EP0256820B1 - Matériau sensible à la lumière développable par la chaleur - Google Patents

Matériau sensible à la lumière développable par la chaleur Download PDF

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Publication number
EP0256820B1
EP0256820B1 EP19870307044 EP87307044A EP0256820B1 EP 0256820 B1 EP0256820 B1 EP 0256820B1 EP 19870307044 EP19870307044 EP 19870307044 EP 87307044 A EP87307044 A EP 87307044A EP 0256820 B1 EP0256820 B1 EP 0256820B1
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Prior art keywords
group
light
sensitive
thermal developing
sensitive material
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German (de)
English (en)
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EP0256820A2 (fr
EP0256820A3 (en
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Junichi Kohno
Tawara Komamura
Ken Okauchi
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Konica Minolta Inc
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Konica Minolta Inc
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Priority claimed from JP18085687A external-priority patent/JPS63153539A/ja
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Publication of EP0256820A3 publication Critical patent/EP0256820A3/en
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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

Definitions

  • the inventor has found that not only the fogging in the thermal development but also the preservability could be simultaneously improved by using a thermal developing light-sensitive material containing a restrainer having a ballast group. However, the degree of the improvement was still insufficient. The inventor also found that if dye-sensitized silver halide emulsions are used, the fogging increases and the sensitivity is reduced during the preservation of the thermal developing light-sensitive materials under a high temperature and a high humidity.
  • thermo developing light-sensitive material containing a novel fogging restrainer.
  • the preferred examples of the compound of formula (1) are those in which the group X 1 represents a residual group of a photographic restrainer having one of the general formulae (3) to (18) set out below.
  • R 1 and R 2 independently represent any of a hydrogen atom, or alkyl group or aryl group each having 1 to 7 carbon atoms, M represents a hydrogen atom, alkali metal atom, ammonium group or organic amine residue.
  • R 1 represents a hydrogen atom, or alkyl group or aryl group each having 1 to 7 carbon atoms, M is same as that in the general formula (3).
  • R 1 represents any of a hydrogen atom, alkyl group having 1 - 7 carbon atoms, aryl group having 1 - 7 carbon atoms or (n is 1 or 2)
  • R 2 and R 3 independently represent a hydrogen atom, or alkyl group having 1 - 7 carbon atoms, or aryl group or nitro group having 1 - 7 carbon atoms, R 2 and R
  • the compounds represented by the above general formula (1) can be synthesized by a conventional method. For example, they can be synthesized with reference to methods disclosed in "Chemische Berichte”, 86, pp. 314 (1953); “Canadian Journal of Chemistry", 37, pp. 101 (1959); “Journal of Chemical Society", 49, pp. 1748 (1927); British Patent No. 1,275,701; U.S. Patent No. 3,266,897; Japanese Patent O.P.I. Publications No. 89034/ 1975, No. 28426/1978, No. 21067/1980, No. 111846/1981; and the like.
  • the ballast groups used in the invention represented by B in the general formula (2) are organic ballast groups individually having molecular size and configuration sufficient enough to reduce or eliminate the diffusibility of the compound used in the invention represented by the general formula (2) or the silver salt thereof (or silver complex) during the thermal developing process.
  • the typical examples of such an organic ballast group include the following; a long-chained alkyl group bonded to the residue of photographic restrainer represented by X 2 , directly, or via a bivalent bonding group represented by L 2 ; a benzene or naphthalene aromatic group directly or indirectly fused into a carbon-containing ring or heterocycle of the residue of photographic restrainer.
  • the compound represented by the general formula (2) may be contained in any of the structural layers of the thermal developing light-sensitive material, and may be simultaneously contained in more than two layers. However, the compound should be favorably contained in the light-sensitive layers containing light-sensitive silver halide.
  • the timing of addition is arbitrarily selected from the period, after the formation of silver halide grains used for the above-mentioned light-sensitive layers, and before the emulsions containing the light-sensitive silver halide grains are applied by coating.
  • the addition method is arbitrarily selected from the conventional methods.
  • the thermal developing light-sensitive material of the invention may have, in addition to the above-mentioned thermal developing light-sensitive layers, the non-light-sensitive layers, such as a subbing layer, intermediate layers, a protective layer, a filter layer, a backing layer and a separation layer, and others.
  • the coating methods similar to those used for preparing, by coating, a conventional silver halide light-sensitive material cna be used.
  • the thermal developing light-sensitive material of the invention contains light-sensitive silver halides.
  • the light-sensitive silver halides used in the invention include silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloro-iodide, silver iodo-bromide and silver chloro-iodo-bromide.
  • the above light-sensitive silver halides can be prepared by an optional method known in the photographic art, such as a single-jet precipitation method and a controlled double-jet precipitation method.
  • Light-sensitive silver halide emulsions containing light-sensitive silver halides prepared in accordance with a conventional method to prepare silver halide gelatin emulsions can be arbitrarily used.
  • Mono-dispersion silver halide grains are preferably used. They may be of core/shell type silver halide grains, and may be giant grains or fine grains. However, a preferred mean grain size is 0.001 to 1.5 am, or more specifically, 0.01 to 0.5 I.Lm.
  • the silver salts of imino group inculde silver benzotriazole silver.
  • benzotriazole silver may be substituted or unsubstituted.
  • substituted benzotriazole silver include alkyl-substituted benzotriazole silver (preferably substituted by an alkyl group having less than 22 carbon atoms, preferably less than 4 carbon atoms, such as methylbenzotriazole silver, ethylbenzotriazole silver, n-octylbenztriazole silver), alkylamidebenzotriazole silver (preferably substituted by an alkylamide group having less than 22 carbon atoms, such as acetamidebenzotriazole silver, propyonamidebenzotriazole silver, iso-butylamidebenzotriazole silver, laurylamidebenzotriazole silver), alkylsulfamoylbenzotriazole silver (preferably substituted by an alkylsulfamoyl group having less than 22 carbon atoms, such
  • a 1 and A 2 individually represent a hydrogen atom, hydroxyl group or amino group, and Dye is identical to Dye in the general formula (2').
  • the typical examples of this compound are disclosed in Japanese Patent O.P.I. Publication No. 124329/1984.
  • Cp 1 represents an organic group (so called a coupler residue) capable of reacting with an oxidized product of a reducing agent, to emit a dye
  • J represents a bivalent bonding group
  • a bond between Cp 1 and J is cleaved by the reaction with the oxidized produce of reducing agent
  • n represents 0 or 1
  • Dye is identical to than in the general formula (2').
  • Cp 1 is preferably substituted with any of various types of ballast group in order to make the coupling dye-emitting type compounds nondiffusible.
  • Cp 2 and F respectively have the same meaning as in the general formula (5');
  • Y represents an alkylene group, arylene group or aralkylene group; 1 represents 0 or 1; Z represents a bivalent organic group; and
  • L represents an ethylenic unsaturated group or a group having an ethylenic unsaturated group.
  • Each of these groups may be substituted with a hydroxyl group, carboxyl group, sulfonyl group, alkoxy group, cyano group, nitro group, alkyl group, aryl group, aryloxy group, acyloxy group, acyl group, sulfamoyl group, carbamoyl group, imide group or halogen atom.
  • substituents are selected in compliance with a requirement for Cp 1 and Cp 2 .
  • one of the substituents in Cp 1 is preferably a ballast group, and substituents in Cp 2 should be preferably determined so as to make the molecular weight of Cp 2 less than 700, preferably, less than 500, less, in order to enhance the diffusibility of the dye to be formed.
  • W 2 represents a group of atoms required for forming a benzene ring (possibly having substituents thereon); and R 11 , r, E, Dye are same as those in the general formula (17').
  • R 11 , r, E, Dye are same as those in the general formula (17').
  • the typical examples of such a compound is disclosed in Japanese Patent O.P.I. Publications No. 124327/1984 and No. 152440/1984. For example, the following compounds are available.
  • W 2 , R11 and Dye are identical to those in the general formula (18').
  • the typical examples of these compounds are disclosed in Japanese Patent O.P.I. Publications No. 154445/1984 and others, wherein the following compounds are available.
  • Such difusible dye residue has molar weight of less than 800, or more favorably, less than 600, to ensure the diffusibility of the dye, and is available as the residues of azo dye, azomethine dye, anthraquinone dye, naphthoquinone dye, styryl dye, nitro dye,quinoline dye, carbonyl dye, phthalocyanine dye.
  • a dye residue may be in the form, where during the thermal developing or transferring it is temporarily rendered shortwave sensitive.
  • these dye residues are the chelating dye residues, as disclosed in Japanese Patent O.P.I. Publications No. 48765/1984 and No. 124337/1984, since they can enhance the light-fastness of image.
  • a method of incorporating the dye-supplying material into the photographic structural layers of a thermal developing material of the invention is arbitrarily determined.
  • the examples of such a method to add the similar material into an emulsion to form the above layers are as follows: a method, wherein a compound is firstly dissolved in a low-boiling solvent (such as methanol, ethanol or ethyl acetate) or high-boiling solvent (such as dibutyl phthalate, dioctyl phthalate or tricresyl phosphate), then, subjected to an ultrasonic dispersion; a method, wherein a dye-supplying material is dissolved in an aqueous alkali solution (for example a 10% aqueous sodium hydroxide solution), and then neutralized by a mineral acid (for example hydrochloric acid or nitric acid); a method, wherein a compound is dispersed together with an aqueous solution of suitable polymer (for example, polyvinyl but
  • the dye-supplying materials used for the thermal developing light-sensitive materials of the invention are dye-supplying materials, as disclosed in Japanese Patent O.P.I. Publications No. 186744/1982, No. 79247/1983, No. 149046/1983, No. 149047/1983, No. 124339/1984, No. 181345/1984, No. 2950/1985, emitting or forming a diffisuble dye by coupling with the oxidized product of reducing agent, the following are useful: p-phenylenediamine and p-aminophenol developing agents, phosphoroamidephenol and sulfonamidephenol developing agents, sulfonamideaniline developing agents, hydrazone color developing agents, as disclosed in U.S. Patents No.
  • the dye-supplying materials used in the invention are, as disclosed in Japanese Patent O.P.I. Publications No. 179840/1982, No. 58543/1983, No. 152440/1984, No. 154445/1984 and the like, the compounds emitting dye when oxidized, or the compounds losing the dye-emitting capacity when oxidized, or the compounds emitting dye when reduced (or, merely a silver image is formed), the developing agents, described below, can be used.
  • phenols such as p-phenylphenol, p-methoxyphenol, 2,6-di-tert-butyl-p-crezol, N-methyl-p-aminophenol
  • sulfonamidephenols such as 4-benzenesulfonamidephenol, 2-benzenesulfonamidephenol, 2,6-dichloro-4-benzenesulfonamidephenol and 2,6-dibromo-4-(p-toluenesulfonamide) phenol
  • polyhydroxybenzenes such as hydroquinone, tert-butylhydroquinone, 2,6-dimethylhydroquinone, chlorohydroquinone, carboxyhydroquinone, cathecol and 3-car- boxycathecol
  • naphthols such as a-naphthol, ,8-naphthol, 4-aminonaphthol, 4-methoxynapht
  • Such binders independently have gelatin and polypyrolidone polymer.
  • polyvinyl pyrolidone polymer may be polyvinyl pyrolidone which is homopolymer of vinyl pyrolidone, or may be copolymer (possibly, graft copolymer) of vinyl pyrolidone and at least one of other copolymerizable monomers. Such a polymer can be used regardless of a degree of polymerization thereof.
  • Such polyvinyl pyrolidone may be substituted polyvinyl pyrolidone.
  • the preferred polyvinyl pyrolidone has a molecular weight of 1,000 - 400,000.
  • copolymerizable with vinyl pyrolidone are as follows: acrylic acid and methacrylic acid, and alkyl ester thereof such as (metha) acrylic esters; vinyl monomers, such as vinyl alcohol, vinyl acetate, vinylimidazole, (metha)acrylamide, vinylcarbinol, vinyl alkylether.
  • vinyl monomers such as vinyl alcohol, vinyl acetate, vinylimidazole, (metha)acrylamide, vinylcarbinol, vinyl alkylether.
  • the preferred example of such a copolymer has a molecular weight of 5,000 - 400,000.
  • the preferred amount of binder to be used is at a ratio of 0.1 - 10 g, preferably, 0.25 - 4 g per one g dye-supplying material.
  • useful supports used for the thermal developing light-sensitive material of the invention are as follows; synthetic plastic films, such as a polyethylene film, cellulose acetate film, polyethylene teerphthalate film and polyvinyl chloride film; paper supports, such as photographic paper, printing paper, baryta paper, resin-coated paper; supports obtained by applying and setting electron beam- setting resin composite upon any of the above supports.
  • n 1 or 2.
  • R represents a group, having 3 to 8, or favorably, 4 to 6 carbon atoms, such as an alkyl group (for example, i-propyl group, n-butyl group, t-butyl group, n-amyl group, i-amyl group, n-hexyl group, n-octyl group or to-octyl group), alkenyl group (for example, allyl group, crotyl group or i-crotyp group), alkoxy group (for example, n-butoxy group, n-amyloxy group, i-amyloxy group or n-hexyloxy group) or alkenyloxy group (for example, allyloxy group, crotyloxy group or i-crotyloxy group).
  • an alkyl group for example, i-propyl group, n-butyl group, t-butyl group, n-amyl
  • the water-insoluble solid heal melting solvents are compounds which are solid at a normal temperature but turn liquid at a higher temperature (higher than 60 C, preferably higher than 100°C, and in particular, higher than 130°C, but less than 250°C) and they also have an inorganic-organic ratio ("Organic Schematics", by Yoshio Kohda, Sanyo Shuppan Co., Ltd., 1984) of 0.5 - 3.0, preferably, 0.7 - 2.5, and in particular, 1.0 - 2.0, as well as the water-solubility, at a normal temperature.
  • the examples further include the following; benzophenone derivatives disclosed in Japanese Patent O.P.I. Publication No. 115540/1974; phenol derivatives disclosed in Japanese Patent O.P.I. Publications No. 24829/1978 and No. 60223/1978; carboxylic acids disclosed in Japanese Patent O.P.I. Publication No. 118640/1983; polyvalent alcohols disclosed in Japanese Patent O.P.I. Publication No. 198038/1983; sul- famoylamide compounds disclosed in Japanese Patent O.P.I. Publication No. 84236/1984; and others.
  • useful anti-fogging agents are as follows: higher aliphatic compounds (such as behenic acid or stearic acid) and the like) disclosed in U.S. Patent No. 3,645,739; mercuric salts disclosed in Japanese Patent Examined Publication No. 11113/1982; N-halogen compounds (such as N-halogenoacetamide or N-halogenoimide succinate) disclosed in Japanese Patent O.P.I. Publication No. 47419/1976; mercapto compound-emitting compounds disclosed in U.S. Patent No. 3,700,457 and Japanese Patent O.P.I. Publication No.
  • the nitrogen-containing organic bases called activator-stabilizers or activator stabilizer precursors, for example a-sulfonyl acetate of 2-aminothiazoline, or trichloro acetate and acylhydrozine compound.
  • the similar light-sensitive material may also have various additives and coating aids such as an antihalation dye, fluorescent whitening agent, hardeners, anti-static agent, plasticizer and spreading agent.
  • various additives and coating aids such as an antihalation dye, fluorescent whitening agent, hardeners, anti-static agent, plasticizer and spreading agent.
  • the development may be exercised in the presence of only a small amount of water, or to develop the light-sensitive material of the invention, a small amount of water may be sprayed or applied onto the material for supplying water thereto, before the material is heated.
  • the material may be developed with a hot steam, or a blast containing moisture.
  • a compound having crystalization water such as sodium phosphate.12H 2 0 or ammonium alum.24H 2 0 may be contained in the thermal developing light-sensitive material.
  • the similar light-sensitive material may also have various additives and coating aids such as an antihalation dye, fluorescent whitening agent, hardeners, anti-static agent, palsticizer and spreading agent.
  • various additives and coating aids such as an antihalation dye, fluorescent whitening agent, hardeners, anti-static agent, palsticizer and spreading agent.
  • the thermal developing light-sensitive material of the invention may contain colloidal silica in the heat developing light-sensitive layer and/or non-light-sensitive layers (such as a subbing layer, intermediate layers and protective layer).
  • ultraviolet absorbing couplers such as a-naphthol cyan-dye forming couplers
  • ultraviolet absorbing polymers such as those disclosed in Japanese Patent O.P.I. Publications No. 111942/1983, No. 178351/1983, No. 181041/1983, No. 19945/1984 and No. 23344/1984.
  • aldehyde or aziridine hardeners such as those disclosed in PB Report No. 19,921, U.S. Patents No. 2,950,197, No. 2,964,404, No. 2,983,611 and No. 3,271,175, Japanese Patent Examined Publication No. 40898/1971, Japanese Patent O.P.I. Publication No. 91315/1974; issoxazoles such as those disclosed in U.S. Patent No. 331,609; epoxy hardeners such as those disclosed in U.S. Patent No. 3,047,394, West German Patent No. 1,085,663, British Patent No. 1,033,518, and Japanese Patent Examined Publication No.
  • High polymer hardeners can be added into the thermal developing light-sensitive layer and/or non-light-sensitive layers (such as the subbing layer, intermediate layers and protective layer) of the thermal developing light-sensitive material of the invention.
  • useful high polymer hardeners are as follows: as disclosed in U.S. Patent No. 3,396,029 and others, polymers having an aldehyde group (for example, copolymer of acroleine) polymers having dichlorotriazine group, as disclosed in U.S. Patent No. 3,362,827, and Research Disclosure No. 17333 (1978); polymers having an epoxy group, as disclosed in U.S. Patent No.
  • useful polymer latex include polymethyl acrylate, polyethyl acrylate, poly-n-butyl acrylate, copolymer of ethylacrylate and acrylic acid, copolymer of vinylidene chloride and butyl acrylate, copolymer of butyl acrylate and acrylic acid, copolymer of vinyl acetate and butyl acrylate, copolymer of vinyl acetate and ethyl acrylate, copolymer of ethyl acrylate and 2-acrylamide.
  • the thermal developing light-sensitive material of the invention may contain various surface active agents in the heat developing light-sensitive layer and/or non-light-sensitive layers (such as a subbing layre, intermediate layers and protective layer).
  • the surface active agents used for the invention are whichever of anionic, amphoteric or nonionic surface active agents.
  • anionic surface active agent having any of acid groups such as carboxy group, sulfo group, phospho group, sulfate and phosphate
  • the thermal developing light-sensitive material of the invention may contain vinyl polymer, having a carboxyl group or sulfo group and disclosed in Japanese Patent O.P.I. Publication No. 104338/1976, in the heat developing light-sensitive layer and/or non-light-sensitive layers (such as a subbing layer, intermediate layers, and protective layer).
  • the amount of such vinyl polymer to be used is, in terms of dry weight ratio, 0.05 - 2.0 against amount of binder in the layer where such vinyl polymer is added.
  • the thermal developing light-sensitive material of the invention should be provided with a protective layer.
  • the matting agent should be added into the protective layer of the invention at a rate of 10 mg - 2.0 g, or more favorably, 20 mg - 1.0 g per m 2 layer.
  • the preferred average grain size of the matting agent is 0.5 - 10 am, or more specifically, 1.0 - 6 ⁇ rn.
  • More than two types of the above matting agents may be combinedly used.
  • the lubricants used in the protective layer of the invention include solid paraffin, oil, surface active agent, natural wax and synthesized wax, and more specifically, those preferred are disclosed in the following: French Patent No. 2,180,465, British Patents No. 955,061, No. 1,143,118, No. 1,270,578, No. 1,320,564 and No. 1,320,757, Japanese Patent O.P.I. Publications No. 5017/1974, No. 141623/1976, No. 159221/1979 and No. 81841/1981, Research Disclosure No. 13969 issue, U.S. Patents No. 1,263,722, No. 2,588,765, No. 2,739,891, No. 3,018,178, No. 3,042,522, No.
  • the protective layer of the invention may contain oil-in water dispersion having oil drops of emulsified and dispersed water-insoluble compound, such as high-boiling organic solvent.
  • photographic additives may be added into such oil-in-water dispersion, in compliance with a requirement.
  • high boiling organic solvent are as follows: as disclosed in U.S. Patents No. 2,322,027, No. 2,533,514 and No. 2,882,157, Japanese Patent Examined Publication No. 23233/1971, British Patents No. 958,441 and No. 1,222,753, U.S. Patents No. 2,353,262, No. 3,676,142 and No.
  • the useful binders used in the protective layer of the invention are synthetic or natural high molecular substances, such as polyvinyl butyral, vinyl polyacetate, ethylcellulose, polymethyl methacrylate, cel- luloseacetatebutylate, polyvinyl alcohol, polyvinyl pyrolidone, polyethylxazoline, polyacrylamide, gelatin and phthalated gelatin. These may be singly used, or more than two of them may be combinedly used.
  • Gelatin may be lime-treated, or acid-treated gelatin, or ion exchange-treated gelatin, or may be ossein gelatin, pig-skin gelatin, hyde-gelatin, or any of the modified gelatins, such as the estrificated or phenylcarbamoyl gelatin derived from the any of the above natural gelatins.
  • the preferred film thickness of the protective layer of the invention is 0.05 - 5 am, or more specifically, 0.1 - 1.0 am.
  • the protective layer may comprise single layer or more than two layers.
  • Still other examples of useful dye-receiving material include, as disclosed in Japanese Patent O.P.I. Publications No. 207250/1982 and the like, those comprising heat-resistant organic high-molecular material whose glass transition temperature is higher than 40 ° C and lower than 250 C.
  • a support also serving as an image receiving layer may be formed.
  • the support may be composed of single layer, or of a plurality of layers.
  • any of the above-mentioned various polymers also serving as a mordant for a dye image may be used as an image-receiving layer.
  • Such an image-receiving layer may be either an independent image-receiving component formed on an appropriate support and having an image-receiving layer, or a single layer which is a part of the thermal developing color light-sensitive material.
  • the light-sensitive material may have an opaque layer (reflective layer), which is used to reflect radiant ray such as visible ray strong enough for enabling the visual observation of a dye image in an image-receiving layer.
  • the opaque layer (reflective layer) may contain various chemical agents, such as titanium oxide, to provide enough reflection.
  • the image-receiving layer in the image-receiving member may be the similar layer which is peeled off from the thermal developing light-sensitive layer. Otherwise, after the thermal developing color light-sensitive material is subjected to the imagewise exposure, the image-receiving layer placed on the thermal developing light-sensitive layer can be uniformly developed by heat. Additionally, after the thermal developing color light-sensitive material is subjected to the imagewise exposing as well as uniform thermal developing, the image-receiving layer placed on the material is heated with a temperature lower than the developing temperature, so as to transfer the dye image emitted from or formed by the dye supplying material onto the light-sensitive material.
  • thermal developing light-sensitive material of the present invention may be processed by the use of an automatic processing apparatus as shown in Fig. 1.
  • the compound of the invention is also effective for the thermal light-sensitive material (dry silver) with which and image is formed only on silver.
  • the image-receiving member (1) was prepared by applying and drying ethylene chloride solution containing polycarbonate (L - 1250; molecular weight, 25000; manufactured by Teijin Kasei Co., Ltd. onto a photographic baryta paper so that the rate of coated polycarbonate became 15.0 g/m 2.
  • the reflective green densities were measured by a photographic densitometer (PDA - 65, manufactured by Konishiroku Photo Industry Co., Ltd.).
  • the minimum densities (fogging), maximum densities, and the desensitization ratios due to standing are listed in Table - 1, wherein the densitization ratio was determined by the following expression.
  • the thermal developing light-sensitive material of the invention when compared to each of the comparison thermal developing light-sensitive materials not having the compound of the invention or having only one of the compound of the invention represented by general formula (1) and the compound of the invention represented by general formula (2), the thermal developing light-sensitive material of the invention features low fogging inspite of its high maximum density, and shows smaller variation in both the minimum density (fogging) and the maximum density even stored under a high temperature and a high humidity, and that the light-sensitive material of the invention also features a low desensitization ratio. In essence, it is apparent that the thermal developing light-sensitive material of the invention has the excellent shelf life.
  • thermal developing light-sensitive materials (15) through (21) were prepared in a manner identical to that of the thermal developing light-sensitive material, except that the compounds of the invention represented by the general formula (1) or (2) were correspondingly used in compliance with the combinations listed in Table - 2.
  • Each sample of the above thermal developing light-sensitive materials (14) through (21) was stored under a high temperature and a high humidity identical to those of Example 1, then exposed and subjected to the thermal developing using the image-receiving member (1).
  • the reflective green density of the negative magenta image formed on the image receiving member was measured by a photographic densitometer (PDA - 65, manufactured by Konishiroku Photo Industry Co., Ltd.).
  • the results of minimum densities (fogging), maximum densities, and the desensitization ratios are listed in Table - 2.
  • anti-color stain agent (SC - 1) was dissolved in 80 ml of ethyl acetate, which was blended with 254 mî of aqueous solution containing 50 mî of 5 weight% Alkanol XC and 12.0 g gelatin, whereby the mixture was emulsified by using an ultrasonic homogenizer, then ethyl acetate was removed by distillation, so as to prepare anti-color stain agent dispersion (1).
  • the thermal developing light-sensitive materials (22) through (31) independently having the multi-layer constitution listed in Table - 3 were prepared, when the compounds of the invention respectively represented by the general formulae (1) and (2) were added, in compliance with the combination listed in Table - 4, into the corresponding materials.
  • thermal developing light-sensitive materials (22) through (31) were exposed with the 2000 CMS exposure through optical step-wedge, whereby each material was combined with the image-receiving member (1) then subjected to the thermal developing with a thermal developing machine (Developer module, Model 277, manufactured by 3M) for one minute at 150°C, then immediately the thermal developing light-sensitive material was removed from the image-receiving member.
  • a thermal developing machine Developer module, Model 277, manufactured by 3M
  • the thermal developing light-sensitive material was removed from the image-receiving member.
  • the blue-, green- and red-reflective densities on the polycarbonate surface of image-receiving member were measured by a photographic densitometer (PDA - 65, manufactured by Konishiroku Photo Industry, Co., Ltd.). The results are listed in Table - 5.
  • the thermal developing light-sensitive material of the invention features limited fluctuation in the minimum density (fogging) as well as the maximum density even when stored under a high temperature and a high humidity. In essence, it is apparent that the thermal developing light-sensitive material of the invention has the excellent shelf life.
  • example dye-supplying material 30.0 g was dissolved in a mixture of 30.0 g dimethyluramide 90.0 ml ethyl acetate, which was blended with 800 ml of aqueous solution containing 100 ml of 5 weight% Alkanol XC (manufactured by DuPont) and 36.0 g gelatin, whereby the mixture was emulsified by using an ultrasonic homogenizer, then ethyl acetate was removed by distillation, and water was added, so as to prepare 900 mî of yellow dye-supplying-material dispersion (2).
  • magenta dye-supplying-material dispersion (2) and cyan dye-supplying material dispersion (2) were correspondingly prepared.
  • the multi-layered thermal developing light-sensitive materials (32) through (41) whose layer constitutions being listed in Table - 6 were prepared. Additionally, the compounds listed in Table - 7 were added into the corresponding light-sensitive materials.
  • These layers independently contain small amounts of surface active agent as well as gelatin hardener in addition to the above components.
  • thermal developing light-sensitive materials (32) through (41) were exposed with the 4000 CMS exposure through optical step-wedge, whereby each material was combined with the previously mentioned image-receiving member (2) then subjected to the thermal developing with a thermal developing machine for one minute at 140°C, then immediately the thermal developing light-sensitive material was removed from the image-receiving member.
  • the reflective density of a transfer dye image formed on an image-receiving member was measured by a photographic densitometer (PDA - 65, manufactured by Konishiroku Photo Industry Co., Ltd.). The results are listed in Table - 8.
  • the thermal developing light-sensitive material of the invention features a high density, suppressed fogging, and does not show deteriorated fogging even when stored under a high temperature and a high humidity, and the maximum density is stably maintained. In essence, it is apparent that the thermal developing light-sensitive material of the invention has the excellent shelf life.

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Claims (22)

1. Matériau photosensible à développement thermique comprenant un support et, sur ce dernier, des couches de structure photographiques comprenant au moins une couche contenant un halogénure d'argent photosensible, ladite couche de structure photographique comprenant un composé représenté par la formule générale (1) :
Figure imgb0258
dans laquelle Xi représente un groupe résiduel d'un retardateur photographique, Li est une simple liaison ou un groupe divalent et A est un atome d'hydrogène, un groupe amino, un groupe hydroxyle, un groupe carboxyle ou un de ses sels, un groupe sulfo ou un de ses sels ou un groupe sulfine ou un de ses sels; et un composé représenté par la formule générale (2) :
Figure imgb0259
dans laquelle X2 représente un groupe résiduel d'un retardateur photographique, L2 est un groupe divalent et B est un groupe de lest, matériau dans lequel le composé représenté par la formule générale (1) est contenu, dans ledit matériau, en une quantité de 10-7 à 10-1 mole par mole dudit halogénure d'argent photosensible et dans lequel le composé représenté par la formule générale (2) est contenu, dans ledit matériau, en une quantité de 10-5 à 10-1 mole par mole dudit halogénure d'argent photosensible.
2. Matériau photosensible à développement thermique selon la revendication 1, dans lequel ledit groupe résiduel d'un retardateur photographique est choisi parmi un groupe résiduel d'un composé organique dont le sel d'argent a une constante de solubilité (pKsp) non inférieure à 10 à 25 ° C dans l'eau.
3. Matériau photosensible à développement thermique selon la revendication 1, dans lequel ledit groupe résiduel représenté par Xi ou par X2 est un résidu monovalent d'un retardateur photographique représenté par la formule générale (4) ou (8) ci-dessous :
Figure imgb0260
dans laquelle R1 est choisi dans le groupe constitué par un atome d'hydrogène, un groupe alkyle comportant 1 à 7 atomes de carbone et un groupe aryle, n est égal à 1 ou 2, R2 et R3 sont choisis indépendamment dans le groupe constitué par un atome d'hydrogène, un groupe alkyle comportant 1 à 7 atomes de carbone, un groupe aryle comportant 1 à 7 atomes de carbone et un groupe nitro, à condition que R2 et R3 puissent être associés l'un à l'autre pour former un noyau à 5 ou 6 chaînons;
Figure imgb0261
dans laquelle Y est choisi dans le groupe constitué par un atome d'oxygène, de soufre, et un groupe
Figure imgb0262
ou
Figure imgb0263
R1 est un groupe thiol ou un groupe -NHR4, R2 et R3 sont choisis indépendamment dans le groupe constitué par un atome d'hydrogène, un groupe alkyle comportant 1 à 7 atomes de carbone, un groupe aryle comportant 1 à 7 atomes de carbone et un groupe nitro, à condition que R2 et R3 puissent être associés l'un à l'autre pour former un noyau à 5 ou 6 chaînons, et R4 est choisi dans le groupe constitué par un atome d'hydrogène, un groupe alkyle comportant 1 à 7 atomes de carbone et un groupe aryle.
4. Matériau photosensible à développement thermique selon la revendication 1, dans lequel Li, dans la formule (1), et L2, dans la formule (2), sont choisis dans le groupe constitué par un groupe alkylène comportant 1 à 7 atomes de carbone, un groupe alcénylène, un groupe arylène, un groupe imino, un groupe carbonyle, un groupe sulfonyle, un groupe éther et une combinaison quelconque de ceux-ci.
5. Matériau photosensible à développement thermique selon la revendication 1, dans lequel ledit composé représenté par la formule générale (1) est choisi dans le groupe de composés représenté par la formule générale (19) :
Figure imgb0264
dans laquelle Li ' et A' ont respectivement les mêmes significations que Li et A dans la formule (1) et Y est un atome d'azote ou un atome de carbone.
6. Matériau photosensible à développement thermique selon la revendication 1, dans lequel ledit groupe de lest est un groupe hydrocarboné aliphatique ou aromatique comportant au moins 8 atomes de carbone.
7. Matériau photosensible à développement thermique selon la revendication 6, dans lequel ledit groupe de lest comporte 8 à 40 atomes de carbone.
8. Matériau photosensible à développement thermique selon la revendication 6, dans lequel ledit groupe de lest est un groupe alkyle comportant 8 à 40 atomes de carbone.
9. Matériau photosensible à développement thermique selon la revendication 6, dans lequel ledit groupe de lest est un groupe alkyle substitué par un groupe hydrophile constitué d'un groupe sulfo et comportant 8 à 30 atomes de carbone.
10. Matériau photosensible à développement thermique selon la revendication 1, dans lequel ledit composé représenté par la formule générale (1) est contenu dans ledit matériau en une quantité de 10-5 à 10-2 mole par mole dudit halogénure d'argent photosensible.
11. Matériau photosensible à développement thermique selon la revendication 1, dans lequel ledit composé représenté par la formule générale (2) est contenu dans ledit matériau en une quantité de 10-4 à 10-2 mole par mole dudit halogénure d'argent photosensible.
12. Matériau photosensible à développement thermique comprenant un support et, sur ce dernier, au moins une couche de structure photographique comprenant une couche d'émulsion d'halogénure d'argent photosensible, ladite couche de structure photographique comprenant un agent réducteur, une substance chromogène, un composé représenté par la formule générale (1) :
Figure imgb0265
dans laquelle Xi représente un groupe résiduel d'un retardateur photographique, Li est une simple liaison ou un groupe divalent et A est un atome d'hydrogène, un groupe amino, un groupe hydroxyle, un groupe carboxyle ou un de ses sels, un groupe sulfo ou un de ses sels ou un groupe sulfine ou un de ses sels; et un composé représenté par la formule générale (2) :
Figure imgb0266
dans laquelle X2 représente un groupe résiduel d'un retardateur photographique, L2 est un groupe divalent et B est un groupe de lest, matériau dans lequel le composé représenté par la formule générale (1) est contenu, dans ledit matériau, en une quantité de 10-7 à 10-1 mole par mole dudit halogénure d'argent photosensible et dans lequel le composé représenté par la formule générale (2) est contenu, dans ledit matériau, en une quantité de 10-5 à 10-1 mole par mole dudit halogénure d'argent photosensible.
13. Matériau photosensible à développement thermique selon la revendication 12, dans lequel ladite couche de structure photographique comprend, en outre, un sel d'argent organique qui peut être un sel renfermant un groupe imino.
14. Matériau photosensible à développement thermique selon la revendication 13, dans lequel ledit sel d'argent organique est un sel d'argent d'un dérivé de benzotriazole.
15. Matériau photosensible à développement thermique selon la revendication 14, dans lequel ledit sel d'argent organique est un sel d'argent d'un dérivé de benzotriazole.
16. Matériau photosensible à développement thermique selon la revendication 15, dans lequel ledit sel d'argent organique est un sel d'argent d'un composé choisi dans le groupe constitué par le 5-méthylbenzotriazole ou un de ses dérivés, un sulfobenzotriazole ou un de ses dérivés et un N-alkylsulfamoylbenzotriazole ou un de ses dérivés.
17. Matériau photosensible à développement thermique selon la revendication 15, dans lequel ladite substance chromogène est un composé représenté par la formule (5') :
Figure imgb0267
dans laquelle Cp2 est un groupe organique qui est capable de former un colorant diffusable par réaction avec un produit d'oxydation d'un agent réducteur, F est un groupe de liaison divalent et B est un groupe de lest.
18. Matériau photosensible à développement thermique selon la revendication 15, dans lequel ladite couche d'émulsion photosensible contient un grain d'halogénure d'argent photosensible ayant une granulométrie de 0,001 à 1,5 um.
19. Matériau photosensible à développement thermique selon la revendication 15, dans lequel ladite couche d'émulsion photosensible contient un grain d'halogénure d'argent photosensible ayant une granulométrie de 0,01 à 0,5 um.
20. Matériau photosensible à développement thermique selon la revendication 15, dans lequel ledit agent réducteur est un composé représenté par la formule générale (1') :
Figure imgb0268
dans laquelle R1 et R2 sont choisis indépendamment dans le groupe constitué par un atome d'hydrogène et un groupe alkyle substitué ou non substitué comportant 1 à 30 atomes de carbone; R3, R4, R5 et R6 sont choisis indépendamment dans le groupe constitué par un atome d'hydrogène, un atome d'halogène, un groupe hydroxyle, un groupe amino, un groupe alcoxy, un groupe acylamide, un groupe sulfonamide, un groupe alkylsulfonamide et un groupe alkyle qui peut être substitué, à condition que R1 et R2, R3 et R1, et R5 et R2 puissent être respectivement associés l'un à l'autre pour former un noyau hétérocyclique; et M est choisi dans le groupe constitué par un atome de métal alcalin, un groupe ammonium, un groupe sel organique azoté et un composé contenant un azote tétravalent.
21. Procédé de développement thermique d'un matériau photosensible selon la revendication 12, caractérisé en ce que le matériau exposé à une image est chauffé à une température de 80 à 200 ° C pendant 1 à 180 secondes.
22. Procédé selon la revendication 21, dans lequel ledit matériau exposé à une image est chauffé à une température de 100 à 170 ° C pendant 1,5 à 120 secondes.
EP19870307044 1986-08-08 1987-08-07 Matériau sensible à la lumière développable par la chaleur Expired EP0256820B1 (fr)

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JP187089/86 1986-08-08
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JP18085687A JPS63153539A (ja) 1986-08-08 1987-07-20 新規な抑制剤を含有し、保存性の優れた熱現像感光材料

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US5441851A (en) * 1991-11-25 1995-08-15 Eastman Kodak Company Use of heterocyclic nitrogen addenda to reduce continued coupling of magenta dye-forming couplers
EP0590620B1 (fr) * 1992-10-01 1999-12-08 Sterling Diagnostic Imaging, Inc. Emulsions à l'halogénure d'argent stabilisées avec des agents anti-voile améliorés
US6902880B2 (en) 2002-11-14 2005-06-07 Agfa-Gevaert Stabilizers for use in substantially light-insensitive thermographic recording materials
US6908731B2 (en) 2002-11-14 2005-06-21 Agfa-Gevaert Stabilizers for use in substantially light-insensitive thermographic recording materials
US7060655B2 (en) 2002-11-14 2006-06-13 Agfa Gevaert Stabilizers for use in substantially light-insensitive thermographic recording materials
EP1422551B1 (fr) * 2002-11-14 2006-12-06 Agfa-Gevaert Stabilisateurs pour emploi en matériaux thermographiques d' enregistrement sensiblement non-sensibles à la lumière
EP1420292B1 (fr) * 2002-11-14 2006-06-28 Agfa-Gevaert Stabilisateurs pour emploi en matériaux thermographiques d' enregistrement sensiblement non-sensibles à la lumière

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