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
  • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
  • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
  • G03C7/407—Development processes or agents therefor
  • G03C7/413—Developers
• • 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
  • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
  • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
  • G03C7/392—Additives
  • G03C7/39208—Organic compounds
  • G03C7/39228—Organic compounds with a sulfur-containing function

Definitions

• This invention relates to anti-color-fogging agents for color photographic recording materials, and to a process for stabilizing color photographic materials by the addition of suitable anti-color-fogging agents which are able to reduce the formation of color fogs.
• Colored images are produced in known manner by developing exposed silver halide emulsions in the presence of conventional color developers, a colored image being produced in addition to the silver image through reaction of the oxidized color developer with color couplers simultaneously present.
• the color couplers can be added in known manner either to the emulsion layers, to the adjacent layers or to the developer solution.
• p-phenylene diamines or their substituted derivatives are normally used as color developers for producing colored images.
• the colored images obtained by the conventional processes often shown colo'r fogging or discoloration.
• the formation of a color fog may be attributed to the fact that the developer compounds are oxidized to a certain degree under the action of air, and to the fact that the oxidized developer has a tendency to couple with the color coupler at those places in the photographic recording material in which no silver image has originally been produced.
• This troublesome oxidation of the developer can be caused by the influence of air or by additives present in the emulsions and can occur uniformly in the individual layers or to a greater extent in one or more layers, resulting either in a uniform color fog or in discoloration of the photographic material.
• color reproduction can be im- 5 proved by arranging, between the photosensitive silver halide emulsion layer and a layer containing the color couplers, an intermediate layer which is built up in such a way that the oxidation products of the developers are unable to diffuse into the layer containing the color couplers.
• compounds of the kind which react with the developer oxidation products to form colorless compounds are incorporated inter alia into this layer.
• white couplers only reduce the color fog to an extent that is inadequate for practical purposes.
• an object of the invention is to provide new anti-color-fogging agents which do not have any of the disadvantages referred to above, in particular can readily be synthesized and do not crystallize'out from their dispersions in aqueous hydrophilic colloid coating compositions before, during or after application, and, even during development,are not oxidized into colored secondary products.
• R-S-CH -C C-R in which R represents alkyl preferably with up to 18 carbon atoms, aryl e.g. phenyl or a heterocyclic radical, for excapto, amino, carboxy, sulfo, sulfamoyl, pyridyl, propymylthio, alkylthio which in turn can be substituted, e.g. with those mentioned above.
• the compounds according to the invention can be used with advantage anywhere where it appears advisable to eliminate undesirable oxidation products of the color developer.
• the anti-color fogging agents according to the invention convert the oxidized form of any primary aromatic amine color developer (used for color developer) into the developer compound or into a form which does not couple with the color coupler.
• the compounds according to the invention are best added as anti-discolorants to any layer of any multilayer color photographic material.
• they can be added to one or more of the photosensitive layers and/or to imtermediate or protective layers applied to or between the photosensitive layers.
• They can be used in color photographic materials which contain color couplers incorporated into the photosensitive emulsion layer, or in multilayer color photographic materials which do not contain any incorporated color couplers.
• the color photographic materials can be recording materials, copying materials or reverse materials. They can also be incorporated in diffusion-resistant form in separating layers of multilayer color materials and, in this way, can contribute towards better color separation so that oxidized colour developer is prevented from passing from one to the other layer.
• color couplers serve to control the gradation of the silver halide layers. They can also be used as non-diffusion-resistant compounds in the photosensitive layers,
• the adjacent layers and in the photographic processing baths for example in stopping baths, fixing baths, hardening baths or simply in aqueous solution and as rinsing solutions during or after the photographic processing in order to prevent color fogging.
• the compounds can be introduced into the photographic materials at any time before chromogenic development of a silver image, or alternatively they can be added to a bath which follows to the development step to inhibit the formation of color fogs produced by unremoved residual color developers with residual color couplers.
• the compounds according to the invention are prepared by known processes, for example according to the process described in German Patent 946,143, by reacting the mercapto or thione derivatives with chloro or bromopropine, preferably in a alkyline medium.
• the preparation of the compounds according to the invention is illustrated in the following examples.
• the rest of the compounds according to the invention can be similarly obtained.
• the compounds according to the invention all show the characteristic E CH-valency frequency at 3,300 cm which, according to substitution, can be slightly shifted and more or less clearly pronounced.
• the compounds according to the invention can be added to the photographic emulsion or auxiliary layers, if any, at any time.
• the compounds used according to the'invention can be used in different concentrations according to the photosensitive silver halide emulsion used in each case, the concentration of silver halide in the emulsion layers and the concentration of dye to be formed.
• the compounds are used in the photographic material, for example in the silver halide emulsionlayers, it is best to use from 0.0001 to 0.01 mol'of compound per mol of silver halogenide, and preferably'0.002 mol per mol of silver halogenide.
• the compounds are introduced into the color photographic materials in the form of a solution, for example in the form of a processing solution, it is best to use concentrations of about mg to 10 g per liter of solution and, preferably, concentrations of 100 mg to' l g per liter of solution.
• concentrations of about mg to 10 g per liter of solution and, preferably, concentrations of 100 mg to' l g per liter of solution.
• concentrations are governed by the particular photographic recording material in which the anti-color-fogging agent is to be used, and can readily be determined by known methods.
• the compounds according to the invention are preferably added in dissolved form to the auxiliary layers or to the photosensitive layer.
• Water, lower aliphatic alcohols, tetrahydrofuran, acetone, ethylacetate, dimethylformamide or mixtures thereof, are used as solvents.
• One preferred method of introduction is to dissolve the compounds according to the invention together with the color coupler and to introduce the resulting solution into the photosensitive silver halide layer.
• the compounds according to the invention are preferably introduced into the photosensitive emulsion after chemical ripening or before casting of the finished emulsion.
• the usual silver halide emulsions are suitable for the color photographic materials which are used in accor dance with the invention. They can contain, as silver halide, silver chloride, silver bromide or mixtures thereof, which may additionally contain a small proportion of silver iodide of up to 10 mol percent.
• Gelatin is preferably used as binder for the photographic layers. However, it can be replaced either wholly or in part by other natural or synthetic binders.
• suitable natural binders include alginic acid and derivatives thereof, such as salts, esters or amides, cellulose derivatives such as carboxymethyl cellulose, alkyl cellulose, such as hydroxyethyl cellulose, starch or derivatives thereof, such as ethers or esters of carragenates.
• suitable synthetic binders polyvinyl alcohol, partially hydrolyzed polyvinyl acetate, and polyvinyl pyrrolidone.
• the emulsions can also be chemically sensitized, for example by the addition during chemical ripening of sulfurcontaining compounds, for example allylisothiocyanate, allylthiourea, or sodiumthiosulfate.
• sulfurcontaining compounds for example allylisothiocyanate, allylthiourea, or sodiumthiosulfate.
• suitable chemical sensitisers include reducing agents, for example the tin compounds described in Belgian Pat. No. 493,464 and 568,687, also polyamines such as diethylene triamine, or aminomethylsulfinic acid derivatives, for example according to Belgian Pat. No. 547,323.
• Noble metals and noble metal compounds such as gold, platinum, palladium iridium, ruthenium or rhodium, also represent suitable chemical sensitizers. This method of chemical sensitization is described in the article by R. Koslowsky, in Z. wiss. Phot.
• the emulsions can also be sensitized with polyalkylene oxide derivatives, for example with polyethylene oxide having a molecular weight of from 1,000 to 20,000, and also with condenzation 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 condenzation products have a molecular weight of at least 700, preferably of more than 1,000.
• these sensitizers can of course be used in combination, as described in Belgian Pat. No. 537,278 and in British Pat. No. 727,982.
• the emulsions can also be optically sensitized, for example with the usual polymethine dyes such as neutrocyanines, basic or acid carbocyanines, rhodacyanines, hemicyanines, styryl dyes, or oxanols. Sensitizers of this kind are described in The Cyanine Dyes and Related Compounds F.M. Hamer, (Interscience Publishers).
• the emulsions can contain the usual stabilizers, such as, for example, homopolar or salt-like compounds of mercury with aromatic or heterocyclic rings, such as mercapto tetrazoles, simple mercury salts, sulfoniummercury double salts and other mercury compounds.
• suitable stabilizers include azaindenes, preferably tetraor penta-azaindenes, especially those substituted by hydroxyl or amino groups. Compounds of this kind are described by Birr in 7.. wiss, Phot. 47, 2 58 1952).
• Other suitable sensitizers include inter alia heterocyclic mercapto compounds, for example phenylmercaptotetrazole. quaternary benzthiazole derivatives or benztriazole.
• the emulsions can be hardened in the usual way. for example with formaldehyde or halogen-substituted al dehydes containing a carboxyl, group, such as mucombromic acid, methane sulfonic acid esters ordialdehydes.
• the emulsions can also contain increasing compounds, plasticizers and coating aids.
• Photographic materials comprising a substrate and, applied one above the other to this substrate, photosensitive silver halide emulsion layers which are sensitive to red, green and blue light, are known to be particularly suitable for the production of multicolored. images.
• Silver images can be developed in layers of this kind and dyes produced image-wise in relation to the developed silver images. It is preferred to produce cyan magenta and yellow dyes. lt is preferred to produce dye images which are in a complementary relationship to that region of the spectrum to which the silver halide emulsion layer is sensitized.
• photographic materials suitable for use according to the invention include recording copying and reverse materials, reprotechnical films or color photographic materials of the kind used, for example, in the dye diffusion process.
• Suitable substrates for the color photographic materials according to the invention include the usual transparent substrates such as, for. example,. filmsof cellulose esters, polycarbonates, especially those based on bis-hydroxyphenyl alkanes, polyesters, especially polyethylene terephthalate and papers such as, for example, baryta paper substrates or papers coated with polyolefins, for example papers coated with polyethylene or polypropylene, which can beiirradiated with electrons other sensitivityto improve adhesion of the emulsion. It is of course also;
• developers include amine, N,N-diethyl-p-phenylenediamine, monomethylp-phenylenediamine, 2-amino-5-diethylamino toluene, N-butyl-N-w-sulfobutyl-p-phenylenediamine and 2- amino'-5-( N-ethyl-N-[3-methanesulfonamidoethylamino)-toluene.
• Other suitable color developers are described for example in J. Amer. Chem; Soc.
• the materials according to the invention can contain color couplers, masking and white couplers differing widely in their constitution which can be incorporated in diffusion-resistant form into hydrophilic binder layers, i.e., for example into a photosensitive silver halide emulsion layer or even into an adjacent nonphotosensitive binder layer.
• the color couplers can be added in the form of alkali salts in aqueous or aqueous-alcoholic solution.
• Water-insoluble couplers can be dispersed by known methods, for example using ethylacetate and a wetting agent, and incorporated into the emulsion in the form of a dispersion.
• coupler shows a tendency to recrystallize in the dispersion
• an oilformer for example dibutylphthalate
• couplers which are not resistant to diffusion and which can'either be incorporated into the hydrophilic layers by means of mordants or incorporated by means of a color developer solution giving a conventional photographic reversal process, as described in US. Pat. No. 2,252,718.
• EXAMPLE l ing to the formula in aqueous-methanolic sodium hydroxide solution were added to 1 kg of a silver iodobromide emulsion containing 0.24 mol of silver salt (consisting of silver bromide with a silver iodide content of 1 mol percent).
• the pH-value of the emulsion was then adjusted to 6.4, followed by the addition of l g of saponin,.dissolved in water, aswetting agent, of 0.5 g of 4-hydroxy-6-methyll,2,3a,7-tetraazaindene in aqueous-alkaline solution as stabilizer and of l g of triaerylformal in methanolic solution as hardener,
• the emulsion thus obtained is di vided into 12 equal parts and the compounds according to the invention as set out in Table 6 below added to the individual samples in the quantities specified.
• Stopping bath a buffer solution of sodium acetate and acetic acid adjusted to pH 6.5.
• Bleach-fixing bath 10 g of the sodium salt of ethylene diamine tetraacetic acid, 2 g of sodium sulfite sicc, 40 g of the sodium-iron(lll) salt of ethylene diamine tetraacetic acid, 13 g of disodium phosphate, 100 g of ammonium thiosulfate, made up with water to 1 liter and adjusted to pH 7.0.
• the processing times after development were as follows: 1 minute in the stopping bath, 1 minutes rinsing, 5 minutes in the bleach-fixing bath, minute s rinsing.
• Table 8 Sample Minimum density at 3 times the developing time 0. l 8 0. 14 0.12 0. l l 0.08 0.09 0.10 0.09 0.1 l 0. 12 0.08 0.08
• Dispersion Sensitivity (iradation Maxi- Minimum mum 1 lg of l X t] density density
• Similar samples containing dispersions l to 10 were developed for 15 minutes at C without exposure described in Example 1, and their minimum density determined.
• the color photographic multilayer material thus prepared was exposed in'a conventional sensitometer behind a test image containing a test image containing a I grey, a blue, a green and a red step wedge.
• a similar color photographic multilayer material was prepared for comparison purposes without any of the compounds according to the invention in the emulsions.
• comparison material B had the same sensitivity, the same gradation and same saem maximum density.
• EXAMPLE 4 Table 13 Minimum density Sample yellow purple blue-green EXAMPLE 5 A color photographic multilayer material on a baryta paper substrate was processed without exposure in the same way described in Example 1, except that treatment in the bleach-fixing bath was followed by rinsing for only 3 minutes instead of 10 minutes.
• sample D The color photographic material was then divided and one half, hereinafter referred to as sample D, was immersed for 1 minute in a buffer solution of sodium acetate and acetic acid with a pH-value of 6.5.
• sample E The other half, hereinafter referred to as sample E, was immersed in the same buffer solution additionally containing l g of compound 32 per liter.
• sample E which had been immersed in a buffer bath containing compound 32 according to the invention gave a 0.02 lower fogging value than comparison sample D in whose case color developer residues left in the material formed a dye with residual color components on drying in air. This reaction was inhibited in the sample according to the invention through the addition of compound 32.
• a process for the production of colored images by chromogenic processing of color photographic material having at least one light sensitive silver halide emulsion layer by imagewise exposure and processing in color photographic processing bath comprising color developingwith a color developer and color coupler and said process including processing in the presence of a stabilizing agent wherein the improvement comprises processing the exposed photographic material in the presence of a stabilizing amount of a 2- propynylthio derivative of the formula in which R represents an alkyl, aryl or heterocyclic group selected from the group consisting of imidazole, oxazole, thiazole, triazole, tetrazole, oxdiazole, thiadiazole, benzimidazole, benzoxazole, benzthiazole, pyridine, pyrimidine, triazine, quinoline, quinazoline, purine,s-triazolo-[4,3-a]-quinoline and R represents hydrogen, sodium or potassium.
• R represents alkyl containing up to l8 carbon atoms, l,3,4- thiadiazole, 1,2,4-triazole, a benzothiazole, a benzimidazole or a carboxyphenyl group.
• a process according to claim 4 wherein the processing bath used is a stopping bath, fixing bath, hardening bath or a rinsing bath.
• a light sensitive color photographic material comprising at least one silver halide emulsion layer and a stabilizing agent the improvement according to which the stabilizing agent capable of stabilizing a color photographic material against the formation of color fog is a 2-propynylthio derivative of the formula R represents an alkyl, aryl or heterocyclic group selected from the group consisting of imidazole, oxazole, thiazole, triazole, tetrazole, oxdiazole, thiadiazole, benzimidazole, benzoxazole, benzthiazole, pyridine, pyrimidine, triazine, quinoline, quinazoline, purine, s-triazolo-[4,3-a]-quinolinc and R represents hydrogen, sodium or potassium.
• R represents an alkyl, aryl or heterocyclic group selected from the group consisting of imidazole, oxazole, thiazole, triazole, tetrazole, o
• R represents alkyl containing up to 18 carbon atoms, a carboxy phenyl group, or a 1,3,4-thiadiazole, a 1,2,4-triazole, a benzothiazole or benzimidazole group.

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• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Spectroscopy & Molecular Physics (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)
• Plural Heterocyclic Compounds (AREA)

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Citations (2)

• 1974
  • 1974-01-18 BE BE1005655A patent/BE809894A/xx unknown
  • 1974-01-25 US US436477A patent/US3910790A/en not_active Expired - Lifetime
  • 1974-01-28 CA CA191,047A patent/CA1011980A/en not_active Expired
  • 1974-01-28 IT IT47980/74A patent/IT1002786B/it active
  • 1974-01-29 FR FR7402946A patent/FR2215647A1/fr not_active Withdrawn
  • 1974-01-30 GB GB432574A patent/GB1429614A/en not_active Expired
  • 1974-01-30 JP JP49011929A patent/JPS49107537A/ja active Pending
  • 1974-01-30 CH CH127274A patent/CH598623A5/xx not_active IP Right Cessation

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