EP0573066A1 - Emulsion positive-directe à l'halogénure d'argent du type à image latente interne et unité de film photographique pour transfert par diffusion de colorants utilisant le-même - Google Patents

Emulsion positive-directe à l'halogénure d'argent du type à image latente interne et unité de film photographique pour transfert par diffusion de colorants utilisant le-même Download PDF

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Publication number
EP0573066A1
EP0573066A1 EP93109036A EP93109036A EP0573066A1 EP 0573066 A1 EP0573066 A1 EP 0573066A1 EP 93109036 A EP93109036 A EP 93109036A EP 93109036 A EP93109036 A EP 93109036A EP 0573066 A1 EP0573066 A1 EP 0573066A1
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Prior art keywords
silver halide
layer
latent image
grains
halide emulsion
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EP93109036A
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German (de)
English (en)
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EP0573066B1 (fr
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Atsushi c/o Fuji Photo Film Co. Ltd. Matsunaga
Seiji c/o Fuji Photo Film Co. Ltd. Akiyama
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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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
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/485—Direct positive emulsions
    • G03C1/48538—Direct positive emulsions non-prefogged, i.e. fogged after imagewise exposure
    • 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
    • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
    • G03C8/02—Photosensitive materials characterised by the image-forming section
    • G03C8/08—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of organic compounds

Definitions

  • the present invention relates to an internal latent image type direct positive silver halide emulsion and a color diffusion transfer photographic film unit using the same.
  • Photographic methods using silver halides are excellent in sensitivity and gradation characteristics, as compared with other photographic methods such as electrophotographic methods and diazo photographic methods, and have previously been widely used.
  • methods of forming direct positive images are well known, which are methods for obtaining positive images by giving uniform exposure or using nucleating agents, when internal latent image type direct positive silver halide photographic emulsions are used and silver halide grains in which internal latent images are formed are developed with surface developing solutions (developing solutions which leave image forming sites in the silver halide grains without substantial development), as disclosed, for example, in U.S. Patent 3,761,276 and JP-B-60-55821 (the term "JP-B" as used herein means an "examined Japanese patent publication").
  • U.S. Patent 2,448,060 discloses that silver halide emulsions can be sensitized by addition of transition metal compounds in some manufacturing stages of the silver halide emulsions.
  • the differences in photographic effects of the transition metal compounds in the silver halide emulsions between the case of adding the transition metal compounds during formation of silver halide grains and the case of adding the compounds after precipitation of the silver halide grains are known to be significant.
  • the transition metal compounds in the former case are called metal dopants. These are described in Research Disclosure , vol. 176, No. 17643 (December, 1978).
  • the six-coordinate transition metal complex is recognized to be contained in a space of a vacant lattice point of a single halide ion in a crystalline structure, which is different from the conventional known view that the transition metal is surrounded as a single ion or atom by silver halide grains.
  • the kinds of transition metals are restricted to rhenium, ruthenium, osmium and iridium, and chromium, manganese, cobalt and rhodium are not described. Also, no internal latent image type direct positive silver halide emulsion is described.
  • JP-A-2-259749 discloses that direct positive silver halide photographic materials high in maximum density, low in minimum density and reduced in development of re-reversal negative images on high illuminance exposure are obtained by use of internal latent image type direct positive silver halide emulsions particularly containing hexacyano iron complexes of iron complexes, but the central metal is restricted to iron. It does not disclose the use of chromium, manganese, cobalt, iridium, ruthenium, rhodium, rhenium and osmium.
  • An object of the present invention is to provide an internal latent image type direct positive silver halide emulsion which is high in sensitivity and contrasty in a low-density portion on a reversal characteristic curve.
  • Another object of the present invention is to provide a color diffusion transfer photographic film unit using such a silver halide emulsion.
  • an internal latent image type direct positive silver halide emulsion comprising a dispersion medium containing at least one metal complex represented by the following formula (I) and silver halide grains formed in the dispresion medium: [M(CN)6] n- (I) wherein M represents Cr, Mn, Co, Ir, Ru, Rh, Re or Os; and n is 3 or 4.
  • the internal latent image type direct positive silver halide emulsion preferably includes tabular silver halide grains having a mean grain diameter of 0.3 ⁇ m or more and a mean grain diameter/mean grain thickness ratio of 2 or more in an amount of 50% or more of the total silver halide grains.
  • a color diffusion transfer photographic film unit comprising (a) a light-sensitive sheet having an image receiving layer, a white reflective layer, a light shielding layer and at least one silver halide emulsion layer combined with at least one dye image forming substance, which are formed on a transparent support, (b) a transparent cover sheet having at least a neutralization layer and a neutralization timing layer, which are formed on a transparent support, and (c) a light shielding alkali processing composition spread between the above-described light-sensitive sheet and the above-described transparent cover sheet, and wherein at least one silver halide emulsion layer in the light-sensitive sheet contains the internal latent image type direct positive silver halide emulsion of the present invention described above.
  • ions of metal hexacyanide complexes used in the present invention ions of alkali metals such as potassium and sodium are preferably employed.
  • the amount of the metal hexacyanide complexes used in the present invention is preferably from 1.0 ⁇ 10 ⁇ 10 to 1.0 ⁇ 10 ⁇ 4 mol per mol of silver halide, and more preferably form 1.0 ⁇ 10 ⁇ 8 to 1.0 ⁇ 10 ⁇ 6 mol per mol of silver halide.
  • the metal hexacyanide complexes used in the present invention may be added to the dispersion medium during preparation of the silver halide grains, namely, at any stage before and after nucleation, growth, physical ripening and chemical sensitization. They are added preferably during growth of grains.
  • the pAg is preferably 6 or more, more preferably 7 to 10, and most preferably 7 to 8.
  • the metal hexacyanide complexes used in the present invention are dissolved in water or appropriate solvents in advance, and are added to the dispersion medium.
  • Aqueous solutions of hydrogen halides (for example, HCl and HBr) or alkali halides (for example, KCl, NaCl, KBr and NaBr) may be added to stabilize the solutions. Further, acids or alkalis may be added if necessary.
  • the metal hexacyanide complexes used in the present invention are preferably directly added to reaction solutions during formation of the silver halide grains, or added to aqueous solutions of halides for forming the silver halide grains, aqueous solution of silver salts or other solutions to form the grains. Furthermore, various addition processes are preferably combined.
  • the hydrogen ion concentration (pH) of the reaction solutions is preferably 1 or more, and more preferably 3 or more.
  • the metal hexacyanide complexes used in the present invention can be used in combination with other metals.
  • the other metals which can be used include Mg, Ca, Sr, Ba, Al, Sc, Y, La, Cr, Mn, Fe, Ni, Cu, Zn, Ga, Ru, Rh, Pd, Re, Os, Pt, Au, Cd, Hg, Tl, In, Sn, Pb and Bi.
  • These metals can be added as long as they are in salt forms which can be dissolved during formation of the grains, such as ammonium salts, acetates, nitrates, sulfates, phosphates, hydroxides, six-coordinate complexes and four-coordinate complexes.
  • the present invention is applied to internal latent image type direct positive silver halide emulsions.
  • the internal latent image type direct positive silver halide emulsion (hereinafter occasionally briefly referred to as an internal latent image type silver halide emulsion) is a silver halide emulsion which forms a latent image mainly in the interior of the silver halide grain, when subjected to image exposure.
  • the internal latent image type silver halide emulsion is defined as an emulsion in which the maximum density obtained when a definite amount of the silver halide emulsion is applied to a transparent support, exposed for a fixed time of 0.01 to 1 second, and developed in the following developing solution A ("internal type” developing solution) at 20°C for 5 minutes is at least 5 times as high as the maximum density obtained when a second sample exposed in a similar manner to that described above is developed in the following developing solution B ("surface type" developing solution) at 20°C for 5 minutes.
  • developing solution A internal type developing solution
  • developing solution B surface type developing solution
  • the maximum density is measured according to a conventional method for measuring photographic density.
  • Developing Solution A N-Methyl-p-aminophenol Sulfite 2 g Sodium Sulfite (Anhydrous) 90 g Hydroquinone 8 g Sodium Carbonate (Monohydrate) 52.5 g Potassium Bromide 5 g Potassium Iodide 0.5 g Water to make 1 liter
  • Developing Solution B N-Methyl-p-aminophenol Sulfite 2.5 g 1-Ascorbic Acid 10 g Potassium Metanitrate 35 g Potassium Bromide 1 g Water to make 1 liter
  • Examples of the internal latent image type silver halide emulsions include conversion type silver halide emulsions as described in U.S. Patents 2,456,953 and 2,592,250, laminated structure type silver halide emulsions in which first phases are different from second phases in silver halide composition as described in U.S. Patent 3,935,014, and core/shell type silver halide emulsions in which core grains doped with metal ions or subjected to chemical sensitization are covered with shells.
  • the core/shell type silver halide emulsions are preferably used as the internal latent image type silver halide emulsions in the present invention. Examples thereof include emulsions described in U.S.
  • a second uniform image exposure is given to the whole surface of the exposed layer before or during development processing, or development processing is carried out in the presence of the nucleating agent, after image exposure.
  • Nucleating agents which can be used in the present invention include hydrazines described in U.S. Patents 2,563,785 and 2,588,982; hydrazides and hydrazones described in U.S. Patent 3,227,552; heterocyclic quaternary salt compounds described in British Patent 1283835, JP-A-52-69613, JP-A-55-138742, JP-A-60-11837, JP-A-62-210451, JP-A-62-291637, U.S.
  • the nucleating agent is used in such an amount that a sufficient maximum density is given when the internal latent image type emulsion is developed with a surface developing solution.
  • the appropriate amount of the nucleating agents contained can vary over a wide range, depending on the characteristics of the silver halide emulsions used, the chemical structure of the nucleating agents and developing conditions.
  • the actually useful amount is generally 0.1 mg to 5 g per mol of silver contained in the internal latent image type silver halide emulsion, and the preferred amount is 0.5 mg to 2 g per mol of silver.
  • the nucleating agent When the nucleating agent is added to a hydrophilic colloidal layer adjacent to the emulsion layer, it may be added in an amount as described above, based on the amount of silver contained in the internal latent image type emulsion having the same area as the adjacent layer.
  • various forms of silver halide grains can be used. Examples thereof include regular crystal forms such as cubic, octahedral, tetradecahedral and rhombic dodecahedral forms; irregular crystal forms such as spherical and tabular forms; forms having high-dimensional faces ((hkl) faces); and mixtures of these forms.
  • the grains having the high-dimensional faces can be referred to Journal of Imaging Science , vol. 30, pages 247 to 254 (1986).
  • the silver halide grains used in the present invention may be either normal crystals free from twin planes or crystals such as explained in The Basis of Photographic Industry, Silver Salt Photography , page 163, edited by Nippon Shashin Gakkai (published by Corona, Co.) such as a single twin containing one twin plane, parallel multiple twins containing two or more parallel twin planes and non-parallel multiple twins containing two or more non-parallel twin planes. These crystals can be selected for use according to their purpose.
  • U.S. Patent 4,865,964 discloses an example in which grains having different forms are mixed with each other. This process can be selected if necessary.
  • the grains having the cubic form comprising a (100) face, the octahedral form comprising a (111) face, and the dodecahedral form comprising a (110) face disclosed in JP-B-55-42737 and JP-A-60-222842 can be used. Furthermore, as reported in Journal of Imaging Science , vol. 30, page 247 (1986), grains having (hll) faces represented by (211), (hhl) faces represented by (331), (hk0) faces represented by (210) and (hkl) faces represented by (321) can also be selected for use according to their purpose although it is necessary to employ suitable techniques for their preparation.
  • Grains in which two or more faces coexist such as a grain having the tetradecahedral form in which the (110) and (111) faces coexist in one grain, a grain in which the (100) and (110) faces coexist and a grain in which the (111) and (110) faces coexist, can also be selected for use according to their purpose.
  • silver halides used for these grains include silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, silver chloroiodide and silver chloride.
  • Silver bromide and silver iodobromide are preferably used among others.
  • other silver salts such as silver thiocyanate, silver cyanate, silver sulfide, silver selenide, silver carbonate, silver phosphate and silver salts of organic acids may be present as additional grains or part of the silver halide grains.
  • the silver halide grain may have different phases or uniform phases in the interior and the exterior layer thereof.
  • the silver halide composition of the grain may be uniform or different in the interior and the exterior thereof, or may have a layered structure (JP-A-57-154232, JP-A-58-108533, JP-A-58-248469, JP-A-59-48755, JP-A-59-52237, U.S. Patents 3,505,068, 4,433,048 and 4,444,877, European Patent 100984 and British Patent 1027146). Further, the grain may have a dislocation line.
  • the silver halide grains are used in which two or more silver halides exist as mixed crystals or with a structure, it is important to control the halogen composition distribution between the grains.
  • a method for measuring the halogen composition distribution between the grains is described in JP-A-60-254032. It is a desirable characteristic that the halogen distribution between the grains is uniform. In particular, a highly uniform emulsion having a coefficient of variation of 20% or less is preferred. Another preferred embodiment is an emulsion having a desired correlation between the grain size and the halogen composition.
  • halogen composition in the vicinity of the surface of the grain.
  • the increased content of silver iodide or silver chloride in the vicinity of the surface changes the adsorption of a dye and the rate of development, so that this can be selected according to its purpose.
  • the halogen composition is changed in the vicinity of the surface, this can be accomplished either by encapsulating the entirety of the grain structure with a composition which has a halogen composition different from the interior, or by adhering a composition which has a halogen composition different from the interior to only part of the grain structure.
  • halogen composition of one face can be changed, or the halogen composition of one of the side faces of a main plane of the tabular grain can be changed.
  • the grain size of the emulsions used in the present invention can be evaluated by the diameter of a circle equivalent to a projected area determined by use of an electron microscope, the diameter of a sphere equivalent to a grain volume calculated from the projected area and a grain thickness, or the diameter of a sphere equivalent to a volume determined by the coulter counter method.
  • the grains are selected for use from ultra-fine grains having a grain size of 0.05 ⁇ m or less to coarse grains having a grain size of more than 10 ⁇ m, calculated as the diameter of an enhanced sphere. Grains having a grain size of 0.1 to 3 ⁇ m are preferred.
  • Monodisperse emulsions are described in U.S. Patents 3,574,628 and 3,655,394, and British Patent 1,413,748. These monodisperse emulsions may be mixed to form a mixture of monodisperse emulsions which can be used.
  • JP-A-63-220238 and JP-A-1-201649 disclose tabular silver halide grains into which dislocation lines are intentionally introduced.
  • the ratio of the mean grain diameter to the mean grain thickness is preferably 2 or more, more preferably 3 to 12, and most preferably 5 to 8, wherein the mean grain diameter in the tabular silver halide grains means a mean value of the diameters of circles equivalent to two parallel or approximately parallel main planes opposite to each other (the diameters of circles having the same projected areas as those of the main planes), and the mean grain thickness means a mean value of the distances between the main planes.
  • the grain diameter/thickness is obtained by averaging the grain diameter/thickness values of the whole tabular grains, but can also be determined by an easier method, namely, by obtaining the ratio of the mean diameter of the whole tabular grains to the mean thickness of the whole tabular grains.
  • emulsions highly uniform in thickness in which the grain thickness has a coefficient of variation of 30% or less, are preferably used.
  • the above-described tabular grains account for 50% or more of the whole grains in an emulsion containing them, preferably 70% or more, and more preferably 90% or more.
  • the grain diameter and the grain thickness of the tabular grains can be measured according to an electron micrograph of the grains, as described in U.S. Patent 4,434,226.
  • the tabular grains are preferably monodisperse.
  • the structure of the monodisperse tabular grains and methods for producing them are described, for example, in JP-A-63-151618.
  • the silver halide emulsions used in the present invention may be subjected to treatment for rounding grains as described in European Patents 96727 and 64412, or to surface modification as disclosed in West German Patent 2306447 and JP-A-60-221320.
  • the surface of the grain is generally flat. It is however preferred in some cases that unevenness is intentionally formed on the surface. Examples thereof include methods for perforating a part of a crystal such as a top or a center of a plane which are described in JP-A-58-106532 and JP-A-60-221320, and a ruffle grain described in U.S. Patent 4,643,966.
  • the silver halide emulsions used in the present invention can be prepared, for example, according to the methods described in Research Disclosure (RD) , vol. 176, No. 17643, pages 22 and 23, "I. Emulsion Preparation and Types" (December, 1978), ibid. , vol. 187, No. 18716, page 648 (November, 1979), ibid. , vol. 307, No. 307105, pages 863 to 865 (November, 1989), P. Glafkides, Chimie et Physique Photographique (Paul Montel, 1967), G.F. Duffin, Photographic Emulsion Chemistry (Focal Press, 1966) and V.L.
  • any of an acid process, a neutral process and an ammonia process may be used.
  • a soluble silver salt and a soluble halogen salt may be reacted with each other by using any of a single jet process, a double jet process and a combination thereof.
  • a so-called reverse mixing process in which grains are formed in the presence of excess silver ions can also be used.
  • As a type of double jet process there can also be used a process for maintaining the pAg in a liquid phase constant, in which a silver halide is formed, namely a so-called controlled double jet process. According to this process, a silver halide emulsion having a regular crystal form and an approximately uniform grain size can be obtained.
  • tabular grains can be easily prepared by methods described in Gutoff, Photographic Science and Engineering , vol. 14, pages 248 to 257 (1970), U.S. Patents 4,434,226, 4,414,310, 4,433,048 and 4,439,520 and British Patent 2,112,157.
  • the silver halide emulsions comprising the above-described regular grains are obtained by controlling the pAg and the pH during formation of the grains. Details thereof are described, for example, in Photographic Science and Engineering , vol. 6, pages 159 to 165 (1962), Journal of Photographic Science , vol. 12, pages 242 to 251 (1964), U.S. Patent 3,655,394 and British Patent 1413748.
  • the monodisperse emulsions are described in JP-A-48-8600, JP-A-51-39027, JP-A-51-83097, JP-A-53-137133, JP-A-54-48521, JP-A-54-99419, JP-A-58-37635, JP-A-58-49938, JP-B-47-11386, U.S. Patent 3,655,394 and British Patent 1413748.
  • the methods of adding silver halide grains previously precipitated to a reaction vessel for preparation of emulsions are preferred. These grains are used as seed crystals, and also are effectively provided as silver halides for growth. In the latter case, an emulsion having a small grain size is preferably added.
  • a method for addition can be selected for use from addition of the total amount at once, addition of several divided portions and continuous addition. Further, in order to modify the surface, it is also effective to add grains of various silver halides in some cases.
  • a mixer used when solutions of a soluble halogen salt and a soluble silver salt are reacted with each other can be selected for use from ones described in U.S. Patents 2,996,287, 3,342,605, 3,415,650 and 3,785,777, West German Patent Publication (OLS) Nos. 2556885 and 2555364.
  • solvents for silver halides are useful.
  • the presence of an excess amount of halogen ions in a reaction vessel is known to promote ripening.
  • other ripening agents can also be used.
  • the ripening agent can be added in the whole amount to a dispersion medium in a reaction vessel before addition of a silver salt(s) and a halide(s), or can also be introduced into the reaction vessel together with addition of the silver salt(s), the halide(s) and a deflocculant.
  • the ripening agent can also be independently introduced in the stage of addison of the halide(s) and the silver salt(s).
  • ripening agents which can be used include ammonia; amine compounds; and thiocyanates such as alkaline metal thiocyanates, particularly sodium and potassium thiocyanates, and ammonium thiocyanate.
  • thiocyanate ripening agents is taught in U.S. Patents 2,222,264, 2,448,534 and 3,320,069.
  • examples of the other ripening agents include organic thioether compounds (such as compounds described in U.S.
  • thione compounds such as four-substituted thiourea described in JP-A-53-82408, JP-A-55-77737 and U.S. Patent 4,221,863, and compounds described in JP-A-53-144319
  • the methods of increasing the rates, the amounts and the concentrations of silver salt solutions (for example, an aqueous solution of AgNO3) and halide solutions (for example, an aqueous solution of KBr) are preferably used to speed growth of the grains.
  • silver salt solutions for example, an aqueous solution of AgNO3
  • halide solutions for example, an aqueous solution of KBr
  • the above-described solvents for silver halides are effective.
  • the method of adding chalcogenide compounds as described in U.S. Patent 3,772,031 during growth of the emulsions is also effective. Besides S, Se and Te, cyanides, thiocyanides, selenocyanides, carbonates, phosphates and acetates may be allowed to be present. These are described in U.S. Patents 2,448,060, 2,628,167, 3,737,313 and 3,772,031, and Research Disclosure , vol. 134, No. 13452 (June, 1975).
  • the internal latent image type silver halide grains used in the present invention have the core/shell structure as described above.
  • shell producing methods reference can be made to the examples of JP-A-63-151618, U.S. Patents 3,206,316, 3,317,322, 3,761,726, 4,269,927 and 3,367,778.
  • the core/shell molar ratio (by weight) in this case is preferably 1/30 to 5/1, more preferably 1/20 to 2/1, and most preferably 1/20 to 1/1.
  • the silver halide emulsions of the present invention it is preferred that core grains subjected to chemical sensitization are coated with shells, followed by further chemical sensitization to the surface of the grains, but in some embodiments of the present invention no chemical sensitization is conducted to the surface of the grains.
  • chemical sensitization to the surface of the grains increases the maximum density and exhibits good reversal characteristics.
  • polymers as described in JP-A-57-13641 may be allowed to coexist.
  • the above-described chemical sensitization can be conducted using active gelatin as described in T.H.
  • the chemical sensitization can also be carried out in the presence of a chemical sensitizing aiding agent.
  • a chemical sensitizing aiding agent compounds are used which are known to depress fogging and to enhance the sensitivity in the course of the chemical sensitization, such as azaindene, azapyridazine and azapyrimidine.
  • Examples of the chemical sensitizing assistants are described in U.S. Patents 2,131,038, 3,411,914 and 3,554,757, JP-A-58-126536, JP-A-62-253159 and G.F. Duffin, Photographic Emulsion Chemistry , pages 138 to 143 (Focal Press, 1966).
  • the interior of the grains can be subjected to reduction sensitization in the course of formation of precipitates as described in JP-B-58-1410 and Moisar et al., Journal of Photographic Science , vol. 25, pages 19 to 27 (1977).
  • the following reduction sensitization can also be utilized as the chemical sensitization.
  • the reduction sensitization can be carried out, for example, using hydrogen as described in U.S. Patents 3,891,446 and 3,984,249, using reducing agents as described in U.S. Patents 2,518,698, 2,743,182 and 2,743,183, or by treatment at a low pAg (for example, lower than 5) or a high pH (for example, higher than 8).
  • Oxidizing agents to silver mean compounds having the function of reacting with metallic silver to convert it to a silver ion.
  • compounds are effective which convert extremely fine silver grains produced as a by-product in the course of formation of the silver halide grains and chemical sensitization to silver ions.
  • the silver ions produced here may form either silver salts slightly soluble in water such as silver halides, silver sulfide and silver selenide, or silver salts easily soluble in water such as silver nitrate.
  • the oxidizing agents to silver may be inorganic compounds or organic compounds.
  • the inorganic oxidizing agents include ozone; hydrogen peroxide and adducts thereof (for example, NaBO2 ⁇ H2O2 ⁇ 3H2O, 2NaCO3 ⁇ 3H2O2, Na4P2O7 ⁇ 2H2O2 and 2Na2SO4 ⁇ H2O2 ⁇ 2H2O); oxygen acid salts such as peroxy acid salts (for example, K2S2O8, K2S2O6 and K2P2O8), peroxy complex compounds (for example, K2[Ti(O2)C2O4] ⁇ 3H2O and 4K2SO4 ⁇ Ti(O2)OH ⁇ SO4 ⁇ 2H2O), permanganates (for example, KMnO4) and chromates (for example, K2Cr2O7); halogen elements such as iodine and bromine; perhalogenates (for example, potassium periodate); salts of high valent metals (for example, potassium hexacyanoferrate (II)); and thio
  • ozone, hydrogen peroxide and the adducts thereof, the halogen elements and the thiosulfonates are preferably used as inorganic oxidizing agents, and the quinones as organic oxidizing agents.
  • the above-described reduction sensitization is used in combination with the oxidizing agent to silver, which is selected for use from the method of subjecting to the reduction sensitization after use of the oxidizing agent, the method of using the oxidizing agent after the reduction sensitization and the method of using both concurrently. These methods can be selectively used either in the grain forming stage or in the chemical sensitization stage.
  • gelatin is advantageously used, but other hydrophilic colloids can also be used.
  • gelatin treated with an acid or gelatin treated with an enzyme as described in Bull. Soc. Sci. Photo. Japan , vol. 16, page 30 (1966) may be used, besides gelatin treated with lime, and a hydrolyzed or enzymatically decomposed product of gelatin can also be used.
  • the emulsions used in the present invention are washed with water for desalination and dispersed with freshly prepared protective colloids.
  • the temperature during washing can be selected according to the purpose, but preferably selected to be 5 to 50°C.
  • the pH during washing can also be selected depending on the purpose, but preferably is selected to be 2 to 10, more preferably 3 to 8.
  • the pAg during washing can also be selected according to the purpose, but preferably is selected to be 5 to 10.
  • a method for washing can be selected for use from the water washing methods with noodle, the dialysis methods using semipermeable membranes, the centrifugal methods, the coagulation precipitation methods and the ion exchange methods.
  • the coagulation precipitation methods which can be selected include methods using nitrates, methods using organic solvents, methods using polymers of washing methods and methods using gelatin derivatives.
  • sensitization can be conducted using sensitizing dyes.
  • the sensitizing dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolarcyanine dyes, hemicyanine dyes, styryl dyes and hemioxanol dyes.
  • they include sensitizing dyes described in U.S. Patent 4,617,257, JP-A-59-180550, JP-A-60-140335, JP-A-61-160739, Research Disclosure , vol. 170, No. 17029, pages 12 and 13 (June, 1978) and Research Disclosure , vol. 176, No. 17643, page 23 (December, 1978).
  • sensitizing dyes may be used alone or in combination. Combinations of the sensitizing dyes are often used, particularly for supersensitization. Typical examples thereof are described in U.S. Patents 2,688,545, 2,977,229, 3,397,060, 3,522,052, 3,527,641, 3,617,293, 3,628,964, 3,666,480, 3,672,898, 3,679,428, 3,703,377, 3,769,301, 3,814,609, 3,837,862 and 4,026,707, British Patents 1344281 and 1507803, JP-B-43-4936, JP-B-53-12375, JP-A-52-110618 and JP-A-52-109925.
  • the emulsions may contain dyes having no color sensitization themselves or substances which do not substantially absorb visible light and exhibit supersensitization, in combination with the sensitizing dyes (as described, for example, in U.S. Patents 3,615,613, 3,615,641, 3,617,295, 3,635,721, 2,933,390 and 3,743,510 and JP-A-63-23145).
  • the sensitizing dyes may be added to the emulsions in any stage of emulsion preparation which has hitherto been known to be useful. Although the sensitizing dyes are usually added between the time when the chemical sensitization is completed and the time when the emulsion is coated, the sensitizing dyes may be added concurrently with addition of the chemical sensitizers to carry out the color sensitization and the chemical sensitization at the same time, as described in U.S. Patents 3,628,969 and 4,225,666. Further, the sensitizing dyes can also be added before the chemical sensitization as described in JP-A-58-113928, or can also be added before completion of precipitation formation of the silver halide grains to initiate the color sensitization.
  • each of these sensitizing dye compounds described above into portions to add each of the portions, namely to add a portion of the compound before the chemical sensitization and the remainder after the chemical sensitization, as described in U.S. Patent 4,225,666.
  • these compounds may be added at any time during formation of the silver halide grains.
  • the sensitizing dyes can be added in an amount of 10 ⁇ 8 to 10 ⁇ 2 mol per mol of silver halide.
  • the sensitizing dyes are more effectively added in an amount of 5 ⁇ 10 ⁇ 5 to 2 ⁇ 10 ⁇ 3 mol.
  • various antifogging agents and photographic stabilizers can be used to prevent a reduction in sensitivity and occurrence of fogging.
  • examples thereof include azoles and azaindenes described in Research Disclosure , vol. 176, No. 17643, pages 24 and 25 (December, 1978) and U.S. Patent 4,629,678; nitrogen-containing carboxylic acid and phosphoric acid compounds described in JP-A-59-168442; mercapto compounds and metal salts thereof described in JP-A-59-111636; and acetylene compounds described in JP-A-62-87957.
  • any support may be used as long as it is a smooth transparent support usually used in a photographic material.
  • the support can be formed of cellulose acetate, polystyrene, polyethylene terephthalate or polycarbonate, and preferably is provided with an undercoating layer. It is preferred that the support usually contain a dye or a pigment such as titanium oxide in small amounts to prevent light piping.
  • the thickness of the support is generally 50 to 350 ⁇ m, preferably 70 to 210 ⁇ m, and more preferably 80 to 150 ⁇ m.
  • a curl balancing layer or an oxygen shielding layer described in JP-A-56-78833 may be formed on the back side of the support as so desired.
  • An image receiving layer which can be used in the present invention generally contains a mordant in a hydrophilic colloid, and may have either a monolayer structure or a multilayer structure in which mordants different from one another in mordant ability are overcoated. This is described in JP-A-61-252551.
  • polymer mordants are preferably used as the mordants.
  • suitable polymer mordants include polymers containing secondary and tertiary amino groups, polymers having nitrogen-containing heterocyclic moieties or polymers containing quaternary cations. Their molecular weight is preferably 5,000 or more, and more preferably 10,000 or more.
  • the amount of the mordants applied is generally 0.5 to 10 g/m2, preferably 1.0 to 5.0 g/m2, and more preferably 2.0 to 4.0 g/m2.
  • hydrophilic colloids used in the image receiving layer examples include gelatin, polyvinyl alcohol, polyacrylamide and polyvinylpyrrolidone. Gelatin is particularly preferred among these.
  • the whiteness of the white reflective layer varies depending on the kind of pigment, the pigment-binder mixture ratio and the amount of the pigment coated. It is, however, desirable that the light reflectance is 70% or more. In general, the whiteness increases with an increase in the amount of the pigment coated. However, when the image forming dye diffuses through this layer, the diffusion of the dye is resisted by the pigment. It is therefore desirable to coat the pigment in suitable amounts.
  • titanium dioxide is present in an amount of 5 to 40 g/m2, preferably 10 to 25 g/m2, to give a white reflective layer having a light reflectance of 78 to 85% at a wavelength of 540 nm.
  • titanium dioxide is preferably used among these.
  • Many of the commercial products are surface treated with alumina, silica, zinc oxide or the like. In order to obtain a high reflectance, it is desirable that the titanium dioxide has at least 5% of the surface treating material.
  • Commercially available titanium dioxide includes, for example, products described in Research Disclosure , No. 15162, as well as Ti-Pure R931 (Du Pont Co., Ltd.).
  • a light shielding layer containing a light shielding agent and a hydrophilic binder is provided between the white reflective layer and a light-sensitive layer.
  • any material may be used as long as it can disperse carbon black.
  • Gelatin is preferably used.
  • Carbon black materials which can be used include carbon black produced by any method such as the channel method, the thermal method and the furnace method, for example, as described in Donnel Voet, Carbon Black , Marcel Dekker Inc. (1976).
  • the particle size of carbon black is preferably 90 to 1,800 ⁇ .
  • a black dye can be sued as a light sielding agent, and the amount thereof may be adjusted depending on the sensitivity of the photographic material to be shaded.
  • a light-sensitive layer comprising a silver halide emulsion layer combined with a dye image forming substance is formed on the above-described light shielding layer.
  • the constitution elements thereof are described below.
  • negative type Y components include components which are oxidized as a result of development and cleaved to release diffusible dyes.
  • the silver halide emulsions of the present invetnion described above are used.
  • the emulsion layer may comprise a plurality of emulsion layers different in sensitivity, and any type of auxiliary layer may be provided between the emulsion layer and the dye image forming substance.
  • the dye image density can be raised by providing a layer containing a nucleating development accelerator described in JP-A-60-173541 or a barrier layer described in JP-B-60-15267, or the sensitivity of the light-sensitive elements can be enhanced by providing a reflective layer.
  • the reflective layer is a layer containing a white pigment and a hydrophilic binder.
  • the white pigment is preferably titanium oxide and the hydrophilic binder is preferably gelatin.
  • the amount of titanium oxide applied is 0.1 to 8 g/m2, and preferably 0.2 to 4 g/m2. Examples of the reflective layers which are preferred embodiments of the present invention are described in JP-A-60-91354.
  • a combined unit of blue-sensitive emulsions, a combined unit of green-sensitive emulsions and a combined unit of red-sensitive emulsions are arranged in turn from the exposure side.
  • This separation layer must therefore be easily separated after processing.
  • materials which can be used for this purpose include ones described in JP-A-47-8237, JP-A-59-220727, JP-A-59-229555, JP-A-49-4653, U.S. Patents 3,220,835 and 4,359,518, JP-A-49-4334, JP-A-56-65133, JP-A-45-24075, U.S. Patents 3,227,550, 2,759,825, 4,401,746 and 4,366,227.
  • water-soluble (or alkali-soluble) cellulose derivatives such as hydroxyethyl cellulose, cellulose acetate-phthalate, plasticized methyl cellulose, ethyl cellulose, cellulose nitrate and carboxymethyl cellulose; various natural polymers such as alginic acid, pectin and gum arabic; various modified gelatins such as acetylated gelatin and phthalated gelatin; water-soluble synthetic polymers such as polyvinyl alcohol, polyacrylate, polymethyl methacrylate and polybutyl methacrylate.
  • the separation layer may be a single layer, or may be composed of a plurality of layers as described, for example, in JP-A-59-220727 and JP-A-60-60642.
  • any support may be used as long as it is a smooth transparent support usually used as a photographic material.
  • the support is formed of cellulose acetate, polystyrene, polyethylene terephthalate or polycarbonate, and preferably provided with an undercoating layer.
  • the support contains a dye in slight amounts to prevent light piping.
  • Patent 3,362,819 copolymers of acrylic acid and acrylates as disclosed in French Patent 2290699; and latex type acidic polymers as disclosed in U.S. Patent 4,139,383 and Research Disclosure , vol. 161, No. 16102 (September, 1977).
  • acidic polymers include copolymers of maleic anhydride and vinyl monomers such as ethylene, vinyl acetate and methyl vinyl ether; copolymers of n-butyl ester thereof, butyl acrylate and acrylic acid; and cellulose acetate hydrogen phthalate.
  • the above-described acidic polymers can be mixed with hydrophilic polymers.
  • Such polymers include polyacrylamide, polymethylpyrrolidone, polyvinyl alcohol (including partially saponified polyvinyl alcohol), carboxymethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose and polymethyl vinyl ether. Polyvinyl alcohol is preferred among these.
  • the above-described acidic polymers may be mixed with polymers other than the hydrophilic polymers, for example, cellulose acetate.
  • the amount of the acidic polymer coated is adjusted according to the amount of the alkali spread in the light sensitive elements.
  • the equivalent ratio of the acidic polymer per unit area to the alkali is preferably 0.9 to 2.0. If the amount of the acidic polymer is too small, the hue of a transfer dye changes or stains are generated on a white ground portion. If the amount is too large, troubles such as a change in hue and a decrease in light fastness are produced. More preferably, the equivalent ratio is 1.0 to 1.3. Too large or too small an amount of the hydrophilic polymer to be mixed deteriorates the quality of a photograph.
  • the weight ratio of the hydrophilic polymer to the acidic polymer is generally 0.1 to 10, and preferably 0.3 to 3.0.
  • additives may be incorporated in the layer having the neutralization function used in the present invention.
  • a hardening agent known in the art can be added to this layer to harden it, and a multivalent hydroxyl compound such as polyethylene glycol, polypropylene glycol or glycerol can be added to this layer to improve brittleness thereof.
  • an antioxidant, a fluorescent brightening agent, a development inhibitor or a precursor thereof can also be added as so desired.
  • Useful polymers for the timing layers used in combination with the neutralization layers include polymers reducing alkali permeability such as gelatin, polyvinyl alcohol, partially acetalized products of polyvinyl alcohol, cellulose acetate and partially hydrolyzed polyvinyl acetate; latex polymers elevating the activation energy of alkali permeance which are produced by copolymerizing a small amount of hydrophilic comonomers such as acrylic acid monomers; and polymers having lactone rings.
  • Particularly useful polymers used for the timing layers include cellulose acetate disclosed in JP-A-54-136328, U.S. Patents 4,267,262, 4,009,030 and 4,029,849; latex polymers produced by copolymerizing a small amount of hydrophilic comonomers such as acrylic acid which are disclosed in JP-A-54-128335, JP-A-56-69629, JP-A-57-6843, U.S. Patents 4,056,394, 4,061,496, 4,199,362, 4,250,243, 4,256,827 and 4,268,604; polymers having lactone rings disclosed in U.S.
  • Patent 4,229,516 and other polymers disclosed in JP-A-56-25735, JP-A-56-97346, JP-A-57-6842, European Patent (EPC) Publication Nos. 31957, 37724 and 48412, among these.
  • timing layers using these polymers can be used alone or in combination of at least two layers.
  • a supplementary neutralization layer may be provided as a layer having neutralization function as described in JP-A-63-168648 and JP-A-63-168649, whereby a change in transfer density with time after processing is decreased.
  • the cover sheet may have a backing layer, a protective layer, a capturing mordant layer, a filter dye layer, etc.
  • the backing layer is provided to control curl or to impart sliding property.
  • a filter dye may be added to this layer.
  • the capturing mordant layer can prevent the delay of image completing time and deterioration of sharpness by capturing a dye diffused on the alkali processing composition side.
  • a dye capturing layer is formed as the outermost layer of the cover sheet.
  • the dye capturing layer contains a polymer mordant in a hydrophilic colloid as is the case with the dye image receiving layer previously described, and is described in JP-A-1-198747 and JP-A-2-282253.
  • the cover sheet can contain a dye to adjust the sensitivity of the light sensitive layer.
  • the filter dye may be directly added to the support of the cover sheet, the layer having neutralization function, the backing layer, the protective layer, the capturing mordant layer or the like, or a separate layer containing the filter dye may be formed.
  • the light-sensitive sheets, the cover sheets or the alkali processing compositions may contain development accelerators described on pages 72 to 91, hardening agents described on pages 146 to 155, surface active agents described on pages 201 to 210, fluorine-containing compounds described on pages 210 to 222, thickeners described on pages 225 to 227, antistatic agents described on pages 227 to 230, polymer latices described on pages 230 to 239 and matte agents described on page 240 in JP-A-62-215272.
  • the alkali processing composition used in the present invention is uniformly spread in the light sensitive elements after exposure thereof, is provided on the back surface of the supports of the light-sensitive sheet and cover sheet or on the side opposite to a processing solution for the light sensitive layer to make a pair with the light shielding layer, thereby completely shielding the light sensitive layer from external light, and concurrently develops the light-sensitive layer with components contained therein.
  • the alkali processing composition contains an alkali, a thickener, a light shielding agent and a developing agent, and further contains a development accelerator for controlling development, a development inhibitor and an antioxidant for preventing the developing agent from deteriorating.
  • a light shielding agent is necessarily contained in the alkali processing composition.
  • the thickener is necessary to spread the processing solution uniformly and to maintain adhesion between the light-sensitive layer and the cover sheet.
  • polyvinyl alcohol, hydroxyethyl cellulose and alkaline metal salts of carboxymethyl cellulose are used, and preferably, hydroxyethyl cellulose and sodium carboxymethyl cellulose are used.
  • either a dye or a pigment, or a combination thereof can be used as long as it does not produce stains by diffusing to the dye image receiving layer.
  • Typical examples thereof include carbon black.
  • Such developing agents may be used alone or in combination, and may be used in the form of precursors. These developing agents may be added to appropriate layers of the light-sensitive elements, or to alkali processing solutions. Specific examples thereof include aminophenols and pyrazolidinone compounds. Of these, the pyrazolidinone compounds are particularly preferred because stains are less produced.
  • Examples of such compounds include 1-phenyl-3-pyrazolidinone, 1-p-tolyl-4,4-dihydroxymethyl-3-pyrazolidinone, 1-(3'-methyl-phenyl)-4-methyl-4-hydroxymethyl-3-pyrazolidinone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidinone and 1-p-tolyl-4-methyl-4-hydroxymethyl-3-pyrazolidinone.
  • Emulsion A-1 (Octahedral Internal Latent Image Type Direct Positive Emulsion for Comparison)
  • octahedral silver halide grains (hereinafter referred to as core grains) which were uniform in grain size and had a mean grain size (a sphere corresponding size) of about 0.8 ⁇ m.
  • the resulting emulsion was washed with water by the flocculation process, and gelatin was added thereto to obtain octahedral silver bromide crystals uniform in size and having a mean grain size (a sphere corresponding size) of about 1.4 ⁇ m (hereinafter referred to as internal latent image type core/shell grains).
  • Emulsion B (Octahedral Internal Latent Image Type Direct Positive Emulsion)
  • a 0.4 M aqueous solution of silver nitrate (300 ml) was added to 1000 ml of an 8wt% aqueous solution of gelatin containing 13 g of potassium bromide and 0.05 g of 1,8-dihydroxy-3,6-dithioctane for 23 minutes, the temperature was maintained at 75°C and the rate of addition of a 0.4 M aqueous solution of potassium bromide was adjusted so as to give a pBr of 1.30 by the controlled double jet process.
  • octahedral silver halide grains (hereinafter referred to as core grains) which were uniform in grain size and had a mean grain size (a sphere corresponding size) of about 0.45 ⁇ m.
  • the resulting emulsion was washed with water by the flocculation process, and gelatin was added thereto to obtain octahedral silver bromide crystals uniform in size and having a mean grain size (a sphere corresponding size) of about 0.8 ⁇ m (hereinafter referred to as internal latent image type core/shell grains).
  • Emulsions A-2 to A-8 Comparison
  • A-9 to A-11 Invention
  • Emulsions A-2 to A-11 were prepared in the same manner as with Emulsion A-1, with the exception that the metal complexes shown in Table 1 were added in amounts (per mol of silver nitrate) shown in Table 1 for the respective emulsions during the formation of the shells.
  • a cover sheet was prepared in the following manner.
  • a transparent polyethylene terephthalate support having a gelatin undercoat and containing a light piping preventing dye was coated with the following layers:
  • Table 4 reveals that the samples of the present invention are high in both midpoint sensitivity and low-density sensitivity and made contrasty in the low-density portions.
  • ammonia was neutralized, and then a 1 M aqueous solution of silver nitrate and a 1 M aqueous solution of potassium bromide were added at an accelerated flow rate (the flow rate at the end is 4 times that at the start) while maintaining the pBr to 2.5 by the double jet process.
  • the aqueous solution of silver nitrate was used in an amount of 600 ml.
  • a 2 M aqueous solution of silver nitrate and a 2.5 M aqueous solution of potassium bromide were added to the core grains thus subjected to chemical sensitization at an accelerated flow rate (the flow rate at the end is 5 times that at the start) by the double jet process, as with the preparation of the core grains.
  • the amount of the aqueous solution of silver nitrate was used in an amount of 810 ml.
  • Emulsions C-2 to C-11 were prepared in the same manner as Emulsion C-1 with the exception that the metal complexes shown in Table 5 were added in amounts (per mol of silver nitrate) shown in Table 5 for the respective emulsions when the shells were formed.
  • a light-sensitive element for comparison having the structure shown in Table 6 (sample 201) was prepared using Emulsion C-1.

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EP19930109036 1992-06-05 1993-06-04 Procédé de formation des images utilisant une émulsion positive-directe à l'halogénure d'argent du type à image latente interne Expired - Lifetime EP0573066B1 (fr)

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JP4221537A JP2913529B2 (ja) 1992-06-05 1992-08-20 内部潜像型直接ポジハロゲン化銀乳剤及びそれを用いたカラー拡散転写写真フィルムユニット

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EP0617323A1 (fr) * 1993-03-25 1994-09-28 Eastman Kodak Company Eléments photographiques positifs directs à haute sensibilité utilisant des émulsions coeur/enveloppe
US5759758A (en) * 1995-04-10 1998-06-02 Fuji Photo Film Co., Ltd. Silver halide photographic material
EP1079270A1 (fr) * 1999-08-20 2001-02-28 Fuji Photo Film Co., Ltd. Emulsion à l'halogénure d'argent tabulaire directement positive formant image latente interne,et matériau couleur diffusion transfert sensible à la lumière utilisant celle-ci

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EP0336689A1 (fr) * 1988-04-08 1989-10-11 EASTMAN KODAK COMPANY (a New Jersey corporation) Emulsions à l'halogénure d'argent dopées à l'intérieur
JPH03252649A (ja) * 1990-03-02 1991-11-11 Fuji Photo Film Co Ltd ハロゲン化銀写真用乳剤
JPH0456846A (ja) * 1990-06-25 1992-02-24 Fuji Photo Film Co Ltd ハロゲン化銀写真感光材料
US5112732A (en) * 1989-03-31 1992-05-12 Fuji Photo Film Co., Ltd. Direct positive silver halide photographic materials
EP0488737A1 (fr) * 1990-11-30 1992-06-03 Konica Corporation Procédé de formation d'image

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JPS613137A (ja) * 1984-06-15 1986-01-09 Fuji Photo Film Co Ltd 内部潜像型コア／シエル直接ポジハロゲン化銀乳剤及びその製造法
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JPH03288145A (ja) * 1990-04-04 1991-12-18 Fuji Photo Film Co Ltd ハロゲン化銀写真感光材料
JPH0659376A (ja) * 1992-08-10 1994-03-04 Fuji Photo Film Co Ltd 内部潜像型直接ポジハロゲン化銀乳剤及びそれを用いたカラー拡散転写感光材料

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US5112732A (en) * 1989-03-31 1992-05-12 Fuji Photo Film Co., Ltd. Direct positive silver halide photographic materials
JPH03252649A (ja) * 1990-03-02 1991-11-11 Fuji Photo Film Co Ltd ハロゲン化銀写真用乳剤
JPH0456846A (ja) * 1990-06-25 1992-02-24 Fuji Photo Film Co Ltd ハロゲン化銀写真感光材料
EP0488737A1 (fr) * 1990-11-30 1992-06-03 Konica Corporation Procédé de formation d'image

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0617323A1 (fr) * 1993-03-25 1994-09-28 Eastman Kodak Company Eléments photographiques positifs directs à haute sensibilité utilisant des émulsions coeur/enveloppe
US5532119A (en) * 1993-03-25 1996-07-02 Eastman Kodak Company High-speed direct-positive photographic elements utilizing core-shell emulsions
US5759758A (en) * 1995-04-10 1998-06-02 Fuji Photo Film Co., Ltd. Silver halide photographic material
EP1079270A1 (fr) * 1999-08-20 2001-02-28 Fuji Photo Film Co., Ltd. Emulsion à l'halogénure d'argent tabulaire directement positive formant image latente interne,et matériau couleur diffusion transfert sensible à la lumière utilisant celle-ci

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JP2913529B2 (ja) 1999-06-28

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