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
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
  • G03C1/34—Fog-inhibitors; Stabilisers; Agents inhibiting latent image regression

Definitions

• the invention relates to a photographic material with a latent image stabilizer, a method for producing this material and a method for producing photographic images.
• Latent image stabilizers are described, for example, in German Offenlegungsschrift 2,827,937, and in British Patents 1,343,904, 1,412,294, 1,378,354, 1,386,630, 1,453,388, 1,458,107 and in U.S. Patents 3,386,831 and 3,881,939.
• An object of the invention is to achieve improved latent image stabilization.
• the compounds to be used according to the invention are so-called Schiff bases. It is already known to add such compounds to photographic recording materials as masked developer substances. However, concentrations of the same order of magnitude as that of the silver halide used are naturally to be used. It is known from US Pat. No. 3,342,599 to use Schiff bases in an amount of preferably 0.5 to 2.5 moles per mole of silver halide as a development precursor in photographic recording materials. However, there is no indication whatsoever that the compounds to be used according to the invention act as a latent image stabilizer at a concentration of at most 10 -2 mol per mol of silver halide. It also follows from column 2, line 10 of US Pat. No. 3,342,599 that the specified compounds hydrolyze and are active only at a pH above 9.
• the compounds of the formula (I) listed in the following table (1) have proven to be particularly suitable.
• the Schiff bases to be used in the manner according to the invention can be prepared by known methods by condensation of the corresponding aromatic aldehydes and p-phenylenediamine derivatives in the presence of an inert solvent.
• the oxidation-sensitive free p-phenylenediamines can be prepared by preparing the free base from the corresponding salt by adding sodium acetate to the reaction solution during the reaction.
• the compounds to be used according to the invention are outstandingly suitable for increasing the stability of the latent image nuclei in light-sensitive photographic materials with at least one silver halide emulsion layer.
• the stability of the latent image nuclei is achieved in an excellent manner while maintaining all the usual photographic properties, which of course are largely determined by the structure of the silver halide emulsion, even when the materials are stored for a long time at normal temperature or at elevated temperature.
• the compounds to be used according to the invention are added to the photographic material in particular after physical ripening of the emulsion added.
• the derivatives are preferably added in dissolved form to the light-sensitive silver halide emulsion during or after chemical ripening or the finished casting solution.
• Lower aliphatic alcohols, tetrahydrofuran, acetone or mixtures thereof are particularly suitable as solvents.
• the concentration of the compounds in the photographic materials can vary within wide limits. It depends on the desired effect, the type of reproduction process and the structure of the photographic material.
• Quantities of at most 10 -2 mol, in particular at most 10 -3 mol, per mol of silver halide have proven suitable. Concentrations between 10 mg and 100.0 mg per mole of silver halide are particularly preferred.
• the compounds to be used according to the invention can be used in conventional light-sensitive materials for stabilizing the latent image nuclei which are suitable for the production of black / white images, e.g. Black and white recording or copying materials or reversing materials. Furthermore, color couplers can be contained in the material without affecting the stabilization.
• These materials are primarily developable silver halide materials with common silver halide emulsions that give a negative image on development, including the reversal materials where the first development after fogging is followed by a second development.
• hydrophilic film-forming agents are suitable as protective colloid or binder for the silver halide emulsion layer, e.g. Proteins, in particular gelatin, alginic acid or their derivatives such as esters, amides or salts, cellulose derivatives such as carboxymethyl cellulose and cellulose sulfates, starch or their derivatives or hydrophilic synthetic binders such as polyvinyl alcohol, partially saponified polyvinyl acetate, polyvinyl pyrrolidone and others.
• Proteins in particular gelatin, alginic acid or their derivatives such as esters, amides or salts, cellulose derivatives such as carboxymethyl cellulose and cellulose sulfates, starch or their derivatives or hydrophilic synthetic binders such as polyvinyl alcohol, partially saponified polyvinyl acetate, polyvinyl pyrrolidone and others.
• the layers can also contain other synthetic binders in dissolved or dispersed form, such as homopolymers or copolymers of acrylic or methacrylic acid or their derivatives, such as esters, amides or nitriles, and also vinyl polymers, such as vinyl esters or vinyl ethers.
• synthetic binders in dissolved or dispersed form, such as homopolymers or copolymers of acrylic or methacrylic acid or their derivatives, such as esters, amides or nitriles, and also vinyl polymers, such as vinyl esters or vinyl ethers.
• the usual substrates can be used for the materials according to the invention, e.g. Carriers made of cellulose esters such as cellulose acetate or cellulose acetobutyrate, furthermore polyesters, in particular polyethylene terephthalate or polycarbonates, in particular based on bisphenylol propane. Also suitable are paper supports, which may contain waterproof polyolefin layers, e.g. made of polyethylene or polypropylene, can also contain supports made of glass or metal.
• the usual silver halide emulsions are suitable for the present invention. These can contain silver chloride, silver bromide or mixtures thereof, possibly with a low silver iodide content of up to 10 mol%, as silver halide.
• the emulsions can also be chemically sensitized, for example by. Addition of sulfur-containing compounds during chemical ripening, for example allyliso thiocyanate, allyl thiourea and sodium thiosulfate or by adding selenium compounds. Reducing agents, for example the tin compounds described in Belgian patent specifications 493 464 or 568 687, and also polyamines such as diethylenetriamine or aminomethylsulfinic acid derivatives, for example in accordance with Belgian patent specification 547 323, can also be used as chemical sensitizers. Precious metals or noble metal compounds such as gold, platinum, palladium, iridium, ruthenium or rhodium are also suitable as chemical sensitizers.
• polyalkylene oxide derivatives for example with polyethylene oxide having a molecular weight between 1000 and 20,000, and also with condensation products of alkylene oxides. and alcohols, aliphatic carboxylic acids, aliphatic amines, aliphatic diamines and amides.
• the emulsions can also be optically sensitized, e.g. with the usual polymethine dyes, such as neutrocyanines, basic or acidic carbocyanines, rhodacyanines, hemicyanines, styryl dyes, oxonols and the like.
• polymethine dyes such as neutrocyanines, basic or acidic carbocyanines, rhodacyanines, hemicyanines, styryl dyes, oxonols and the like.
• sensitizers are in the work of F.M. Hamer "The Cyanine Dyes and related Compounds", (1964).
• the materials can be combined with. contain the further stabilizers to be used according to the invention, for example azaindenes, preferably tetra- or penta-azaindenes, in particular those which are substituted by hydroxyl or amino groups.
• azaindenes preferably tetra- or penta-azaindenes, in particular those which are substituted by hydroxyl or amino groups.
• azaindenes preferably tetra- or penta-azaindenes, in particular those which are substituted by hydroxyl or amino groups.
• azaindenes preferably tetra- or penta-azaindenes
• Such a verb are in the article by Birr, Z.wiss.Phot. 47, 2-58 (1952).
• Other suitable stabilizers include heterocyclic mercapto compounds, for example phenyl mercaptotetrazole, quaternary benzothiazole derivatives, benzotriazole and the like.
• the layers of the photographic material can be hardened in the usual manner, for example with formaldehyde or halogen-substituted aldehydes which contain a carboxyl group, such as mucobromic acid, diketones, methanesulfonic acid esters, dialdehydes and the like.
• the photographic layers can be hardened with hardeners of the epoxy type, the heterocyclic ethylene imine or the acryloyl type.
• hardeners of the diazine, triazine or 1,2-dihydroquinoline series are alkyl or arylsulfonyl group-containing diazine derivatives, derivatives of hydrogenated diazines or triazines, such as, for example, 1,3,5-hexahydrotriazine, fluorine-substituted diazine derivatives, such as, for example, fluoropyrimidine, esters of 2-substituted 1,2-dihydroquinoline or 1,2-dihydroisoquinoline-N-carboxylic acids.
• Vinyl sulfonic acid hardeners, carbodiimide hardeners or carbamoyl hardeners can also be used, such as, for example, in the German patent applications 2,263,602, 2,225,230 and 1,808,685, French patent 1,491,807, German patent 872,153 and GDR patent 721.8.
• Other useful hardeners are described, for example, in British Patent 1,268,550.
• the present invention can both. can be used for the production of black and white, as well as colored photographic images.
• Colored photographic images can e.g. according to the known principle of chromogenic development in the presence of color couplers, which react with the oxidation product of color-producing p-phenylenediamine developers to form dyes.
• the color couplers can be added to the color developer, for example, according to the principle of the so-called development process.
• the photographic material itself contains the usual color couplers, which are usually incorporated into the silver halide layers.
• the red-sensitive layer can contain a non-diffusing color coupler for producing the blue-green partial color image, generally a coupler of the phenol or ⁇ -naphthol type.
• the green-sensitive layer can contain, for example, at least one non-diffusing color coupler for producing the purple partial color image, color couplers of the 5-pyrazolone or imidazolone type usually being used.
• the blue-sensitive layer can, for example, be a non- diffusing color couplers to generate the yellow partial color field, usually contain a color coupler with an open-chain ketomethylene grouping.
• Color couplers of this type are known in large numbers and are described in a large number of patents. Examples include the publication "Color Coupler” by W. Pelz in “Messages from the Research Laboratories of Agfa, Leverkusen / Kunststoff", Volume III (1961) and K. Venkataraman in “The Chemistry of Synthetic Dyes", Vol. 4, 341 to 387, Academic Press, 1971.
• the non-diffusing color couplers and coloring compounds are added to the light-sensitive silver halide emulsions or other casting solutions by customary known methods. If the compounds are soluble in water or alkali, they can be added to the emulsions in the form of aqueous solutions, optionally with the addition of water-miscible organic solvents such as ethanol, acetone or dimethylformamide.
• non-diffusing color couplers and coloring compounds are water- or alkali-insoluble compounds
• they can be emulsified in a known manner, for example by dissolving these compounds in a low-boiling organic solvent directly with the silver halide emulsion or initially with an aqueous gelatin solution is mixed, whereupon the organic solvent is removed in a conventional manner becomes.
• a gelatin emulsate of the respective compound thus obtained is then mixed with the silver halide emulsion.
• coupler solvents or oil formers are additionally used to emulsify such hydrophobic compounds; these are generally higher-boiling organic compounds which include the compounds in the form of oily droplets which release non-diffusing color couplers and development inhibitors to be emulsified in the silver halide emulsions.
• coupler solvents or oil formers are generally higher-boiling organic compounds which include the compounds in the form of oily droplets which release non-diffusing color couplers and development inhibitors to be emulsified in the silver halide emulsions.
• the photographic materials can be processed with conventional black and white developers, e.g. Hydroquinone, pyrocatechol, p-methylaminophenol and 1-phenyl-3-pyrazolidone and with color developing agents, especially of the p-phenylenediamine type, e.g.
• Other useful color developers are described, for example, in J.Amer. Chem.Soc. 73, 3100 (1951).
• a highly sensitive silver bromide iodide emulsion with 6 mol% silver iodide is prepared in the usual way, flocculated and freed from the soluble salts. It is then redispersed, mixed with gelatin and ripened with sulfur and gold compounds in a known manner.
• the emulsion had a silver nitrate / gelatin ratio of 1: 1 and contained 95 g of silver per kg, calculated as silver nitrate.
• the emulsions were then poured onto a cellulose acetate support in such a way that the silver coating, calculated as silver nitrate, was 5.5 g per m 2 .
• the samples were dried in the customary manner, exposed in a sensitometer behind a grayscale wedge and after the treatments shown in Table 2 at 20 ° C. 7 or
• the results of the sensitometric evaluation are shown in Table 2 below.
• the evaluation of the sensitivity in Table 2 is carried out relative to the test drawn as a type. Differences in sensitivity are thus indicated. An increase of this value by three units means a doubling of the sensitivity.
• the sensitivity itself is determined at a density of 0.2 over fog.
• Color photographic materials for reverse processing are produced by successively applying the layers listed below to a cellulose triacetate support provided with an adhesive layer.
• the sample is prepared as described for sample I, except that 100 mg / kg of compound 1, dissolved in methanol, are added to the yellow layer (layer 5).

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• Physics & Mathematics (AREA)
• Chemical & Material Sciences (AREA)
• Spectroscopy & Molecular Physics (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• General Physics & Mathematics (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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• 1980
  • 1980-10-16 DE DE19803039168 patent/DE3039168A1/de not_active Withdrawn
• 1981
  • 1981-10-06 DE DE8181107953T patent/DE3161248D1/de not_active Expired
  • 1981-10-06 EP EP81107953A patent/EP0050260B1/fr not_active Expired
  • 1981-10-09 US US06/309,972 patent/US4358531A/en not_active Expired - Fee Related
  • 1981-10-13 JP JP56162121A patent/JPS57100425A/ja active Pending

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