EP0119615B1 - Trocken-Bildaufzeichnungsverfahren - Google Patents

Trocken-Bildaufzeichnungsverfahren Download PDF

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Publication number
EP0119615B1
EP0119615B1 EP19840102945 EP84102945A EP0119615B1 EP 0119615 B1 EP0119615 B1 EP 0119615B1 EP 19840102945 EP19840102945 EP 19840102945 EP 84102945 A EP84102945 A EP 84102945A EP 0119615 B1 EP0119615 B1 EP 0119615B1
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EP
European Patent Office
Prior art keywords
dye
group
light
silver
fixing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
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EP19840102945
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English (en)
French (fr)
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EP0119615A3 (en
EP0119615A2 (de
Inventor
Koichi Nakamura
Toshiaki Aono
Kozo Sato
Hiroshi Hara
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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Priority claimed from JP4209283A external-priority patent/JPS59168439A/ja
Priority claimed from JP5517283A external-priority patent/JPS59182447A/ja
Application filed by Fuji Photo Film Co Ltd filed Critical Fuji Photo Film Co Ltd
Publication of EP0119615A2 publication Critical patent/EP0119615A2/de
Publication of EP0119615A3 publication Critical patent/EP0119615A3/en
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Publication of EP0119615B1 publication Critical patent/EP0119615B1/de
Expired legal-status Critical Current

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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
    • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
    • G03C8/40—Development by heat ; Photo-thermographic processes
    • G03C8/4013—Development by heat ; Photo-thermographic processes using photothermographic silver salt systems, e.g. dry silver

Definitions

  • the present invention relates to a completely dry image-forming process using a silver halide light-sensitive material
  • a dry image-forming process which comprises heat developing a light-sensitive material comprising a support having thereon at least a photosensitive silver halide, a binder, and a dye-releasing redox compound, said dye-releasing redox compound being reductive to the photosensitive silver halide and being capable of releasing a hydrophilic dye upon reaction with the photosensitive silver halide under heating, after or simultaneously with imagewise exposure, to form imagewise a mobile hydrophilic dye and heating, after or simultaneously with the heat development, the light-sensitive material together with a dye-fixing layer in the presence of a hydrophilic thermal solvent to thereby transfer the mobile hydrophilic dye onto the dye-fixing layer to form a dye image and fix the dye image thereon.
  • a photographic process using silver halide is excellent in photographic properties such as sensitivity and gradation control as compared to other photographic processes such as electrophotography and diazo photographic process, the silver halide photographic process has hitherto been most widely used.
  • a technique capable of more easily and rapidly obtaining images has been developed by changing an image-forming process of a silver halide photographic material from a conventional wet process such as a process which uses a liquid developer to a dry process such as a developing process which uses heating.
  • Heat-developable photographic materials are known in this art and the heat-developable materials and image-forming processes using these heat-developable materials are described in, for example, Shahin Kogaku no Kiso (The Basis of Photographic Engineering), pages 553-555, published by Corona K.K. in 1979; Eizo Jooho (Image Information), page 40, published in April, 1978; Nebletts Handbook of Photography and Reprography, 7th ed., pages 32-33, (Van Nostrand Reinhold Company); U.S. Patents 3,152,904, 3,301,678, 3,392,020, 3,457,075; U.K. Patents 1,131,108 and 1,167,777; and Research Disclosure (RD-17029), pages 9-15, June 1978.
  • This process is an image-forming process wherein a photosensitive material capable of releasing a mobile hydrophilic dye is heated in a state containing substantially no water to release the mobile hydrophilic dye and the hydrophilic dye is transferred onto a dye-fixing layer mainly in the presence of a solvent.
  • DE-A-3 215 485 and EP-A-66 282 describe a dry image forming process which comprises heat developing a light sensitive material comprising a support having thereon at least a photo-sensitive silver halide, a binder and a dye-releasing redox compound which is reductive to the photosensitive halide and capable of releasing a hydrophilic dye upon heating the material after imagewise exposure. It is possible to heat the light-sensitive material together with a dye-fixing layer to thereby transfer the mobile hydrophilic dye onto the dye-fixing layer in the presence of a thermal solvent and of a base on the support of the light-sensitive material. However, the image quality and preservative property of dye images obtained according to this process are not sufficient.
  • An object of the present invention is, therefore, to provide a process of fixing a hydrophilic dye image formed by heat development, which is performed after or simultaneously with imagewise exposure, on a dye-fixing material suited for the image-forming process, which comprises a support having provided thereon one or more layers containing at least a dye-fixing agent, a thermal solvent and a base and/or a base precursor.
  • a dry image-forming process which comprises heat developing a light-sensitive material comprising a support having thereon at least a photosensitive silver halide, a binder, and a dye-releasing redox compound being reductive to the photo- sensitive silver halide and being capable of releasing a hydrophilic dye upon reaction with the photosensitive silver halide under heating, after or simultaneously with imagewise exposure, to form imagewise a mobile hydrophilic dye and heating, after or simultaneously with the heat development, the light-sensitive material together with a dye-fixing layer in the presence of a hydrophilic thermal solvent to thereby transfer the mobile hydrophilic dye onto the dye-fixing layer to form a dye image and fix the dye image thereon, which is characterized in that said dye-fixing layer is provided in a dye-fixing material which comprises a support having thereon at least a dye-fixing agent, a hydrophilic thermal solvent and a base and/or a base precursor.
  • an oxidation reduction reaction occurs between the photosensitive silver halide and the reductive dye releasing redox compound with the exposed photosensitive silver halide as a catalyst upon heating in a state containing substantially no water after or simultaneously with image exposure, whereby an image of a mobile hydrophilic dye released from the dye releasing redox compound, which has become an oxidized product by being oxidized with the silver halide, is obtained together with a silver image at the exposed area.
  • the development step is called “heat development” but it is difficult to distinguish the released mobile hydrophilic dye image by the heat development only since the unreacted dye releasing redox compound is co-present.
  • the dye of the dye image obtained is a mobile hydrophilic dye
  • the dye can be transferred onto a dye-fixing layer in an atmosphere wherein the hydrophilic dye has an affinity, whereby a dye image having excellent image quality and preservative property can be obtained.
  • This step is “dye fixing” step in the invention. It was already disclosed in European Patent Application 0076492 that in this case the atmosphere having an affinity with the hydrophilic dye can be realized by mainly supplying a solvent.
  • the atmosphere having an affinity with the hydrophilic dye is realized by the existence of a hydrophilic thermal solvent and hence, it is not necessary to particularly supply a solvent. Accordingly, a dye image having a color reproducibility can be formed by a completely dry process without need of supplying a solvent in the whole of steps from light exposure to heat development and dye fixing.
  • the oxidation-reduction reaction of a photo-sensitive silver halide and a dye releasing redox compound and the subsequently occurred dye-releasing reaction can take place upon heating in a state containing substantially no solvent.
  • heating means heating to 80°C to 250°C
  • a state containing substantially no water means that the reaction system is in an equilibrium state with moisture in air and hence, water is not supplied for causing the reaction or for accelerating the reaction.
  • Such a state is described in The Theory of the Photographic Process, 4th Edition, page 374, Edited by T. H. James, published by Macmillan.
  • dyes which are released can be selected by selecting dye releasing redox compounds and therefore, various colors can be reproduced. Accordingly, by selecting a combination of dye-releasing redox compounds, multicolour images can be obtained, dye images in the invention include not only monochromatic images but also multicolor images, and the monochromatic images include a monochromatic image composed of a mixture of two or more colors.
  • the dye releasing reaction is caused by the attack of a so-called nucleophilic reagent and the reaction is usually performed in an aqueous solution having a high pH as higher than 10. Therefore, it is quite exceptional that a light-sensitive material shows a high reactivity upon mere heating in a state containing substantially no water as the case of the light-sensitive material used in the invention.
  • the dye releasing redox compound used in the invention can cause an oxidation-reduction reaction with a silver halide without need of the aid of a so-called auxiliary developing agent (see European Patent Application 0076492).
  • reaction proceeds particularly well when an organic silver salt oxidizing agent is co-present in the reaction system, and a high image density can be obtained. Therefore, it is a particularly preferred embodiment that an organic silver salt oxidizing agent is co-present in the reaction system.
  • the dye releasing redox compound which releases a hydrophilic diffusible dye used in the present invention is preferably represented by the following general formula (I): wherein Ra represents a reducing group capable of being oxidized by the silver halide; and D represents an image forming dye portion containing a hydrophilic group.
  • the reducing group Ra in the dye releasing redox compound Ra-S0 2- D has an oxidation-reduction potential to a saturated calomel electrode of 1.2 V or less measuring the polarographic half wave potential using acetonitrile as a solvent and sodium perchlorate as a base electrolyte.
  • Preferred examples of the reducing group Ra include those represented by the following general formulae (II) to (IX).
  • Ra, R a 2 , R3 and Ra each represents a hydrogen atom or a substituent selected from an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an aralkyl group, an acyl group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an aryloxyalkyl group, an alkoxyalkyl group, an N-substituted carbamoyl group, an N-substituted sulfamoyl group, a halogen atom, an alkylthio group or an arylthio group.
  • the alkyl moiety and the aryl moiety in the above described substituents may be further substituted with an alkoxy group, a halogen atom, a hydroxy group, a cyano group, an acyl group, an acylamino group, a substituted carbamoyl group, a substituted sulfamoyl group, an alkylsulfonylamino group, an arylsulfonylamino group, a substituted ureido group or a carboalkoxy group.
  • the hydroxy group and the amino group included in the reducing group represented by Ra may be protected by a protective group capable of reproducing the hydroxy group and the amino group by the action of a nucleophilic agent.
  • the reducing group Ra is represented by the following general formula (X).
  • X represents an electron donating substituent when n is 1 or substituents, which may be the same or different, one of the substituents being an electron donating group and the second or second and third substituents being selected from an electron donating group or a halogen atom when n is 2 or 3, respectively;
  • X 10 groups may form a condensed ring with each other or with OR a 10 ; and the total number of the carbon atoms included in R 10 a and X 10 is not less than 8.
  • reducing groups represented by the general formula (X) more preferred reducing groups Ra are represented by the following general formulae (Xa) and (Xb): wherein Ga represents a hydroxy group or a group giving a hydroxy group upon hydrolysis; R a 11 and R a 12 , which may be the same or different, each represents an alkyl group or R a 11 and R a 12 may be bonded to each other to form a ring; R a 13 represents a hydrogen atom or an alkyl group; R a 10 represents an alkyl group or an aromatic group; X" and X 12 , which may be the same or different, each represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, an acylamino group or an alkylthio group; and R a 10 and X 12 or R a 10 and R a 13 may be bonded to each other to form a ring, wherein Ga represents a hydroxy group or a group giving a hydroxy group upon
  • the reducing group Ra is represented by the following general formula (XI). wherein Ga, X 10 , R a 10 and n each has the same meaning as Ga, X 10 , R a 10 and n defined in the general formula (X).
  • reducing groups represented by the general formula (XI) more preferred reducing groups Ra are represented by the following general formulae (Xla), (Xlb) and (Xlc) wherein Ga represents a hydroxy group or a group giving a hydroxy group upon hydrolysis; R a 21 and R a 22 , which may be the same or different, each represents an alkyl group or an aromatic group, and R a 21 and R a 22 may be bonded to each other to form a ring; R a 23 represents a hydrogen atom, an alkyl group or an aromatic group; R a 24 represents an alkyl group or an aromatic group; R a 25 represents an alkyl group, an alkoxy group, an alkylthio group, an arylthio group, a halogen atom or an acylamino group; p is 0, 1 or 2; R a 24 and R a 25 may be bonded to each other to form a condensed ring; R a 21 and R a 24 may be bonded to each
  • Ga represents a hydroxy group or a group giving a hydroxy group upon hydrolysis
  • R a 31 represents an alkyl group or an aromatic group
  • R; 2 represents an alkyl group or an aromatic group
  • R a 33 represents an alkyl group, an alkoxy group, an alkylthio group, an arylthio group, a halogen atom or an acylamino group
  • q is 0, 1 or 2
  • R; 2 and R a 33 may be bonded to each other to form a condensed ring
  • R a 31 and R a 22 may be bonded to each other to form a condensed ring
  • R a 31 and R a 31 may be bonded to each other to form a condensed ring
  • the total number of the carbon atoms included in R a 31 , R a 32 and (R a 33 ) q is more than 7.
  • Ga represents a hydroxy group or a group giving a hydroxy group upon hydrolysis
  • R a 41 represents an alkyl group or an aromatic group
  • R a 42 represents an alkyl group, an alkoxy group, an alkylthio group, an arylthio group, a halogen atom or an acylamino group
  • r is 0, 1 or 2
  • the group of represents a group in which 2 to 4 saturated hydrocarbon rings are.condensed, the carbon atom in the condensed ring which is connected to the phenol nucleus (or a precursor thereof), represents a tertiary carbon atom which composes one of the pivot of the condensed ring, a part of the carbon atoms (excluding the above described tertiary carbon atom) in the hydrocarbon ring may be substituted for oxygen atom(s), the hydrocarbon ring may have a substituent, and an aromatic ring may be further condensed to the hydrocarbon ring; R a 41 or Ra 2 and the group of
  • the essential part in the groups represented by the general formulae (Ill) and (IV) is a para(sulfonyl)aminophenol part.
  • Specific examples of these reducing groups are described in U.S. Patents, 3,928,312 and 4,076,529, U.S. Published Patent Application B 351,673, U.S. Patents 4,135,929 and 4,258,120. These groups are also effective for the reducing group Ra according to the present invention.
  • the reducing group Ra is represented by the following general formula (XII). wherein Ballast represents a diffusion-resistant group; Ga represents a hydroxy group or a precursor of a hydroxy group; Ge represents an aromatic ring directly condensed to the benzene nucleus to form a naphthalene nucleus; and n and m are dissimilar positive integers of 1 to 2.
  • the reducing groups represented by the above described general formulae (V), (VII), (VIII) and (IX) are characterized by containing a heterocyclic ring. Specific examples of the groups are described in U.S. Patent 4,198,235, JP ⁇ A ⁇ 46730/78 and U.S. Patent 4,273,855.
  • dyes which can be used for image forming dye include azo dyes, azomethine dyes, anthraquinone dyes, naphthoquinone dyes, styryl dyes, nitro dyes, quinoline dyes, carbonyl dyes and phthalocyanine dyes. Representative examples of them are set forth below and are calssified by hue. Further, these dyes can be used in a form temporarily shifted to shorter wavelength region which is capable of regeneration during the development processing.
  • R" to R; 6 each represents a hydrogen atom or a substituent selected from an alkyl group, a cycloalkyl group, an aralkyl group, an alkoxy group, an aryloxy group, an aryl group, an acylamino group, an acyl group, a cyano group, a hydroxyl group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkylsulfonyl group, a hydroxyalkyl group, a cyanoalkyl group, an alkoxycarbonylalkyl group, an alkoxyalkyl group, an aryloxyalkyl group, a nitro group, a halogen atom, a sulfamoyl group, an N-substituted sulfamoyl group, a carbamoyl group, an N-substituted carbamoyl group, an N-substi
  • alkyl moiety and the aryl moiety in the above described substituents may be further substituted with a halogen atom, a hydroxy group, a cyano group, an acyl group, an acylamino group, an alkoxy group, a carbamoyl group, a substituted carbamoyl group, a sulfamoyl group, a substituted sulfamoyl group, a carboxy group, an alkylsulfonylamino group, an arylsulfonylamino group or a ureido group.
  • hydrophilic groups include a hydroxy group, a carboxy group, a sulfo group, a phosphoric acid group, an imido group, a hydroxamic acid group, a quaternary ammonium group, a carbamoyl group, a substituted carbamoyl group, a sulfamoyl group, a substituted sulfamoyl group, a sulfamoylamino group, a substituted sulfamoylamino group, a ureido group, a substituted ureido group, an alkoxy group, a hydroxyalkoxy group, an alkoxyalkoxy group.
  • those in which the hydrophilic property thereof is increased by dissociation of a proton under a basic condition are particularly preferred.
  • these groups include a phenolic hydroxy group, a carboxy group, a sulfo group, a phosphoric acid group, an imido group, a hydroxamic acid group, a (substituted) sulfamoyl group, a (substituted) sulfamoylamino group.
  • Characteristics required for the image forming dye are as follows.
  • H 2 NS0 2 - represents a group necessary to bond to the reducing group.
  • the dye releasing redox compound used in the present invention can be introduced into a layer of the light-sensitive material by known methods such as a method as described in U.S. Patent 2,322,027.
  • a method as described in U.S. Patent 2,322,027 In this case, an organic solvent having a high boiling point or an organic solvent having a low boiling point as described below can be used.
  • the dye releasing redox compound is dispersed in a hydrophilic colloid after dissolved in an organic solvent having a high boiling point, for example, a phthalic acid alkyl ester (for example, dibutyl phthalate and dioctyl phthalate), a phosphoric acid ester (for example diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, and dioctylbutyl phosphate), a citric acid ester (for example, and tributyl acetylcitrate), a benzoic acid ester-(for example, octyl benzoate), an alkylamide (for example, diethyl laurylamide), an aliphatic acid ester (for example, dibutoxyethyl succinate, and dioctyl azelate), a trimesic acid ester (for example, tributyl trimesate), or an organic solvent having a high boiling
  • An amount of the organic solvent having a high boiling point used in the present invention is 10 g per g of the dye releasing redox compound used or less and preferably 5 g per g or less.
  • the silver halide used in the present invention includes silver chloride, silver chlorobromide, silver chloroiodide, silver bromide, silver iodobromide, silver chloroiodobromide and silver iodide.
  • silver halide in the embodiment of the present invention in which the organic silver salt oxidizing agent is not used together with but with silver halide is used alone, particularly preferred silver halide is silver halide partially containing a silver iodide crystal in its particle. That is, the silver halide the X-ray diffraction pattern of which shows that of pure silver iodide is particularly preferred.
  • a silver halide containing two or more kinds of halogen atoms can be used.
  • Such a silver halide yields a completely mixed crystal in a conventional silver halide emulsion.
  • the particle of silver iodobromide shows X-ray diffraction pattern at a position corresponding to the mixed ratio of silver iodide crystal and silver bromide crystal but not at a position corresponding to pure silver iodide crystal and pure silver bromide crystal separately.
  • silver halide used in the present invention include silver chloroiodide, silver iodobromide, and silver chloroiodo-bromide each containing silver iodide crystal in its particle and showing X-ray diffraction pattern of silver iodide crystal.
  • the process for preparing those silver halides is explained taking the case of silver iodobromide. That is, the silver iodobromide is prepared by first adding silver nitrate solution to potassium bromide solution to form silver bromide particles and then adding potassium iodide to the mixture.
  • Two or more kinds of silver halides in which a particle size and/or a halogen composition are different to each other may be used in mixture.
  • An average particle size of the silver halide used in the present invention is preferably from 0.001 Il m to 10 pm and more preferably from 0.001 um to 5pm.
  • the silver halide used in the present invention may be used as is. However, it may be chemically sensitized with a chemical sensitizing agent such as compounds of sulfur, selenium or tellurium, or compounds of gold, platinum, palladium, rhodium or iridium, a reducing agent such as tin halide, or a combination thereof.
  • a chemical sensitizing agent such as compounds of sulfur, selenium or tellurium, or compounds of gold, platinum, palladium, rhodium or iridium, a reducing agent such as tin halide, or a combination thereof.
  • a chemical sensitizing agent such as compounds of sulfur, selenium or tellurium, or compounds of gold, platinum, palladium, rhodium or iridium, a reducing agent such as tin halide, or a combination thereof.
  • a particularly preferred embodiment is to use an organic silver salt oxidizing agent in the light-sensitive material.
  • the silver halide used is not always required to have a feature that the silver halide contains a pure silver iodide crystal in the case of using silver halide solely, but all silver halides used in the field of the art can be used.
  • the organic silver salt oxidizing agent used in the invention is one which reacts with, when heated at above 80°C, preferably at above 100°C in the presence of an exposed silver halide, the foregoing image-forming material or, if necessary, a reducing agent which exists together with the image-forming material to form a silver image.
  • the light-sensitive material coloring in higher density can be obtained by using an organic silver salt oxidizing agent together with the silver halide in the light-sensitive material.
  • organic silver salt oxidizing agent examples include silver salts of organic compounds having a carboxy group and typically silver salts of aliphatic carboxylic acids and silver salts of aromatic carboxylic acids.
  • silver salts of aliphatic carboxylic acids include silver behenate, silver stearate, silver oleate, silver laurate, silver caprate, silver myristate, silver palmitate, silver maleate, silver fumarate, silver tartarate, silver furoate, silver linolate, silver oleate, silver adipate, silver sebacate, silver succinate, silver acetate, silver butyrate and silver camphorate.
  • These silver salts which are substituted with a halogen atom or a hydroxy group are also effectively used.
  • Examples of the silver salts of aromatic carboxylic acid and other carboxyl group containing compounds include silver benzoate, a silver substituted benzoate such as silver 3,5-dihydroxybenzoate, silver o-methylbenzoate, silver m-methylbenzoate, silver p-methylbenzoate, silver 2,4-dichlorobenzoate, silver acetamidobenzoate, silver p-phenylbenzoate, silver gallate, silver tannate, silver phthalate, silver terephthalate, silver salicylate, silver phenylacetate, silver pyromellitate, a silver salt of 3-carboxymethyl-4-methyl-4-thiazoline-2-thione, as described in U.S. Patent 3,785,830, and a silver salt of an aliphatic carboxylic acid containing a thioether group as described in U.S. Patent 3,330,663.
  • a silver substituted benzoate such as silver 3,5-dihydroxybenzoate, silver o-methylbenzoate
  • a silver salt of a compound containing a mercapto group or a thione group and a derivative thereof can be used.
  • Examples of these compounds include a silver salt of 3-mercapto-4-phenyl-1,2,4-triazole, a silver salt of 2-mercaptobenzimidazole, a silver salt of 2-mercapto-5-aminothiadiazole, a silver salt of 2-mercaptobenzothiazole, a silver salt of 2-(S-ethylglycolamido)benzothiazole, a silver salt of thioglycolic acid such as a silver salt of of an S-alkyl thioglycol acetic acid (wherein the alkyl group has from 12 to 22 carbon atoms) as described in JP-A-28221n3, a silver salt of dithiocarboxylic acid such as a silver salt of dithioacetic acid, a silver salt of thiomamide, a silver salt of 5-carboxyl-1-methyl-2-phenyl-4-thiopyridine, a silver salt of mercaptotriazine, a silver salt of 2-mercap
  • Patent 4,123,274 for example, a silver salt of 1,2,4-mercaptotriazole derivative such as a silver salt of 3-amino-5-benzylthio-1,2,4-triazole, a silver salt of thione compound such as a silver salt of 3-(2-carboxyethyl)-4-methyl-4-thiazoline-2-thione as described in U.S. Patent 3,301, 678.
  • 1,2,4-mercaptotriazole derivative such as a silver salt of 3-amino-5-benzylthio-1,2,4-triazole
  • thione compound such as a silver salt of 3-(2-carboxyethyl)-4-methyl-4-thiazoline-2-thione as described in U.S. Patent 3,301, 678.
  • a silver salt of a compound containing an imino group can be used.
  • these compounds include a silver salt of benzotriazole and a derivative thereof as described in JP-B-30270/69 and 18416/70, for example, a silver salt of benzotriazole, a silver salt of alkyl substituted benzotriazole such as a silver salt of methylbenzotriazole, a silver salt of a halogen substituted benzotriazole such as a silver salt of 5-chlorobenzotriazole, a silver salt of carboimidobenzotriazole such as a silver salt of butylcarbo- imidobenzotriazole, a silver salt of 1,2,4-triazole or 1-H-tetrazole as described in U.S. Patent 4,220,709, a silver salt of carbazole, a silver salt of saccharin, a silver salt of imidazole and an imidazole derivative.
  • the silver salts as described in Research Disclosures, Vol. 170, No. 17029 of June, 1978 and organic metal salts such as copper stearate, can be also used as the foregoing various silver salts.
  • the organic silver salt oxididing agents may be used solely or as a mixture of two or more thereof.
  • the so-called auxiliary developing agent can be used even when the dye releasing redox compound is used.
  • the auxiliary developing agent in this case is a compound which is oxidized upon the silver halide to form its oxidized product having an ability to oxidize the reducing group Ra in the dye releasing redox compound.
  • auxiliary developing agents examples include hyroquinone, alkyl substituted hydroquinones such as tertiary butylhydroquinone, 2,5-dimethylhydroquinone, catechols, pyrogallols, halogen substituted hydroquinones such as chlorohydroquinone, dichlorohydroquinone, alkoxy substituted hydroquinones such as methoxyhydroquinone, and polyhydroxybenzene derivatives such as methyl hydroxynaphthalene.
  • alkyl substituted hydroquinones such as tertiary butylhydroquinone, 2,5-dimethylhydroquinone, catechols, pyrogallols
  • halogen substituted hydroquinones such as chlorohydroquinone, dichlorohydroquinone
  • alkoxy substituted hydroquinones such as methoxyhydroquinone
  • polyhydroxybenzene derivatives such as methyl hydroxynaphthalene.
  • methyl gallate, ascorbic acid, ascorbic acid derivatives, hydroxylamines such as N,N-di(2- ethoxyethyl)hydroxylamine, pyrazolidones such as 1-phenyl-3-pyrazolidone, 4-methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidone, reductones and hydroxy tetronic acids are useful.
  • the auxiliary developing agent can be used in an amount of a fixed range.
  • a suitable range is 0.0005 times by mol to 20 times by mol based on silver.
  • a particularly suitable range is 0.001 time by mol to 4 times by mol.
  • the heat development mechanism in the present invention upon heating has not yet been sufficiently clarified but is considered as follows.
  • the dye releasing redox compound of the invention acts as a reducing agent to reduce the silver halide and/or the organic silver halide oxidizing agent with the latent image nuclei as a catalyst to form silver, and the dye releasing redox compound itself is oxidized.
  • the thus oxidized dye releasing redox compound is cleaved to release a dye.
  • the organic silver salt oxidizing agent is further used together, it is necessary for quickly initiating the reaction that the silver halide and the organic silver salt oxidizing agent exist within a substantially effective distance from each other. Accordingly, it is preferred that the silver halide and the organic silver halide oxidizing agent exist in the same layer.
  • thermal solvent in the invention a thermal solvent can be used as a means for improving the forgoing inconvenience.
  • the term 'thermal solvent means a non-hydrolyzable organic material which is solid at an ambient temperature but melts together with other components at a temperature of heat treatment or below.
  • thermal solvents incude compounds which can act as a solvent for the developing agent and compounds having a high dielectric constant which accelerate physical development of silver salts.
  • preferred thermal solvents include polyglycols as described in U.S.
  • Patent 3,347,675 for example, polyethylene glycol having an average molecular weight of 1,500 to 20,000, derivatives of polyethylene oxide such as polyethylene oxide oleic acid ester, beeswax, monostearin, compounds having a high dielectric constant which have an -S0 2 - or -CO- group such as acetamide, succinimide, ethylcarbamate, urea, methylsulfonamide or ethylene carbonate, polar substances as described in U.S.
  • Patent 3,667,959 lactone of 4-hydroxybutanoic acid, methylsulfinylmethane, tetrahydrothiophene-1,1-dioxide and 1,10-decanediol, methyl anisate and biphenyl suberate as described in Research Disclosure, pages 26 to 28 (Dec., 1976).
  • the role of the thermal solvent in the invention is not always clear but it is considered that the main role is to accelerate the diffusion of the reaction molecules at development.
  • the light-sensitive silver halide and the organic silver salt oxididing agent used in the present invention are prepared in the binder as described below. Further, the dye releasing redox compound is dispersed in the binder described below.
  • the binder which can be used in the present invention can be employed individually or in a combination thereof.
  • a hydrophilic binder can be used as the binder according to the present invention.
  • the typical hydrophilic binder is a transparent or translucent hydrophilic colloid, examples of which include a natural substance, for example, protein such as gelatin, a gelatin derivative, a cellulose derivative, a polysaccharide such as starch, gum arabic, and a synthetic polymer, for example, a water-soluble polyvinyl compound such as polyvinyl pyrrolidone, acrylamide polymer.
  • Another example of the synthetic polymer compound is a dispersed vinyl compound in a latex form which is used for the purpose of increasing dimensional stability of a photographic material.
  • the silver halide used in the present invention can be spectrally sensitized with methine dyes or other dyes.
  • Suitable dyes which can be employed include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonal dyes. Of these dyes, cyanine dyes, merocyanine dyes and complex merocyanine dyes are particularly useful. Any conventionally utilized nucleus for cyanine dyedsuch as basic heterocyclic nuclei, is applicable to these dyes.
  • nuclei having a ketomethylene structure 5-or 6-membered heterocyclic nuclei such as a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidin-2,4-dione nucleus, a thiazolidin-2,4-dione nucleus, a rhodanine nucleus, and a thiobarbituric acid nucleus, may also be applicable.
  • 5-or 6-membered heterocyclic nuclei such as a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidin-2,4-dione nucleus, a thiazolidin-2,4-dione nucleus, a rhodanine nucleus, and a thiobarbituric acid nucleus
  • Useful sensitizing dyes include those described in German Patent 929,080, U.S. Patents 2,231,658, 2,493,748, 2,503,776, 2,519,001, 2,912,329, 3,656,959, 3,672,897, 3,694,217, 4,025,349 and 4,046,572, British Patent 1,242,588, JP-B-14030/69 and 24844/77.
  • sensitizing dyes can be employed individually, and can also be employed in combination thereof.
  • a combination of sensitizing dyes is often used, particularly for the purpose of supersensitization.
  • the sensitizing dyes may be present in the emulsion together with dyes which themselves do not give rise to spectrally sensitizing effects but exhibit a supersensitizing effect or materials which do not substantially absorb visible light but exhibit a supersensitizing effect.
  • aminostilbene compounds substituted with a nitrogen-containing heterocyclic group e.g., those described in U.S. Patents 2,933, 390 and 3,635,721
  • aromatic organic acid-formaldehyde condensates e.g., those described in U.S. Patent 3,743,510
  • cadmium salts e.g., those described in U.S. Patent 3,743,510
  • cadmium salts e.g., those described in U.S. Patent 3,743,510
  • cadmium salts e.g., those described in U.S. Patent 3,743,510
  • cadmium salts e.g., those described in U.S. Patent 3,743,510
  • various dye releasing activators can be used by various manners, for example, by incorporating them in any one of the layers of the light-sensitive material or the dye-fixing material.
  • the dye releasing activator is a compound capable of accelerating the oxidation-reduction of the photosensitive silver halide and/or the organic silver salt oxidizing agent with the dye releasing redox compound or capable of nucleophilically reacting with the oxidized dye releasing redox compound in the subseqeuent dye releasing reaction to accelerate the release of dye.
  • Bases or base precursors are useful as the dye releasing activators.
  • amines which include trialkylamines, hydroxylamines, aliphatic polyamines, N-alkyl substituted aromatic amines, N-hydroxyalkyl substituted aromatic amines and bis[p-(dialkylamino)phenyl]methanes.
  • amines which include trialkylamines, hydroxylamines, aliphatic polyamines, N-alkyl substituted aromatic amines, N-hydroxyalkyl substituted aromatic amines and bis[p-(dialkylamino)phenyl]methanes.
  • betaine tetramethylammonium iodide and diaminobutane dihydrochloride as described in U.S.
  • the base precursor is a substance which releases a basic component by heating. Examples of typical base precursors are described in British Patent 998,949.
  • a preferred base precursor is a salt of a carboxylic acid and an organic base, and examples of the suitable carboxylic acids include trichloroacetic acid and trifluoroacetic acid and examples of the suitable bases include guanidine, piperidine, morpholine, p-toluidine and 2-picoline. Guanidine trichloroacetate as described in U.S. Patent 3,220,846 is particularly preferred.
  • aldonic amides as described in JP ⁇ A ⁇ 22625/75 are preferably used because they decompose at a high temperature to form bases.
  • dye releasing activators can be used in an amount of a broad range.
  • a useful range is up to 50% by weight based on the amount of dry layer coated of the light-sensitive material.
  • a range of 0.01 % by weight to 40% by weight is more preferred.
  • a 1 , A 2 , A3 and A4 which may be the same or different, each represents a hydrogen atom or a substituent selected from an alkyl group, a substituted alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, a substituted aryl group and a heterocyclic group; and A 1 and A 2 or A3 and A4 may combine with each other to form a ring.
  • the compounds include H 2 NS0 2 NH 2 , H 2 NS0 2 N(CH 3 ) 2 , H 2 NSO 2 N(C 2 H 5 ) 2 , H 2 NSO 2 NHCH 3 , H 2 NSO 2 N(C 2 H 4 OH) 2 , CH 3 NHS0 2 NHCH 3 ,
  • the above described compound can be used in an amount of broad range.
  • a useful range is up to 20% by weight based on the amount of a dry layer coated of the light-sensitive material.
  • a range of 0.1 % by weight to 15% by weight is more preferred.
  • the water releasing compound means a compund which releases water by decomposition during heat development.
  • These compounds are particularly known in the field of printing of fabrics, and NH Fe(S0 4 ) 2' 12H 2 0, as described in JP ⁇ A ⁇ 88386/75 are useful.
  • a support used in the present invention is that which can endure at the processing temperature.
  • an ordinary support not only glass, paper, metal or analogues thereof may be used, but also an acetyl cellulose film, a cellulose ester film, a polyvinyl acetal film, a polystyrene film, a polycarbonate film, a polyethylene terephthalate film, and a film related thereto or a plastic material may be used.
  • the polyesters described in U.S. Patents 3,634,089 and 3,725,070 are preferably used.
  • a coating composition used in the invention can be prepared by blending, before use, a silver halide and an organic metal salt oxidizing agent formed separately, and it is also effective for the preparation of the coating composition to blend both the components in a ball mill for a long period of time. It is also effective to add a halogen-containing compound to the organic silver salt oxidizing agent to form a silver halide with silver in the organic silver salt oxidizing agent.
  • a suitable coating amount of the light-sensitive silver halide and the organic silver salt oxidizing agent employed in the present invention is in a total of from 50 mg/m 2 to 10 g/m 2 calculated as an amount of silver.
  • the photographic emulsion layer and other hydrophilic colloid layers in the light-sensitive material of the present invention may contain various surface active agents for various purposes, for example, as coating aids or for prevention of electrically charging, improvement of lubricating property, emulsification, prevention of adhesion, improvement of photographic properties (for example, acceleration of development, rendering hard tone or sensitization).
  • nonionic surface active agents such as saponin (steroid), alkylene oxide derivatives (for example, polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkylamine or amides, polyethylene oxide adducts of silicone), glycidol derivatives (for example, alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), polyhydric alcohol aliphatic acid esters or saccharide alkyl esters; anionic surface active agents containing acid groups such as a carboxy group, a sulfo group, a phospho group, a sulfate group, a phosphate group, such as alkylcarboxylic acid salts, alkylsulfonic acid salts, alkyl
  • polyethylene glycol type nonionic surface active agents having a recurring unit of ethylene oxide in their molecules may be preferably incorporated into the light-sensitive material. It is particularly preferred that the molecule contains 5 or more of the recurring units of ethylene oxide.
  • nonionic surface active agents capable of satisfying the above described conditions are well known as to their structures, properties and methods of synthesis. These nonionic surface active agents are widely used even outside this field. Representative references relating to these agents include: Surfactant Science Series, Vol. 1, Nonionic Surfactants (edited by Martin J. Schick, Marcel Dekker Inc., 1967), and Surface Active Ethylene Oxide Adducts, (edited by Schoufeldt N. Pergamon Press, 1969). Among the nonionic surface active agents described in the above mentioned references, those capable of satisfying the above described conditions are preferably employed in connection with the present invention.
  • the nonionic surface active agents can be used individually or as a mixture of two or more of them.
  • the polyethylene glycol type nonionic surface active agents can be used in an amount of less than 100% by weight, preferably less than 50% by weight, based on a hydrophilic binder.
  • the light-sensitive material of the present invention may contain a cationic compound containing a pyridinium salt.
  • a cationic compound containing a pyridinium group used are described in PSA Journal Section B 36 (1953), U.S. Patents 2,648,604 and 3,671,247, JP-B-30074/69 and 9503/69.
  • a compound which activates development simultaneously while stabilizing the image it is preferred to use isothiuroniums including 2-hydroxyethylisothiuronium trichloroacetate as described in U.S. Patent 3,301,678, bisisothiuroniums including 1,8-(3,6-dioxaoctane)-bis(isothiuronium trifluoroacetate), etc., as described in U.S. Patent, 3,669,670, thiol compounds as described in German Patent Application (OLS) No.
  • isothiuroniums including 2-hydroxyethylisothiuronium trichloroacetate as described in U.S. Patent 3,301,678, bisisothiuroniums including 1,8-(3,6-dioxaoctane)-bis(isothiuronium trifluoroacetate), etc., as described in U.S. Patent, 3,669,670, thiol compounds as described in German Patent Application (OL
  • thiazolium compounds such as 2-amino-2-thiazolium trichloroacetate, 2-amino-5-bromoethyl-2-thiazolium trichloroacetate, as described in U.S. Patent 4,012,260, compounds having a-sulfonylacetate as an acid part such as bis(2-amino-2-thiazolium)methylene-bis(sulfonylacetate), 2-amino-2-thiazolium phenylsulfonyl-acetate, as described in U.S. Patent 4,060,420, and compounds having 2-carboxycarboxamide as an acid part as described in U.S. Patent 4,088,496.
  • the light-sensitive material used in the present invention may contain, if necessary, various additives known for the heat-developable light-sensitive materials and may have a layer other than the light-sensitive layer, for example, an antistatic layer, an electrically conductive layer, a protective layer, an intermediate layer, an antihalation layer, a strippable layer.
  • a layer other than the light-sensitive layer for example, an antistatic layer, an electrically conductive layer, a protective layer, an intermediate layer, an antihalation layer, a strippable layer.
  • additives examples include those described in Research Disclosure, Vol. 170, No. 17029 (June, 1978), for example, plasticizers, dyes for improving sharpness, antihalation dyes, sensitizing dyes, matting agents, fluorescent whitening agents and fading preventing agent.
  • the protective layer, the intermediate layer, the subbing layer, the back layer and other layers can be produced by preparing each coating solution and applying to a support by various coating methods such as a dip coating method, an air-knife coating method, a curtain coating method or a hopper coating method as described in U.S. Patent 2,681,294 and drying in the same manner as used in preparing the heat-developable light-sensitive layer of the present invention, by which the light-sensitive material is obtained.
  • various coating methods such as a dip coating method, an air-knife coating method, a curtain coating method or a hopper coating method as described in U.S. Patent 2,681,294 and drying in the same manner as used in preparing the heat-developable light-sensitive layer of the present invention, by which the light-sensitive material is obtained.
  • two or more layers may be applied at the same time by the method as described in U.S. Patent 2,761,791 and British Patent 837,095.
  • the resulting latent image can be developed by heating the whole material to a suitably elevated temperature, for example, about 80°C to about 250°C for about 0.5 second to about 300 seconds.
  • a higher temperature or lower temperature can be utilized to prolong or shorten the heating time, if it is within the above described temperature range.
  • a temperature range of about 110°C to about 160°C is useful.
  • the light-sensitive material can be heated for development by an ordinary means such as a simple heating plate, a heating iron, a heat roller, a heating element utilizing carbon or titanium white, or a similar means.
  • the transfer of the mobile dye may be initiated simultaneously with the release of the dye or after completing the release of the dye. Accordingly, heating for the transfer of the mobile dye may be after heat development or similtaneously with heat development.
  • heating simultaneously with heat development means that heating for development also acts as heating for transferring the dye released.
  • the optimum heating temperature for development and the heating time necessary for the development do not always coincide with those for transferring the dye and hence, the heating temperatures may be selected independently.
  • the heating temperature for transferring the dye is 60°C to 250°C from the viewpoints of preservative property and workability of the light-sensitive material
  • a material which exhibits the action as a hydrophilic thermal solvent in this temperature range may be properly used. It is, as a matter of course, necessary that the hydrophilic thermal solvent assists the quick transfer of dye, but considering also the heat resistance of the light-sensitive material, the hydrophilic thermal solvent is required to have a melting point of 40°C to 250°C, preferably 40°C to 200°C, more preferably 40°C to 150°C.
  • the "hydrophilic thermal solvent” referred to in the invention is defined to be a compound which is in a solid state at room temperature but becomes in a liquid state upon heating, has an (inorganic property/ organic property) value of larger than 1, and has a solubility in water at room temperature of higher than 1.
  • the term "inorganic property/organic property” is a conception for estimating the properties of a compound and is described in detail in, for example, Kagaku no Ryoiki (The Domain of Chemistry), 11, page 719 (1957).
  • the hydrophilic thermal solvent has a role for assisting the transfer of the hydrophilic dye, it is preferred that the hydrophilic thermal solvent is a compound capable of acting as a solvent for the hydrophilic dye.
  • the (inorganic property/organic property) value of the solvent is close to the (inorganic property/organic property) value of the organic compound.
  • the (inorganic property/organic property) value of the dye releasing redox compound used in the present invention is about 1, and the (inorganic property/organic property) value of the hydrophilic dye released from the dye releasing redox compound is larger than the (inorganic property/organic property) value of the dye releasing redox compound and is preferably larger than 1.5, more preferably larger than 2.
  • the hydrophilic thermal solvent used in the invention transfers only the hydrophilic dye and does not transfer the dye releasing redox compound, it is necessary that the (inorganic property/organic property) value of the hydrophilic thermal solvent is larger than the (inorganic property/organic property) value of the dye releasing redox compound. That is, it is necessaryy that the (inorganic property/organic property) value of the hydrophilic thermal solvent used in the invention be larger than 1, preferably larger than 2:
  • the molecular weight of the hydrophilic thermal solvent used in the invention be low, i.e., less than about 200, preferably less than about 100.
  • the hydrophilic thermal solvent used in the invention can substantially assist the transfer of the hydrophilic dye formed from the dye releasing redox compound by heat development onto a dye-fixing layer. Therefore, the hydrophilic thermal solvent may be incorporated in not only a dye-fixing layer but also a photosensitive layer or in both the dye-fixing layer and the photosensitive layer. Furthermore, an independent layer containing a hydrophilic thermal solvent may be provided in the light-sensitive material and/or independent dye-fixing material having the dye-fixing layer. However, from the viewpoint of increasing the transfer efficiency of the dye onto the dye-fixing layer, it is preferred that the hydrophilic thermal solvent be incorporated in the dye-fixing layer and/or a layer adjacent to the dye-fixing layer.
  • the hydrophilic thermal solvent is usually dissolved in water and dispersed in a binder, but it may be used by dissolving in an alcohol such as methanol, ethanol, etc.
  • the hydrophilic thermal solvent used in the invention can be used in a coating amount of 5 to 500% by weight, preferably 20 to 200% by weight, more preferably 30 to 150% by weight, based on the total coating amount of the coating compositions for the light-sensitive material and/or the dye-fixing material.
  • hydrophilic thermal solvent there are, for example, ureas, pyridines, amides, sulfonamides, imides, alcohols, oximes, and other heterocyclic compounds.
  • the compounds (1), (2), (3), and (10) in ureas, the compounds (17) and (19) in pyridines, the compounds (26), (30), and (33) in amides, the compounds (34) and (36) in sulfonamides, the compounds (40), (41), (43), and (44) in imides, and the compounds (46) and (54) in alcohols are particularly preferred.
  • the foregoing compounds used as the hydrophilic thermal solvent may be used solely or as a mixture of two or more thereof.
  • the light-sensitive material of this invention is composed of a support having thereon at least a photosensitive layer (I) containing a silver halide, an organic silver salt oxidizing agent which may be used if necessary, a dye releasing redox compound which is also a reducing agent for the organic silver salt oxidizing agent, and a binder and dye-fixing layer (II) capable of receiving a mobile hydrophilic dye formed in the layer (I).
  • a photosensitive layer (I) and a dye-fixing layer (II) may be formed on the same support or separate supports respectively.
  • the dye-fixing layer (II) and the photosensitive layer (I) may be peeled off from each other.
  • the dye-fixing layer (II) or the photosensitive layer (I) may be peeled off from the other.
  • a light-sensitive material having the photosensitive layer (I) on a support and a dye- fixing material having the dye-fixing layer (II) on another support are prepared separately, after imagewise exposing the light-sensitive material and uniformly heating, the dye-fixing material is superposed on the resulting light-sensitive material to thereby transfer the mobile dye onto the dye-fixing layer (II).
  • the light-sensitive material can be closely brought into contact with the dye-fixing material by usual manners such as those by press roller, etc., and in this case, for sufficiently performing the close contact of both the materials, the heating is employable during the contacting.
  • the latter heating can contribute to only the dye transfer and hence, the heating temperature and the heating time for the latter heating may be selected independent on the heating for development.
  • the heating for development it is preferred to perform the heating for development such that the heating contributes to the dye transfer as less as possible, and that the reaction for the development is finished in a short period of time.
  • the heating for transferring the dye released imagewise is performed at a temperature of as low as possible such that the heat reaction of the unexposed area does not occur, in a proper range of a transferring period of time.
  • the dye-fixing layer (II) may have a white reflection layer.
  • a layer of titanium dioxide dispersed in gelatin may be formed on a mordanting layer provided on a transparent support.
  • the titanium dioxide layer forms a white opaque layer and hence, when the transferred dye image is viewed from the side of the transparent support, a reflection-type color image can be viewed.
  • the dye transfer from the light-sensitive layer to the dye-fixing layer can be carried out using a dye transfer assistant.
  • useful dye transfer assistant include water and an alkaline aqueous solution containing sodium hydroxide, potassium hydroxide or an inorganic alkali metal salt.
  • a solvent having a low boiling point such as methanol, N,N-dimethylformamide, acetone, and diisobutyl ketone, and a mixture of such a solvent having a low boiling point with water or an alkaline aqueous solution can be used.
  • the dye transfer assistant can be employed by wetting the image receiving layer with the transfer assistant or by incorporating it in the form of water of crystalliszation or microcapsules into the material.
  • the dye-fixing layer may contain a dye mordant for fixing the dye, a hydrophilic thermal solvent for assisting the transfer of the dye, a base and/or a base precursor for accelerating the dye releasing reaction, and further a binder for these materials.
  • a dye mordant for fixing the dye for fixing the dye
  • a hydrophilic thermal solvent for assisting the transfer of the dye
  • a base and/or a base precursor for accelerating the dye releasing reaction
  • a binder for these materials may be particularly preferred.
  • the dye in the light-sensitive material may transferred into the individually provided dye-fixing material, in order to obtain a high-quality ultimate image fixed in the dye- fixing material, a specific means is required. That is, in order to increase the quality of the dye image transferred onto the dye-fixing layer, it is useful to incorporate a base and/or a base precursor into any one of the layers constituting the dye-fixing material.
  • a base and/or a base precursor into the dye-fixing layer or a layer provided on the dye-fixing layer because the image density is sufficiently high as well as a sharp dye image can be obtained.
  • a base and/or base precursor the above-described bases and/or base precursors as the dye releasing activators useful in the light-sensitive material can, for example, be exemplified.
  • the ultimate image is formed in the dye-fixing material which is not light-sensitive.
  • the function for imparting "light sensitivity" and that for fixing the ultimate image be imparted to the light-sensitive material and the dye-fixing material independently, materials which sufficiently exhibit the respective functions can be widely selected.
  • base and/or base precursor used in the dye-fixing material of the invention usual inorganic or organic bases and/or base precursor are useful.
  • base precursors mean ones releasing a basic component upon thermal decomposition.
  • Examples of the inorganic base include hydroxides of alkali metals or alkaline earth metals, disphosphates, triphosphates, borates, carbonates, quinolinates, pyrophosphates, metaphosphates, ammonium hydroxide, quaternary alkylammonium hydroxides, and other hydroxides.
  • these inorganic bases include lithium hydroxide, sodium hydroxide, potassium hydroxide, barium hydroxide, sodium carbonate, potassium carbonate, sodium quinolinate, potassium quinolinate, sodium diphosphate, potassium diphosphate, sodium triphosphate, potassium triphosphate, sodium pyrophosphate, potassium pyrophosphate, sodium metaphosphate, potassium metaphosphate, borax, ammonium hydroxide, tetramethylammonium, tetrabutylammonium, ammonia.
  • Examples of the organic base used for the dye releasing activator of the present invention include aliphatic amines, aromatic amines, heterocyclic amines, amidines, cyclic amidines, quanidines, and cyclic quanidines, with those having a pKa of higher than 8 being particularly useful.
  • precursors of these organic bases can be used as preferred base precursors.
  • Examples of such base precursors include salts of thermally decomposable organic acids such as trichloroacetic acid, cyanoacetic acid, and acetoacetic acid, and salts of 2-carboxy carboxide as disclosed in U.S. Patent 4,088,496.
  • base precursors as disclosed in British Patent 998,945, U.S. Patent 3,220,846 and JP- ⁇ -22625n5 can also be used.
  • bases which are used as alkaline agents and buffers in the conventional photographic materials and their treating solutions may also be used.
  • the base precursor used in the invention can be used in a wide range in terms of its amount. But it is suitably used in an amount of less than 50% by weight, preferably 0.01 to 40% by weight, as calculated on the basis of the weight of the coated surface of the dye-fixing layer.
  • the base and/ or base precursor may be used either alone or in admixture of two or more thereof.
  • the base and/or base precursor is usually dissolved in water or an alcohol and then dispersed in the dye-fixing layer.
  • the dispersion may be performed in accordance with a method as disclosed in U.S. Patent 2,322,027 in which an organic solvent having a high boiling point is used.
  • the base and/or base precursor is dissolved in an organic solvent having a boiling point of about 30 to 160°C, such as lower alkyl acetates (e.g., ethyl acetate or butyl acetate), ethyl proprionate, sec- butyl alcohol, methyl isobutyl ketone, (3-ethoxyethyt acetate, methyl cellosolve acetate, cyclohexane, and then dispersed in the dye-fixing layer.
  • an organic solvent having a boiling point of about 30 to 160°C such as lower alkyl acetates (e.g., ethyl acetate or butyl acetate), ethyl proprionate, sec- butyl alcohol, methyl isobutyl ketone, (3-ethoxyethyt acetate, methyl cellosolve acetate, cyclohexane, and then dispersed in the dye-fixing layer.
  • organic solvent having a high boiling point examples include, for example, a phthalic acid alkyl ester (for example, dibutyl phthalate, and dioctyl phthalate), a phosphoric acid ester (for example, diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, and dioctylbutyl phosphate), a citric acid ester (for example, tributyl acetylcitrate), a benzoic acid ester (for example, octyl benzoate), an alkylamide (for example, diethyl laurylamide), an aliphatic acid ester (for example, dibutoxyethyl succinate, dioctyl azelate), a trimesic acid ester (for example, tributyl trimesate).
  • a phthalic acid alkyl ester for example, dibutyl phthalate, and dioctyl phthal
  • organic solvents having a high boiling point and organic solvents having a low boiling point may be used as a mixture thereof. Further, it is possible to use a dispersion method using a polymer as described in JP-B-29853n6 and JP-A-59943/76.
  • the dye-fixing material of the invention may be constructed by plural layers of the dye-fixing layer and a layer or layers other than the dye-fixing layers, e.g., a protective layer, an interlayer.
  • the dye-fixing layer of the invention is constructed by a single layer or plural layers and contains a dye mordant for fixing the dye.
  • the base and/or base precursor is used by dispersing in a layer or layers containing the dye mordant.
  • the base and/or base precursor may be used by dispersing in a binder in a layer adjacent to the layer containing the dye mordant.
  • various mordants can be used. Among them are particularly preferred polymer mordants.
  • the polymer mordant and the base and/or base precursor can be dispersed in the binder described below.
  • the binder which can be used in the present invention can be employed individually or in a combination thereof.
  • a hydrophilic binder can be preferably used as the binder according to the present invention.
  • the typical hydrophilic binder is a transparent or translucent hydrophilic colloid, examples of which include a natural substance, for example, protein such as gelatin, a gelatin derivative, and a cellulose derivative, a polysaccharide such a starch, and gum arabic, and a synthetic polymer, for example, a water-soluble polyvinyl compound such as polyvinyl pyrrolidone, and acrylamide polymer.
  • Another example of the synthetic polymer compound is a dispersed vinyl compound in a latex form which is used for the purpose of increasing dimensional stability of a photographic material.
  • the dye mordant is a polymer mordant
  • the mordant also acts as a binder and hence, the amount of the binder may be reduced or the binder may not particularly be used. Contrarily, when the binder has a function as a mordant, the dye mordant may not be used. Any materials which are usually used as a binder for photographic light-sensitive materials can be used as the binder in the invention.
  • the mordant used for the dye-fixing layer of the invention can be properly selected from conventional mordants and among them, polymer mordants are particularly preferred.
  • Polymer mordants used in the present invention are polymers containing secondary and tertiary amino groups, polymers containing nitrogen-containing heterocyclic moieties, polymers having quaternary cation groups thereof, having a molecular weight of from 5,000 to 200,000, and particularly from 10,000 to 50,000.
  • mordants disclosed in U.S. Patents 2,675,316 and 2,882,156 can be used.
  • mordants capable of cross-linking with a matrix such as gelatin, water-insoluble mordants, and aqueous sol (or latex dispersion) type mordants are preferably used.
  • gelatin for the mordant layer Various kinds of known gelatins can be employed as gelatin for the mordant layer.
  • gelatin which is produced in a different manner such as lime-processed gelatin, acid-processed gelatin, or a gelatin derivative which is prepared by chemically modifying gelatin such as phthalated gelatin, sulfonylated gelatin, can be used.
  • gelatin subjected to a desalting treatment can be used, if desired.
  • the ratio of polymer mordant to gelatin and the amount of the polymer mordant coated can be easily determined by one skilled in the art depending on the amount of the dye to be mordanted, the type and composition of the polymer mordant and further on the image-forming process used.
  • the ratio of mordant to gelatin is from 20/80 to 80/20 (by weight) and the amount of the mordant coated is from 0.5 to 8 g/ m2.
  • a typical dye-fixing material used in the invention can be obtained by coating a mixture of a polymer containing an ammonium salt and gelatin on a transparent support.
  • a protective layer may be formed thereon, if desired.
  • a protective layer materials usually used for protective layers for photographic light-sensitive materials can be used, but when the dye-fixing layer is formed on a support different from the support of the light-sensitive material, it is preferred that the protective layer is rendered hydrophilic in order to prevent hindering the transfer of the hydrophilic dye.
  • the above described support used in the light-sensitive material can be optionally chosen.
  • organic polymers which are resistant to the heating for the development or the dye transfer are preferred.
  • organic polymers used in the dye-fixing material of the invention include polystyrene having a molecular weight of 2,000 to 85,000, polystyrene derivatives having a substituent of up to 4 carbon atoms, polyvinylcyclohexane, polyvinylbenzene, polyvinylpyrrolidone, polyvinylcarbazole, polyallyl- benzene, polyvinyl alcohol, polyacetals (e.g., polyvinylformal or polyvinylbutyral), polyvinyl chloride, chlorinated polyethylene, polyethylene trichlorofluoride, polyacrylonitrile, poly-N,N-dimethylallylamide, a polyacrylate having a p-cyanophenyl group, a pentachlorophenyl group, or a 2,4-dichlorophenyl group, a pentachlorophenyl group, or a 2,4-dichlorophenyl group, polyacryl
  • Examples of the support advantageously used in this invention are films of cellulose acetates such as triacetate, diacetate; films of polyamides such as combinations of heptamethylenediamine and terephthalic acid, fluorenedipropylamine and adipic acid, hexamethylenediamine and diphenic acid, hexamethylenediamine and isophthalic acid; films of polyesters such as the combinations of diethylene glycol and diphenylcarboxylic acid, bis-p-carboxyphenoxybutane and ethylene glycol, etc., polyethylene terephthalate films, polycarbonate films. These films may be denatured.
  • a polyethylene terephthalate film denatured by using cyclohexane dimethanol, isophthalic acid, methoxypolyethylene glycol, 1,2-dicarbomethoxy-4-benzenesulfonic acid, as a denaturant is advantageously used.
  • the photographic emulsion layer and other binder layers may contain inorganic or organic hardeners. It is possible to use chromium salts (chromium alum, and chromium acetate), aldehydes (formaldehyde, glyoxal, and glutaraldehyde), N-methylol compounds (dimethylolurea, methylol and dimethylhydantoin), dioxane derivatives (2,3-dihydroxydioxane), active vinyl compounds (1,3,5-triacryloylhexahydro-s-triazine, and 1,2-vinylsulfonyl-2-propanol), active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine), mucohalogenic acids (mucochloric acid, and mucophenoxychloric acid), which are used individually or as a combination thereof.
  • chromium salts chromium alum, and chromium
  • heating means for transferring the dye various heating means as described above in regard to the heating means for the heat development can be used.
  • the light-sensitive material having the photosensitive layer and the dye-fixing layer on the same support or the dye-fixing material having the dye-fixing layer on a different support from that of the light-sensitive material can be prepared by coating respective coating compositions for the dye- fixing layer, protective layer, interlayer, subbing layer, backing layer, in the same manner as described in the case of forming the photosensitive layer or other layer using a dipping method, an air knife method, a curtain coating method, or a hopper coating method as described in U.S. Patent No. 3,681,294, followed by drying.
  • Latent images are obtained by imagewise exposure by radiant rays including visible rays.
  • light sources used for conventional color prints can be used, examples of which include tungsten lamps, mercury lamps, halogen lamps such as iodine lamps, xenon lamps, laser light sources, CRT light sources, fluorescent tubes and light-emitting diodes.
  • the original may be line drawings or photographs having gradation. Further, it is possible to take a photograph of a portrait or landscape by means of a camera. Printing from the original may be carried out by contact printing by superposing the original on the material or may be carried out by reflection printing or enlargement printing.
  • CTR cathode ray tube
  • FOT fiber optical tube
  • LED light-emitting diode
  • the light-sensitive material is produced using a construction such that the green-sensitive part (layer) contains a yellow dye releasing redox compound, the red-sensitive part (layer) contains a magenta dye releasing redox compound and the infrared-sensitive part (layer) contains a cyan dye releasing redox compound.
  • Other combinations can be utilized, if necessary.
  • the image-forming process of the invention is a very convenient image-forming process wherein the whole of steps from light exposure to heat development and dye-fixing can be performed in a completely dry system without particularly supplying a solvent from the outside. Furthermore, since in the image-forming process of the invention, not only sensitivity of a conventional so-called silver halide photographic material can be maintained but also dye image formed is fixed in the dye-fixing material, the quality and the preservative property of the dye image thus formed are very good, the color reproducibility is good, and in spite of the completely dry system, the reproduction of color images can be sufficiently performed.
  • the image-forming process of the invention having such excellent features can be applied for the field of photography as well as can meet the recent requirement for the transfer of so-called soft images to hard images.
  • the dye image formed is fixed in the dye- fixing layer, whereby the dye image has a good preservative property and hence, the process of the invention can be conveniently utilized even in the case of requiring the preservation of dye images for a long period of time.
  • the image-forming process of the invention exceeds conventional photographic techniques in the foregoing points.
  • a silver iodobromide emulsion was prepared by the following manner.
  • the pH of the silver iodobromide emulsion thus obtained was adjusted to cause sedimentation, and after removing excessive salts, the pH of the emulsion was adjusted to 6.0 to provide 400 g of the silver iodobromide emulsion.
  • magenta dye releasing redox compound (42) In 20 ml of ethyl acetate were dissolved 5 g of the magenta dye releasing redox compound (42), 0.5 g of a surface active agent, succinic acid 2-ethylhexyl ester sodium sulfonate, and 5 g of tricresyl phosphate (TCP) under heating to about 60°C to form a homogeneous solution.
  • the solution was mixed with 100 g of an aqueous solution of 10% limed gelatin with stirring and mixture was treated by means of a homogenizer for 10 minutes at 10,000 r.p.m. to provide a dispersion of the magenta dye releasing redox compound.
  • a photosensitive layer was formed as follows.
  • a protective layer was formed on the photosensitive layer thus formed by the following manner.
  • a mixture of the foregoing components was coated on the photosensitive layer at a wet thickness of 25 um and then dried to provide light-sensitive material D-1.
  • the mixture was uniformly coated on the layer thus formed at a wet thickness of 60 11 m and dried.
  • the 2nd layer was called as a hydrophilic thermal solvent layer.
  • dye-fixing material R-2 was prepared.
  • dye-fixing materials R-3 and R-4 were prepared, respectively.
  • dye- fixing material R-5 was prepared.
  • dye-fixing material R-6 was prepared.
  • dye-fixing material R-7 was prepared.
  • Light-sensitive material D-1 was imagewise exposed for 10 seconds using a tungsten lamp at 2,000 lux and thereafter was uniformly heated for 20 seconds on a heat block heated to 140°C.
  • each of dye-fixing materials R-1 to R-9 was closely brought into contact with the light-sensitive material so that the coated layers were in a face-to-face relationship with each other and each assembly was heated for 30 seconds on a heat block at 120°C.
  • Each of light-sensitive materials D-1 to D-3 in Examples 1 to 3 was exposed and heat developed as in Example 15.
  • Each of the light-sensitive materials was closely brought into contact with dye-fixing material R-1 shown in Example 6 with the coated layers in a face-to-face relationship and each assembly was heated for 30 seconds on a heat block at 120°C.
  • the dye-fixing material was peeled off from each of the light-sensitive sheets, each of negative magenta, yellow, and cyan images was obtained on the dye- fixing material.
  • the densities of each negative image thus obtained were measured using a Macbeth densitometer (RD-504) and the results are shown in Table 2.
  • Each of light-sensitive materials D-4 to D-6 in Example 6 was imagewise exposed for 10 seconds using a tungsten lamp at 2,000 lux. Each of the light-sensitive materials was closely brought into contact with dye-fixing material R-8 in Example 13 with the coated layers in a face-to-face relationship with each other and each assembly was heated for 30 seconds on a heat block of 130°C.
  • dye-fixing material R-10 was prepared.
  • Light-sensitive material D-8 was imagewise exposed for 10 seconds using a tungsten lamp at 2,000 lux and thereafter was uniformly heated for 20 seconds to 130°C. Then, the light-sensitive material was closely brought into contact with dye-fixing material R-10 with the coated layer in a face-to-face relationship with each other and the assembly was heated for 20 seconds to 120°C. When the dye-fixing material was peeled off from the light-sensitive material, a negative magenta image having a high density was obtained on the dye-fixing material. When the density of the negative color image was measured using a Macbeth densitometer (RD-504), the maximum density was 1.22 and the minimum density was 0.19. Thus, it has been confirmed that a dye image having a high density can be obtained by heating in a short period of time without supplying water by incorporating the hydrophilic thermal solvent in the light-sensitive material.
  • RD-504 Macbeth densitometer
  • Dye-fixing material R-11 used in the invention was prepared as follows.
  • Light-sensitive material D-1 was imagewise exposed for 10 minutes using a tungsten lamp at 2,000 lux and thereafter was uniformly heated for 20 seconds on a heat block heated to 140°C.
  • the light-sensitive material was closely brought into contact with dye-fixing material R-11 with the coated layers in a face-to-face relationship with each other and the assembly was heated for 30 seconds on a heat block at 120°C.
  • the pH of the silver iodobromide emulsion thus obtained was adjusted to cause sedimentation and after removing excessive salts, the pH of the emulsion was adjusted to 6.0 to provide 400 g of the silver iodobromide emulsion.
  • a photosensitive coating composition was prepared by the following manner.
  • a protective layer was formed on the photosensitive layer thus formed by the following manner.
  • a mixture of the foregoing components was coated on the photosensitive layer at a wet thickness of 25 um.
  • a dye-fixing material containing a dye-fixing agent was by the following manner.
  • solution A was uniformly coated on the layer thus formed at a wet thickness of 60 ⁇ m.
  • This coating sample was dried and used as a dye-fixing material (hereinafter "sheet A”).
  • sheet A a dye-fixing material
  • solution B a coating solution
  • a dye-fixing material was obtained in the same manner as above (this dye-fixing material being hereinafter referred to "sheet B").
  • the light-sensitive material as obtained above was imagewise exposed for 10 seconds using a tungsten lamp at 2,000 lux.
  • each of the dye-fixing materials as prepared above was closely brought into contact with the light-sensitive material so that the coated layers were in a face-to-face relationship with each other and each assembly was heated for 30 seconds on a heat block at 130°C.
  • Example 21 A sample was prepared in the same manner as in Example 21 except that 0.8 g of guanidine trichloroacetate was used as a base precursor in the solution A, and then treated in the same manner as in Example 21. The results obtained are shown below.
  • Example 21 The same procedure as in Example 21 was repeated except that each of the dye releasing redox compounds as shown below was used in place of the dye releasing redox compound (42). Thus, a dispersion of dye releasing redox compound was prepared.
  • Example 24 is an example in which an organic silver salt oxidizing agent was used.
  • a benzotriazole silver emulsion was prepared by the following manner.
  • a photosensitive coating composition was prepared by the following manner.
  • the sheet A and sheet B as used in Example 21 were respectively used.
  • the light-sensitive material as obtained above was imagewise exposed for 10 seconds using a tungsten lamp at 2,000 lux.
  • each of the dye-fixing materials (sheet A and sheet B) was closely brought into contact with the exposed light-sensitive material so that the coated layers were in a face-to-face relationship with each other and each assembly was heated for 30 seconds on a heat block at 130°C.
  • each of the solution (hereinafter “solutions D, E, F, G and H”, respectively) was uniformly coated on a layer containing the dye-fixing agent as in Example 21 at a wet thickness of 60 pm. Then, each coated sample was dried to prepare dye-fixing materials (hereinafter “sheets D, E, F, G and H", respectively).
  • hydrophilic thermal solvents used are as follows.
  • the light-sensitive material as obtained in Example 24 was imagewise exposed for 10 seconds using a tungsten lamp at 2,000 lux.
  • each of the dye-fixing materials was closely brought into contact with the exposed light-sensitive material so that the coated layers were in a face-to-face relationship with each other and each assembly was heated for 30 seconds on a heat block at 130°C.

Claims (17)

1. Trockenes Bildherstellungsverfahren, bei dem ein lichtempfindliches Material, umfassend einen Träger mit wenigstens einem lichtempfindlichen Silberhalogenid, einem Bindemittel und einer farbstofffreisetzenden Redoxverbindung, wärmeentwickelt wird, wobei die farbstofffreisetzende Redoxverbindung gegenüber dem lichtempfindlichen Silberhalogenid reduzierend ist und einen hydrophilen Farbstoff bei Reaktion mit dem lichtempfindlichen Silberhalogenid unter Erwärmen, nach oder gleichzeitig mit der bildweisen Belichtung, freisetzen kann, um bildweise einen beweglichen hydrophilen Farbstoff zu bilden, und das lichtempfindliche Material zusammen mit einer Farbstoffixierschicht in Gegenwart eines hydrophilen thermischen Lösungsmittels nach oder gleichzeitig mit der Wärmeentwicklung erwärmt wird, um dadurch den beweglichen hydrophilen Farbstoff auf die Farbstoffixierschicht zu übertragen zur Bildung eines Farbstoffbildes und Fixierung des Farbstoffbildes darauf, dadurch gekennzeichnet, daß die Farbstoffixierschicht in einem Farbstoffixiermaterial vorgesehen ist, das einen Träger mit wenigstens einem Farbstoffixiermittel, einem hydrophilen thermischen Lösungsmittel und einer Base und/oder einem Basenvorläufer umfaßt.
2. Verfahren nach Anspruch 1, worin die Wärmeentwicklung in einem im wesentlichen wasserfreien Zustand durchgeführt wird.
3. Verfahren nach Anspruch 1 oder 2, worin die farbstofffreisetzende Redoxverbindung eine Verbindung der allgemeinen Formel
Figure imgb0140
ist, worin Ra eine reduzierende Gruppe bedeutet, die durch das Silberhalogenid oxidiert werden kann, und D einen bildbildenden Farbstoffteil, der eine hydrophile Gruppe enthält, bedeutet.
4. Verfahren nach einem der Ansprüche 1 bis 3, worin das lichtempfindliche Silberhalogenid Silberchlorjodid, Silberjodbromid oder Silberchlorjodbromid ist.
5. Verfahren nach einem der Ansprüche 1 bis 4, worin ein organisches Silbersalzoxidationsmittel zusammen mit dem lichtempfindlichen Silberhalogenid vorliegt.
6. Verfahren nach Anspruch 5, worin das organische Silbersalzoxidationsmittel ein Silbersalz einer aliphatischen oder aromatischen Carbonsäure ist.
7. Verfahren nach einem der Ansprüche 1 bis 6, worin das lichtempfindliche Material weiterhin einen farbstofffreisetzenden Aktivator umfaßt.
8. Verfahren nach Anspruch 7, worin der farbstofffreisetzende Aktivator eine Base und/oder ein Basenvorläufer ist.
9. Verfahren nach einem der Ansprüche 1 bis 8, worin das lichtempfindliche Material weiterhin eine Verbindung der allgemeinen Formel
Figure imgb0141
umfaßt, worin A" A2, A3 und A4, die gleich oder verschieden sein können, jeweils ein Wasserstoffatom oder A ein Substituent, gewählt aus einer Alkylgruppe, einer substituierten Alkylgruppe, einer Cycloalkylgruppe, einer Aralkylgruppe, einer Arylgruppe, einer substituierten Arylgruppe und einer heterocyclischen Gruppe, bedeutet und worin A, und A2 oder A3 und A4 sich zur Bildung eines Rings miteinander verbinden können.
10. Verfahren nach einem der Ansprüche 1 bis 9, worin das lichtempfindliche Material weiterhin ein wasserfreisetzendes Mittel, das Wasser durch Zersetzung während der Wärmeentwicklung freisetzt, umfaßt.
11. Verfahren nach einem der Ansprüche 1 bis 10, worin das Erwärmen zur Entwicklung bei einer Temperatur von 80°C bis 250°C durchgeführt wird.
12. Verfahren nach einem der Ansprüche 1 bis 11, worin das Erwärmen zur Übertragung bei einer Temperatur von 60°C bis 250°C durchgeführt wird.
13. Verfahren nach einem der Ansprüche 1 bis 12, worin das hydrophile thermische Lösungsmittel ein nichthydrolisierbares organisches Material ist, das bei Umgebungstemperatur fest ist, jedoch zusammen mit anderen Komponenten bei einer Temperatur der Wärmebehandlung oder darunter schmilzt.
14. Verfahren nach Anspruch 13, worin das hydrophile thermische Lösungsmittel einen (anorganische Eigenschaft/organische Eigenschaft) -Wert von größer als 1 und eine Löslichkeit in Wasser bei Raumtemperatur von mehr als 1 besitzt.
15. Verfahren nach einem der Ansprüche 1 bis 14, worin das farbstofffixierende Mittel ein Farbstoffbeizmittel ist.
16. Verfahren nach einem der Ansprüche 1 bis 15, worin der Träger des farbstoffixierenden Materials mit dem Träger des lichtempfindlichen Materials identisch ist.
17. Verfahren nach einem der Ansprüche 1 bis 15, worin der Träger des farbstoffixierenden Materials von dem Träger des lichtempfindlichen Materials verschieden ist.
EP19840102945 1983-03-16 1984-03-16 Trocken-Bildaufzeichnungsverfahren Expired EP0119615B1 (de)

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JP42092/83 1983-03-16
JP4209283A JPS59168439A (ja) 1983-03-16 1983-03-16 乾式画像形成方法
JP55172/83 1983-04-01
JP5517283A JPS59182447A (ja) 1983-04-01 1983-04-01 乾式画像形成のための色素固定材料

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JPS6291942A (ja) * 1985-10-18 1987-04-27 Fuji Photo Film Co Ltd 画像形成方法
DE3539996A1 (de) * 1985-11-12 1987-05-21 Agfa Gevaert Ag Waermeentwicklungsverfahren und hierfuer geeignetes farbfotografisches aufzeichnungsmaterial
US6277537B1 (en) * 1991-12-06 2001-08-21 Eastman Kodak Company Dye diffusion image separation systems with thermal solvents
US5240809A (en) * 1992-04-20 1993-08-31 Minnesota Mining And Manufacturing Company Imageable articles having dye selective interlayers
US5238792A (en) * 1992-04-20 1993-08-24 Minnesota Mining And Manufacturing Company Imageable articles having dye selective interlayers
US5264321A (en) * 1992-07-16 1993-11-23 Minnesota Mining And Manufacturing Company Photothermographic elements with novel layer structures
US5275927A (en) * 1992-07-16 1994-01-04 Minnesota Mining And Manufacturing Company Photothermographic articles containing novel barrier layers
US5262272A (en) * 1992-10-08 1993-11-16 Minnesota Mining And Manufacturing Company Dye permeable polymer interlayers
EP0687572B1 (de) 1994-06-15 1997-08-20 Agfa-Gevaert N.V. Wärmeempfindliches Aufzeichnungsverfahren
DE69505605T2 (de) 1994-07-13 1999-05-27 Agfa Gevaert Nv Wärmeempfindliches Aufzeichnungsmaterial
EP0775592B1 (de) 1995-11-27 2002-09-11 Agfa-Gevaert Wärmeempfindliches Bildaufzeichnungsverfahren
EP0775595B1 (de) 1995-11-27 1999-09-15 Agfa-Gevaert N.V. Wärmeempfindliches Auszeignungsmaterial, das Phosphorsäurederivaten als Schmiermitteln enthält
EP0782043B1 (de) 1995-12-27 2003-01-15 Agfa-Gevaert Wärmeempfindliches Aufzeichnungsmaterial mit verbesserter Tonwiedergabe
EP0845709B1 (de) 1996-11-29 2006-01-18 Agfa-Gevaert Wärmeempfindliches Aufzeichnungselement und Verfahren zur Herstellung einer lithographischen Druckform damit

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US3438776A (en) * 1964-12-28 1969-04-15 Eastman Kodak Co Non-aqueous silver halide photographic process
DE1572048C3 (de) * 1965-09-10 1978-10-26 Hoechst Ag, 6000 Frankfurt Wärmeentwickelbares Diazotypiematerial
JPS57179840A (en) * 1981-04-30 1982-11-05 Fuji Photo Film Co Ltd Heat developing color photosensitive material
JPS57198458A (en) * 1981-06-01 1982-12-06 Fuji Photo Film Co Ltd Heat developing color photosensitive material

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