fr) * 2002-11-14 2006-12-06 Agfa-Gevaert Stabilisateurs pour emploi en matériaux thermographiques d' enregistrement sensiblement non-sensibles à la lumière
JP4369876B2 (ja) 2004-03-23 2009-11-25 富士フイルム株式会社 ハロゲン化銀感光材料および熱現像感光材料
US20060057512A1 (en) 2004-09-14 2006-03-16 Fuji Photo Film Co., Ltd. Photothermographic material
JPWO2007010777A1 (ja) 2005-07-20 2009-01-29 コニカミノルタエムジー株式会社 画像形成方法
US7504200B2 (en) 2007-02-02 2009-03-17 Konica Minolta Medical & Graphic, Inc. Photothermographic material

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6849392B2 (en) 2003-01-14 2005-02-01 Eastman Kodak Company Thermally developable emulsions and materials containing triazine-thione compounds
US6737227B1 (en) 2003-03-07 2004-05-18 Eastman Kodak Company Thermally developable emulsions and materials containing heterocyclic disulfide compounds
WO2017123444A1 (fr) 2016-01-15 2017-07-20 Carestream Health, Inc. Procédé de préparation de savons de carboxylate d'argent

Also Published As

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JPH05341432A (ja) 1993-12-24
JP3249621B2 (ja) 2002-01-21
DE69326090D1 (de) 1999-09-30
DE69326090T2 (de) 2000-03-30
EP0559228A1 (fr) 1993-09-08
CA2087480A1 (fr) 1993-09-07

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