Classifications

• • 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
  • 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
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
  • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
  • C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two 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
  • C07D233/84—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
  • 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
  • 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
  • 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
  • C07D263/60—Naphthoxazoles; Hydrogenated naphthoxazoles
• • 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
• • 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
• • 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

Definitions

• the invention relates to a photographic material comprising at least one silver halide emulsion layer the photographic properties of which have been improved by the addition of benzirnidazoline 2-thione-N,N'-dicarbonic acid esters.
• Another kind of fog is frequently formed in photographic materials comprising a paper support in particular a baryta-coated paper support.
• thiosulfate frequently is carried from the fixing bath into the developing bath.
• a silver halide solvent e.g. thiosulfate is added to the developing bath.
• thiosulfate-containing developing compositions are used in the development of photographic paper, a more or less pronounced yellow to brown fog is produced, depending on the type and age of the photographic paper.
• this fog may also be colored blue to blue violet. This fog consists of finely divided silver deposited in the barytes layer.
• this yellow fog is due to silver salts which migrate during casting from the emulsion into the barytes layer where they are retained by adsorption. On storage of these finished papers, these silver salts are reduced to silver, a process which takes place particularly in the first months of storage. If silver halide solvents such as thiosulfates are added to the developer during the processing of the papers, the dissolved silver salts are reduced on the silver nuclei of the barytes-coating, and yellow fog and patches are produced.
• the yellow fog is particularly pronounced on areas of the paper previously exposed to atmospheric moisture, e.g., at the edges of the paper and on the top sheet of a package.
• the yellow fog also occurs if types of gelatin containing compounds that dissolve silver halide are used in the production of the emulsion or of the baryta layer and if in addition there are present degradation products of gelatin which forms nuclei. These types of gelatin also produce a yellow fog in photographic films.
• emulsions that have not been fully ripened and which have a steep gradation also tend to produce a yellow fogging, especially if high-contrast-developers with a high content of potassium bromide are used for developing the latent silver image.
• the compounds to be used according to the invention are prepared by reacting the benzimidazoline-Z-thione from which they are derived with pyrocarbonic acid esters, preferably in diluents.
• the photographic materials are prepared in accordance with common practice including the steps of:
• the bisimidazoline compounds of the present invention can be added to any photographic layer within the photographic material.
• the stabilizers are added to a silver halide emulsion layer or to the baryta-coating depending somewhat on the desired effect. If fog inhibition in the silver halide emulsion layer is desired they are added preferably to an emulsion layer. On the other hand if the formation of yellow fog in the baryta-coating is to be prevented the stabilizers are preferably added to the baryta-coating.
• the stabilizers of the present invention can also be incorporated into any other auxiliary photographic layer since in any case the compounds diffuse into the other layers of the photographic material during development.
• the auxiliary layers may be waterpermeable intermediate layer protective layers or as in the silver salt diffusion process it may also be an imagereceiving layer.
• the stabilizers can be added to the photographic layers at any stage of their production. They are added to the silver halide emulsions preferably after the chemical ripening to the casting solution for the emulsion layer. It is, however, also possible to add the stabilizers to the silver halide emulsion before chemical ripening.
• the benzimidazoline compounds can be used in any silver halide emulsion.
• Suitable silver halides for the emulsion are silver chloride, silver bromide or mixtures thereof, if desired containing up to 10 mols-percent of silver iodide.
• the silver halides may be dispersed in the usual hydrophilic compounds such as carboxymethyl cellulose, polyvinyl alcohol, polyvinylpyrrolidone, alginic acid and its salts, esters or amides or, preferably, gelatin.
• the methods of incorporating the compounds in the photographic layers are relatively simple and well-known to those skilled in the photographic art. It is convenient to add the stabilizers from solutions in appropriate solvents whereby the solvent should be completely free from any deleterious elfect on the ultimate light-sensitive material. Suitable are in particular solvents miscible with water such as methanol, ethanol alone or in admixtures, tetra- 6 phenylolpropane or opaque supports such as paper, in particular baryta-coated paper which may be provided with hydrophobic layers of, for example, polyolefines such as polyethylene or polypropylene.
• the photographic material may comprise any kind of 70 support customarily used for photographic materials. Suitable supports are, for example, transparent films of cellulose esters such as cellulose acetate, of polyesters in particular on the basis of polyethyleneglycol-terephthalic hydlofill'ane of acetone-
• the photographic materials can be processed by the The concentration of the stabilizers in the layers can usual processing techniques. Any photographic developer vary widely, for instance from about 1 mg. to 0.5 g-, or developer combination is operative for developing the preferably 22-200 mg. per mol silver. halide. In the exposed photographic material.
• the developer combaryta-coating the compounds are added in amounts of pounds can be added to a photographic layer or to the 0.01 to..-2.0 g., preferably 0.1 to 1.0 g. per kg. barium 1 aqueous processing bath. For example, it is possible to sulfate.
• the optimum concentration depends on the type use developers of the hydroquinone type, pyrocatechol of. the layer and on the effects desired.
• the optimum type, p-methylaminophenol, compounds of the l-phenylconcentration will be apparent to those skilled in the art pyrazolidone-3 series or phenylenediamine developers. upon making the tests and observations customarily
• the following examples illustrate the invention: employed in the art.
• the emulsions can also be optically sensitized with Example 1 cyaflmet rhodacyanme lgemcyamn? dyes such as A very highly sensitive silver iodobromide emulsion smbed by Hamel T cyamlfe Dy:s and and containing 5 mols percent of silver iodide is prepared in .l'elated p Intersclence Publlshers, the usual manner, the silver nitrate being introduced at The emulsions may also contain chemical sensitizFrst intervals into a solution which contains gelatin in addie.g.
• reducing agents such as stannous salts, polyamlnes tion to KI and K313
• the emulsion i fl l t d i h such as diethyltriamine or sulfur compounds as described mohium lfat in a known manner and f e d f the in US. Pat. No. 1,574,944.
• soluble salts one may further add to the given emulsions salts of noble h fluocg late i di d i warm water d h m t
• noble h fluocg late i di d i warm water d h m t Such as ruthenium. rhodium, Palladium. iridium, required quantity of gelatin which contains sulfur is Platinum gold, as described in the article y added.
• the emulsion is then divided into several parts, lowsky, Wiss- Phot- 65-72 T emulsions the first part containing no additive whereas a stabilizer m y also contain p y y oxides, p ially p yis added to each of the other parts.
• Noble metal salts, ethylene oxide, and derivatives thereof, as chemical senpreferably gold salts, are then added to all the samples of sitizers. emulsion and the samples are ripened to their optimum
• the silver halide emulsions may additionally contain sensitivity. the usual stabilizers, e.g.
• homopolar or salt-type com- The emulsions are then prepared ready for casting by pounds of mercury with aromatic or heterocyclic rings, the addition of 200 mg. of 4-hydroxy-6-methyl-1,3,3a,7- such as mercaptotriazoles, simple mercury salts, sultetraazaindene as stabilizer, 600 mg. of saponin as wetting fonium mercury double salts, and other mercury comagent and 10 ml. of 10 percent aqueous solution of pounds.
• Other stabilizers which may be used include formaldehyde, the amounts being in each case based on azaindenes, especially tetraor penta-azaindenes, in par- 1 kg. of emulsion.
• the emulsion is cast on a layer support ticlllal' those Substituted with y amino p of cellulose acetate.
• Some of the film samples are stored Compounds of this type have been described in the article 40 at 60 f 3 d y Bin, WiSS- P other Suitable
• Stabilizers include 'y mercapto Compounds, in the art behind a step wedge, the emulsion layers are lphenyl's'mel'capto tetrazole, quaternary benlthiazole developed in a developer of the following composition: derivatives and benztriazoles.
• the photographic layer may be hardened in the usual manner, for example, with formaldehyde or halogen-sub- Sod S fi nhy r s stituted aldehydes that contain a carboxyl group, e.g. Borax 7.0 mucobromic acid, diketones, methanesulfonic acid esters Hydroquinone 3.5 and dialdehydes.
• p-Monomethylaminophenol sulfate 3.5 The stabilizers which we have described may be used S di citrate 7,0 in various kinds of photographic emulsions.
• potassium id 0,4 to being useful in X-ray and other non-optically sen- Made up with Water to 1 1 sitized emulsions they may also be used in ortho-chro- Developer temperature: 0 C. matic, panchromatic and infrared-sensitive emulsion. They may also be used for emulsions suitable for use in the The results of the SBIlSilIOlIlGiIiC test are shown in the silver salt diifusion process for color-photographic emulfollowing table.
• the samples of the emulsions are applied onto a barytacoated paper support and dried.
• the dried layers contain 1.5 to 1.6 g. silver in the form of silver halide pro m.
• the samples were developed at 2, 4 and 6 minutes at a temperature of 30 C.
• Aqueous baryta paste (BaSO -content 'by The above suspension is divided into several parts. To these samples are added per kg. suspension 0.15 g. of stabilizers 1, 2, 5 and 6 in form of a 1% by weight aqueous solution of acetone. The raw paper is baryta-coated therewith three times in known manner. Thereafter an unrinsed silver chlorobromide emulsion as described in Example 2 is applied onto the baryta-coated paper support.
• Example 1 Processing and measurement of the yellow fog is accomplished as described in Example 1. Whereas the samples containing the stabilizers show no yellow fog after the heated cupbroad storage a dark brown, patchy yellow fog is visible with a control sample.
• a light-sensitive photographic material having at least one support silver halide emulsion layer which contains a stabilizing amount of a benzimidazoline-2-thio ne- N,N-dicarbonic acid ester having the following formula:
• R straight chain or branched alkyl having up to 6 carbon atoms
• R hydrogen, alkyl having up to 6 carbon atoms, alkoxy having up to 6 carbon atoms, halogen, aroxy, nitro, carboxy, carbamoyl, sulfo or sulfamoyl and It 1 or 2.
• Photographic material of claim 1 including a barytacoated paper support wherein the benzimidazoline-2- thione-N,N'-dicarbonic acid ester is contained in the baryta-coating.

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

Applications Claiming Priority (2)

Publications (1)

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Family Applications (1)

Country Status (7)

Cited By (5)

• 1971
  • 1971-08-17 CA CA120,711A patent/CA979709A/en not_active Expired
  • 1971-08-17 GB GB3848171A patent/GB1340544A/en not_active Expired
  • 1971-08-25 US US00174930A patent/US3761278A/en not_active Expired - Lifetime
  • 1971-08-25 BE BE771731A patent/BE771731A/nl unknown
  • 1971-08-26 CH CH1253671A patent/CH571233A5/xx not_active IP Right Cessation
  • 1971-08-27 JP JP6524171A patent/JPS559695B1/ja active Pending
  • 1971-08-27 FR FR7131204A patent/FR2107076A5/fr not_active Expired

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