Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
  • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
  • C07D239/20—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
  • C07D239/22—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms directly attached to ring carbon atoms
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  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
  • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
  • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D215/36—Sulfur atoms
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  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
  • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
  • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
  • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D231/18—One oxygen or sulfur atom
  • C07D231/20—One oxygen atom attached in position 3 or 5
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  • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
  • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
  • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
  • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D231/44—Oxygen and nitrogen or sulfur and nitrogen atoms
• • C—CHEMISTRY; METALLURGY
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  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
  • C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
  • C07D233/28—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D233/30—Oxygen or sulfur atoms
  • C07D233/42—Sulfur atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
  • C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
  • C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
  • C07D235/24—Benzimidazoles; Hydrogenated benzimidazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
  • C07D235/28—Sulfur atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
  • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
  • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
  • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
  • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
  • C07D239/56—One oxygen atom and one sulfur atom
• • C—CHEMISTRY; METALLURGY
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  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
  • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
  • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
  • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
  • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
  • C07D239/58—Two sulfur atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
  • C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
  • C07D241/38—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with only hydrogen or carbon atoms directly attached to the ring nitrogen atoms
  • C07D241/40—Benzopyrazines
  • C07D241/44—Benzopyrazines with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the hetero ring
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
  • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
  • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
  • C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D249/12—Oxygen or sulfur atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D257/00—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms
  • C07D257/02—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms not condensed with other rings
  • C07D257/04—Five-membered rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
  • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
  • C07D263/30—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
  • C07D263/34—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D263/46—Sulfur atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
  • C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
  • C07D263/54—Benzoxazoles; Hydrogenated benzoxazoles
  • C07D263/58—Benzoxazoles; Hydrogenated benzoxazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D271/00—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms
  • C07D271/02—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms not condensed with other rings
  • C07D271/10—1,3,4-Oxadiazoles; Hydrogenated 1,3,4-oxadiazoles
  • C07D271/113—1,3,4-Oxadiazoles; Hydrogenated 1,3,4-oxadiazoles with oxygen, sulfur or nitrogen atoms, directly attached to ring carbon atoms, the nitrogen atoms not forming part of a nitro radical
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
  • C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
  • C07D277/62—Benzothiazoles
  • C07D277/68—Benzothiazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
  • C07D277/70—Sulfur atoms
  • C07D277/74—Sulfur atoms substituted by carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
  • C07D285/01—Five-membered rings
  • C07D285/02—Thiadiazoles; Hydrogenated thiadiazoles
  • C07D285/04—Thiadiazoles; Hydrogenated thiadiazoles not condensed with other rings
  • C07D285/12—1,3,4-Thiadiazoles; Hydrogenated 1,3,4-thiadiazoles
  • C07D285/125—1,3,4-Thiadiazoles; Hydrogenated 1,3,4-thiadiazoles with oxygen, sulfur or nitrogen atoms, directly attached to ring carbon atoms, the nitrogen atoms not forming part of a nitro radical
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
  • C07D285/01—Five-membered rings
  • C07D285/02—Thiadiazoles; Hydrogenated thiadiazoles
  • C07D285/04—Thiadiazoles; Hydrogenated thiadiazoles not condensed with other rings
  • C07D285/12—1,3,4-Thiadiazoles; Hydrogenated 1,3,4-thiadiazoles
  • C07D285/125—1,3,4-Thiadiazoles; Hydrogenated 1,3,4-thiadiazoles with oxygen, sulfur or nitrogen atoms, directly attached to ring carbon atoms, the nitrogen atoms not forming part of a nitro radical
  • C07D285/135—Nitrogen atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
  • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
  • C07D471/04—Ortho-condensed systems
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D473/00—Heterocyclic compounds containing purine ring systems
  • C07D473/02—Heterocyclic compounds containing purine ring systems with oxygen, sulphur, or nitrogen atoms directly attached in positions 2 and 6
  • C07D473/22—Heterocyclic compounds containing purine ring systems with oxygen, sulphur, or nitrogen atoms directly attached in positions 2 and 6 one oxygen and one sulfur atom
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D473/00—Heterocyclic compounds containing purine ring systems
  • C07D473/26—Heterocyclic compounds containing purine ring systems with an oxygen, sulphur, or nitrogen atom directly attached in position 2 or 6, but not in both
  • C07D473/36—Sulfur atom
  • C07D473/38—Sulfur atom attached in position 6
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
  • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
  • C07D487/04—Ortho-condensed systems
• • 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
  • G03C1/00—Photosensitive materials
  • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
  • G03C1/775—Photosensitive materials characterised by the base or auxiliary layers the base being of paper

Definitions

• This invention relates to an improved photographic material comprising a silver halide emulsion layer and containing an organic compound preventing the formation of yellow fog.
• thiosulfate is frequently transferred from the fixing bath into the developer.
• a silver halide solvent generally thiasulfate
• a yellow to brown fogging is produced, of varying intensity depending on the type and the age of the photographic paper.
• this fogging may also be blue to bluish violet in color. With photographic papers, this fogging is due to finely divided silver deposited in the baryta-coating.
• This yellow fogging produced with baryta-coated photographic papers results from the passing, during the casting process, of silver salts from the silver halide emulsion into the baryta coating Where they are adsorbed by the baryta. During the storage of the papers, these silver salts are reduced to silver, particularly in the first months of storage. If the developer used in the processing of such papers contains silver halide solvents, such as thiosulfates, the dissolved silver salts are reduced on the silver nuclei of the baryta and a yellow fogging and spot formation is produced. Furthermore, the properties of the starting materials play a large part in the formation of spots or stains.
• the yellow fogging appears particularly strongly at those areas of the papers which were exposed to the humidity of the air, ie at the edges of the papers and on the uppermost sheet of a pack.
• This yellow fogging occurs particularly when using unwashed silver chloride or chlorobromide emulsions because the chlorides present in excess are able to form soluble silver complex salts.
• This yellow fogging also occurs if, in the production of the emulsion or the baryta, types of gelatin are used which contain compounds capable of dissolving silver halide and if in addition nucleus-forming degradation products of the gelatin are present. Such types of gelatin also cause which is capable of a yellow fogging with photographic films.
• emulsions which have only just ripened and have a steep gradation are particularly liable to produce yellow fogging when steeply operating developers with a relatively high content of potassium bromide are used for developing the silver image.
• R represents a nitrogen-containing heterocyclic ring system
• X represents sulfur or oxygen bonded to a carbon atom of the heterocyclic ring
• R represents alkyl, cycloalkyl, aryl, aralkyl
• Z. represents oxygen or sulfur
• suitable heterocyclic ring sys tems R are the ring systems of diazoles, oxazoles, triazoles, imidazoles, thiazoles, thiadiazoles, thiadiazolidines, oxadiazoles, tetrazoles, diazines, triazines, imidazolines, benzthiazoles, benzoxazoles, benzimidazoles, naphtriazoles, benztriazoles, quinoline, pyrimidine, partially hydrogenated pyrimidine, quinazoline, quinoxaline, purine, azaindolizines or other heterocyclic ring systems which form part of heterocyclic compounds that are capable of forming diflicultly soluble silver salts and which are used in the photographic art as stabilizers or antifoggants for silver halide emulsions.
• the heterocyclic ring systems are derived from said heterocyclic compounds by subtracting therefrom a mercapto or hydroxy group which is bonded to the heterocyclic system or by subtracting therefrom a hydrogen atom which is bonded to nitrogen atom forming part of the heterocyclic system.
• a suitable class of compounds may more specifically be represented by the following formula:
• Y represents S, NH, or a chemical represents sulfur or oxygen
• 11 represents an integer from 0 to 10
• R has the same meaning as in Formula I.
• R represents alkyl having 1 to 18 carbon atoms, cycloalkyl or carboxyalkyl, preferably up to 5 carbon atoms
• X represents S, NH or a chemical bond
• X represents S, NH, N-alkyl, N-alkenyl or and Z and R have the same meaning as in Formula I.
• Suitable compounds are those of the following formulae: 89 N N t .l 34"- -I
• the compounds may be produced by reaction of about equivalent amounts of the heterocyclic compounds containiug either a hydrogen atom bonded to a heterocyclic nitrogen atom or a mercapto or hydroxy group bonded to a carbon atom of the heterocyclicnucleus with chloroformic or chlorothioformic acid esters in the presence of sodium hydroxide in acetone or dioxane at temperatures of 040 C.
• the crude products which are not soluble in ether are purified by Washing with water and recrystallizing. The other crude products are dissolved in ether and after evaporation of the ether recrystallized from suitable solvents.
• Compound 42 is set out in Beilstein, vol. 26, page 40.
• Methanol is used for recrystallizing compounds 1, 9, 10, 15, 16, 22, 24, 26, 27, 28, 29, 38, 39, 44, toluene for recrystallizing compound 2 and petrolether for recrystallizing compound 8.
• Compounds 6, 7, 35, 36, 43 are purified by dissolving the raw products in ether, washing the ethereal solution with water, evaporating the ether, dissolving the residue in methanol and precipitating with water.
• the raw product of compound 3 is purified by dissolving it in Inethylenechloride, evaporating the solvent, reprecipitating the residue from dimethylformamid and water and dissolving the precipitate in ether and evaporating the ether.
• the raw products of compounds 4 and 5 are first dissolved in methylenechloride, the methylenechloride is evaporated, the residue is redissolved in petrolether and the solvent is evaporated.
• the raw products of compounds 11, 12, 13, 14, 17, 18, 19, 20, 21, 25, 31, 33, 34, 37, 40, 45, 46, 47, 49, 50, 51, 52, 53, 57 are purified by dissolving them in ether, washing the ethereal solution with water, evaporating the ether, redissolving the residue in ether, methanol and acetone and each time evaporating the solvent.
• the raw products of compounds 30, 54 are purified by dissolving them in methylenechloride or dioxane respectively and evaporating the solvent.
• the substances of the present invention are probably not adsorbed by the silver halide grains of the emulsion, but are disposed in the gelatin phase between the silver halide grains.
• the carboxy group is split off and the compound reacts with the soluble silver salts, thus preventing the formation of yellow fogging.
• silver halide emulsion it is possible to use emulsions containing silver chloride or silver bromide or mixtures thereof. Furthermore, the emulsion may contain up to about of silver iodide, as calculated on total silver halide.
• binding agents for the baryta layer can be used animal glues preferably gelatin which may be partially replaced by film-forming hydrophilic products such as polyvinyl alcohol, polyvinyl-pyrrolidone, alginic acid or derivatives thereof such as alkali metal salts, esters in particular with lower aliphatic glycols, or amides, and in addition, carboxyethylcellulose, starch or the like.
• hydrophilic products such as polyvinyl alcohol, polyvinyl-pyrrolidone, alginic acid or derivatives thereof such as alkali metal salts, esters in particular with lower aliphatic glycols, or amides, and in addition, carboxyethylcellulose, starch or the like.
• baryta pigment can be used mineral products such as processed heavy spar or artificial products such as permanent white or blanc fixe.
• the compounds according to the invention can be added to any desired layer of the photographic material, but advantageously to the baryta and/ or light-sensitive silver halide emulsion layer. It will depend on the photographic material and the compound in which layer the optimum efficacy is achieved. However, this can be established by a few simple experiments without any difficulties.
• the concentration to be used depends on the layer in which the compounds are incorporated and this can also be established by simple tests.
• the compounds are added in amounts of about 2-300 mg., advantageously 5-60 mg. per mol of silver halide.
• concentration of 0.0.ll.0 g./l. and advantageously 0.050.15 g./l. of casting solution are suitable. These amounts correspond to 0.022 mg, preferably 0.04-0.3 mg. per gram of barium sulfate.
• the compounds according to the invention can be added at any time, but advantageously to the prepared casting solution.
• the photographic emulsions can be either sensitized or non-sensitized optically.
• other chemical ripening compounds can also be added to them, for example sulfur compounds or noble metal salts.
• the emulsions can further contain alkylcne oxide polymerization products as chemical sensitizers.
• the new stabilizers can be used together with other stabilizers which are already known. They can furthermore be used in 8 emulsions which contain color couplers or silver halide developer substances.
• the conventional developer combinations In the processing of the photographic materials according to the invention, it is possible to employ the conventional developer combinations.
• the process does not depend on any particular developer substances. It is for example possible to use as developer substances hydroquinone, pyrocatechol, p-methylaminophenol, 1-phenyl-3- pyrazolidones or phenylene diamines.
• Example 1 An unrinsed silver chlorobromide emulsion containing 0.12 mol of silver halide per litre, has added thereto, prior to casting, 2 mg. of compound 15 dissolved in alcohol. After adding the conventional hardening and wetting agents, the emulsion is then applied in known manner to a baryta-coated paper and dried. The paper, both when fresh and after being kept for 2 days in a hot cupboard at 60 C., was developed for 1, 2, 3, 5 and 7 minutes at 30 C. in a p-methylaminophenol-hydroquinone developer, to which 10 g./l. of crystallized sodium thiosulfate had been added in order to test for yellow fogging.
• Example 2 One liter of silver chloride emulsion, containing 0.08 mol of silver halide, has 5 mg. of compound 39, dissolved in alcohol, added thereto prior to casting. After adding the usual hardening and wetting agents, the emulsion is then applied in known manner to a baryta-coated paper and dried. The test for yellow fogging is carried out as described in Example 1. Whereas the control specimen shows a bluish-yellow fogging after being kept in the heated cupboard, no fogging is visible with the specimen according to the invention. Instead of the aforementioned compound 39 it is also possible for 5 mg./l. of compound 36 or 10 mg./l. of compound 52 to be added to the emulsion with the same result.
• Example 3 A phototechnical emulsion, which contains about 0.4
• mol/L of silver halide (silver iodobromide emulsion), has 5 mg. of compound 56, dissolved in alcohol, added thereto prior to casting.
• the emulsion is applied in known manner to a film or paper support and dried.
• the test for yellow fogging is carried out as described in Example 1. The specimen does not show any yellow fogging, Whereas a yellow fogging is visible on the control specimen after being stored in the heated cupboard.
• Example 4 A baryta-coating solution has added thereto 0.15 g./l. of the compound 2, dissolved in alcohol, and a paper is baryta-coated therewith three times in known manner. An unrinsed silver chlorobromide emulsion is thereafter applied to this paper in known manner.
• the baryta-coating solution may be obtained in known manner from 15 kg. of barium sulfate (containing 20% of water), 1.5 kg. of gelatin in the form of a 5% aqueous solution, cm. of a 20% aqueous sodium hexametaphosphate solution, 300
• the baryta coating solution may have added thereto per liter 30 mg. of compound 10, 12 or 15, 20 mg. of compound 28 or 50 mg. of compound 35.
• Example 1 The test for yellow fogging is carried out as described in Example 1. Whereas the experimental samples shows no yellow fogging after the heated chamber storage, a dark brown patchy yellow fogging is visible with the control specimen.
• a photographic material comprising a support carrying a light sensitive silver halide emulsion layer, said emulsion being in contact with a heterocyclic compound having a to 6 membered nitrogen containing heterocyclic ring substituted with a member selected from the group consisting of esterified carboxyl and esterified thiocarboxyl, said substituent being bonded directly to a ring nitrogen, or through only a sulfur or oxygen atom to a ring carbon in a-position to a ring nitrogen, said heterocyclic being capable of splitting off said substituent and forming difficultly soluble silver compounds and being present in amount sufiicient to substantially inhibit the formation of yellow fog.
• a photographic material according to claim 1, wherein said heterocyclic ring is a five membered ring containing one to two nitrogen atoms and a sulfur atom.
• a photographic material comprising a support, a baryta layer and a silver halide emulsion layer, the baryta layer being arranged between the support and the silver halide emulsion layer, at least one of said layers containing a heterocyclic compound of the formula O X: X: wherein:
• R is a member of the group consisting of alkyl having 1 to 18 carbon atoms, cycloalkyl, aryl and aralkyl,
• Y a member of the group consisting of sulfur, oxygen and nitrogen;
• X a member of the group consisting of sulfur and oxyrz an integer of 0 to 10;
• n an integer of 0 to 1.
• R is a member of the group consisting of alkyl having 1 to 18 carbon atoms, cycloalkyl, aryl and aralkyl; R is a member of the group consisting of alkyl having 1 to 18 carbon atoms, cycloalkyl, and earboxyalkyl;
• X is a member of the group consisting of sulfur and nitrogen;
• X is a member of the group consisting of S, NH, N-al kenyl and /alkyl ⁇ alkyl the alkyl groups having 1 to 6 carbon atoms; and
• Z is a member of the group consisting of sulfur and oxygen,
• heterocyclic compound being present: in amount sufficient to substantially inhibit the formation of yellow fog.
• the heterocyclic ring is a thiodiazole ring and the substituent is connected through a sulfur atom to a ring carbon.

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