EP0226953A2 - Matériau d'enregistrement photographique couleur - Google Patents

Matériau d'enregistrement photographique couleur Download PDF

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Publication number
EP0226953A2
EP0226953A2 EP86117222A EP86117222A EP0226953A2 EP 0226953 A2 EP0226953 A2 EP 0226953A2 EP 86117222 A EP86117222 A EP 86117222A EP 86117222 A EP86117222 A EP 86117222A EP 0226953 A2 EP0226953 A2 EP 0226953A2
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EP
European Patent Office
Prior art keywords
recording material
color
layer
silver halide
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.)
Granted
Application number
EP86117222A
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German (de)
English (en)
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EP0226953B1 (fr
EP0226953A3 (en
Inventor
Günter Dr. Helling
Manfred Dr. Peters
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Agfa Gevaert AG
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Agfa Gevaert AG
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Publication of EP0226953A2 publication Critical patent/EP0226953A2/fr
Publication of EP0226953A3 publication Critical patent/EP0226953A3/de
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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
    • 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
    • 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
    • G03C1/053—Polymers obtained by reactions involving only carbon-to-carbon unsaturated bonds, e.g. vinyl polymers

Definitions

  • the invention relates to a color photographic recording material having at least one photosensitive silver halide emulsion layer applied to a layer support and at least one non-diffusing coloring compound associated with the silver halide emulsion layer, the silver halide emulsion layer or an adjacent binder layer containing a synthetic polymer as an additional binder.
  • color photographic (color photothermographic) recording materials for example. It is known to produce colored images by heat treatment using suitable color photographic recording materials. Particularly suitable as a color-providing compound are 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 suitable recording material for this is described, for example, in DE-AS-32 15 485.
  • a recording material with a layer that is in a hydrobene bandage medium contains a combination of silver halide, silver benzotriazolate, a color releaser and guanidine trichloroacetate (base donor), exposed imagewise and then subjected to heat treatment in contact with an image-receiving sheet, the color-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 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 task of specifying a color photographic recording material which is further improved in terms of the Dmin / Dmax ratio and in terms of sensitivity.
  • the present invention relates to a color photographic recording material having at least one light-sensitive silver halide emulsion layer applied to a layer support and at least one non-diffusing coloring compound associated with the silver halide emulsion layer, which has at least one binder layer which is either a light-sensitive silver halide emulsion layer or is adjacent to such a layer and which is homo -or contains a copolymer with repeating units of a polymerized monomer M, characterized in that the monomer M contains at least one urethane and / or a urea group and that the copolymer contains, in addition to the repeating units of the polymerized monomer M, repeating units with at least one further monomer M contains copolymerizable monomer C, which in polymerized form does not enable color formation under the photographic processing conditions is.
  • alkyl, cycloalkyl, aryl, aralkyl and heterocyclic radicals represented by R 1 to R 4 as well as the alkylene, arylene and aralkylene radicals represented by L 1 , L 2 and L 3 may optionally be further substituted.
  • Substituents for the alkyl, aralkyl or aryl groups represented by R 1 to R 4 or the alkylene, aralkyl or phenylene groups represented by L 1 to L 4 include aryl (e.g. a phenyl group), nitro, hydroxy, cyano, sulfo, alkoxy (e.g. a methoxy group), aryloxy (e.g. a phenoxy group, acyloxy (e.g. an acetoxy group), acylamino (e.g. a acetylamino group), sulfonamido (e.g.
  • a methanesulfonamido group a sulfamoyl (e.g. a methylsulfamoyl group), halogen (e.g. a fluorine atom, a chlorine atom, a bromine atom), carboxy, carbamoyl (e.g. a methylcarbamoyl group), alkoxycarbonyl (e.g. a methoxycarbonyl group) and sulfonyl (e.g. a methylsulfonyl group).
  • substituents When there are two or more substituents, they may be the same or different.
  • the monomer M is preferably free of groups which are capable of color formation, in particular the formation of diffusible dyes, under the photographic processing conditions.
  • the rings marked with "S” are saturated rings.
  • the monomers M can be prepared, for example, by reacting a monomer containing isocyanate groups with a compound containing amino or hydroxyl groups. Another possibility is the reaction of monomers containing an amino group with a chloroformate. However, there is also the possibility of starting from a compound which already contains a urea or urethane group and reacting it with a reactive monomer.
  • the copolymers according to the invention contain, in addition to the repeating units from the monomer M, repeating units of at least one further copolymerized monomer C.
  • comonomers C include esters and amides, of acrylic acid and their derivatives, for example of acrylic acid, ⁇ -chloroacrylic acid, methacrylic acid) (for example acrylamide , Methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, n-hexyl acrylate, octyl methacrylate, lauryl methacrylate and methylenebisacrylamide), vinyl esters (for example vinyl acetate, vinyl propionate and vinyl lauryl, methylene nitrililililate, methacrylonitrililililate, methacrylonitrililililate, methacryl
  • the molecular weights of the polymers according to the invention are preferably greater than 5,000, in particular greater than 20,000.
  • the upper limit is not critical and can reach values of more than 10 million, in particular if C bifunctional or polyfunctional monomers are used as additional comonomer.
  • Two or more of the comonomers C described above can be used together.
  • the ethylenically unsaturated comonomer C can be selected in such a way that it has a favorable effect on the physical properties and / or chemical properties of the copolymer to be produced, for example the solubility, compatibility with a binder such as gelatin or other photographic additives such as color compounds, ultraviolet rays absorbing agents, Antioxidants and the like, and affects the flexibility and thermal stability of the layer compositions or the color photographic recording materials.
  • the polymers according to the invention are used as a polymer dispersion or as a polymer latex.
  • Such a polymer dispersion can be prepared, for example, by an emulsion polymerization process or by polymerization in an organic solvent and then dispersing the latex obtained or the solution in latex form in an aqueous solution of gelatin.
  • the polymerization of the ethylenically unsaturated monomers is generally initiated by free radicals which are formed by thermal decomposition of a chemical initiator, by the action of a reducing agent on an oxidizing compound (redox initiator) or by physical action, such as irradiation with ultraviolet rays or other high-energy radiation , high frequencies, etc.
  • free radicals which are formed by thermal decomposition of a chemical initiator, by the action of a reducing agent on an oxidizing compound (redox initiator) or by physical action, such as irradiation with ultraviolet rays or other high-energy radiation , high frequencies, etc.
  • Examples of chemical initiators include a persulfate (e.g. ammonium persulfate or potassium persulfate etc.), a peroxide (e.g. hydrogen peroxide, Benzoyl peroxide or tert. Butyl peroctoate, etc.) and an azonitrile compound (for example, 4,4'-azobis-4-cyanovaleric acid and azobisisobutyronitrile, etc.).
  • a persulfate e.g. ammonium persulfate or potassium persulfate etc.
  • a peroxide e.g. hydrogen peroxide, Benzoyl peroxide or tert. Butyl peroctoate, etc.
  • an azonitrile compound for example, 4,4'-azobis-4-cyanovaleric acid and azobisisobutyronitrile, etc.
  • Examples of conventional redox initiators include hydrogen peroxide iron (II) salt, potassium persulfate, sodium metabisulfite and cerium IV salt alcohol, etc.
  • a compound having a surface-active effect is used as the emulsifier which can be used in the emulsion polymerization.
  • Preferred examples include soaps, sulfonates, sulfates, cationic compounds, amphoteric compounds and high molecular weight protective colloids. Specific examples of the emulsifiers and their functions are described in Belgische Chemische Industrie, vol. 28, pages 16 to 20, 1963.
  • An organic solvent which may be used in the preparation of the polymer or in the dispersion of the polymer in an aqueous gelatin solution can be removed from the casting solution prior to casting.
  • suitable solvents are those which have a certain degree of water solubility so that they can easily be removed by washing with water in a gelatin noodle state, and those which can be removed by spray drying, vacuum or steam rinsing.
  • solvents examples include esters (e.g. ethyl acetate), ethers, ketones, halogenated hydrocarbons (e.g. methylene chloride, trichlorethylene), alcohols (e.g. methanol, ethanol, butanol) and combinations thereof.
  • Suitable light-sensitive silver halide emulsions for the color photographic recording materials according to the invention are emulsions of silver chloride, silver bromide or mixtures thereof, possibly with a silver iodide content of up to 40 mol-X in one of the hydrophilic binders commonly used.
  • Gelatin is preferably used as a binder for the photographic layers. However, this can be replaced in whole or in part by other natural or synthetic binders.
  • an essentially non-light-sensitive silver salt may be mixed with the light-sensitive silver halide.
  • the amount of light-sensitive silver halide in the respective layer between 0.01 and 5.0 g per m 2 , preferably between 0.1 and 1.0 g, the amount of the silver halide used due to its catalytic function (as exposed silver halide) in some embodiments in the lower part of the specified Area can move.
  • 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, 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-methyl benzoate, 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 for example the silver salts of 3-mercapto-4-phenyl-2,2,4-triazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptooxadiazole, mercaptotriazine, thioglycolic acid and also the Silver salts of dithiocarboxylic acids, such as the silver salt of dithioacetate.
  • 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, and also the silver salts of 1,2,4-triazole, 1-H-tetrazole, carbazole, saccharin and silver salts of imidazole, benzimidazole and their derivatives.
  • benzotriazole and its derivatives e.g. Silver salts of alkyl and / or halogen substituted benzotriazoles, e.g. 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, benzimi
  • the application amount of essentially non-photosensitive silver salt according to the present invention is in the respective layer between 0.01 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, for example as a result can be generated that a substantially non-photosensitive silver salt is treated in the presence of halide ions, whereby photosensitive centers of photosensitive silver halide are formed on the surface of the particles from the essentially non-photosensitive silver salt by 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).
  • the emulsions can be chemically and / or spectrally sensitized in the usual way and the emulsion layers as well as other non-light-sensitive layers can be hardened in the usual way with known hardening agents.
  • Color photographic recording materials usually contain at least one silver halide emulsion layer for recording light from each of the three spectral ranges red, green and blue.
  • the light-sensitive layers are spectrally sensitized in a known manner by means of suitable sensitizing dyes.
  • Blue-sensitive silver halide emulsion layers do not necessarily have to contain a spectral sensitizer, because for the recording of blue light in in many cases the intrinsic sensitivity of the silver halide is sufficient.
  • Each of the said photosensitive layers can consist of a single layer or in a known manner, e.g. in the so-called double-layer arrangement, also two or more
  • Silver halide emulsion partial layers include (DE-C-1 121470).
  • red-sensitive silver halide emulsion layers are arranged closer to the support than green-sensitive silver halide emulsion layers and these are in turn closer than blue-sensitive layers, with a non-light-sensitive yellow filter layer generally being located between green-sensitive layers and blue-sensitive layers.
  • a layer which is not sensitive to light is generally arranged between layers of different spectral sensitivity and can contain means for preventing the incorrect diffusion of developer oxidation products.
  • silver halide emulsion layers of the same spectral sensitivity they can be directly adjacent to one another or be arranged such that a light-sensitive layer with a different spectral sensitivity is located between them (DE-A-1 958 709, DE-A-2 530 645, DE-A -2 622 922).
  • Color photographic recording materials for producing multicolored images usually contain, in spatial and spectral assignment to the silver halide emulsion layers of different spectral sensitivity, coloring compounds, for example color couplers or color releasers, to generate the different partial color images cyan, purple and yellow.
  • the coloring compound is in such a spatial relationship to the silver halide emulsion layer that an interaction between them is possible, an image-like correspondence between the silver image formed during development and the color image generated from the coloring compound allows. This is generally achieved by the fact that the color-providing compound is contained in the silver halide emulsion layer itself or in a neighboring, optionally non-light-sensitive binder layer.
  • Spectral assignment is to be understood to mean that the spectral sensitivity of each of the light-sensitive silver halide emulsion layers and the color of the partial color image generated from the spatially assigned coloring compound are in a certain relationship to one another, each of the spectral sensitivities (red, green, blue) having a different color related partial color image (in general, for example, the colors cyan, purple or yellow in this order).
  • Each of the differently spectrally sensitized silver halide emulsion layers can be assigned one or more coloring compounds. If several silver halide emulsion layers are the same
  • each of them can contain a coloring compound, the latter need not necessarily be identical. They should only result in at least approximately the same color during color development, normally a color that is complementary to the color of the light, for which the silver halide emulsion layers in question are predominantly sensitive.
  • red-sensitive silver halide emulsion layers are therefore assigned at least one non-diffusing coloring compound for producing the blue-green partial color image.
  • Green-sensitive silver halide emulsion layers are assigned at least one non-diffusing coloring compound for producing the purple partial color image.
  • blue-sensitive silver halide emulsion layers are assigned at least one non-diffusing coloring compound for producing the yellow partial color image.
  • the coloring compounds can be customary color couplers from which the image dyes can be obtained using a conventional chromogenic development process; be formed.
  • so-called color releasers are used as color-imparting compounds, from which diffusible dyes are released imagewise during processing under alkaline conditions and can be transferred to a suitable image-receiving layer to form a colored transfer image.
  • the imaging processing usually after the imagewise coating, is carried out by heat treatment.
  • the color releasing agents used in this embodiment of the invention can be a variety of connection types, all of which are distinguished by a linkage which is redox-dependent in terms of their binding strength and which links a dye residue to a carrier residue containing a ballast residue.
  • 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 residues are either directly or indirectly, e.g. connected via one of the following groups:
  • 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 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 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, if appropriate together with the intermediate member can also be important for the diffusion, pickling and stability 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.
  • 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 oxidizable 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.
  • Oxidizable color releasers particularly suitable for the recording materials according to the invention are described, for example, in DE-A-26 45 656.
  • 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 color releaser is reducible, then 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 is in addition to the Color releaser, the light-sensitive silver halide and optionally the substantially non-light-sensitive silver salt is contained in the same binder layer.
  • a so-called electron donor compound or an electron donor precursor compound which in this case is in addition to the Color releaser, the light-sensitive silver halide and optionally the substantially non-light-sensitive silver salt is contained in the same binder layer.
  • 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, is colored under the conditions of development, for example when the imagewise exposed color is heated photographic material, in accordance with the degree of exposure under the catalytic effect of the latent image nuclei produced by exposure in the silver halide by the substantially non-photosensitive silver salt and the photosensitive silver halide, and is consequently 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 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 which are formed in the layer from corresponding electron donor precursor compounds only under the conditions of heat development, ie electron donor compounds which only exist in the recording material before development in a masked form 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 polymer described with the repeating units of the monomer M containing urea or urethane groups is contained in at least one binder layer, which may be a light-sensitive layer or a non-light-sensitive layer, the binder in this layer preferably being a hydrophilic binder, for example gelatin .
  • the polymer according to the invention is preferably used in a layer which contains a coloring compound.
  • the color density of the color image produced from the coloring compounds can be increased significantly.
  • the amount in which the polymer according to the invention is used is generally such that the binder consists of 10 to 90% by weight of the polymer according to the invention and 90 to 10% by weight of the hydrophilic layer binder.
  • the polymer according to the invention is preferably contained in the layer to 30 to 80% by weight.
  • the optimal amount can easily be determined by routine series tests.
  • a thickener e.g. Polystyrene sulfonic acid may also be present, for example in an amount up to 5% by weight.
  • the color photographic recording material of the present invention may contain further constituents and auxiliaries which, for example in the case of the heat development process, are conducive to carrying out the heat treatment and the color transfer taking place here.
  • 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-pyrazolidone and their derivatives. Since the auxiliary developers have a catalytic function, it is not necessary for them to be present in stoichiometric amounts. Generally enough it 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 are suitable for this, for example Na 2 SO 4 .10H 2 O, NH 4 Fe (SO 4 ) 2 -12H 2 O, and also compounds of the sodium benzotriazolate type which are complexed with various amounts of water (bis 24 mol H 2 0) crystallize and which are described in US-A-4 418 139.
  • 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 agents1, 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.
  • thermal solvents or development and diffusion promotion agents1 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 this 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, such as, for example, its oleic acid ester, beeswax, monostearin, compounds with a high dielectric constant, which have a -S0 2 - or -CO group, such as acetamide, lactams, succinamide, ethyl carbamate, urea, methylsulfonamide, and also polar substances, as described in US Pat. No.
  • the development of the imagewise exposed color photographic recording material according to the invention comprises, for example in the case of the heat development process, the substeps of silver halide development, producing an imagewise distribution of diffusible dyes and diffusion transfer of this image 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.
  • 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 dye 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, the silver halide development and dye release taking place in a first step at temperatures between 80 and 250 ° C., followed by the color image transfer from the light-sensitive part to one in a second step image receiving part brought into contact with it, for example by heating to a temperature between 50 and 150 ° C., preferably to 70 to 90 ° C., in which case diffusion aids (solvents), such as water, 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 and a mordant 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, for example in gelatin, polyvinylpyrrolidone, completely or partially hydrolyzed Cellulose esters.
  • binders can also act as mordants, for example 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.
  • Others Useful pickling binders 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 pickling binders become different Add binders such as 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 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, 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.
  • the photosensitive member thus produced is referred to as Sample 1.
  • Further samples 2 to 4 were prepared in an analogous manner, the polymers P2, P3 to P4 (in each case 1 g) being added instead of the polymer P1 according to the invention.
  • Another sample 5 received no additive and another sample 6 received 1 g gelatin as an additive instead of a polymer according to the invention.
  • the polymers or comparison substances according to the invention were each added to the casting solution as an aqueous dispersion.
  • a sample of the light-sensitive element (samples 1 to 6) was exposed through a step wedge.
  • the development took place in two steps; in the first, the photosensitive element was heated at 120 ° C for 60 s. This was done with the help of a heating plate, the sample being placed on the layer on the heating plate and covered with another plate.
  • the sample was brought into contact with the image-receiving element on the layer side, the image-receiving element having previously been soaked with water.
  • the set formed in this way was treated for 2 minutes at 70 ° C. using the same procedure as in the first step. 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. A purple negative image of the exposure original was obtained on the bid receiving element.
  • Example 1 was repeated, with the difference that instead of compound P1, 1 g of one of the compounds P5, P6, P7 and P8 according to the invention was added to layer 1. In this way, samples 7 to 10 were obtained. The introduction into the casting solution was also carried out in aqueous dispersion.
  • the polymer P-X was added as a reference substance instead of one of the compounds according to the invention.
  • Table 2 shows that, compared with the comparison substance PX, a significant increase in density can be observed above all in the compounds P5, P6, P7 and P8 according to the invention.
  • Example 1 was repeated, but with the difference that 4 g of compound P7 according to the invention were used in layer 1 instead of compound P1 (sample 12). In two further samples, 4 g each of the comparison substances P-X (sample 13) and P-Y (sample 14) were added.
  • the compound P7 according to the invention shows a significantly improved Dmin / Dmax relation even with increased orders compared to the comparison substances P-X and P-Y.
  • sample 15 was obtained. Further samples were prepared in an analogous manner, but with 4 g each of the polymers P10 (sample 16) or P11 (sample 17) according to the invention. Another sample 18 (without addition) served as a comparison.
  • the polymers according to the invention also lead to an improved Dmin / Dmax ratio with a wide variation in the comonomer ratios.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
EP86117222A 1985-12-21 1986-12-10 Matériau d'enregistrement photographique couleur Expired EP0226953B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3545607 1985-12-21
DE19853545607 DE3545607A1 (de) 1985-12-21 1985-12-21 Farbfotografisches aufzeichnungsmaterial

Publications (3)

Publication Number Publication Date
EP0226953A2 true EP0226953A2 (fr) 1987-07-01
EP0226953A3 EP0226953A3 (en) 1988-01-07
EP0226953B1 EP0226953B1 (fr) 1989-01-18

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Application Number Title Priority Date Filing Date
EP86117222A Expired EP0226953B1 (fr) 1985-12-21 1986-12-10 Matériau d'enregistrement photographique couleur

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Country Link
US (1) US4987061A (fr)
EP (1) EP0226953B1 (fr)
DE (2) DE3545607A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0343476B1 (fr) * 1988-05-21 1994-12-14 Hoechst Aktiengesellschaft Dérivés éthyléniques non saturés d'urée et procédé de leur préparation
EP0903623A1 (fr) * 1997-09-17 1999-03-24 Agfa-Gevaert N.V. Liants pour des produits thermographiques
US6300052B1 (en) 1997-09-17 2001-10-09 Agfa-Gevaert Binders for thermographic materials

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5888719A (en) * 1995-08-02 1999-03-30 Agfa-Gevaert Ag Color photographic silver halide material
ATE202640T1 (de) * 1996-04-26 2001-07-15 Fuji Photo Film Co Ltd Verfahren zur herstellung eines photothermographischen materiales
US6228571B1 (en) * 1996-06-18 2001-05-08 Fuji Photo Film Co., Ltd. Photothermographic material
JP6194620B2 (ja) * 2013-04-19 2017-09-13 株式会社リコー 活性エネルギー線硬化型のインクジェット記録用インク

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE585940A (fr) * 1959-12-23
DE1472871A1 (de) * 1964-12-21 1969-03-20 Eastman Kodak Co Photographische Gelatine-Silberhalogenidemulsion
JPS5141056B2 (fr) * 1972-09-04 1976-11-08
US4089688A (en) * 1975-12-08 1978-05-16 Polaroid Corporation Polymeric N-alkenyl carbamate silver halide peptizer
JPS52102722A (en) * 1976-02-24 1977-08-29 Fuji Photo Film Co Ltd Photosensitive material for color photography
JPS59229556A (ja) * 1983-06-13 1984-12-24 Konishiroku Photo Ind Co Ltd 熱現像カラ−感光要素
US4594315A (en) * 1983-09-21 1986-06-10 Konishiroku Photo Industry Co., Ltd. Light-sensitive silver halide photographic element with electron beam cured interlayer

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0343476B1 (fr) * 1988-05-21 1994-12-14 Hoechst Aktiengesellschaft Dérivés éthyléniques non saturés d'urée et procédé de leur préparation
EP0903623A1 (fr) * 1997-09-17 1999-03-24 Agfa-Gevaert N.V. Liants pour des produits thermographiques
US6300052B1 (en) 1997-09-17 2001-10-09 Agfa-Gevaert Binders for thermographic materials

Also Published As

Publication number Publication date
DE3661866D1 (en) 1989-02-23
DE3545607A1 (de) 1987-07-02
US4987061A (en) 1991-01-22
EP0226953B1 (fr) 1989-01-18
EP0226953A3 (en) 1988-01-07

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