EP0002763B1 - Photographic material with stabilisers and reversal process for producing a photograph - Google Patents

Photographic material with stabilisers and reversal process for producing a photograph Download PDF

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Publication number
EP0002763B1
EP0002763B1 EP78101736A EP78101736A EP0002763B1 EP 0002763 B1 EP0002763 B1 EP 0002763B1 EP 78101736 A EP78101736 A EP 78101736A EP 78101736 A EP78101736 A EP 78101736A EP 0002763 B1 EP0002763 B1 EP 0002763B1
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Prior art keywords
group
denote
development
aryl
acyl
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German (de)
French (fr)
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EP0002763A2 (en
EP0002763A3 (en
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Ubbo Dr Wernicke
Heinrich Dr. Odenwälder
Friedhelm Dipl.Chem. Sommer
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Agfa Gevaert AG
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Agfa Gevaert AG
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    • 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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Description

Die Erfindung betrifft ein photographisches Material mit mindestens einer Silberhalogenidemulsionsschicht, das durch Zusatz von Thiocarbohydrazid-Derivaten verbessert ist. Die Erfindung betrifft weiterhin ein Verfahren zur Herstellung photographischer Bilder in Gegenwart derartiger Verbindungen.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.

Lichtempfindliche Silberhalogenidemulsionen neigen bekanntlich zur Bildung von Schleiern, d.h. Keimen, die ohne Belichtung entwickelbar sind. Eine derartige Schleierbildung tritt verstärkt bei längeren Entwicklungszeiten oder einer Entwicklung bei höheren Temperaturen auf. Die Schleierbildung ist sowohl bei Materialien, die einer Negativentwicklung unterogen werden als auch bei Materialien, die einer Umkehrverarbeitung in den üblichen Bädern unterworfen sind, störend. Beispielsweise bewirken Schleierkeime, daß bei der Umkehrverarbeitung im Erstentwickler auch an den unbelichteten Stellen Silberhalogenid reduziert wird, so daß bei der Zweitenwicklung zuwenig Silberhalogenid zur Verfügung steht mit der Folge, daß zu geringe Maximal-Dichten erhalten werden.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. 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. For example, 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.

Es ist bekannt, photographischen Silberhalogenidemulsionen zur Verminderung der Schleierbildung sogennannte Antischleiermittel oder Stabilisatoren zuzusetzen. Stabilisierende Wirkung besitzen u.a. heterocyclische Mercaptoverbindungen, z.B. solche, die in der DT-B-1 183 371, DT-A-2 308 530 und DT-A-1 622 271 beschrieben sind.It is known to add so-called antifoggants or stabilizers to photographic silver halide emulsions to reduce the formation of fog. Among other things, they have a stabilizing effect. heterocyclic mercapto compounds, e.g. those described in DT-B-1 183 371, DT-A-2 308 530 and DT-A-1 622 271.

Es sind weiterhin aus der DT-A-2 548 880 Inhibitoren bekannt, die als Fluchtgruppen in DIR-Verbindungen vorliegen. DIR-Verbindungen reagieren mit dem Oxidationsprodukt von p-Phenylendiamin Farbentwicklern unter Abspaltung eines Restes, welcher die Reduktion von Silberhalogenid zu metallischem Silber hemmt. Diese Reste werden auch als "Fluchtgruppen" bezeichnet.From DT-A-2 548 880 inhibitors are also known which are present as escape groups in DIR compounds. 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".

Derartige Inhibitoren und Stabilisatoren können sich aber bei der Umkehrverarbeitung während der Erstentwicklung am restlichen Silberhalogenid anreichern und die Zweitentwicklung behindern, so daß nur verminderte Farbdichten erhalten werden.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.

Um eine derartige Behinderung der Farbstoffbildung zu vermeiden, ist in der DT-A 2 548 880 vorgeschlagen worden, die photographischen Materialien vor der Zweitentwicklung mit bestimmten chemischen Verschleierungsbädern zu behandeln. Nachteilig an der Verwendung derartiger Verschleierungsbäder ist jedoch deren Instabilität.In order to avoid such a hindrance to dye formation, it has been proposed in DT-A 2 548 880 to treat the photographic materials with certain chemical fogging baths before the second development. However, the disadvantage of using such veiling baths is their instability.

Eine Aufgabe der Erfindung ist es daher, Verbindungen für photographische Materialien mit mindestens einer Silberhalogenidemulsschichtaufzufinden, die eine Schleierbildung vermindern, jedoch die Nachteile bekannter Stabilisatoren vermeiden und die Zweitentwicklung bei einer Umkehrverarbeitung nicht nachteilig beeinflussen. Eine weitere Aufgabe ist es, ein Verfahren zur Herstellung photographischer Bilder durch Verarbeitung photographischer Materialien in Gegenwart derartiger Verbindungen aufzufinden.It is therefore an object of the invention to find compounds for photographic materials with at least one silver halide emulsion layer which reduce fogging but avoid the disadvantages of known stabilizers and do not adversely affect the secondary development in reverse processing. Another object is to find a method for producing photographic images by processing photographic materials in the presence of such compounds.

Es wurde nun gefunden, daß bestimmte Thiocarbohydrazid-derivate bei der Verarbeitung von photographischen Materialien in den üblichen Schwarzweiß-Einwicklern, wie sie beispielsweise als Erstentwickler bei Farbumkehrprozessen verwendet werden, als Stabilisator wirken, jedoch bei der Umkehrverarbeitung in den üblichen (Farb)-Zweitentwicklern nicht entwicklungsinhibierend wirken, sondern die Farbentwicklung im Zweitentwickler begünstigen, gegebenenfalls so, daß auf eine Zweitbelichtung oder die üblichen Bäder zur chemischen Verschleierung verzichtet werden kann.It has now been found that certain thiocarbohydrazide derivatives act as stabilizers in the processing of photographic materials in the conventional black-and-white developers, such as those used, for example, as first developers in color reversal processes, but not in reverse processing in the usual (color) secondary developers have a development-inhibiting effect, but favor the color development in the second developer, if necessary in such a way that a second exposure or the usual baths for chemical fogging can be dispensed with.

Gefunden wurde ein lichtempfindliches photographisches Material mit mindestens einer Silberhalogenidemulsionschicht und mindestens einer Verbindung der folgenden Formel I

Figure imgb0001
worin

  • R',R4 gleiche oder verschiedene Reste bedeuten und zwar Wasserstoff, eine gesättigte oder olefinisch ungesättigte aliphatische Gruppe, Aryl, eine heterocyclische Gruppe oder Acyl;
  • R2,R3 gleiche oder verschiedene Reste bedeuten und zwar Wasserstoff, eine gesättigte oder olefinisch ungesättigte aliphatische Gruppe, Aryl oder eine heterocyclische Gruppe;
  • R5 Wasserstoff bedeutet

und worin ferner
  • R1 zusammen mit R2

und/oder
  • R3 zusammen mit R4 Alkyliden bedeuten kann, vorzugsweise eine gegebenenfalls durch Alkyl, Aryl, eine heterocyclische Gruppe oder Acyl substituierte Methylidengruppe, wobei zwei derartige Substituenten zusammen mit dem Kohlenstoffatom der Methylidengruppe einen carbocyclischen oder heterocyclischen Ring vervollständigen können, beispielsweise einen Cyclopentan-, Indan-, Indanon-, Indandion-, Piperidin- oder Pyrrolidonring. Beispiele für nicht ringgeschlossene substituierte Methylidengruppen sind Äthyliden, 3,3-Dimethyl-2-butyliden, Benzyliden und Furfuryliden;

und/oder
  • R' zusammen mit R4 oder R5 den zur Vervollständigung eines 5- oder 6-gliedrigen heterocyclischen Ringes, insbesondere eines 1,2,3,4-Tetrazolidin-5-thionringes, eines Hexahydro-1,2,4,5-tetrazin-3-thionringes, eines Hexahydro-1,2,4-triazin-3-thionringes oder eines 2,3,4,5-Tetrahydro-1,2,4-triazin-3-thionringes erforderlichen Rest bedeuten kann; hierbei handelt es sich in der Regel um eine Methylengruppe, die gegebenenfalls einfach oder zweifach weiter substituiert sein kann, z.B. mit Alkyl, Cycloalkyl, Aralkyl oder Aryl; zwei derartige Substituenten, z.B. zwei Alkylreste, können ihrerseits zusammen mit dem Kohlenstoffatom der Methylengruppe einen Ring, insbesondere einen carbocyclischen Ring bilden, wie beispielsweise einen Cyclopentan-, Cyclohexan- oder 3,3,5-Trimethylcyclohexanring.
A light-sensitive photographic material having at least one silver halide emulsion layer and at least one compound of the following formula I was found
Figure imgb0001
 wherein
  • R ', R 4 are identical or different radicals, namely hydrogen, a saturated or olefinically unsaturated aliphatic group, aryl, a heterocyclic group or acyl;
  • R 2 , R 3 represent identical or different radicals, namely hydrogen, a saturated or olefinically unsaturated aliphatic group, aryl or a heterocyclic group;
  • R 5 means hydrogen

and what further
  • R 1 together with R 2

and or
  • R 3 together with R 4 can denote alkylidene, preferably a methylidene group optionally substituted by alkyl, aryl, a heterocyclic group or acyl, where two such substituents together with the carbon atom of the methylidene group can complete a carbocyclic or heterocyclic ring, for example a cyclopentane, indane -, indanon, Indanedione, piperidine or pyrrolidone ring. Examples of non-ring-closed substituted methylidene groups are ethylidene, 3,3-dimethyl-2-butylidene, benzylidene and furfurylidene;

and or
  • R 'together with R 4 or R 5 to complete a 5- or 6-membered heterocyclic ring, in particular a 1,2,3,4-tetrazolidine-5-thione ring, a hexahydro-1,2,4,5-tetrazine -3-thione ring, a hexahydro-1,2,4-triazine-3-thione ring or a 2,3,4,5-tetrahydro-1,2,4-triazine-3-thione ring may be the radical required; this is generally a methylene group which can optionally be mono- or disubstituted further, for example with alkyl, cycloalkyl, aralkyl or aryl; two such substituents, for example two alkyl radicals, can in turn form a ring, in particular a carbocyclic ring, together with the carbon atom of the methylene group, such as a cyclopentane, cyclohexane or 3,3,5-trimethylcyclohexane ring.

Beispiele für gesättigte aliphatische Gruppen sind Alkylreste, die geradkettig, verzweigt oder cyclisch sein können und bis zu 18 C-Atome enthalten sowie weiter substituiert sein können, beispielsweise mit Carboxyl, Carbamoyl oder Nitril.Examples of 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.

Eine geeignete olefinisch ungesättigte aliphatische Gruppe ist beispielsweise Allyl, qeeiqnete heterocyclische Gruppen sind insbesondere stickstoffhaltige 5- oder 6-gliedrige Ringe, vor allem die oben angegebenen.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.

Als Aryl kommt insbesondere Phenyl in Frage, das substituiert sein kann, beispielsweise durch Halogen, Hydroxyl, Alkoxy, Alkylthio, Carboxyl, Sulfamoyl, Amino und/oder Alkyl.Particularly suitable aryl is phenyl, which can be substituted, for example by halogen, hydroxyl, alkoxy, alkylthio, carboxyl, sulfamoyl, amino and / or alkyl.

Als Acylreste werden solche verstanden, die sich ableiten von aliphatischen oder aromatischen Carbon- oder Sulfonsäuren, einschließlich (Thio-) Kohlensäuremonoestern, Carbaminsäuren oder Sulfaminsäuren. Beispiele für derartige Acylreste sind Acetyl, Benzoyl, Phenylsulfonyl, Carbamoyl, Phenylcarbamoyl, Äthoxycarbonyl, Äthoxythiocarbonyl.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.

Die Verbindungen gemäß Formel (I) können gegebenenfalls mit einem diffusionsfest machenden Rest versehen sein, z.B. mit einer langkettigen Alkyl- oder Alkylengruppe, der gegebenenfalls über ein Heteroatom angeknüpft ist.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.

Besonders geeignete Verbindungen entsprechend der Formel (I) sind solche, bei denen mindestens einer der Reste R' und R4 einen Acylrest mit R2, R3 und R5 Wasserstoff bedeuten, beispielsweise die folgenden Verbindungen:

Figure imgb0002
Figure imgb0003
Figure imgb0004
Figure imgb0005
 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:
Figure imgb0002
Figure imgb0003
Figure imgb0004
Figure imgb0005

Die erfindungsgemäßen Verbindungen können nach bekannten Methoden aus Thiocarbohydrazid erhalten werden, wie sie beispielsweise in der Literatur zu finden sind in J. Indian Chem. Soc. 1, 141 und in J. Org. Chem. 34, 756.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.

Aus der Zeitschrift "Research Disclosure", Mai 1977, Artikel Nr. 15 750 ist bereits ein Verfahren zur Herstellung farbphotographischer Bilder nach dem Farbstoffdiffusionsübertragungsverfahren sowie ein hierfür geeignetes photographisches Material bekannt, welches Verbindungen enthält, die in oxidierter Form in alkalischen Entwicklermedium einen diffundierenden Farbstoff in Freiheit zu setzen vermögen. Die Entwicklung derartiger Emulsionen muß unter schleiernden Bedingungen vorgenommen werden, wofür Thiocarbohydrazide verwendbar sind. Demgegenüber bezeiht sich die vorliegende Erfindung weder auf Farbstoffdiffusionsübertragungsverfahren noch auf dafür geeignete Materialien.From the journal "Research Disclosure", May 1977, Article No. 15 750, a process for producing color photographic images by the dye diffusion transfer process and a photographic material suitable for this purpose are already known, which contains compounds which, in oxidized form, contain a diffusing dye in an alkaline developer medium Can set freedom. The development of such emulsions must be carried out under foggy conditions, for which thiocarbohydrazides can be used. In contrast, the present invention relates neither to dye diffusion transfer processes nor to suitable materials.

Herstellung der VerbindungliProduction of the connection

In einer Suspension von 53 g Thiocarbohydrazid in 350 ml Pyridin werden unter Rühren und Kühlung 116 ml Benzoylchlorid bei einer Temperatur von 25°C; zugetropft. Nach beendeter Zugabe wird noch 3 weitere Stunden bei Raumtemperatur gerührt und danach mit 6 Liter Wasser versetzt. Der erhaltene Niederschlag wird abgetrennt, aus Methanol/Wasser umgefällt und nach Trocknen an der Luft mit 1,7 liter siedendem Essigester verrührt und nach Erkalten abgesaugt und an der Luft getrocknet. Es werden 112 g 1,5-Bisbenzoyl-thiocarbohydrazid erhalten, das bei 117­-179°C unter Zersetzung schmilzt.In a suspension of 53 g of thiocarbohydrazide in 350 ml of pyridine, 116 ml of benzoyl chloride at a temperature of 25 ° C .; dripped. After the addition has ended, the mixture is stirred for a further 3 hours at room temperature and then mixed with 6 liters of water. The precipitate obtained is separated off, reprecipitated from methanol / water and, after drying in air, stirred with 1.7 liters of boiling ethyl acetate and, after cooling, filtered off with suction and air-dried. 112 g of 1,5-bisbenzoyl-thiocarbohydrazide are obtained, which melts at 117-179 ° C. with decomposition.

Gegenstand der Erfindung ist weiterhin ein Umkehrverfahren zur Herstellung von photographischen Bildern durch bildmäßige Belichtung, Erstentwicklung, Verschleierung und Zweitentwicklung eines photographischen Materials, wobei die Erstentwicklung und gegebenenfalls die Verschleierung und die Zweitenwicklung in Gegenwart der erfindungsgemäß zu verwendenden Substanzen durchgeführt wird.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.

Die erfindungsgemäßen Materialien können nach den üblichen Verfahren mit dem üblichen Entwicklern verarbeitet werden. Als Schwarz/VJeiß-Entwicklersubstanzen können beispielsweise verwendet werden: Hydrochinon, p-Methylaminophenol und 1-Phenyl-3-pyrazolidon. Als Farbentwicklersubstanzen können beispielsweise verwendet werden:

  • N,N-Dimethyl-p-phenylendiamin, 4-Amino-3-methyl-N-äthyl-N-methoxyäthylanilin, Monomethylp-phenylendiamin, 2-Amino-5-diäthylaminotoluol, N-Butyl-N- sulfobutyl-p-phenylendiamin, 2-Amino-5-(N-äthyl-N-ß-methansulfonamidäthyl-amino)-toluol, N-Äthyl-N-ß-hydroxyäthyl-p-phenylendiamin, N,N-Bis-(ß-hydroxyäthyl)-p-phenylendiamin, 2-Amino-5-(N-äthyl-N-ß-hydroxyäthylamino)-toluol und dergleichen. Weitere brauchbare Farbentwickler sind beispielsweise beschrieben in J.Amer.Chem. Soc. 73, 3100 (1951).
The materials according to the invention can be processed by the customary methods with the customary developers. Examples of black / VJeiß developer substances that can be used are: hydroquinone, p-methylaminophenol and 1-phenyl-3-pyrazolidone. For example, the following can be used as color developer substances:
  • N, N-dimethyl-p-phenylenediamine, 4-amino-3-methyl-N-ethyl-N-methoxyethylaniline, monomethylp-phenylenediamine, 2-amino-5-diethylaminotoluene, N-butyl-N-sulfobutyl-p-phenylenediamine, 2-amino-5- (N-ethyl-N-ß-methanesulfonamidäthyl-amino) -toluene, N-ethyl-N-ß-hydroxyethyl-p-phenylenediamine, N, N-bis- (ß-hydroxyethyl) -p- phenylenediamine, 2-amino-5- (N-ethyl-N-β-hydroxyethylamino) toluene and the like. Other useful color developers are described, for example, in J.Amer.Chem. Soc. 73, 3100 (1951).

Für die vorliegende Erfindung sind die üblichen Silberhalogenidemulsionen geeignet. Diese können als Silberhalogenid, Silberchlorid, Silberbromid, Silberjodid oder Gemische davon enthalten.The usual silver halide emulsions are suitable for the present invention. These can contain as silver halide, silver chloride, silver bromide, silver iodide or mixtures thereof.

Das erfindungsgemäß hergestellte photographische Material kann die üblichen Farbkuppler enthalten, die in der Regel den Silberhalogenidschichten selbst einverleibt sind. So enthält die rotempfindliche Schicht beispielsweise einen nicht diffundierenden Farbkuppler zur Erzeugung des blaugrünen Teilfarbenbildes, in der Regel einen Kuppler vom Pheno!- oder a-Naphtholtyp. Die grünempfindliche Schicht enthält mindestens einen nicht diffundierenden Farbkuppler zur Erzeugung des purpurnen Teilfarbenbildes, wobei üblicherweise Farbkuppler vom Typ des 5-Pyrazolons oder des Indazolons Verwendung finden. Die blauempfindliche Schichteinheit schließlich enthält mindestens einen nicht diffundierenden Farbkuppler zur Erzeugung des gelben Teilfarbenbildes, in der Regel einen Farbkuppler mit einer offenkettigen Ketomethylengruppierung. Farbkuppler dieser Arten sind in großer Zahl bekannt und in einer Vielzahl von Patentschriften beschrieben. Beispielhaft sei hier auf die Veröffentlichung "Farbkuppler" von W. Pelz in "Mitteilungen aus den Forschungslaboratorien der Agfa, Leverkusen/ München", Band 111 (1961) und K. Venkataraman in "The Chemistry of Synthetic Dyes", Vol. 4, 341 bis 387 Academic Press 1971 hingeweisen.The photographic material produced according to the invention can contain the usual color couplers, which are usually incorporated into the silver halide layers themselves. For example, 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. Finally, 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. Color couplers of these types are known in large numbers and are described in a large number of patents. Examples include the publication "Farbkuppler" by W. Pelz in "Mitteilungen aus dem Forschungslaboratorien der Agfa, Leverkusen / München", Volume 111 (1961) and K. Venkataraman in "The Chemistry of Synthetic Dyes", Vol. 4, 341 to 387 Academic Press in 1971.

Als nicht diffundierende Farbkuppler können 2-Äquivalentkuppler verwendet werden; diese enthalten in der Kupplungsstelle einen abspaltbaren Substituenten, so daß sie zur Farbbildung nur zwei Äquivalente Silberhalogenid benötigen im Unterschied zu den üblichen 4-Äquivalentkupplern. Zu den einsetzbaren 2-Äquivalentkupplern gehorren beispielsweise die bekannten DIR-Kuppler, bei denen der abspaltbare Rest nach Reaktion mit Farbentwickleroxydationsprodukten als diffundierender Entwicklungsinhibitor in Freiheit gesetzt wird. Weiterhin können zur Verbesserung der Eigenschaften des photographischen Materials die sogenannten Weißkuppler eingesetzt werden.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.

Die nicht diffundierenden Farbkuppler und farbgebenden Verbindungen werden den lichtempfindlichen Silberhalogenidemulsionen oder sonstigen Gießlösungen nach üblichen bekannten Methoden zugesetzt. Wenn es sich um wasser-oder alkalilösliche Verbindungen handelt, können sie den Emulsionen in Form von wäßrigen Lösungen, gegebenenfalls unter Zusatz von mit Wasser mischbaren organischen Lösungsmitteln wie Äthanol, Aceton oder Dimethylformamid, zugestzt werden. Soweit es sich bein den nicht diffundierenden Farbkupplem und farbgebenden Verbindungen um wasser- bzw. alkyliunlösliche Verbindungen handelt, können sie in bekannter Weise emulgiert werden z.B., indem eine Lösung dieser Verbindungen in einem niedrigsiedenden organischen Lösungsmittel direkt mit der Silberhalogenidemulsion oder zunächst mit einer wäßrigen Gelatinelösung vermischt wird, worauf das organische Lösungsmittel in üblicher Weise entfernt wird. Ein so erhaltenes Gelatine-emulgat der jeweiligen Verbindung wird anschließend mit der Silberhalogendemulsion vermischt. Gegebenenfalls verwendet man zur Einemulgierung derartiger hydrophober Verbindungen zusätzlich noch sogenannte Kupplerlösungsmittel oder Ölformer; das sind in der Regel höhersiedende organische Verbindungen, die die in den Silberhalogenidemulsionen zu emulgierenden nicht diffundierenden Farbkuppler und Entwicklungsinhibitor abspaltenden Verbindungen in Form öliger Tröpfchen einschließen. Verwiesen sei in diesem Zusammenhang beispielsweise auf die US-Patentschriften 2 322 027; 2 533 514; 3 689 271; 3 764 336 und 3 765 897.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. To the extent that the 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. If necessary, so-called 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. In this connection, reference is made, for example, to US Pat. Nos. 2,322,027; 2,533,514; 3,689,271; 3,764,336 and 3,765,897.

Als Bindemittel für die photographischen Schichten wird vorzugsweise Gelatine verwendet. Diese kann jedoch ganz oder teilweise durch andere natürliche oder synthetische Bindemittel ersetzt werden. An natürlichen Bindemitteln sind z.B. Alginsäure und deren Derivate wie Salze, Ester oder Amide, Cellulosederivate wie Carboxymethylcellulose, Alkylcellulose wie Hydroxyäthylcellulose, Stärke oder deren Derivate wie Äther oder Ester oder Caragenate geeignet. An synthetischen Bindemitteln seien erwähnt Polyvinylalkohol, teilweise verseiftes Polyvinylacetat, Polyvinylpyrrolidon und dergleichen.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. Examples of 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.

Die Emulsionen können auch chemisch sensibilisiert werden, z.B. durch Zusatz schwefelhaltiger Verbindungen bei der chemischen Reifung, beispielsweise Allylisothiocyanat, Allylthioharnstoff, Natriumthiosulfat und ähnliche. Als chemische Sensibilisatoren können ferner auch Reduktionsmittel, z.B. die in den belgischen Patentschriften 493 464 oder 568 687 beschriebenen Zinnverbindungen, ferner Polyamine wie Diäthylentriamin oder Aminomethylsulfinsäurederivate, z.B. gemäß der belgischen Patentschrift 547 323 verwendet werden.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.

Geeignet als chemische Sensibilisatoren sind auch Edelmetalle bzw. Edelmetallverbindungen wie Gold, Platin, Palladium, Iridium, Ruthenium oder Rhodium. Diese Methode der chemischen Sensibilisierung ist in dem Artikel von R. Koslowsky, Z.wiss.Phot. 46, 65-72, (1951) beschrieben.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).

Es ist ferner möglich, die Emulsionen mit Polyalkylenoxid-derivaten zu sensibilisieren, z.B. mit Polyäthylenoxid eines Molekulargewichtes zwischen 1000 und 20 000, ferner mit Kondensationsprodukten von Alkylenoxiden und aliphatischen Alkoholen, Glykolen, cyclischen Dehydratisierungsprodukten von Hexitolen, mit alkylsubstituierten Phenolen, aliphatischen Carbonsäuren, aliphatischen Aminen, aliphatischen Diaminen und Amiden. Die Kondensationsprodukte haben ein Molekulargewicht von mindestens 700, vorzugsweise von mehr als 1000. Zur Erzielung besonderer Effekte kann man diese Sensibilisatoren selbstverständlich kombiniert verwenden, wie in der belgischen Patentschrift 537 278 und in der britischen Patentschrift 727 982 beschrieben.It is also possible to sensitize the emulsions with polyalkylene oxide derivatives, e.g. with polyethylene oxide of a molecular weight between 1000 and 20,000, also with 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. To achieve special effects, these sensitizers can of course be used in combination, as described in Belgian patent 537 278 and British patent 727 982.

Die Emulsionen können auch optisch sensibilisiert sein, z.B. mit den üblichen Polymethinfarbstoffen, wie Neutrocyanine, basischen oder sauren Carbocyaninen, Rhodacyaninen, Hemicyaninen, Styrylfarbstoffen, Oxonolen und ähnlichen. Derartige Sensibilisatoren sind in dem Werk von F. M. Hamer "The Cyanine Dyes and related Compounds", (1964) beschrieben.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. Such sensitizers are described in the work by F. M. Hamer "The Cyanine Dyes and related Compounds", (1964).

Die Emulsionen können zusätzlich die üblichen Stabilisatoren enthalten, wie z.B.:

  • Azaindene, vorzugsweise Tetra- oder Pentaazaindene, insbesondere solche, die mit Hydroxyl-oder Aminogruppen substituiert sind. Derartige Verbindungen sind in dem Artikel von Birr, Z. Wiss. Phot. 47 (1952) 2 bis 58 beschrieben. Weitere geeignete Stabilisatoren sind u.a. heterocyclische Mercaptoverbindungen, z.B. Phenylmercaptotetrazol, quaternäre Benzthiazolderivate, Benztriazol und ähnliche.
The emulsions can additionally contain the usual stabilizers, such as:
  • Azaindenes, preferably tetra- or penta-azaindenes, in particular those which are substituted by hydroxyl or amino groups. Such connections are described in the article by Birr, Z. Wiss. Phot. 47 (1952) 2 to 58. Other suitable stabilizers include heterocyclic mercapto compounds, for example phenyl mercaptotetrazole, quaternary benzothiazole derivatives, benzotriazole and the like.

Die Emulsionen können in der üblichen Weise gehärtet sein, beispielsweise mit Formaldehyd oder halogensubstituierten Aldehyden, die eine Carboxylgruppe enthalten, wie Mucobromsäure, Diketonen, Methansulfonsäureester, Dialdehyden und dergleichen.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.

Weiterhin können die photographischen Schichten mit Härtern des Epoxityps, des heterocyclischen Äthylenimins oder des Acryloyltyps gehärtet werden. Beispiele derartiger Härter sind z.B. in der deutschen Offenlegungsschrift 2 263 602 oder in der britischen Patentschrift 1 266 655 beschrieben. Weiterhin ist es auch möglich, die Schichten gemäß dem Verfahren der deutschen Offenlegungsschrift. 2 218 009 zu härten, um farbphotographische Materialien zu erzielen, die für eine Hochtemperaturverarbeitung geeignet sind.Furthermore, the photographic layers can be hardened with hardeners of the epoxy type, the heterocyclic ethylene imine or the acryloyl type. Examples of such hardeners are e.g. in German laid-open specification 2 263 602 or in British patent specification 1 266 655. Furthermore, it is also possible to use the layers in accordance with the procedure of the German patent application. 2 218 009 to obtain color photographic materials suitable for high temperature processing.

Es ist ferner möglich, die photographischen Schichten bzw. die farbphotographischen Mehrschichtenmaterialien mit Härtern der Diazin-, Triazin- oder 1,2-Dihydrochinolin-Reihe zu härten, wie in den britischen Patentschriften 1 193 290, 1 251 091, 1 306 544, 1 266 655, der französischen Patentschrift 7 102 716 oder der deutschen Offenlegungsschrift 23 32 317 beschrieben ist. Beispiele derartiger Härter sind Alkyl- oder Arylsulfonylgruppen-haltige Diazinderivate, Derivate von hydrierten Diazinen oder Triazinen, wie z.B. 1,3,5-Hexahydrotriazin; Fluor-sübstituierte Diazinderivate, wie z.B. Fluorpyrimidin, Ester von 2-substituierten 1,2-Dihydrochinolin- oder 1,2-Dihydroisochinolin-N-carbonsäuren. Brauchbar sind weiterhin Vinylsulfonsäurehärter, Carbodiimid- oder Carbamoylhärter, wie z.B. in den deutschen Offenlegungsschriften 22 63 602, 22 25 230 und 18 08 685, der französischen Patentschrift 1 491 807, der deutschen Patentschrift 872 153 und der DDR-Patentschrift 7218 beschrieben. Weitere brauchbare Härter sind beispielsweise in der britischen Patentschrift 1 268 550 beschrieben.It is also possible to harden the photographic layers or the color photographic multilayer materials with hardeners of the diazine, triazine or 1,2-dihydroquinoline series, as in British Patents 1 193 290, 1 251 091, 1 306 544, 1 266 655, French Patent 7 102 716 or German Laid-Open Specification 23 32 317. Examples of such hardeners 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.

Die erfindungsgemäß zu verwendenden Verbindungen können in diffusionsfähiger oder in diffusionsfester Form in mindestens eine Schicht oder Zwischenschicht eines photographischen Materials sowohl in emulgierter als auch in dispergierter oder löslicher Form eingebracht werden. Sie können den lichtempfindlichen Silberhalogenidemulsionsschichten nach der chemischen Reifung oder der fertigen Gießlösung zugesetzt oder auch zusammen mit der letzten Schutzschicht aufgebracht werden. Gegebenenfalls können die erfindungsgemäß zu verwendenden Verbindungen in die photographischen Materialien vor der Erstentwicklung mittels eines Bades eingebracht werden.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.

Die Konzentration der erfindungsgemäß zu verwendenden Verbindungen in den Schichten oder in einem Bad kann innerhalb weiter Grenzen schwanken. Sie richtet sich nach dem gewünschten Effekt und der Zusammensetzung des photographischen Materials. Bei Verwendung in einer photographischen Schicht haben sich Mengen von 10-7 bis 10-4 mol pro m2 als geeignet erweisen. Bevorzugt sind Mengen zwischen 10-6 und 10-5 mol/mz.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.

Auch für den Fall, daß die erfindungsgemäß zu verwendenden Verbindungen in das Material vor der Erstenwicklung eingebadet werden sollen, sind optimale Konzentrationen im Bad leicht durch wenige einfache Handversuch zu ermitteln. Hier haben sich Konzentrationen zwischen 10-6 bis 10-2 mol/I als ausreichend erwiesen. Besonders bevorzugt sind Konzentrationen zwischen 10-5-10-3 Mol/1 Behandlungsbad.Even in the event that the compounds to be used according to the invention are to be bathed in the material before the first winding, optimum concentrations in the bath are easily achieved to determine a few simple manual tests. Concentrations between 10- 6 to 10- 2 mol / l have proven to be sufficient here. Concentrations between 10 -5 -10 -3 mol / 1 treatment bath are particularly preferred.

Die vorteilhaften Eigenschaften der erfindungsgemäß zu verwendenden Verbindungen sind um so erstaunlicher, als hier durch eine chemische Substanz zwei an sich einander entgegengerichtete Wirkungen gezielt erreicht werden können: Eine stabilisierende Wirkung bei der Erstentwicklung von photographischen Umkehrmaterialien und eine verschleiernde Wirkung bei der Zweitentwicklung von photographischen Umkehrmaterialien. Die Verbindungen, insbesondere beispielsweise die Verbindungen der Formel (11), können überdies einen stabilisierenden Effekt bei der üblichen Color-Negativ-Entwicklung bewirken.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.

Ein weiteres Kennzeichen der genannten Verbindungen ist ihre sehr gleichmäßige Wirkung auf die verschiedenen Emulsionschichten, die in Abhängigkeit von der angewandten Konzentration der Verbindungen bei gleicher Entwicklungszeit zu einer Parallelverschiebung der Gradationen führt oder aber eine weitgehend beliebige Einstellung der Erstentwicklungszeit ermöglicht.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.

Die Vorteilhaftigkeit der erfindungsgemäß zu verwendenden Stabilisatoren wird anhand der folgenden Beispiele deutlich, ohne daß die Erfindung auf die Ausführungsformen in diesen Beispielen beschränkt ist.The advantageousness of the stabilizers to be used according to the invention is clear from the following examples, without the invention being restricted to the embodiments in these examples.

Beispielexample

Auf einen Schichtträger aus Zellulosetriacetat mit einer Antihaloschicht aus schwarzem kolloidalem Silber werden nacheinander aufgetragen:The following are applied in succession to a layer of cellulose triacetate with an antihalation layer made of black colloidal silver:

Schicht 1:Layer 1:

Eine Blaugrünschicht, enthaltend eine Silberbromidjodidemulsion mit 7 Mol-% Jodid, hergestellt gemäß Glafkides "Photographic Chemistry", Vol. 1, Seite 289 ff, Fountain Press, London 1958. Der Silbergehalt der Emulsion beträgt - ausgedrückt in AgN03 - 100 g pro kg Emulsion. Die Emulsion wird in bekannter Weise durch Zusätze von Schwefelverbindungen und Gold-I-Verbindungen gereift. Sie ist für den roten Spektralbereich sensibilisiert und enthält einen Farbkuppler folgender Formel:

Figure imgb0006
. 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:
Figure imgb0006

Schicht 2:Layer 2:

Eine zweite Blaugrünschicht, enthaltend eine Silberbromidjodidemulsion mit 6 Mol-% Jodid, hergestellt nach dem unter Schicht 1 beschriebenen Verfahren, jedoch mit einer höheren Empfindlichkeit. Die Schicht enthält den gleichen Farbkuppler wie Schicht 1.A second cyan layer containing a silver bromide iodide emulsion with 6 mol% iodide, produced by the process described under layer 1, but with a higher sensitivity. The layer contains the same color coupler as layer 1.

Schicht 3:Layer 3:

Eine Purpurschicht, enthaltend eine Silberbromidjodidemulsion wie unter Schicht 1 beschrieben, jedoch für den grünen Spektralbereich sensibilisiert. Sie enthält einen Kuppler folgender Formel:

Figure imgb0007
A purple layer containing a silver bromide iodide emulsion as described under layer 1, but sensitized to the green spectral range. It contains a coupler of the following formula:
Figure imgb0007

Schicht 4:Layer 4:

Eine zweite Purpurschicht enthaltend eine Emulsion, wie unter Schicht 2 beschrieben, jedoch für den grünen Spektralbereich sensibilisiert und mit dem gleichen Kuppler wie Schicht 3.A second purple layer containing an emulsion as described under layer 2, but sensitized to the green spectral range and with the same coupler as layer 3.

Schicht 5:Layer 5:

Eine Gelbfilterschicht aus einem Silbersol.A yellow filter layer made of a silver sol.

Schicht 6:Layer 6:

Eine Gelbschicht, enthaltend eine Silberbromidjodidemulsion mit 4 Mol-% Jodid, hergestellt wie unter Schicht 1 beschrieben, die für den blauen Spektralbereich empfindlich ist. Die Schicht enthält einen Kuppler folgender Formel:

Figure imgb0008
A yellow layer containing a silver bromide iodide emulsion with 4 mol% iodide, produced as described under layer 1, which is sensitive to the blue spectral range. The layer contains a coupler of the following formula:
Figure imgb0008

Schicht 7:Layer 7:

Eine weitere Gelbschicht enthaltend eine Silberbromidjodidemulsion mit 6 Mol-% Jodid, hergestellt wie unter Schicht 1 beschrieben, jedoch mit einer höheren Empfindlichkeit im blauen Spektralbereich als Schicht 6. Die Schicht enthält den gleichen Farbkuppler wie Schicht 6.Another yellow layer containing a silver bromide iodide emulsion with 6 mol% iodide, produced as described under layer 1, but with a higher sensitivity in the blue spectral range than layer 6. The layer contains the same color coupler as layer 6.

Schicht 8:Layer 8:

Der Aufbau wird mit einer Schutzschicht abgeschlossen. Die hierzu verwendete Gießlösung enthält neben dem Härtungs- und Netzmittel 1,6% Gelatine. Auftrag entsprechend 50 ml/qm.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.

Die Gießlösung für Schicht 8 wird wie folgt variiert (Menge pro Liter Gießlösung):

  • A: Gießlösung ohne weiteren Zusatz
  • B: Gießlösung mit 100 mg Vergleichssubstanz
  • C: Gießlösung mit 100 mg Verbindung II
  • D: Gießlösung mit 100 mg Verbindung V
  • E: Gießlösung mit 200 mg Verbindung II
  • F: Gießlösung mit 60 mg Verbindung III
The casting solution for layer 8 is varied as follows (amount per liter of casting solution):
  • A: Pouring solution without further addition
  • B: Casting solution with 100 mg reference substance
  • C: Casting solution with 100 mg of compound II
  • D: Casting solution with 100 mg of compound V
  • E: Casting solution with 200 mg of compound II
  • F: Casting solution with 60 mg of compound III

Als Vergleichssubstanz wird das als Stabilisator bekannte 1-Phenyl-5-mercaptotetrazol verwendet.1-Phenyl-5-mercaptotetrazole, known as a stabilizer, is used as the reference substance.

Die Materialien werden in üblicher Weise bildmäßig belichtet und einer Umkehrverarbeitung mit den folgenden Bädern unterworfen:The materials are exposed imagewise in the usual way and subjected to reverse processing with the following baths:

Verarbeigung /Processing /

Das photographische Material wird 8 Minuten lang bei 30°C in dem folgenden Erstentwickler I entwickelt. Anschließend wird das photographische Material einem Stopbad unterworfen, gewässert, zweitbelichtet und 6 Minuten lang in dem Entwickler II entwickelt. Nach der Zweitentwicklung wird wie üblich gestoppt, gewässert, gebleicht und fixiert, gewässert und getrocknet.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.

Entwickler 1 (Konzentration pro Liter)Developer 1 (concentration per liter)

Figure imgb0009
Figure imgb0009

Entwickler II (Konzentration pro Liter)Developer II (concentration per liter)

Figure imgb0010
Figure imgb0010
Figure imgb0011
Figure imgb0011

Verarbeitung IIProcessing II

Es wird wie unter Verarbeitung 1 angegeben verfahren mit folgender Abänderung:

  • Die Zweitbelichtung wird ausgelassen, statt dessen wird das Material 2 Minuten mit einem wäßrigen Bad behandelt, welches lediglich 30 g NaOH pro Liter enthält.
The procedure is as indicated under processing 1 with the following change:
  • The second exposure is omitted, instead the material is treated for 2 minutes with an aqueous bath which contains only 30 g NaOH per liter.

Es werden folgende Maximaldichten erhalten:

Figure imgb0012
The following maximum densities are obtained:
Figure imgb0012

Während demnach bekannte Stabilisatoren die Farbstoffbildung im Zweitentwickler behindern, wird die Farbstoffbildung durch die erfindungsgemäß zu verwendenden Substanzen derart begünstigt, daß auf eine Zweitbelichtung verzichtet werden kann.Accordingly, while known stabilizers hinder dye formation in the second developer, 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.

Claims (9)

1. Reversal process for the production of images by imagewise exposure, first development, fogging and second development of a photographic material, which contains at least one silver halide emulsion layer, characterised in that the first development, and, if appropriate, the fogging and the second development, of the photographic material is carried out in the presence of at least one compound of the following. formula
Figure imgb0017
wherein
R' and R4 are identical or different and denote hydrogen, a saturated or olefinically unsaturated aliphatic group, aryl, a heterocyclic group or acyl;
R2 and R3 are identical or different and denote hydrogen, a saturated or olefinically unsaturated group, aryl or a heterocyclic group; and R5 denotes hydrogen,

and wherein, furthermore,
R1 together with R2, and/or R3 together with R4 can denote methylidene groups which are optionally substituted by alkyl, aryl, a heterocyclic group or acyl, it being possible for two such substituents, together with the carbon atom of the methylidene group, to complete a carbocyclic or heterocyclic ring;

and wherein, furthermore,
R1 together with R4 or R5 can denote the radical required to complete a 5-membered or 6- membered heterocyclic ring.
2. Reversal process according to Claim 1, characterised in that, in the formula given, R1 and/or R4 denotes an acyl group which is derived from aliphatic or aromatic carboxylic or sulphonic acids, including carbonic acid monoesters, thiocarbonic acid monoesters, carbamic acids or sulphamic acids.
3. Reversal process according to Claim 1, characterised in that, in the formula given, R1 together with R2, and/or R3 together with R4 denote a methylidene group which is part of a cyclopentane, cyclohexane, indane, indanone, indanedione, piperidine or pyrrolidone ring.
4. Reversal process according to Claims 1 and 2, characterised in that R2, R3 and R5 denote hydrogen.
5. Light-sensitive photographic material with at least one silver halide emulsion layer and at least one non-diffusible coupling compound, characterised in that it contains at least one compound of the formula
Figure imgb0018
wherein
Rt and R4 are identical or different and denote hydrogen, a saturated or olefinically unsaturated aliphatic group, aryl, a heterocyclic group or acyl,
R2 and R3 are identical or different and denote hydrogen, a saturated or olefinically unsaturated group, aryl or a heterocyclic group, and R5 denotes hydrogen,

and wherein, furthermore,
R' together with R2, and/or R3 together with R4 can denote methylidene groups which are optionally substituted by alkyl, aryl, a heterocyclic group or acyl, it being possible for two such substituents, together with the carbon atom of the methylidene group, to complete a carbocyclic or heterocyclic ring,

and wherein
Rt together with R4 or R5 can denote the radical required to complete a 5-membered or 6- membered ring.
6. Material according to Claim 5, characterised in that, in the formula given, Rt and/or R4 denotes an acyl group which is derived from aliphatic or aromatic carboxylic or sulphonic acids, including carbonic acid monoesters, thiocarbonic acid monoesters, carbamic acids or sulphamic acids.
7. Material according to Claim 5, characterised in that, in the formula given, R1 together with R2, and/or R3 together with R4 denote a methylidene group which is part of a cyclopentane, cyclohexane, indane, indanone, indanedione, piperidine or pyrrolidone ring.
8. Material according to Claim 6, characterised in that R2, R3 and R5 denote hydrogen.
9. Material according to Claim 5, characterised in that it is a material for reversal processing by first development, fogging and second development.
EP78101736A 1977-12-29 1978-12-16 Photographic material with stabilisers and reversal process for producing a photograph Expired EP0002763B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2758720 1977-12-29
DE19772758720 DE2758720A1 (en) 1977-12-29 1977-12-29 PHOTOGRAPHIC MATERIAL WITH STABILIZERS

Publications (3)

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EP0002763A2 EP0002763A2 (en) 1979-07-11
EP0002763A3 EP0002763A3 (en) 1979-07-25
EP0002763B1 true EP0002763B1 (en) 1982-02-03

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EP (1) EP0002763B1 (en)
JP (1) JPS5497418A (en)
CA (1) CA1138245A (en)
DE (2) DE2758720A1 (en)

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JPS57150845A (en) * 1981-03-13 1982-09-17 Fuji Photo Film Co Ltd Silver halide photographic material
US20060063827A1 (en) * 2004-09-23 2006-03-23 Yu Ruey J Systemic administration of therapeutic amino acids and N-acetylamino acids

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Publication number Priority date Publication date Assignee Title
GB561875A (en) * 1942-12-03 1944-06-08 John David Kendall Improvements in or relating to photographic materials
FR1393033A (en) * 1963-05-10 1965-03-19 Agfa Ag stabilized photographic silver halide emulsions
DE1183371B (en) * 1963-05-10 1964-12-10 Agfa Ag Process for stabilizing photographic silver halide emulsions with mercury compounds and organic stabilizers
FR1497205A (en) * 1964-04-20 1967-10-06 Eastman Kodak Co New process for developing photographic images and new photographic products
DE1251327B (en) * 1964-10-26 1967-10-05 Eastman Kodak Company, Rochester, NY (V St A) Process for the preparation of 1 aryl-1H-tetrazoles substituted in the 5-position
US3397987A (en) * 1965-05-24 1968-08-20 Eastman Kodak Co Photographic emulsion containing mercapto development anti-foggants
FR1492132A (en) * 1965-05-24 1967-08-18 Eastman Kodak Co New photographic emulsions and new photographic products containing these emulsions
US3486901A (en) * 1966-10-21 1969-12-30 Eastman Kodak Co Direct-print silver halide emulsions containing a halogen acceptor and an amine compound as a stabilizer
GB1203051A (en) * 1967-02-15 1970-08-26 Agfa Gevaert Nv Improvements in or relating to photographic light-sensitive silver halide materials
DE1772088C3 (en) * 1967-03-30 1976-01-08 Fuji Shashin Film K.K., Ashigara, Kanagawa (Japan) Fixing solution for silver halide photographic light-sensitive materials
GB1237192A (en) * 1967-06-21 1971-06-30 Agfa Gevaert Nv Information-recording processes and materials
US3666471A (en) * 1968-11-01 1972-05-30 Mitsubishi Paper Mills Ltd Silver halide photographic sensitized paper producing black or blue black image
JPS4926586B1 (en) * 1970-09-16 1974-07-10
DE2719371A1 (en) * 1977-04-30 1978-11-02 Agfa Gevaert Ag PHOTOGRAPHIC REVERSAL PROCEDURE
DE2746965A1 (en) * 1977-10-19 1979-04-26 Agfa Gevaert Ag PROCESS FOR PRODUCING DIRECT POSITIVE PHOTOGRAPHIC IMAGES

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DE2758720A1 (en) 1979-07-19
CA1138245A (en) 1982-12-28
EP0002763A2 (en) 1979-07-11
JPS5497418A (en) 1979-08-01
EP0002763A3 (en) 1979-07-25
US4282313A (en) 1981-08-04

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