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
  • G03C1/346—Organic derivatives of bivalent sulfur, selenium or tellurium
• • 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
  • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
  • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
  • G03C5/50—Reversal development; Contact processes

Definitions

• the invention relates to a photographic material with at least one silver halide emulsion layer, which is improved by adding thiocarbohydrazide derivatives.
• the invention further relates to a method for producing photographic images in the presence of such compounds.
• Photosensitive silver halide emulsions are known to tend to form fog, i.e. Germs that can be developed without exposure. Such fogging occurs increasingly with longer development times or development at higher temperatures.
• fogging occurs increasingly with longer development times or development at higher temperatures.
• the formation of fog is disruptive both in the case of materials which are subjected to a negative development and in the case of materials which are subjected to reverse processing in the customary baths.
• fog nuclei have the effect that silver halide is also reduced in the unexposed areas during reverse processing in the first developer, so that too little silver halide is available in the second winding, with the result that the maximum densities obtained are too low.
• heterocyclic mercapto compounds e.g. those described in DT-B-1 183 371, DT-A-2 308 530 and DT-A-1 622 271.
• DIR compounds react with the oxidation product of p-phenylenediamine color developers with elimination of a residue which inhibits the reduction of silver halide to metallic silver. These residues are also known as "escape groups".
• Such inhibitors and stabilizers can accumulate in the reverse processing during the first development on the remaining silver halide and hinder the second development, so that only reduced color densities are obtained.
• saturated aliphatic groups are alkyl radicals, which can be straight-chain, branched or cyclic and contain up to 18 carbon atoms and can be further substituted, for example with carboxyl, carbamoyl or nitrile.
• a suitable olefinically unsaturated aliphatic group is, for example, allyl, qeeiqnete heterocyclic groups are in particular nitrogen-containing 5- or 6-membered rings, especially those mentioned above.
• aryl is phenyl, which can be substituted, for example by halogen, hydroxyl, alkoxy, alkylthio, carboxyl, sulfamoyl, amino and / or alkyl.
• Acyl radicals are understood to be those which are derived from aliphatic or aromatic carboxylic or sulfonic acids, including (thio) carbonic acid monoesters, carbamic acids or sulfamic acids.
• Examples of such acyl radicals are acetyl, benzoyl, phenylsulfonyl, carbamoyl, phenylcarbamoyl, ethoxycarbonyl, ethoxythiocarbonyl.
• the compounds of formula (I) may optionally be provided with a diffusion-proofing residue, e.g. with a long-chain alkyl or alkylene group, which is optionally linked via a hetero atom.
• Particularly suitable compounds corresponding to formula (I) are those in which at least one of the radicals R 'and R 4 is an acyl radical with R 2 , R 3 and R 5 being hydrogen, for example the following compounds:
• the compounds according to the invention can be obtained from thiocarbohydrazide by known methods, as can be found, for example, in the literature in J. Indian Chem. Soc. 1, 141 and in J. Org. Chem. 34, 756.
• the invention further relates to a reversal process for the production of photographic images by imagewise exposure, first development, fogging and second development of a photographic material, the first development and optionally the fogging and the second winding being carried out in the presence of the substances to be used according to the invention.
• silver halide emulsions are suitable for the present invention. These can contain as silver halide, silver chloride, silver bromide, silver iodide or mixtures thereof.
• the photographic material produced according to the invention can contain the usual color couplers, which are usually incorporated into the silver halide layers themselves.
• the red-sensitive layer contains a non-diffusing color coupler for producing the blue-green partial color image, usually a coupler of the pheno! Or a-naphthol type.
• the green-sensitive layer contains at least one non-diffusing color coupler for producing the purple partial color image, color couplers of the 5-pyrazolone or indazolone type usually being used.
• the blue-sensitive layer unit contains at least one non-diffusing color coupler for producing the yellow partial color image, usually a color coupler with an open-chain ketomethylene grouping.
• 2-equivalent couplers can be used as non-diffusing color couplers; these contain a removable substituent in the coupling point, so that they only require two equivalents of silver halide to form the color, in contrast to the usual 4-equivalent couplers.
• the 2-equivalent couplers that can be used include, for example, the known DIR couplers, in which the cleavable residue is released as a diffusing development inhibitor after reaction with color developer oxidation products.
• the so-called white couplers can also be used to improve the properties of the photographic material.
• 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, if appropriate with the addition of water-miscible organic solvents such as ethanol, acetone or dimethylformamide.
• non-diffusing color couplers and coloring compounds are water- or alkyl-insoluble compounds
• they can be emulsified in a known manner, for example by mixing a solution of these compounds in a low-boiling organic solvent directly with the silver halide emulsion or initially with an aqueous gelatin solution is, whereupon the organic solvent is removed in a conventional manner.
• 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 non-diffusing color coupler and development inhibitor compounds in the form of oily droplets which split off in the silver halide emulsions.
• coupler solvents or oil formers are generally higher-boiling organic compounds, which include the non-diffusing color coupler and development inhibitor compounds in the form of oily droplets which split off in the silver halide emulsions.
• Gelatin is preferably used as the binder for the photographic layers. However, this can be replaced in whole or in part by other natural or synthetic binders.
• natural binders are alginic acid and its derivatives such as salts, esters or amides, Cellulose derivatives such as carboxymethyl cellulose, alkyl cellulose such as hydroxyethyl cellulose, starch or their derivatives such as ether or ester or caragenate are suitable.
• Synthetic binders include polyvinyl alcohol, partially saponified polyvinyl acetate, polyvinyl pyrrolidone and the like.
• the emulsions can also be chemically sensitized, e.g. by adding sulfur-containing compounds during chemical ripening, for example allyl isothiocyanate, allyl thiourea, sodium thiosulfate and the like.
• Reducing agents e.g. the tin compounds described in Belgian patents 493,464 or 568,687, also polyamines such as diethylenetriamine or aminomethylsulfinic acid derivatives, e.g. according to Belgian patent 547 323.
• Precious metals or noble metal compounds such as gold, platinum, palladium, iridium, ruthenium or rhodium are also suitable as chemical sensitizers. This method of chemical sensitization is described in the article by R. Koslowsky, Z.wiss.Phot. 46, 65-72, (1951).
• polyalkylene oxide derivatives e.g. with polyethylene oxide of a molecular weight between 1000 and 20,000
• condensation products of alkylene oxides and aliphatic alcohols, glycols, cyclic dehydration products of hexitols, with alkyl-substituted phenols, aliphatic carboxylic acids, aliphatic amines, aliphatic diamines and amides The condensation products have a molecular weight of at least 700, preferably more than 1000.
• these sensitizers can of course be used in combination, as described in Belgian patent 537 278 and British patent 727 982.
• 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 described in the work by F. M. Hamer "The Cyanine Dyes and related Compounds", (1964).
• the emulsions 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.
• 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 are e.g. in German laid-open specification 2 263 602 or in British patent specification 1 266 655.
• hardeners of the diazine, triazine or 1,2-dihydroquinoline series are alkyl or arylsulfonyl group-containing diazine derivatives, derivatives of hydrogenated diazines or triazines, e.g. 1,3,5-hexahydrotriazine; Fluorine-substituted diazine derivatives, e.g.
• Fluoropyrimidine esters of 2-substituted 1,2-dihydroquinoline or 1,2-dihydroisoquinoline-N-carboxylic acids.
• Vinyl sulfonic acid hardeners, carbodiimide or carbamoyl hardeners such as e.g. in German laid-open publications 22 63 602, 22 25 230 and 18 08 685, French patent specification 1 491 807, German patent specification 872 153 and GDR patent specification 7218.
• Other useful hardeners are described, for example, in British Patent 1,268,550.
• the compounds to be used according to the invention can be introduced in diffusible or in diffusion-resistant form in at least one layer or intermediate layer of a photographic material both in emulsified and in dispersed or soluble form. They can be added to the light-sensitive silver halide emulsion layers after chemical ripening or the finished casting solution, or they can be applied together with the last protective layer. If appropriate, the compounds to be used according to the invention can be introduced into the photographic materials by means of a bath before the first development.
• the concentration of the compounds to be used according to the invention in the layers or in a bath can vary within wide limits. It depends on the desired effect and the composition of the photographic material. When used in a photographic layer, amounts of 10 -7 to 10- 4 mol per m 2 have proven to be suitable. Amounts are preferably between 10- 6 and 10- 5 mol / m z.
• the advantageous properties of the compounds to be used according to the invention are all the more astonishing since two mutually opposing effects can be specifically achieved here by means of a chemical substance: a stabilizing effect in the first development of photographic reversal materials and a concealing effect in the second development of photographic reversal materials.
• the compounds in particular, for example, the compounds of the formula (11), can moreover have a stabilizing effect in the customary color-negative development.
• Another characteristic of the compounds mentioned is their very uniform effect on the different emulsion layers, which, depending on the concentration of the compounds used, leads to a parallel shift of the gradations for the same development time or else allows a largely arbitrary adjustment of the first development time.
• a cyan layer containing ff a silver bromoiodide emulsion containing 7 mole% iodide prepared according Glafkides "Photographic Chemistry", Vol 1, page 289, Fountain Press, London, 1958.
• the silver content of the emulsion is - expressed in AgN0 3 to 100 g per kg Emulsion.
• the emulsion is ripened in a known manner by adding sulfur compounds and gold I compounds. It is sensitized to the red spectral range and contains a color coupler with the following formula:
• the layer contains the same color coupler as layer 1.
• a yellow filter layer made of a silver sol.
• the layer contains a coupler of the following formula:
• the layer contains the same color coupler as layer 6.
• the structure is completed with a protective layer.
• the casting solution used for this contains 1.6% gelatin in addition to the hardening and wetting agent. Order corresponding to 50 ml / sqm.
• the photographic material is developed in the following first developer I for 8 minutes at 30 ° C.
• the photographic material is then subjected to a stop bath, watered, exposed twice and developed in developer II for 6 minutes. After the second development, it is stopped, washed, bleached and fixed, washed and dried as usual.
• the dye formation is favored by the substances to be used according to the invention in such a way that a second exposure can be dispensed with.

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• Physics & Mathematics (AREA)
• Chemical & Material Sciences (AREA)
• General Physics & Mathematics (AREA)
• Spectroscopy & Molecular Physics (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)

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• 1977
  • 1977-12-29 DE DE19772758720 patent/DE2758720A1/de not_active Withdrawn
• 1978
  • 1978-12-16 EP EP78101736A patent/EP0002763B1/de not_active Expired
  • 1978-12-16 DE DE7878101736T patent/DE2861613D1/de not_active Expired
  • 1978-12-20 US US05/971,445 patent/US4282313A/en not_active Expired - Lifetime
  • 1978-12-27 CA CA000318676A patent/CA1138245A/en not_active Expired
  • 1978-12-27 JP JP16027478A patent/JPS5497418A/ja active Pending

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