EP0195979A2 - Matériau d'enregistrement phtographique en couleurs développable à la chaleur - Google Patents

Matériau d'enregistrement phtographique en couleurs développable à la chaleur Download PDF

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Publication number
EP0195979A2
EP0195979A2 EP86103310A EP86103310A EP0195979A2 EP 0195979 A2 EP0195979 A2 EP 0195979A2 EP 86103310 A EP86103310 A EP 86103310A EP 86103310 A EP86103310 A EP 86103310A EP 0195979 A2 EP0195979 A2 EP 0195979A2
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EP
European Patent Office
Prior art keywords
sensitive
light
silver halide
color
silver
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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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EP86103310A
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German (de)
English (en)
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EP0195979A3 (fr
Inventor
Günther Dr. Schenk
Karl-Wilhelm Dr. Schranz
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Agfa Gevaert AG
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Agfa Gevaert AG
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Publication of EP0195979A2 publication Critical patent/EP0195979A2/fr
Publication of EP0195979A3 publication Critical patent/EP0195979A3/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
    • G03C8/4033—Transferable dyes or precursors
    • 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
    • G03C8/404—Photosensitive layers

Definitions

  • 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).
  • 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 suitable recording material for this is described, for example, in DE-A-32 15 485.
  • a recording material having a layer which contains a combination of silver halide, silver benzotriazole, a color releaser and guanidine trichloroacetate (base donor) is exposed imagewise and then subjected to heat treatment in contact with an image-receiving sheet, the imagewise released dye being transferred to the image-receiving sheet.
  • the silver halide in each of these combinations being sensitive to a different spectral range of 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 to the color of the light for which the silver halide in question is predominantly sensitive.
  • Such assignments can be arranged in different layers one above the other; however, it is often observed with such an arrangement that sufficient heat transfer from the photosensitive layer furthest from the image-receiving layer is difficult to achieve in the heat development
  • packet emulsions of which several, each with different spectral sensitivity, are contained in a single light-sensitive layer as a so-called “mixed comulsion”.
  • Each of these packet emulsions consists in a Bindemittefphase dispersed particles - ( "packets") in which photosensitive silver halide of a particular spectral sensitivity and a spectrally associated color-providing compound, for example a color coupler or a dye releasing compound are combined (US-A-2 698 79 4, DE -A-26 45 656).
  • the color rendering can, however, be improved by adding a yellow dye to the red or green-sensitive emulsion portions is introduced - (GB-A-475 191, US-A-2 168 182).
  • a yellow dye to the red or green-sensitive emulsion portions
  • the red or. green-sensitized emulsion portions especially in the lower area of the layer, showed a considerable decrease in the sensitivity to blue.
  • the desired yellow filter effect on the red or. green-sensitive packets mainly limited to the lower layer areas.
  • US-A-2 168 182 also describes a recording material in which the mixed-emulsion layer contains only red-sensitive and green-sensitive packets and is overlaid with a blue-sensitive silver halide emulsion layer, with the two layers a yellow filter layer is located in both light-sensitive layers
  • 10 -1 to 10- 2 erg / cm 2 is also not suitable for the heat development process because the emulsion systems used there, for example silver behenate / behenic acid or silver benzotriazolate, each partially converted to silver halide, have a very much lower sensitivity with 10 -1 to 10 3 erg / cm 2 .
  • the use of chloride instead of bromide or a mixture of bromide and iodide is prohibited for the conversion in order not to lose basic sensitivity again.
  • hydrophilic emulsion systems for example silver benzotriazolate in gelatin as a binder, a conversion to AgCI is generally no longer possible due to the solubility product ratios.
  • the invention is based on the object of specifying a color photographic recording material which can be developed by heat treatment and which provides multicolored images with improved color rendering, in particular improved color separation.
  • the object is achieved with a recording material which has a mixed-emulsion layer which is over or under-layered (depending on the direction of exposure) with a yellow filter layer and in which a plurality of differently spectrally sensitive emulsion components are contained, each with spectrally assigned color separators, at least one of the said emulsion components being blue-sensitive and a higher one Has sensitivity than the green or red-sensitive emulsion components.
  • multicolored images with good color rendering in particular improved color separation, can be produced in a simple manner by heat treatment, which, according to the wishes and depending on the coloring compounds used, either in a negative-positive or in a positive-positive relationship the scanned original (if the pictures are positive).
  • the images are particularly characterized by uniformly low minimum color densities (veils) in the different colors.
  • the recording material contains, as a light-sensitive layer on a dimensionally stable support, a binder layer in which all light-sensitive substances and all coloring compounds are contained in the form of the complex coacervates mentioned.
  • the recording material further contains a yellow filter layer adjacent to the photosensitive layer. The latter is arranged so that the exposure light passes through the yellow filter layer into the light-sensitive layer.
  • the yellow filter layer is over the photosensitive layer; however, if the support is transparent, it can also be arranged under the photosensitive layer be.
  • the yellow filter layer has an optical density (for blue light) between 0.5 and 1.2, preferably between 0.7 and 0.9. It can contain yellow colloidal silver or suitable yellow organic dyes in the usual way.
  • the yellow filter layer can be equipped with additional functions by incorporating suitable additives.
  • the yellow filter layer can take on the function of a hardening layer if hardening agents are added to its casting solution, for example formaldehyde, succinaldehyde, glutaraldehyde, N, N ', N "-trisacryloylhexahydro-1,3,5-triazine, mucochloric acid, halogen-substituted aldehydes.
  • the yellow filter layer can be formed by suitable additives as an adhesive and contact layer, by adding suitable polymers or polymer mixtures to it, and finally it can also contain hard particles of an inorganic or organic nature as matting agents or spacers.
  • the light-sensitive layer of the recording material according to the invention contains several of the complex coacervates mentioned, each of these complex coacervates being assigned to a different spectral region of the light and containing as essential components at least one light-sensitive silver halide 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.
  • the light-sensitive silver halide is present in combination with a further essentially non-light-sensitive silver salt.
  • a complex coacervate is understood to mean a dispersion form 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 by 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 diluted 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 is obtained 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 possibly other auxiliaries) are included. 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.
  • the hydrophilic colloids that can be used in complex coacervation can be divided into two groups.
  • a first group includes compounds containing a nitrogen atom; an aqueous solution thereof has a negative charge at a pH higher than its isoelectric point and a positive charge at a pH lower than its isoelectric point (i.e. a cationic compound or polymer). Examples of these compounds include gelatin, casein, albumin, hemoglobin, polyvinylpyrrolidone.
  • a second group includes compounds of which an aqueous solution always has a negative charge regardless of pH (i.e. an anionic compound).
  • Examples of these compounds include a natural colloid such as sodium alginate, gum arabic, agar agar, pectin, konjac, a synthetic polymer with an acidic group or an alkaline salt thereof, such as a copolymer of vinyl methyl ether or ethylene and maleic anhydride, carboxymethyl cellulose, polyvinyl sulfonic acid, a condensation product of naphthalenesulfonic acid and formalin or a gelatin derivative in which a part which would be capable of carrying a positive charge is blocked by esterification.
  • a natural colloid such as sodium alginate, gum arabic, agar agar, pectin, konjac
  • a synthetic polymer with an acidic group or an alkaline salt thereof such as a copolymer of vinyl methyl ether or ethylene and maleic anhydride, carboxymethyl cellulose, polyvinyl sulfonic acid, a condensation product of naphthalenesulfonic acid and formal
  • Preferred examples of the anionic polymer which can be used according to the invention include compounds having repeating units, the carboxylate and / or contain sulfonate groups and have a molecular weight of not less than 1000, preferably not less than 3000.
  • gelatin agar agar, sodium alginate can be gelled by cooling.
  • Gelatin is particularly suitable for the production of the package emulsion, since it can be gelled by cooling and easily hardened with a hardening agent.
  • a combination of gelatin and an anionic polymer is preferably used to carry out the complex coacervation.
  • the amount of the colloidal substances used varies depending on the charge density of the substances at the time of the coacervate formation.
  • the colloid of one group is generally used in an amount ranging from 1/20 to 20 times the amount by weight of the colloid of the other group. It is preferable to use a weight ratio of 0.5: 1 to 4: 1 in a combination of gelatin and gum arabic and a weight ratio of 10: 1 to 40: 1 in a combination of gelatin and a condensation product of naphthalenesulfonic acid and formafin.
  • the concentration of the hydrophilic colloid in both the first group and the second group must be in the range of 0.5 to 6%, preferably 1 to 4%.
  • the pH must not be above 5.5.
  • the size of the packet emulsion particles largely varies depending on the pH value, but also fundamentally on the degree of mixing.
  • the optimum pH value varies depending on the type of colloid used, but in most cases in the range from 5.2 to 4, 0, preferably from 5.0 to 4.5.
  • the size of the packet emulsion particles used is usually in the range from 1 to 100 ⁇ m, preferably from 2 to 60 ⁇ m and particularly preferably from 5 to 30 ⁇ m.
  • the temperature of the system must be higher than the solidification temperature of the aqueous colloid solution.
  • the temperature In the case of gelatin, the temperature must not be below 35 ° C and is preferably in the range from 40 to 55 ° C.
  • the amount of co-existing inorganic salt must not exceed a certain critical value that is characteristic of the type of salt.
  • the preparation of the packet emulsion by complex coacervation is generally carried out by one of the following two methods
  • hydrophilic colloids each selected from the first group and the second group, are mixed in a suitable ratio and an aqueous solution thereof is prepared in a concentration of 1 to 4% by weight.
  • the temperature of the solution is in kept in the range of 35 to 60 ° C, and the pH is kept above 5.5.
  • the pH is reduced by adding an acid to cause coacervation.
  • a temperature (not less than 35 ° C.) and a pH (not more than 5.5) are maintained under conditions under which the coacervation can take place, and an aqueous hydrophilic colloid solution with a concentration of at least 6 at first % By weight is diluted by adding warm water until the concentration suitable for coacervate formation is reached
  • the amount of the packet emulsion is very small compared to the volume of the diluted continuous phase of the hydrophilic colloid. Therefore, a large amount of binder e.g. Gelatin can be added so that the emulsion can be used directly for coating.
  • binder e.g. Gelatin
  • Various methods can be used to concentrate and dry the packet emulsion. According to a known method, the dilute colloid solution, which contains a packet emulsion dispersed, is filtered. According to another method, the colloid solution is left to precipitate the packet emulsion. The supernatant liquid is then removed by decanting. A centrifuge separator can also be used for accelerated precipitation.
  • the packet emulsion can be atomized using spray drying methods such as are known, for example, for the production of microcapsules.
  • curing agents examples include chromium salts (for example chromium alum, chromium acetate), aldehydes (for example formaldehyde, glyoxal, glutaraldehyde), N-methylol compounds - (for example dimethylolurea, methyloldimethylhydantoin), dioxane derivatives (for example 2.3 Dihydroxydioxane), active vinyl compounds (for example 1,3,5-triacryloythexahydro-s-triazine, 1,3-vinylsulfonyl-2-propanol), active halogen compounds (for example 2,4-dichloro-6-hydroxy-s-triazine), and mucohalogenic acids (e.g. mucochloric acid, mucophenoxychloric acid). These curing agents can be used individually or as a mixture.
  • chromium salts for example chromium alum, chromium acetate
  • aldehydes
  • packet emulsions according to the invention enables the combination of 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 a color distortion. This is possible because of the amount of exposure of a particular silver halide particle is almost exclusively decisive for the extent of the dye release from that 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 changes.
  • the light-sensitive silver halide can consist of silver chloride, silver bromide, silver iodide or mixtures thereof and have a particle size between 0.02 and 2.0 IJ, 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 5.0 g per m ', or even more.
  • the actual amount of silver halide used due to its catalytic function (as exposed silver halide) in some embodiments, is mainly in the lower part of the range given.
  • the amount of silver halide used is mainly in the upper range: preferably 0.25-1.0 g / m 2 for each emulsion fraction .
  • 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.
  • silver salts of aliphatic carboxylic acids are silver behenate, silver stearate, silver oleate, silver laurate, silver caprate, silver myristate, silver palmitate, silver maleate, silver tartrate, silver furoate, silver linolate, silver adipate, silver sebacate, silver sulfate, for example, Hydroxyl groups or thioether groups can be substituted.
  • 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 compounds having an imino group are also suitable.
  • Preferred examples include the silver salts of benzotriazole and its derivatives, e.g. Silver salts of alkyl and / or halogen substituted benzotriazoles, e.g. 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 is in the respective layer between 0.05 and 5 g per m 2 .
  • the substantially non-photosensitive silver salt and the photosensitive silver salt can furthermore be present in the coacervate particles next to one another as separate particles or in a combined form which can be produced, for example, by treating an essentially non-photosensitive silver salt in the presence of halide ions, whereby on the surface of the particles of the essentially non-light-sensitive silver salt by double reaction - (conversion) form light-sensitive centers of light-sensitive silver halide.
  • halide ions double reaction - (conversion) form light-sensitive centers of light-sensitive 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 component in the coacervate particles 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 is a redox-active group, i.e. a group which is oxidizable or reducible 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 Remainder DYE is split off, and
  • DYE the rest of a diffusible dye, e.g. a yellow, purple or teal dye, or the rest of a dye precursor.
  • 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 are generally suitable, which contain straight-chain or branched aliphatic groups with generally 8 to 20 carbon atoms and optionally also carbocyclic or heterocyclic optionally aromatic groups. These radicals are either directly or indirectly connected to the rest of the molecule, for example via one of the following groups: -NHCO-, -NHSO 2 -, -NR-, where R is hydrogen or alkyl, -0-or -S-.
  • ballast residue can also contain water-solubilizing groups, such as sulfo groups or carboxyl groups, which can 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 dispensed with here with regard to the above-mentioned overview article in Angew. 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 be a substituent which can have a direct influence on the absorption and, if appropriate, complex formation properties (for example a post-complexable chromophore) 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 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 used according to the invention or can only result from the cleavage of the dye residue from the carrier residue which contains ballast groups.
  • dyes that are particularly suitable for the process according to the invention, mention should be made of: azo dyes, azomethine dyes, anthraquinone dyes, phthalocyanine dyes, indigo dyes, triphenylmethane dyes, including 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 between dye residues and the residues of dye precursors is of essential importance, the latter are also to 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.
  • the color releaser is oxidizable, then it itself represents a reducing agent which is directly or indirectly with the participation of electron transfer agents (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. This creates a pictorial differentiation in terms of the ability to release the diffusible dye.
  • ETA electron transfer agents
  • the color releaser is reducible
  • it is expediently used in combination with a reducing agent present in a limited amount, a so-called electron donor compound or an electron donor precursor compound, which in this case, in addition to the color releaser, the light-sensitive silver halide and optionally the essentially non-light-sensitive silver salt in the The same caacervate particles are contained.
  • a so-called electron donor compound or an electron donor precursor compound which in this case, in addition to the color releaser, the light-sensitive silver halide and optionally the essentially non-light-sensitive silver salt in the The same caacervate particles are contained.
  • the participation of electron transfer agents generally proves to be favorable.
  • the alkyl radicals represented by R ', R 2 , R 3 and R 5 in formula I can be straight-chain or branched and generally contain up to 18 carbon atoms. Examples are methyl, n-propyl, tert-butyl, tetradecyl, octadecyl.
  • the aryl radicals represented by the radicals R ', R 2 and R 3 mentioned are, for example, phenyl groups which can be substituted, for example by long-chain alkoxy groups.
  • acylamino radical represented by R 3 the acyl group is derived from aliphatic or aromatic carboxylic or sulfonic acids.
  • the fused-on rings completed by R 2 and R 3 are preferably carbocyclic rings, for example fused-on benzene or bicyclo- [2,2,1] -heptene rings.
  • An alkyl radical represented by R 4 can be straight-chain or branched, substituted or unsubstituted and contain up to 21 C atoms. Examples are methyl, nitromethyl, phenylmethyl (benzyl), heptyl, tridecyl; Pentadecyl, heptadecyl, -C 21 H 43 .
  • Preferred embodiments of the color releasers used according to the invention are those in which R ', R' and R 3 together in a quinoid carrier radical contain no more than 8, in particular not more than 5, carbon atoms, and R 4 is an alkyl radical with at least 11 carbon atoms represents.
  • Preferred embodiments are furthermore those in which R 'is an alkoxyphenyl radical having at least 12 C atoms in the alkoxy group and R 2 , R 3 , R 4 together contain no more than 8 C atoms.
  • 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 No. 24 305 (July 1984). It has been found that the electron donor compounds mentioned also meet the requirements imposed on them under the conditions of heat development and are therefore also suitable as electron donor compounds for the recording material of the present invention. Particularly suitable are those electron donor compounds which are formed in the layer from corresponding electron donor precursor compounds only under the conditions of heat development, 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 silver salt in the different emulsion parts differs in terms of spectral sensitivity and the color releaser in the different emulsion parts in terms of the color of the dye released, this does not necessarily also apply to the electron donor compound which may be present.
  • the electron donor compound can therefore be the same for all three assignments. It can also be wholly or partly contained in the common binder phase, although it is also preferred to include it in the coacervate particles together with the silver salt and the color releaser.
  • the silver halide in the different emulsion parts is sensitized differently according to the respective assignment to a color releasing agent or the color of the dye released from it.
  • the blue-sensitive emulsion component has a higher sensitivity than the other emulsion components, but the sensitivity essentially results from the totality of the constituents contained in the individual coacervate particles of the emulsion component in question, i.e. also taking into account the filter effect of the colored compounds contained in the coacervate particles the silver halide.
  • the blue-sensitive emulsion component for blue light is at least 0.5 log I ⁇ t units more sensitive than the green-sensitive emulsion component for green light or the red-sensitive emulsion component for red light.
  • the sensitivity advantage of the blue-sensitive emulsion component is preferably in the range from 0.7 to 0.9 log I • t units.
  • the light-sensitive binder layer of the color photographic recording material according to the invention may contain further constituents and auxiliaries which are beneficial, for example, for carrying out the heat treatment and the color transfer which takes place here.
  • these further constituents or auxiliary substances are preferably contained in the common binder phase of the light-sensitive layer or in one of the other layers.
  • 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 of up to 112 moles per mole of color releaser. The 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 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 ink cleavers 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, for example The water released during the heating process favors the development and diffusion processes required for image generation.
  • thermal solvents which are generally understood to mean non-hydrolyzable organic compounds which are solid under normal conditions, but which melt when heated to the temperature of the heat treatment and thereby deliver a liquid medium in which the development processes can take place more quickly.
  • thermal solvents can act as diffusion accelerators, for example.
  • Preferred examples of the thermal solvents include polyglycols, as described, for example, in US Pat. No.
  • 3,347,675 for example polyethylene glycol with an average molecular weight of 1500 to 20,000, derivatives of polyethylene oxide, for example its oleic acid ester, beeswax, monostearin, compounds with a high dielectric constant, which have a - SO 2 or --CO group, such as acetamide, succinamide, ethyl carbamate, urea, methylsulfonamide, ethylene carbonate, and also polar substances, as described in the US -A-3 667 959, the lactone of 4-hydroxybutanoic acid or 4-hydroxybutyric acid, dimethyl sulfoxide, tetrahydrothiophene-1,1-dioxide and 1,10-decanediol, methyl anisate, biphenyl suberate etc., as described in Research Disclosure, pages 26 to 28 (December 1976) etc.
  • the development of the imagewise exposed color photographic recording material of the invention comprises the substeps of silver halide development, generation of an imagewise distribution of diffusible dyes and D i f-fusion transfer of this imagewise distribution in the image receiving layer It is initiated that 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 time of about 0.5 to 300 s.
  • suitable conditions for the development processes, including dye diffusion are created in the recording material without the need to supply a liquid medium, for example in the form of a developer bath.
  • dyes which are diffusible in terms of image are released 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 in a second step by color image transfer from the photosensitive 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 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 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. those 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 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. eg in gelatin, polyvinyl pyrrolidone, completely or partially hydrolysed cellulose esters.
  • binder may act as a mordant, such as polymers of nitrogen-containing, optionally quaternary bases, such as N-methyl-4-vinylpyridine, 4-vinylpyridine, 1-vinylimidazole as described for example in US-A-2 484 4 30th
  • Further usable 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 acylstyrene polymers, as described, for example, in DE-A-20 09 498. In general, however, the latter binding agents are used add other binders, such as gelatin.
  • the image-receiving layer remains in layer contact with the light-sensitive element even after development has been completed, there is usually an alkali-permeable, pigment-containing light-reflecting binder layer between them, which serves as an optical separation between negative and positive, and serves as an aesthetically pleasing background for the transferred positive color image.
  • the yellow filter layer used according to the present invention is on the side of the light-sensitive layer which lies opposite the pigment-containing light-reflecting binder layer.
  • 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 by means of transparent layer supports.
  • Dispersant 1 (cyan paint releasing agent)
  • dye releaser 3 (cyan) were dissolved in a mixture of 40 g of cresyl phosphate and 35 g of palmitic acid diethylamide and dispersed in 1260 g of 6% aqueous gelatin solution in the presence of 2.6 g of sodium dodecylbenzenesulfonate.
  • Dispersant 2 magenta paint releasing agent
  • color releaser 12 50 g of color releaser 12 (magenta) were dissolved in a mixture of 64 g of tricresyl phosphate and 21 g of diethyl laurylamide and dispersed in 833 g ⁇ 6% aqueous gelatin solution in the presence of 1.7 g of sodium dodecylene benzenesulfonate.
  • Dispersant 3 color releaser yellow
  • color releaser 4 (yellow) were dissolved in a mixture of 47 g of tricresyl phosphate and 46 g of palmitic acid diethylamide and dispersed in the presence of 3.0 g of sodium dodecylbenzenesulfonate in 1280 g of 6% aqueous gelatin solution
  • Dispersant 5 (auxiliary developer)
  • 34.4 g of emulsion 2 were melted at 40 ° C. and spectrally sensitized by adding a 0.1% strength methanolic solution of a red sensitizer in an amount of 4x10 ⁇ 4 mol per mol of silver halide and digested for 70 min at 40 ° C. Then 25. 6 g of emulsion 1 and 35 ml of water at 40 ° C. were added, and 44.8 g of disperse 1 (cyan) and 11.2 g of disperse 4 were added, and 55 ml of a 10% strength gum arabic solution were added and the mixture was stirred for 15 minutes , whereupon 140 ml of 40 ° C warm water were added dropwise within 4 min.
  • PE-2 magenta
  • PE-3 yellow
  • PE-3 yellow
  • PE-4 cyan
  • PE-4 was also produced in an analogous manner to that described for PE-1, but with the following particularity
  • PE-5 was also produced in an analogous manner to that described for PE-2, but with the following particularity
  • a partial casting solution was prepared from each of the packet emulsions PE- 1 , PE-2, PE-3, PE-4, PE-5 mentioned as follows. Each of the packet emulsions was washed with 100 ml of water for 10 minutes. homogenized and mixed with 40 ml of a 10% aqueous guanidine trichloroacetate solution, 4 ml of Triton X 100 wetting agent (4%), 18.4 g of dispersant 5 (auxiliary developer) and a solution of 19 g of gelatin in 170 ml of water
  • the image-receiving material thus obtained is used in the following examples as a coating base for the production of integral recording materials. It is also suitable as a separate image receiving sheet
  • a photographic recording material according to the invention was produced by coating with the following layers
  • the photographic recording materials described in Examples 5 and 6 were exposed through a combination of separation filters (with gray scale) with red, green and blue light, to determine the D m i n and Dmax values of Mischkomemulsion with light of each respective spectrum third of a normal exposure and a total exposure was carried out with light from the other two thirds of the spectrum.
  • the recording materials were then heated to 137 ° C. for 60 s using a heatable drum, then left to swell in water for 30 s and finally heated to 75 ° C. on a heating bench for 60 s.
  • the D min and D max values were determined using a computer densitometer of the color wedges transferred to the image-receiving layer (Table 1).
  • the absolute yellow filter densities in the two recording materials were identical. It can be seen from Table 1 that both the Dmin values and the Dmax values of the color transfer were comparable in the recording material according to the invention. In the comparison material without the separate yellow filter layer according to the invention, this was probably true for the D max values, but not also for the Dmin values. The comparison material had a high yellow veil that was intolerable.
EP86103310A 1985-03-23 1986-03-12 Matériau d'enregistrement phtographique en couleurs développable à la chaleur Withdrawn EP0195979A3 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3510685 1985-03-23
DE19853510685 DE3510685A1 (de) 1985-03-23 1985-03-23 Durch waermebehandlung entwickelbares farbfotografisches aufzeichnungsmaterial

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EP0195979A2 true EP0195979A2 (fr) 1986-10-01
EP0195979A3 EP0195979A3 (fr) 1987-05-13

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EP (1) EP0195979A3 (fr)
JP (1) JPS61223741A (fr)
DE (1) DE3510685A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0258971A2 (fr) * 1986-08-29 1988-03-09 Minnesota Mining And Manufacturing Company Elément photothermographique
EP0295492A2 (fr) * 1987-06-13 1988-12-21 Agfa-Gevaert AG Procédé de diffusion couleur

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2105052A (en) * 1981-09-02 1983-03-16 Fuji Photo Film Co Ltd Heat-developable color photographic material
GB2136980A (en) * 1983-02-08 1984-09-26 Kodak Ltd Sensitive silver halide photothermographic materials for producing dye images
EP0157639A2 (fr) * 1984-04-03 1985-10-09 Konica Corporation Matériau à plusieurs couches sensible à la lumière, en couleurs, développable à chaud

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2105052A (en) * 1981-09-02 1983-03-16 Fuji Photo Film Co Ltd Heat-developable color photographic material
GB2136980A (en) * 1983-02-08 1984-09-26 Kodak Ltd Sensitive silver halide photothermographic materials for producing dye images
EP0157639A2 (fr) * 1984-04-03 1985-10-09 Konica Corporation Matériau à plusieurs couches sensible à la lumière, en couleurs, développable à chaud

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0258971A2 (fr) * 1986-08-29 1988-03-09 Minnesota Mining And Manufacturing Company Elément photothermographique
EP0258971A3 (en) * 1986-08-29 1988-11-02 Minnesota Mining And Manufacturing Company Photothermographic element
EP0295492A2 (fr) * 1987-06-13 1988-12-21 Agfa-Gevaert AG Procédé de diffusion couleur
EP0295492A3 (en) * 1987-06-13 1989-05-24 Agfa-Gevaert Ag Color diffusion process

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Publication number Publication date
JPS61223741A (ja) 1986-10-04
DE3510685A1 (de) 1986-09-25
EP0195979A3 (fr) 1987-05-13

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