EP0261567A2 - Procédé de développement thermique et matériau de reproduction photographique couleur approprié à cet effet - Google Patents

Procédé de développement thermique et matériau de reproduction photographique couleur approprié à cet effet Download PDF

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Publication number
EP0261567A2
EP0261567A2 EP87113515A EP87113515A EP0261567A2 EP 0261567 A2 EP0261567 A2 EP 0261567A2 EP 87113515 A EP87113515 A EP 87113515A EP 87113515 A EP87113515 A EP 87113515A EP 0261567 A2 EP0261567 A2 EP 0261567A2
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EP
European Patent Office
Prior art keywords
color
recording material
development
silver
light
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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.)
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EP87113515A
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German (de)
English (en)
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EP0261567A3 (fr
Inventor
Günther Dr. Schenk
Manfred Dr. Peters
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Agfa Gevaert AG
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Agfa Gevaert AG
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Publication of EP0261567A2 publication Critical patent/EP0261567A2/fr
Publication of EP0261567A3 publication Critical patent/EP0261567A3/fr
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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
    • 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
    • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
    • G03C8/24—Photosensitive materials characterised by the image-receiving section
    • G03C8/246—Non-macromolecular agents inhibiting image regression or formation of ghost images

Definitions

  • the invention relates to a heat development process in which an imagewise exposed color photographic recording material which contains a binder layer with silver halide and at least one coloring compound on a common layer support in contact with an image receiving layer which is an integral part of the recording material or can be arranged on a separate layer support is subjected to the development of a heat treatment, at least one so-called thermal development and diffusion promoting agent being present.
  • color-imparting compounds are those which can be embedded in the layer of a photographic recording material in a non-diffusing form and which, as a result of the development, can release a diffusible dye (color releaser).
  • a recording material having a layer containing a combination of silver halide, silver benzotriazole, a color releasing agent and guanidine trichloroacetate is exposed imagewise and then subjected to a heat treatment in contact with an image-receiving sheet, whereby the image-released dye is transferred to the image-receiving sheet .
  • the silver halide in each of these combinations being sensitive to a different spectral range of the light and, according to 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.
  • melt-formers so-called melt-formers or "thermal solvents", as described, for example, in RESEARCH DISCLOSURE publications 15027 (October 1976), 15,108 (November. 1976), 17 029 (June 1978) or in DE-A-33 39 810, EP-AO 119 615 and EP-AO 112 512.
  • the compounds mentioned are generally solid under normal conditions, but are in molten form at the higher temperature of the heat treatment and, owing to their dipolar character, form a medium which promotes the development processes.
  • Most of the thermal solvents mentioned are compounds with a protic character.
  • the heat treatment is dry, i.e. can be carried out without moistening the recording materials or the image-receiving sheets, and in this case considerable results are achieved, it is desirable to further improve the process and in this way to shorten the required treatment time and / or to achieve higher color transfer densities.
  • the invention relates to a heat development process for producing colored images, in which an imagewise exposed color photographic recording material with at least one on a layer support arranged binder layer, which contains light-sensitive silver halide, optionally in combination with a substantially non-light-sensitive silver salt, and at least one non-diffusing coloring compound which, as a result of the development, is able to release a diffusible dye, is developed by heat treatment in the presence of a thermal development and diffusion promoting agent , wherein the dye released imagewise from the non-diffusing coloring compound is transferred into an image-receiving layer which can be colored by diffusible dyes, characterized in that the thermal development and diffusion promoting agent corresponds to the following formula I: in what mean X -SO2- or -CO-; R1 - R4 alkyl, cycloalkyl, aralkyl or aryl; R5, R6 acyl or a radical as indicated for R1 - R4; wherein R1 together with R5, R2 together with R6,
  • Another object of the invention is a color photographic recording material which is suitable for the heat development process and contains at least one thermal development and diffusion promoting agent of the type specified in at least one of its layers.
  • R1 to R6 can be the same or different. They are preferably identical in pairs (R1, R2; R3, R4; R5, R6).
  • An alkyl group represented by R1 to R6 can be unbranched or branched and optionally substituted and preferably contain 1 to 4 carbon atoms. Examples include methyl, ethyl, propyl, isopropyl, n-butyl, s-butyl, methoxymethyl, cyclohexylmethyl, hydroxyethyl.
  • the alkyl groups, in particular those represented by R3 and R, can also individually contain up to 18 carbon atoms.
  • a cycloalkyl group represented by R1 to R6 is, for example, cyclohexyl.
  • An aralkyl group represented by R1 to R6 is, for example, benzyl.
  • An aryl group represented by R1 to R6 is, for example, phenyl, tolyl, methoxyphenyl, N-methyl-N-acetylamino-phenyl.
  • An acyl group represented by R5 or R6 can be derived from aliphatic or aromatic carboxylic or sulfonic acids or also from carbamic or sulfamic acids. Acetyl, methylsulfonyl, phenylsulfonyl, p-methoxyphenylsulfonyl and p-nitrophenylsulfonyl are examples of this.
  • Heterocyclic rings which are formed by R1 and R5, R2 and R6, R3 and R4 and / or R1 and R2 are preferably 5- or 6-membered and have at least one nitrogen atom and optionally further heteroatoms.
  • a heterocyclic ring formed by R1 together with R2 has at least 2 nitrogen atoms. Examples of such heterocyclic rings are pyrrolidine, piperidine, morpholine, imidazolidine and hexahydropyrimidine.
  • the thermal development and diffusion promoting agents according to the invention apparently act under the conditions of heat development as a solvating medium for the reactions taking place such as development of the silver halide or the organic silver salt under the influence of a reducing agent, release of the diffusible Dyes from the coloring compounds and diffusion of the dyes into an image-receiving layer.
  • TEDM thermal development and diffusion promoting agents
  • Appropriate variation of the substituents R1 to R6, in particular the substituents R1 and R2 allows the solvent properties of the TEDM according to the invention to be influenced in a targeted manner in the direction of a more hydrophilic or hydrophobic character.
  • thermal development and diffusion promoting agents (TEDM-) according to the invention are listed below:
  • N, N-di-n-butyl sulfamic acid chloride (compound A) 129 g (1.0 mol) of di-n-butylamine were slowly added dropwise to 135 g (1.0 mol) of sulfuryl chloride with ice cooling and vigorous stirring within 5 h. The mixture was then stirred for a further 5 h at 90 ° C., mixed with ether after cooling and stirring, and the precipitate obtained was filtered off with suction. The ether phase was washed once with water, once with concentrated sodium hydrogen carbonate solution and again with water, dried over sodium sulfate and concentrated on a rotary evaporator. The oil obtained was distilled in vacuo and gave 60 g of compound A (bp 1mm 110-112 ° C).
  • Thermal solvents which are solid at normal temperature
  • Water-insoluble TEDM can be introduced in dispersed form.
  • the amount used can be varied within a wide range; This depends, among other things, on whether the compounds are introduced distributed over several or all layers of the recording material according to the invention, or whether they are used in a concentrated manner only in a specific layer.
  • the amount to be used per square meter also depends, of course, on the amount of binder used. The skilled worker can easily determine the appropriate concentration using simple routine tests.
  • the concentration used can be between 2 and 100% by weight, based on the binder, but preferably in the range between 20 and 50% by weight. However, overdosing on TEDM usually leads to high color fog (Dmin).
  • a color photographic recording material suitable for carrying out the heat development process according to the invention contains, on a dimensionally stable support, at least one binder layer in which a light-sensitive silver halide, optionally in combination with an essentially non-light-sensitive silver salt and a non-diffusing coloring compound, which contains a diffusible dye due to heat development can deliver, and the color photographic recording material further contains in one of its layers one or more of the thermal development and diffusion promoting agents (TEDM) according to the invention.
  • TDM thermal development and diffusion promoting agents
  • An essential component of the heat-developable recording material of the present invention is the silver halide, which consists of silver chloride, silver bromide, silver iodide or mixtures thereof and can have a particle size between 0.01 and 2.0 ⁇ m, preferably between 0.1 and 1.0 ⁇ m. It can be in the form of an unsensitized silver halide or it can also be chemically and / or spectrally sensitized by suitable additives.
  • 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 silver halide used due to its catalytic function (as exposed silver halide) in some embodiments mainly in the lower part of the range given emotional.
  • the essentially non-light-sensitive silver salt can be, for example, a silver salt which is comparatively stable to light, e.g. trade 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, Sil berpalmitate, silver maleate, silver fumarate, silver tartrate, silver furoate, silver linolate, silver adipate, silver sebacate, silver succinate, silver acetate or silver butyrate.
  • 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.
  • the silver salts of 3-mercapto-4-phenyl-1,2,4-trizole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptooxadiazole, mercaptotriazine, thioglycolic acid furthermore the silver salts of dithiocarboxylic acids, e.g. the silver salt of dithioacetic acid.
  • the silver salts of compounds having an imino group are also suitable.
  • Preferred examples include the silver salts of benzotriazole and its derivatives, for example silver salts of alkyl and / or halogen-substituted benzotriazoles, such as the silver salts of methylbenzotriazole, 5-chlorobenzotriazole, as well as the silver salts of 1,2,4-triazole, 1-H-tetrazole, carbazole, saccharin and silver salts of imidazole and its derivatives.
  • the application amount of essentially non-photosensitive silver salt according to the present invention in the respective layer is between 0.05 and 5 g per m2.
  • the substantially 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.
  • 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 constituent of the recording material according to the invention is a 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 color releasers of the formula have proven to be particularly advantageous BALLAST - REDOX - DYE, in what mean BALLAST a ballast remnant REDOX is a redox-active group, i.e. a group that can be oxidized or reduced under the conditions of alkaline development and, depending on whether it is in the oxidized or in the reduced state, is subject to different degrees to an elimination reaction, a nucleophilic displacement reaction, a hydrolysis or another cleavage reaction with the result that the rest of DYE is split off, and DYE the rest of a diffusible dye, for example a yellow, purple or cyan dye, or the rest of a dye precursor.
  • a ballast remnant REDOX is a redox-active group, i.e. a group that can be oxidized or reduced under the conditions of alkaline development and, depending on whether it is in the oxidized or in the reduced state, is subject to different degrees to an elimination reaction, a nucleophilic
  • Such residues are to be regarded as ballast residues which make it possible to store the color releasers according to the invention in a diffusion-resistant manner in the hydrophilic colloids usually used in photographic materials.
  • Organic radicals which generally contain straight-chain or branched aliphatic groups with generally 8 to 20 C atoms and optionally also carbocyclic or heterocyclic optionally aromatic groups are preferably suitable for this purpose. With the rest of the molecule, these radicals are either directly or indirectly, for example connected via one of the following groups: -NHCO-, -NHSO2-, -NR-, where R is hydrogen or alkyl, -O- or -S-.
  • ballast residue also contain water-solubilizing groups, such as sulfo groups or carboxyl groups, which may also be in anionic form. Since the diffusion properties depend on the molecular size of the total compound used, it is sufficient in certain cases, for example if the total molecule used is large enough, to use shorter-chain residues as ballast residues.
  • 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 overview article in the app. Chem. Int. Ed. Engl. 22 (1983) 191-209.
  • 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 are 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 classes of dyes are suitable as dye residues insofar as they are sufficiently diffusible 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.
  • Suitable color releasing agents are described, for example, in: US-A-3,227,550, US-A-3,443,939, USA-A-3,443,940, DE-A-19 30 215, DE-A-22 42 762, DE-A- 24 02 900, DE- A- 24 06 664, DE-A- 25 05 248, DE-A- 25 43 902, DE-A- 26 13 005, DE-A- 26 45 656, DE-A- 28 09 716, DE-A- 28 23 159, BE-A- 861 241, EP-A- 0 004 399, EP-A- 0 004 400, DE-A- 30 08 588, DE-A- 30 14 669, GB-A- 80 12 242 .
  • the color releasers can be used as oxidizable or couplable color releasers, in other than 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.
  • Oxidizable color releasers which are particularly suitable for the heat-developable recording materials according to the invention are, for example, in DE-A-22 42 762, DE-A-25 05 248, DE-A-26 13 005, DE-A-26 45 656 and GB-A-80 12 242.
  • the paint releaser 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 expediently used in combination with a reducing agent present in a limited amount, a so-called ten 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 light-sensitive silver halide and optionally the substantially non-light-sensitive silver salt.
  • a reducing agent present in a limited amount
  • a so-called ten 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 light-sensitive silver halide and optionally the substantially non-light-sensitive 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.
  • a recording material according to the invention which contains reducible color releasers with a carrier residue of the following formula is suitable, for example, for producing positive color images of positive originals (original) when using negative working silver halide emulsions: in what mean R1 ⁇ alkyl or aryl; R2 ⁇ is alkyl, aryl or a group which together with R3 ⁇ completes a fused ring; R3 ⁇ hydrogen, alkyl, aryl, hydroxyl, halogen such as chlorine or bromine, amino, alkylamino, dialkylamino including cyclic amino groups (such as piperidino, morpholino), acylamino, alkylthio, alkoxy, aroxy, sulfo, or a group which together with R2 ⁇ fused one Ring completed; R4 ⁇ alkyl; R5 ⁇ alkyl or preferably hydrogen; and wherein at least one of the radicals R1 ⁇ to R4 ⁇ contains a ballast radical.
  • reducible dye releasers and others which are also suitable in the context of the present invention are described, for example, in DE-A-28 09 716, EP-A-O 004 399, DE-A-30 08 588, DE-A-30 14 669.
  • 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 that photosensitive silver halide oxidizes and is therefore no longer available for reaction with the color releaser. This creates an image-like distribution of unused electron donor compound.
  • electron donor compounds are known from DE-A-29 47 425, DE-A-30 06 268, DE-A-31 30 842, DE-A-31 44 037, DE-A-32 17 877, 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.
  • Electron donor compounds which are formed from the corresponding electron donor precursor compounds only under the conditions of heat development in the layer, i.e. Electron donor compounds that are only in a masked 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.
  • the electron donor precursor compounds mentioned are also understood as electron donor compounds.
  • the above-mentioned essential constituents of the recording material used in the process according to the invention namely the light-sensitive silver halide, the possibly non-light-sensitive reducible silver salt and the color releaser, optionally in combination with an electron donor compound, are dispersed next to one another in a binder.
  • a binder can be hydrophobic as well as hydrophilic binders, but the latter are preferred and gelatin is preferably used, but it can also be replaced in whole or in part by other natural or synthetic binders.
  • polyurethanes optionally in a mixture with gelatin, have proven to be suitable binders, as described, for example, in DE-A-35 30 156.
  • the light-sensitive binder layer contains one or more color releasers associated with the light-sensitive silver halide and optionally the non-light-sensitive silver salt, from which dyes of a specific color are released.
  • the overall resulting color can be obtained by mixing several dyes.
  • the color photographic recording material used in the method according to the invention contains several, ie generally three, assignments of color releasers and in each case differently spectrally sensitized silver halide, preferably the absorption range of the dye released from the color releaser with the range of the spectral sensitivity of the assigned Silver halide essentially coincides.
  • the different assignments of color releaser and assigned silver halide can be accommodated in different binder layers of the color photographic recording material, preferably between these different binder layers there are separating layers made of a water-permeable binder, for example gelatin, which essentially have the function of separating the different assignments from one another and to counteract color distortion in this way.
  • separating layers made of a water-permeable binder, for example gelatin, which essentially have the function of separating the different assignments from one another and to counteract color distortion in this way.
  • the color photographic recording material includes, for example, a light-sensitive binder layer in which the silver halide contained therein is predominantly red-sensitive due to spectral sensitization, a further light-sensitive binder layer in which the silver halide contained therein is predominantly green-sensitive due to spectral sensitization, and a third light-sensitive binder layer in which the contained therein Silver halide is predominantly blue-sensitive due to its inherent sensitivity or due to spectral sensitization.
  • the electron donor compounds optionally contained in the three light-sensitive layers can be the same or different.
  • a complex coacervate is understood to mean a form of dispersion in which a mixture of the essential constituents is enclosed in a common covering made of a hardened binder. Such dispersions are also called packet emulsions. They are obtained through complex coacervation.
  • complex coacervation means the occurrence of two phases when mixing an aqueous solution of a polycationic colloid and a polyanionic colloid, a concentrated colloid phase (hereinafter referred to as a complex coacervate) and a dilute colloid phase (hereinafter referred to as an equilibrium solution) ) are formed due to an electrical interaction.
  • the complex coacervate is separated from the equilibrium solution in the form of droplets and appears as a white turbidity.
  • a solid such as silver halide or fine oil droplets
  • a dispersion of coacervate particles in which the solid (in the present case the light-sensitive silver halide and optionally the essentially non-light-sensitive silver salt) and oily droplets of a solution of the organic constituents (in the present case the color releasing agent and optionally further auxiliaries) are included are. It is then hardened with a hardening agent so that the original shape of the particles is not destroyed in the following steps for producing the photographic recording material, such as producing the casting solution and coating.
  • the dispersion is expediently cooled to a temperature of 25 ° C. or below, preferably 10 ° C. or below, before curing, whereby a good quality packet emulsion is obtained.
  • packet emulsions makes it possible to combine several emulsion components of different spectral sensitivity, including the relevant color releasers, in a single binder layer, without losing the spectral assignment and thereby causing color falsification. This is possible because the degree of exposure of a particular silver halide particle becomes almost exclusively the determining factor for the degree of dye release from the color releaser which is in the same coacervate particle (package) as the silver halide.
  • packet emulsions thus enables the accommodation of a blue-sensitive, a green-sensitive and a red-sensitive silver halide emulsion with any additional, essentially non-light-sensitive silver salt and spectrally assigned color separators in the same binder layer, without fear of serious color falsification.
  • the color photographic recording material used in the method according to the invention can contain further constituents and auxiliary substances which are used, for example, for carrying out the heat treatment and the process taking place here Color transfer are beneficial.
  • These further constituents or auxiliary substances can be contained in a light-sensitive layer or in a non-sensitive layer.
  • auxiliary substances are, for example, auxiliary developers.
  • suitable auxiliary developers include hydroquinone, pyrocatechol, pyrogallol, hydroxylamine, ascorbic acid, 1-phenyl-3-pyrazolidone and their derivatives.
  • 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 of up to 1/2 mol per mol of color releaser. Familiarization with the The layer can be made, for example, from solutions in water-soluble solvents or in the form of aqueous dispersions 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.
  • Sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, sodium acetate and organic bases, in particular amines such as alkylamines, pyrrolidine, piperidine, amidine, guanidine and their salts, in particular salts with aliphatic carboxylic acids, are to be mentioned here, for example.
  • a suitable 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 dye releasers and their transfer to the image-receiving sheet.
  • auxiliaries are, for example, compounds which are able to release water under the action of heat.
  • inorganic salts containing water of crystallization are suitable, for example Na2SO4.1OH2O, NH4Fe (SO4) 2.12H2O, and also compounds of the sodium benzotriazolate type which crystallize as a complex with various amounts of water (up to 24 mol H2O) and which are described in US Pat. A-4 418 139.
  • the water released during heating favors the development and diffusion processes required for image formation.
  • TEDM further essential auxiliary substances
  • these compounds do not necessarily have to be present in the same layer which also contains the light-sensitive silver halide and the color splitter. Rather, it is sufficient if any binder layer which is in contact with the light-sensitive layers during the heat treatment contains the TEDM mentioned in the required amount.
  • the TEDM forms a suitable solubilizing medium that is conducive to the development and color diffusion processes in the layers that are involved in the development and color diffusion processes.
  • the TEDM according to the invention can thus be contained in a light-sensitive layer which contains silver halide and a coloring compound, or in a non-light-sensitive binder layer or in several of the layers mentioned.
  • the TEDM can also be contained in an image-receiving layer of a separate image-receiving material, provided contact is only made with the light-sensitive layers of the heat-developable photographic recording material during the heat treatment.
  • the TEDM according to the invention can also be contained in dispersed form in an auxiliary sheet which is brought into contact with the light-sensitive recording material and is subjected to a heat treatment together with it.
  • a corresponding method is described for example in DE-A-35 23 361.
  • the TEDM according to the invention can also be used in combination with one or more of the so-called thermal solvents of the prior art, such as those described in DE-A-33 39 810, EP-A-0 119, without going beyond the scope of the invention 615 and EP-A-0 122 512.
  • the development of the imagewise exposed color photographic recording material 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 brought to an elevated temperature, for example in the range from 80 to 250 ° C., for a period of about 0.5 to 300 s.
  • a heat treatment in which the photosensitive binder layer is brought to an elevated temperature, for example in the range from 80 to 250 ° C., for a period of about 0.5 to 300 s.
  • the Color-releasing, imagewise diffusible dyes are released 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 time.
  • 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 in a second step by color image transfer from the light-sensitive part to an image receiving part brought into contact with it, e.g. by heating to a temperature between 50 and 150 ° C., preferably to 70 to 90 ° C., in which case diffusion aids (solvents) can still be applied externally before the photosensitive part and the image receiving part are laminated.
  • 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 consists essentially of a binding agent, the mordant for the determination of the non-diffusing color cleavage released diffusible dyes contains. Long-chain quaternary ammonium or phosphonium compounds are preferably used as mordants for anionic dyes, for example those as described in US Pat. Nos. 3,271,147 and 3,271,148.
  • certain metal salts and their hydroxides which form poorly soluble compounds with the acid dyes, can also be used.
  • Polymeric mordants should also be mentioned here, such as those described in DE-A-23 15 304, DE-A-26 31 521 or DE-A-29 41 818.
  • the dye mordants are dispersed in the mordant layer in one of the usual hydrophilic binders, e.g. in gelatin, polyvinylpyrrolidone, completely or partially hydrolyzed cellulose esters.
  • some binders can also act as mordants, e.g.
  • polymers of nitrogen-containing, optionally quaternary bases such as, for example, of N-methyl-4-vinylpyridine, 4-vinylpyridine, 1-vinylimidazole, as described, for example, in US Pat. No. 2,484,430.
  • Further usable binding agents are, for example, guanylhydrazone derivatives of alkyl vinyl ketone polymers, such as described, for example, in US Pat. No. 2,882,156, or guanylhydrazone derivatives of acylstyrene polymers, as described, for example, in DE-A-20 09 498.
  • other binders eg Add gelatin.
  • the image-receiving layer also after completion Development remains in layer contact with the light-sensitive element, there is usually an alkali-permeable pigment-containing light-reflecting binder layer between them, which serves for the optical separation between negative and positive and as an aesthetically pleasing background for the positive color image.
  • an alkali-permeable pigment-containing light-reflecting binder layer between them, which serves for the optical separation between negative and positive and as an aesthetically pleasing background for the positive color image.
  • the image-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 also be present as the uppermost layer in an integral color photographic recording material, in which case the exposure is expediently carried out through the transparent layer support.
  • a light-sensitive element of a thermally developable photographic recording material according to the invention was produced in that the following layers were applied in succession to a transparent support made of polyethylene terephthalate 175 ⁇ m thick. The quantities given relate to 1m2.
  • a layer consisting of 1 g guanidinium trichloroacetate, 0.03 g of wetting agent B, 0.24 g 4-methyl-4-hydroxymethylphenidone, 0.06 g sodium sulfite; 1.5 g of gelatin and 0.25 g or 0.5 g or 1.0 g of the compound TEDM-1 according to the invention.
  • a hardening layer consisting of 0.5 g gelatin and 0.15 g hardening agent CAS Reg.-Nr. 65 411-60-1.
  • the photosensitive element thus produced is referred to as material 1.
  • Further materials 2 and 3 were produced, which differed from material 1 in that the compound TEDM-1 according to the invention was used in layer 2 in modified amounts, specifically Material 2 - 0.5 g Material 3 - 1.0 g
  • Another material 4 was produced as a comparative material, which had the specified layers, but contained no TEDM in layer 2.
  • An image-receiving element was produced in that the following layers were applied to a layer support made of paper laminated with polyethylene.
  • the quantities given here also refer to 1 m2.
  • a pickling layer consisting of 2 g of polyurethane pickle of 4,4'-diphenylmethane diisocyanate and N-ethyldiethanolamine, quaternized with epichlorohydrin (according to DE-A-26 31 521, preparation example 1), 0.035 g of wetting agent B and 2 g of gelatin.
  • a hardening layer consisting of 0.8 g gelatin and 0.5 g of the hardening agent already mentioned.
  • the photosensitive element materials 1-4
  • processing was carried out in two steps.
  • the photosensitive element was treated at 115 ° C. for 60 s. This was done with the help of a heating plate, the material being covered with another plate.
  • the image-receiving element was laminated onto the already heat-treated, light-sensitive element after immersion in water, and the set thus formed was then treated under pressure analogously to the first process step for 2 min at 70 ° C. During this time the color transfer from the photosensitive element to the image receiving element took place. The two layer elements were then separated from one another. The image-receiving element showed a purple-colored negative image from the exposure original.
  • Table 1 shows, when the compound TEDM-1 according to the invention is added, a clear increase in density can be observed in comparison to the layer structure without addition, without the minimum densities increasing in the same ratio.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
EP87113515A 1986-09-26 1987-09-16 Procédé de développement thermique et matériau de reproduction photographique couleur approprié à cet effet Withdrawn EP0261567A3 (fr)

Applications Claiming Priority (2)

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DE3632737 1986-09-26
DE19863632737 DE3632737A1 (de) 1986-09-26 1986-09-26 Waermeentwicklungsverfahren und hierfuer geeignetes farbfotografisches aufzeichnungsmaterial

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EP0261567A2 true EP0261567A2 (fr) 1988-03-30
EP0261567A3 EP0261567A3 (fr) 1989-09-06

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US6114080A (en) * 1993-12-21 2000-09-05 Eastman Kodak Company Chromogenic black and white imaging for heat image separation
CA2215849A1 (fr) 1997-09-11 1999-03-11 Christophe Michot Nouveau solvant et composition electrolytique a haute conductivite ayant une stabilite a large plage
EP1459239B1 (fr) 2001-12-24 2012-04-04 L-1 Secure Credentialing, Inc. Documents d identification comprenant des informations invis ibles variables et leurs procedes de production
CA2470547C (fr) 2001-12-24 2008-05-20 Digimarc Id Systems, Llc Elements de securite grave au laser destines a des documents d'identification et procedes de fabrication de ces elements
CA2470600C (fr) 2001-12-24 2009-12-22 Digimarc Id Systems, Llc Systemes, compositions et procedes de gravure au laser en couleur de documents d'identification
US7815124B2 (en) 2002-04-09 2010-10-19 L-1 Secure Credentialing, Inc. Image processing techniques for printing identification cards and documents
US7694887B2 (en) 2001-12-24 2010-04-13 L-1 Secure Credentialing, Inc. Optically variable personalized indicia for identification documents
DE60232918D1 (de) * 2001-12-24 2009-08-20 Clariant Internat Ag Lasergravierverfahren sowie mit lasergravur versehene artikel
US7728048B2 (en) 2002-12-20 2010-06-01 L-1 Secure Credentialing, Inc. Increasing thermal conductivity of host polymer used with laser engraving methods and compositions
US7824029B2 (en) 2002-05-10 2010-11-02 L-1 Secure Credentialing, Inc. Identification card printer-assembler for over the counter card issuing
US7804982B2 (en) 2002-11-26 2010-09-28 L-1 Secure Credentialing, Inc. Systems and methods for managing and detecting fraud in image databases used with identification documents
US7763179B2 (en) * 2003-03-21 2010-07-27 Digimarc Corporation Color laser engraving and digital watermarking
US7225991B2 (en) 2003-04-16 2007-06-05 Digimarc Corporation Three dimensional data storage
PL440023A1 (pl) 2021-12-29 2023-07-03 Polska Wytwórnia Papierów Wartościowych Spółka Akcyjna Sposób wytwarzania podłoża polimerowego ulegającego karbonizacji opatrzonego wyczuwalnym w dotyku oznakowaniem w postaci reliefu z efektem płaskorzeźby, oraz wytworzone tym sposobem zabezpieczone podłoże polimerowe

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JPS5456423A (en) * 1977-10-14 1979-05-07 Asahi Chemical Ind Thermal silver picture forming material
JPS59182446A (ja) * 1983-04-01 1984-10-17 Fuji Photo Film Co Ltd 熱現像カラー感光材料およびそれを用いた画像形成方法
JPS61132952A (ja) * 1984-11-30 1986-06-20 Fuji Photo Film Co Ltd 色素転写方法

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DE3632737A1 (de) 1988-03-31
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EP0261567A3 (fr) 1989-09-06

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