EP0212534B1 - Matériau d'enregistrement photographique couleur développable à la chaleur - Google Patents

Matériau d'enregistrement photographique couleur développable à la chaleur Download PDF

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Publication number
EP0212534B1
EP0212534B1 EP86111108A EP86111108A EP0212534B1 EP 0212534 B1 EP0212534 B1 EP 0212534B1 EP 86111108 A EP86111108 A EP 86111108A EP 86111108 A EP86111108 A EP 86111108A EP 0212534 B1 EP0212534 B1 EP 0212534B1
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EP
European Patent Office
Prior art keywords
layer
silver
color
recording material
binder
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
Application number
EP86111108A
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German (de)
English (en)
Other versions
EP0212534A2 (fr
EP0212534A3 (en
Inventor
Karl-Wilhelm Dr. Schranz
Günther Dr. Schenk
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Agfa Gevaert AG
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Agfa Gevaert AG
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Publication of EP0212534A2 publication Critical patent/EP0212534A2/fr
Publication of EP0212534A3 publication Critical patent/EP0212534A3/de
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Publication of EP0212534B1 publication Critical patent/EP0212534B1/fr
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Classifications

    • 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
    • G03C8/408—Additives or processing agents not provided for in groups G03C8/402 - G03C8/4046
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/04—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with macromolecular additives; with layer-forming substances
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • 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
    • G03C1/49863—Inert additives, e.g. surfactants, binders

Definitions

  • the invention relates to a color photographic recording material which can be developed by heat treatment and has at least one binder layer which is applied to a layer support and which contains light-sensitive silver halide and a non-diffusing coloring compound, the binder layer containing a synthetic polymer as binder.
  • color-providing compound those which can be embedded in the layer of a photographic recording material in non-diffusing form and which, as a result of the development, are able to release a diffusible dye (color releaser).
  • color releaser a diffusible dye
  • the particular suitability of such color releasers is based on the fact that the imagewise released dyes can be transferred to special image-receiving layers with the formation of a brilliant color image which is not overlaid with disruptive image silver or silver halide and accordingly does not require any aftertreatment. Combining the heat development process with the color diffusion process thus results in an advantageous rapid process for producing colored images.
  • a recording material suitable for this is described, for example, in DE-A-3 215 485.
  • a recording material having a layer which contains a combination of silver halide, silver benzotriazole, a color releaser and guanidine trichloroacetate (base donor) in a hydrobene binder is exposed imagewise and then subjected to a heat treatment in contact with an image-receiving sheet, the imagewise released dye the image receiving sheet is transferred.
  • the silver halide in each of these combinations being sensitive to a different spectral range of the light and, in accordance with its spectral sensitivity, containing a color releaser which releases a dye of a different color, usually a color that is complementary is the color of the light for which the silver halide in question has a predominant sensitivity.
  • Such assignments can be arranged one above the other in different layers.
  • the color images obtained with the known color photographic recording material which can be developed by heat treatment have rather low maximum color densities and high fog.
  • the recording material also leaves something to be desired in terms of sensitivity.
  • the application is therefore based on the object of specifying a color photographic recording material which can be developed by heat treatment and which is further improved in terms of the Dmin / Dmax variation and in terms of sensitivity.
  • the present invention relates to a heat treatment-developable photographic recording material having at least one binder layer applied to a layer, which contains light-sensitive silver halide, optionally combined with a substantially non-light-sensitive silver salt, and at least one non-diffusing color-providing compound which, as a result of the development by heat treatment is able to release a diffusible dye, which is characterized in that the binder of said binder layer contains at least 30% by weight. consists of a polyurethane containing anionic groups.
  • the color photographic recording material according to the invention contains, on a dimensionally stable support, at least one binder layer which contains, as essential components, a light-sensitive silver halide, optionally in combination with an essentially non-light-sensitive silver salt, and a non-diffusing color-imparting compound which can produce a diffusible dye through heat development.
  • the light-sensitive silver halide can consist of silver chloride, silver bromide, silver iodide or mixtures thereof and a particle size between 0.01 and 2.0 ⁇ m. preferably have between 0.1 and 1.0 ⁇ m. It can be in the form of an unsensitized silver halide or it can also be chemically sensitized, e.g. B. with compounds of sulfur, selenium or tellurium, or with compounds of gold, platinum, palladium, rhodium or iridium, or with a reducing agent, such as. B. a tin halide, or a combination thereof.
  • the silver halide can additionally be spectrally sensitized with known organic sensitizing dyes.
  • the amount of light-sensitive silver halide in the respective layer can be between 0.01 and 2.0 g per m 2 , the actual amount of the silver halide used, due to its catalytic function (as exposed silver halide) in some embodiments, mainly in the lower part of the stated Area moved.
  • the substantially non-light-sensitive silver salt can be, for example, a silver salt which is comparatively stable to light, e.g. B. act an organic silver salt.
  • Suitable examples include the silver salts of aliphatic or aromatic carboxylic acids and the silver salts of nitrogen-containing heterocycles; also silver salts of organic mercapto compounds.
  • Preferred examples of silver salts of aliphatic carboxylic acids are silver behenate, silver stearate, silver oleate, silver laurate, silver caprate, silver myristate, silver palmitate, silver maleate, silver fumarate, silver tartrate, silver furoate, silver linolate, silver adipate, silver sebacate, silver succinate, silver acetate or silver acetate.
  • the carboxylic acids on which these silver salts are based can be substituted, for example, by halogen atoms, hydroxyl groups or thioether groups.
  • silver salts of aromatic carboxylic acids and other compounds containing carboxyl groups include silver benzoate, silver 3,5-dihydroxybenzoate, silver o-methylbenzoate, silver m-methylbenzoate, silver p-methylbenzoate, silver 2,4-dichlorobenzoate, silver acetamidobenzoate , Silver gallate, silver tannate, silver phthalate, silver terephthalate, silver salicylate, silver phenylacetate, silver pyromellitate, silver salts of 3-carboxymethyl-4-methyl-4-thiazolin-2-thione or similar heterocyclic compounds.
  • Silver salts of organic mercaptans e.g. B.
  • the silver salts of compounds having an imino group are also suitable.
  • Preferred examples include the silver salts of benzotriazole and its derivatives, e.g. B. silver salts of alkyl and / or halogen-substituted benzotriazoles, such as. B. the silver salts of methylbenzotriazole, 5-chlorobenzotriazole and also the silver salts of 1,2,4-triazole, 1-H-tetrazole, carbazole, saccharin and silver salts of imidazole, benzimidazole and their derivatives.
  • the application amount of essentially non-photosensitive silver salt according to the present invention is in the respective layer between 0.05 and 5 g per m 2 .
  • the essentially non-light-sensitive silver salt and the light-sensitive silver halide can be present side by side as separate particles or in a combined form, which can be produced, for example, by treating a substantially non-light-sensitive silver salt in the presence of halide ions, the surface of which Particles of the essentially non-photosensitive silver salt are formed by double conversion (conversion) of photosensitive centers from photosensitive silver halide.
  • halide ions the surface of which Particles of the essentially non-photosensitive silver salt are formed by double conversion (conversion) of photosensitive centers from photosensitive silver halide.
  • conversion conversion
  • the essentially non-light-sensitive silver salt serves as a reservoir for metal ions, which are reduced to elemental silver when heat is developed in the presence of a reducing agent under the catalytic influence of the imagewise exposed silver halide and thereby serve as an oxidizing agent (for the reducing agent present).
  • Another essential component of the recording material according to the invention is at least one non-diffusing coloring compound which, as a result of a redox reaction taking place during development, is able to release a diffusible dye and which is referred to below as a color releasing agent.
  • the dye releasers used according to the invention can be a variety of connection types, all of which are distinguished by a link which is redox-dependent in terms of their bond strength and which links a dye residue to a carrier residue containing a ballast residue.
  • Redox-active carrier residues of the BALLAST-REDOX structure and corresponding color releasers are known in a wide variety of embodiments. A detailed description can be omitted here with regard to the above-mentioned overview article in the app. Chem. Lnt. Ed. Engl. 22 (1983) 191-209.
  • redox-active carrier residues Some examples of redox-active carrier residues are listed below, by way of explanation only to which a dye residue is split off in accordance with an image-related oxidation or reduction:
  • the groups enclosed in brackets are functional groups of the dye residue and are separated together with this from the remaining part of the carrier residue.
  • the functional group can be a substituent which can have a direct influence on the absorption and, if appropriate, complex formation properties of the released dye.
  • the functional group can also be separated from the chromophore of the dye by an intermediate link or a link.
  • the functional group together with the intermediate member may also be of importance for the diffusion and pickling behavior of the released dye.
  • Suitable intermediate members are, for example, alkylene or arylene groups.
  • the residues of dyes of all dye classes are suitable as dye residues insofar as they are sufficiently diffusible to be able to diffuse from the light-sensitive layer of the light-sensitive material into an image-receiving layer.
  • the dye residues can be provided with one or more alkali-solubilizing groups.
  • Suitable alkali-solubilizing groups include carboxyl groups, sulfo groups, sulfonamide groups and aromatic hydroxyl groups.
  • Such alkali-solubilizing groups can already be pre-formed in the dye releasers or can only result from the cleavage of the dye residue from the carrier residue containing ballast groups.
  • Suitable dyes include: azo dyes, azomethine dyes, anthraquinone dyes, phthalocyanine dyes, indigoid dyes, triphenylmethane dyes, including those dyes that are complexed or complexable with metal ions.
  • the residues of dye precursors are to be understood as the residues of those compounds which, in the course of photographic processing, in particular under the conditions of heat development, either by oxidation, by coupling, by complex formation or by exposure of an auxochromic group in a chromophoric system, for example by saponification, can be converted into dyes.
  • Dye precursors in this sense can be leuco dyes, couplers or dyes that are converted into other dyes during processing. Unless a distinction is made between dye residues and the residues of dye precursors, the latter should also be understood below as dye residues.
  • the color releasers can be present as oxidisable or couplable color releasers, in others as reducible color releasers.
  • the dye is released from the oxidized or from the reduced form of the color releasing agent, negative or positive illumination is obtained from the original when conventional negative-working silver halide emulsions are used. You can therefore create positive or negative images by selecting suitable color releasing systems.
  • DE-A-2 645 656 is described, for example, in DE-A-2 645 656 which is particularly suitable for the heat-developable recording materials according to the invention.
  • the color splitter can be oxidized, then it is itself a reducing agent which, directly or indirectly, with the participation of electron transfer agents (electron transfer agent, ETA) through the imagewise exposed silver halide or through the essentially non-photosensitive silver salt under the catalytic action of the imagewise exposed Silver halide is oxidized.
  • electron transfer agent electro transfer agent
  • the paint releaser is reducible, then it is suitably used in combination with one; reducing agent present in a limited amount, a so-called electron donor compound or an electron donor precursor compound, which in this case is contained in the same binder layer in addition to the color releaser, the photosensitive silver halide and, if appropriate, the essentially non-photosensitive silver salt.
  • reducing agent present in a limited amount, a so-called electron donor compound or an electron donor precursor compound, which in this case is contained in the same binder layer in addition to the color releaser, the photosensitive silver halide and, if appropriate, the essentially non-photosensitive silver salt.
  • electron transfer agents can also prove to be advantageous in the case of the use of reducible color releasers in combination with electron donor compounds.
  • the electron donor compound used in combination with a reducible color releasing agent also serves as a reducing agent for the silver halide, the essentially non-photosensitive silver salt and the color releasing agent. Because the essentially non-light-sensitive silver salt and the color releaser compete with each other to a certain extent in the oxidation of the electron donor compound, but the latter is in any case superior to the latter in the presence of exposed silver halide, the silver halide present becomes determinant for that in accordance with a previous imagewise exposure Image areas within which the color releaser is converted into its reduced form by the electron donor compound.
  • the electron donor compound which is present in a limited amount, under the conditions of development, in the present case when the imagewise exposed color photographic material is heated, in accordance with the extent of the exposure under the catalytic effect of the latent image nuclei produced by exposure in the silver halide by the essentially non-light-sensitive silver salt and
  • the light-sensitive silver halide oxidizes and is therefore no longer available for a reaction with the color releaser. This creates an image-like distribution of unused electron donor compound.
  • electron donor compounds are disclosed in DE-A-2 947 425, DE-A-3 006 268, DE-A-3 130 842, DE-A-3 144 037, DE-A-3 217 877 and EP-A- 0 124 915 and Research Disclosure 24 305 (July 1984). It has been shown that the electron donor compounds mentioned also meet the requirements placed on them under the conditions of heat development and are therefore also suitable as electron donor compounds in the context of the present invention. Particularly suitable are those electron donor compounds that are formed in the layer from corresponding electron donor precursor compounds only under the conditions of heat development, i. H. Electron donor compounds that are only in a capped form in the recording material before development, in which they are practically ineffective. Under the conditions of heat development, the electron donor compounds, which are initially ineffective, are then converted into their effective form, for example by hydrolytically cleaving off certain protective groups. In the present case, the electron donor precursor compounds mentioned are also understood as electron donor compounds.
  • the binder consists of at least 30% by weight of a polyurethane containing anionic groups.
  • the remaining (up to 100% by weight. Missing) portion of the binder mainly consists of a conventional hydrophilic layer binder, mostly of natural origin, in particular gelatin.
  • Binder compositions preferred according to the invention are mixtures of gelatin and a polyurethane containing anionic groups, the latter preferably being present in an amount between 50 and 95% by weight, based on the total amount of binder.
  • the polyurethane mentioned can also be the sole binder.
  • Water-insoluble compounds that can be added are gelatin-compatible plastic latices of polyacrylic acid esters and their copolymers and polyvinyl ethers or their copolymers.
  • the compounds according to the invention can advantageously be combined with dispersions of water-insoluble polyethers of the type described in GB-A-1 053 568 or with dispersions of other water-insoluble compounds with a boiling point above 250 ° C.
  • polyurethanes to be used according to the invention are distinguished by the fact that they contain chemically incorporated hydrophilic groups, in particular anionic groups, preferably sulfate, sulfonate or carboxylate groups.
  • Suitable polyurethanes are, for example, those which contain an anionic group content of at least 5 milliequivalents per 100 g solid, preferably from 9 to 35 milliequivalents per 100 g solid.
  • the polyurethanes are generally formed by the reaction (polyaddition) of polyisocyanates with compounds which contain several reactive hydrogen atoms.
  • polyester polyacetals, polyethers, polyamides or polyesteramides, and such compounds with a lower molecular weight, the so-called chain extenders.
  • the reactive hydrogen atoms are usually those of hydroxyl, amino or carboxyl groups.
  • Common starting products for the production of polyurethanes are, for example, hydroxyl-containing polyesters, in particular linear polyesters with two terminal free hydroxyl groups.
  • Particularly suitable polyisocyanates are diisocyanates, for example all aromatic and aliphatic diisocyanates, such as. B. 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, di- and tetraalkyldiphenylmethane diisocyanate, 4,4'-dibenzyte diisocyanate, 1,3-phenylene diisocyanate.
  • diisocyanates for example all aromatic and aliphatic diisocyanates, such as. B. 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, di- and tetraalkyldiphenylmethane diisocyanate, 4,4'-dibenzyte diisocyan
  • 1,4-phenylene diisocyanate the isomers of tolylene diisocyanate, optionally in a mixture, chlorinated and brominated diisocyanates, preferably the aliphatic diisocyanates, butane-1,4-diisocyanate, hexane-1,6-diisocyanate, dicyclohexylmethane diisocyanate, cyclohexane-1,4-diisocyanate as well as prepolymers containing isocyanate groups.
  • the introduction of the anionic groups into the molecule of the polyurethanes can be achieved in that compounds which contain at least one active hydrogen atom and at least one anionic group or a group which can be converted into an anionic group are already present during the polyaddition reaction which leads to the polyurethanes . These latter compounds are incorporated into the polymer molecule by reaction with some of the isocyanate groups present. If the isocyanate groups present are not completely consumed in the production of the polyurethanes, the anionic groups can also be introduced by means of the compounds mentioned after the formation of the polyurethanes.
  • the subsequent introduction of the anionic or anionizable groups can also be achieved in a known manner by reaction with compounds which have an alkylating or acylating function and can form an anionic group in the reaction concerned.
  • compounds mostly have a cyclic structure; Dicarboxylic anhydrides, sulfones, lactones, epoxy carboxylic acids and cyclic sulfates are examples of this.
  • the polyaddition can be carried out, for example, with the use of solvents, with low-boiling solvents such as acetone, ethanol, methanol, tert-butanol, methyl ethyl ketone, which may optionally contain a proportion of water, preferably being suitable.
  • solvents with low-boiling solvents such as acetone, ethanol, methanol, tert-butanol, methyl ethyl ketone, which may optionally contain a proportion of water, preferably being suitable.
  • Water can be used as a solvent for inorganic bases and the compounds having at least one hydrogen atom reacting with isocyanate groups and at least one anionic group, if appropriate without the addition of organic solvents.
  • the resulting predominantly linear, high molecular weight anionic group-containing polyurethanes can be converted into the aqueous phase by adding water and the organic solvents can be removed simultaneously or subsequently. Dispersions are obtained in the form of latices or solutions. Processes for the preparation of suitable polyurethanes containing anionic groups are described, for example, in GB-A-1 076 688, US-A-3 479 310, US-A-4 108 814, US-4 092 286, DE-A-2 725 589 and DE-A-2 811 148.
  • Polyaddition product composed of 218.5 g of adipic acid-hexanediol-neopentylglycol polyester (OH number 63), 55 g of 1,6-hexanediisocyanate and 27.8 g of sodium 1,2-diaminoethane-N-pro-pansulfonate.
  • Polyaddition product composed of 218.5 g of adipic acid-hexanediol-neopentyl glycol polyester, 55 g of 1,6-hexanediisocyanate and 29.8 g of potassium 1,2-diaminoethane-N-propanesulfonate.
  • Polyaddition product composed of 218.5 g of adipic acid-hexanediol-neopentylglycol polyester, 30.6 g of 1,6-hexanediisocyanate and 31.9 g of a 20% aqueous sodium ethanesulfonate solution.
  • Polyaddition product composed of 218.5 g of adipic acid-hexanediol-neopentyl glycol polyester, 45.5 g of 1,6-hexanediisocyanate and 138.0 g of a 20% aqueous sodium aminoethanesulfonate solution.
  • Polyaddition product composed of 218.5 g of adipic acid-hexanediol-neopentyl glycol polyester, 44.2 g of 1,6-hexanediisocyanate and 92.0 g of a 20% aqueous sodium aminoethanesulfonate solution.
  • Polyaddition product composed of 218.5 g of adipic acid-hexanediol-neopentyl glycol polyester, 39.0 g of 1,6-hexanediisocyanate and 92.0 g of a 20% aqueous sodium aminoethanesulfonate solution.
  • Polyaddition product composed of 218.5 g of adipic acid-hexanediol-neopentyl glycol polyester, 32.6 g of 1,6-hexanediisocyanate and 46 g of a 20% aqueous sodium aminoethanesulfonate solution.
  • Polyaddition product composed of 218.5 g of adipic acid-hexanediol-neopentyl glycol polyester, 34.6 g of 1,6-hexanediisocyanate and 61.2 g of a 20% aqueous sodium aminoethanesulfonate solution.
  • Polyaddition product composed of 218.5 g of adipic acid-hexanediol-neopentylglycol polyester, 52.0 g of 1,6-hexanediisocyanate and 184.0 g of a 20% aqueous sodium aminoethanesulfonate solution.
  • Polyaddition product composed of 218.5 g of adipic acid-hexanediol-neopentyl glycol polyester, 42.0 g of 1,6-hexanediisocyanate, 12.9 g of diethylenetriamine, 12.5 g of succinic anhydride and 4.9 g of potassium hydroxide.
  • Polyaddition product composed of 218.5 g of adipic acid-hexanediol-neopentyl glycol polyester, 42.0 g of 1,6-hexanediisocyanate, 12.9 g of diethylenetriamine, 12.5 g of succinic anhydride and 6.3 g of potassium hydroxide.
  • Polyaddition product composed of 218.5 g of adipic acid-hexanediol-neopentyl glycol polyester, 38.0 g of 1,6-hexanediisocyanate and 14.9 g of potassium 1,2-diaminoethane-N-propanesulfonate.
  • Polyaddition product made from 218.5 g adipic acid-hexanediol-neopentyl glycol polyester, 32.5 g of 1,6-hexanediisocyanate and 7.5 g of potassium 1,2-diaminoethane-N-propanesulfonate.
  • Polyaddition product composed of 218.5 g of adipic acid-hexanediol-neopentyl glycol polyester, 36.7 g of 1,6-hexanediisocyanate and 11.2 g of potassium 1,2-diaminoethane-N-propanesulfonate.
  • Polyaddition product made from 106.3 g adipic acid-hexanediol-neopentyl glycol polyester (OH number 65.85), 128.5 g 1,6-hexane diisocyanate, 52.0 g neopentyl glycol and 29.8 g potassium 1,2-diaminoethane N-propane sulfonate.
  • Polyaddition product made from 106.3 g adipic acid-hexanediol-neopentyl glycol polyester (OH number 65.85), 121.0 g of 1,6-hexane diisocyanate, 26.5 g of diethylene glycol, 26.0 g of neopentyl glycol and 29.8 g of potassium 1,2-diaminoethane-N-propanesulfonate.
  • Polyaddition product made from 212.5 g adipic acid-hexanediol-neopentyl glycol polyester (OH number 65.85), 89.0 g of 1,6-hexane diisocyanate and 59.6 g of potassium 1,2-diaminoethane-N-propanesulfonate.
  • Polyaddition product consisting of 212.5 g adipic acid-hexanediol-neopentylglycol polyester (OH number 65.85), 72.0 g of 1,6-hexane diisocyanate and 44.7 g of potassium 1,2-diaminoethane-N-propanesulfonate.
  • Polyaddition product made from 250.0 g polypropylene glycol (OH number 56), 48.0 g 1,6-hexane diisocyanate and 29.8 g potassium 1,2-diaminoethane-N-propanesulfonate.
  • the color photographic recording material can contain further constituents and auxiliary substances which are beneficial, for example, for carrying out the heat treatment and the color transfer which takes place in the process.
  • these further constituents or auxiliary substances can be contained in a light-sensitive layer or in a non-sensitive layer.
  • auxiliaries are, for example, auxiliary developers.
  • ETA electron transfer agents
  • auxiliary developers examples include hydroquinone, pyrocatechol, pyrogallol, hydroxylamine, ascorbic acid, 1-phenyl-3-pyrazolinone and their derivatives. Since the auxiliary developers have a catalytic function, it is not necessary for them to be present in stoichiometric amounts. In general, it is sufficient if they are present in the layer in amounts up to a maximum of 1/2 mol per mol of color releaser. Incorporation into the layer can take place, for example, from solutions in water-soluble solvents or in the form of aqueous dispersions which have been obtained using oil formers.
  • auxiliaries are, for example, basic substances or compounds which are able to provide basic substances under the influence of the heat treatment.
  • a suitable alkaline medium is created during the heat treatment in the light-sensitive layer and the adjacent layers in order to ensure the release of the diffusible dyes from the color releasers and their diffusion into the image-receiving layer.
  • auxiliaries are, for example, compounds which are able to release water under the action of heat.
  • inorganic salts containing water of crystallization come into question, e.g. B. Na 2 S0 4 -10H 2 0, NH4Fe (S04h.12H20, and also compounds of the sodium benzotriazolate type, which crystallize as a complex with various amounts of water (up to 24 mol H 2 0) and which in US-A-4 418 139 are described.
  • the water released during heating favors the development and diffusion processes required for image formation.
  • auxiliaries are, for example, the so-called thermal solvents or development and diffusion promotion agents, which are generally understood to mean non-hydrolyzable organic compounds which are solid or liquid under normal conditions, but in any case provide a liquid medium at the temperature of the heat treatment, in which the development and diffusion processes can run faster.
  • Preferred examples of these include polyglycols as described, for example, in US-A-3,347,675, e.g. B. polyethylene glycol with an average molecular weight of 1500 to 20,000, derivatives of polyethylene oxide, such as its oleic acid ester, beeswax, monostearin, compounds with a high dielectric constant, which have a -S0 2 - or -CO group, such as. B.
  • the development of the imagewise exposed color photographic recording material according to the invention comprises the partial steps of silver halide development, generation of an imagewise distribution of diffusible dyes and diffusion transfer of this imagewise distribution into the image receiving layer. It is initiated by subjecting the exposed recording material to a heat treatment in which the photosensitive binder layer is heated to an elevated temperature, e.g. B. is brought in the range of 80 to 250 ° C. This makes suitable ones in the recording material Conditions for the development processes including dye diffusion are created without the addition of a liquid medium, e.g. B. in the form of a developer bath. During development, diffusible dyes are released imagewise from the color releasers and transferred to an image-receiving layer which is either an integral part of the color photographic recording material according to the invention or is in contact with it at least during the development period.
  • Image-wise silver development, dye release and color transfer take place synchronously in a one-step development process.
  • the color image formation with the color photographic recording material according to the invention can also be carried out in a two-step development process, silver halide development and dye release taking place in a first step, followed by color image transfer in a second step from the light-sensitive part to an image receiving part brought into contact with it, e.g. . B. by heating to a temperature between 50 and 150 ° C, preferably to 70 to 90 ° C, in which case diffusion aids (solvents) can be applied externally before the lamination of the light-sensitive part and the image receiving part.
  • diffusion aids solvents
  • the image-receiving layer can accordingly be arranged on the same layer support as the light-sensitive element (single sheet material) or on a separate layer support (two-sheet material). It essentially consists of a binder which contains mordants for the determination of the diffusible dyes released from the non-diffusing paint releasers. Long-chain quaternary ammonium or phosphonium compounds, e.g. B. As described in US-A-3,271,147 and US-A-3,271,148.
  • certain metal salts and their hydroxides which form poorly soluble compounds with the acid dyes, can also be used.
  • polymeric mordants such as those described in DE-A-2 315 304, DE-A-2 631 521 or DE-A-2 941 818.
  • the dye mordants are dispersed in the mordant layer in one of the usual hydrophilic binders, e.g. B. in gelatin, polyvinyl pyrrolidone, completely or partially hydrolyzed cellulose esters.
  • some binders can also act as mordants, e.g. B.
  • polymers of nitrogen-containing, optionally quaternary bases such as N-methyl-4-vinylpyridine, 4-vinylpyridine, 1-vinylimidazole, as described, for example, in US Pat. No. 2,484,430.
  • Other useful binding agents are, for example, guanylhydrazone derivatives of alkyl vinyl ketone polymers, as described, for example, in US Pat. No. 2,882,156, or guanylhydrazone derivatives of acyl styrene polymers, as described, for example, in DE-A-2 009 498.
  • other binders e.g. B. add gelatin.
  • the image-receiving layer remains in layer contact with the light-sensitive element even after development is complete, there is usually an alkali-permeable, pigment-containing, light-reflecting image middle layer between them, which serves as an optical separation between negative and positive and serves as an aesthetically pleasing background for the positive color image.
  • the binder-receiving layer is arranged between the support and the photosensitive element and is separated from the latter by a pre-formed light-reflecting layer, either the support must be transparent so that the color transfer image produced can be viewed through it, or the photosensitive element together with the light-reflecting layer of the image-receiving layer are removed to expose the latter.
  • the image-receiving layer can, however, also be present as the top layer in an integral color photographic recording material, in which case the exposure is expediently carried out through the transparent layer support.
  • emulsion 2 For spectral sensitization, parts of emulsion 2 (crude emulsion) were melted at 40 ° C., per mol of Ag with 4 x 10- 4 mol red sensitizer, 4 x 10- 4 mol green sensitizer or 8 x 10- 4 mol blue sensitizer, each in methanolic solution or slurry , added and digested in a closed vessel for about 70 min.
  • Dispersant 1 (paint releasing agent C 1)
  • Dispersant 2 (paint releasing agent M -1)
  • Dispersant 3 (paint releasing agent M - 2)
  • Dispersant 4 (paint releasing agent Y - 1)
  • Dispersant 5 (auxiliary developer precursor compound)
  • auxiliary developer precursor compound 62 g were dissolved in 120 g of diethyl laurylamide and 150 ml of ethyl acetate and dispersed in 612 g of 10% aqueous gelatin solution in the presence of 3.5 g of sodium dodecylbenzenesulfonate; and then the auxiliary solvent was removed as for Dispersate 1. Yield: 997 g of disperse 5
  • the Ti0 2 layer can be dispensed with.
  • the light-sensitive parts of non-inventive (comparison) and color photographic recording materials according to the invention for the color diffusion transfer process were produced as follows:
  • dispersant 1 color releasing agent C -1
  • disperse 5 auxiliary developer precursor compound
  • 66 g of 20% gelatin 150 mg of mercury-II chloride dissolved in 30 ml of water and 3.2 g of guanidine trichloroacetate in 30 ml of water were added and the mixture was then brought to a final weight of 320 g with water.
  • the solution was applied with a wet layer thickness of 100 ⁇ m to a layer support made of polyethylene terephthalate and covered with a 1% aqueous gelatin solution (wet layer thickness 40 ⁇ m) containing a hardening agent and rocked.
  • the finished casting solution was applied with a wet layer thickness of 100 ⁇ m to a layer support made from polyethylene terephthalate and dried at 35 ° C. With a 1% aqueous gelatin solution containing a hardening agent was overlaid (wet layer thickness 40 microns) and dried.
  • the samples produced according to Example 4 were exposed with a tungsten lamp, the exposure in the case of samples 1, 2, 4, 5 and 7 being carried out behind a transparent yellow filter with a density of 1.25.
  • the intensity and duration of the exposure can be seen from Table 1.
  • the samples were then dried to 110 ° C for development; the duration of this treatment is also shown in Table 1.
  • the samples were then swollen in water for 10 s and laminated together with an image-receiving sheet (from Example 3) which had been swollen in water for 30 s and heated on a regulated heating bench at 75 ° C. for 2 minutes, then separated and then immediately dried. Sharp, brilliant color transfers were obtained on the image-receiving sheets.
  • the Dmin and Dmax values are also shown in Table 1.
  • Integral recording materials for the color diffusion transfer process consisting of the light-sensitive part and the image-receiving part were produced by applying the layer-coating solutions described below on a layer support made of polyethylene terephthalate.
  • Samples 8, 9 and 10 were exposed to a tungsten lamp with 1000 lux through the transparent support for 10 s, in the case of samples 8 and 9 behind a transparent yellow filter with a density of 1.25. Then dry development was carried out for 60 s at 110 ° C. on a heating bench and the dry developed samples 8, 9 and 10 were only exposed to a water vapor atmosphere of 75 ° C. for 4 minutes. It was then dried briefly at room temperature. The Dmin and Dmax values obtained are shown in Table 2.
  • the process variant described here does not require any processing baths; Rather, heat is sufficient and secondly water vapor, for example at 75 ° C. However, the second treatment step can also consist in swelling the (dry developed) recording material in water and then heating it to 75 ° C., for example on a heating bench.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)

Claims (4)

1. Matériau d'enregistrement photographique en couleurs développable par un traitement à la chaleur, comprenant au moins une couche de liant appliquée sur un support de couche, qui contient un halogénure d'argent photosensible, éventuellement en combinaison avec un sel d'argent essentiellement non photosensible, et au moins un composé chromogène non diffusant capable de libérer un colorant diffusible à la suite du développement par le traitement à la chaleur, caractérisé en ce que le liant de la couche de liant en question consiste pour au moins 30 % en poids en un polyuréthanne contenant des groupes anioniques.
2. Matériau d'enregistrement selon la revendication 1, caractérisé en ce que le liant de la couche de liant en question consiste pour 50 à 95 % en poids en un polyuréthanne contenant des groupes anioniques, pour 5 à 50 % en poids en un liant hydrophile pour couches et le cas échéant pour 0 à 5 % en poids en un agent épaississant.
3. Matériau d'enregistrement selon la revendication 2, caractérisé en ce que le liant hydrophile pour couches consiste en gélatine.
4. Matériau d'enregistrement selon l'une des revendications 1 à 3, caractérisé en ce que le polyuréthanne contient au moins 5 milliéquivalents de groupes anioniques pour 100 g de matière solide.
EP86111108A 1985-08-23 1986-08-12 Matériau d'enregistrement photographique couleur développable à la chaleur Expired EP0212534B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19853530156 DE3530156A1 (de) 1985-08-23 1985-08-23 Durch waermebehandlung entwickelbares farbfotografisches aufzeichnungsmaterial
DE3530156 1985-08-23

Publications (3)

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EP0212534A2 EP0212534A2 (fr) 1987-03-04
EP0212534A3 EP0212534A3 (en) 1987-12-16
EP0212534B1 true EP0212534B1 (fr) 1989-01-04

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US (1) US4810628A (fr)
EP (1) EP0212534B1 (fr)
JP (1) JPS6250754A (fr)
DE (2) DE3530156A1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3768246D1 (de) * 1987-01-16 1991-04-04 Agfa Gevaert Nv Bildempfangsmaterial zur verwendung in diffusionsuebertragungs-umkehrverfahren.
DE3708307A1 (de) * 1987-03-14 1988-09-22 Agfa Gevaert Ag Farbfotografisches aufzeichnungsmaterial fuer das farbdiffusionsuebertragungsverfahren
US5084331A (en) * 1989-01-23 1992-01-28 International Business Machines Corporation Electroerosion recording medium of improved corrosion resistance
US5176947A (en) * 1990-12-07 1993-01-05 International Business Machines Corporation Electroerosion printing plates
EP0839337B1 (fr) * 1995-07-18 2002-05-22 Agfa-Gevaert Materiau d'enregistrement photothermographique

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1472746B2 (de) * 1965-03-17 1977-02-17 Agfa-Gevaert Ag, 5090 Leverkusen Photographisches aufzeichnungsmaterial
US4036650A (en) * 1974-08-27 1977-07-19 Canon Kabushiki Kaisha Heat developable photosensitive material containing compounds of sulfur
JPS59229556A (ja) * 1983-06-13 1984-12-24 Konishiroku Photo Ind Co Ltd 熱現像カラ−感光要素

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Publication number Publication date
EP0212534A2 (fr) 1987-03-04
DE3661660D1 (en) 1989-02-09
EP0212534A3 (en) 1987-12-16
DE3530156A1 (de) 1987-03-05
JPS6250754A (ja) 1987-03-05
US4810628A (en) 1989-03-07

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