EP0050260B1 - Photographic material, process for its production and method for the production of photographic pictures - Google Patents

Photographic material, process for its production and method for the production of photographic pictures Download PDF

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Publication number
EP0050260B1
EP0050260B1 EP81107953A EP81107953A EP0050260B1 EP 0050260 B1 EP0050260 B1 EP 0050260B1 EP 81107953 A EP81107953 A EP 81107953A EP 81107953 A EP81107953 A EP 81107953A EP 0050260 B1 EP0050260 B1 EP 0050260B1
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EP
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Prior art keywords
silver halide
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photographic
compounds
silver
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EP81107953A
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German (de)
French (fr)
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EP0050260A1 (en
Inventor
Anita Dr. von König
Franz Dr. Moll
Lothar Dr. Rosenhahn
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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

Definitions

  • the invention relates to a photographic material with a latent image stabilizer, a method for producing this material and a method for producing photographic images.
  • the fading of the latent image is usually noticeable in that an exposed material that was stored before development is less sensitive than a material that was not stored after exposure.
  • the reasons for the regression of the latent image have not yet been fully clarified, but it is believed that they are caused by substances in the emulsion, e.g. B. impurities or additives, which oxidize part of the silver that makes up the latent image.
  • the regression of the latent image is extremely troublesome in practice, not only for the recording materials, which are usually stored in the exposed state for a long time before development, but also for copying materials if the latter are not developed immediately after exposure. Especially when processing roll copy materials, these are often only developed a few days after exposure.
  • Latent image stabilizers are described, for example, in German Offenlegungsschrift 2,827,937 and in British Patents 1,343,904, 1,412,294, 1,378,354, 1,386,630, 1453388 and in U.S. Patents 3,386,831 and 3,881,939.
  • An object of the invention is to achieve improved latent image stabilization.
  • the compounds to be used according to the invention are so-called Schiff bases. It is already known to add such compounds to photographic recording materials as masked developer substances. However, concentrations of the same order of magnitude as that of the silver halide used are naturally to be used. It is known from US-A-3,342,599 to use Schiff bases in an amount of preferably 0.5 to 2.5 moles per mole of silver halide as a development precursor in photographic recording materials. There is, however, absolutely no indication that the present invention as the compounds to be used at a concentration of up to 10- 2 mol per mol of silver halide Latent image stabilizer act. It also follows from column 2, line 10, of US Pat. No. 3,342,599 that the compounds indicated only hydrolyze and are active at a pH above 9.
  • the Schiff bases to be used in the manner according to the invention can be prepared by known methods by condensation of the corresponding aromatic aldehydes and p-phenylenediamine derivatives in the presence of an inert solvent.
  • the oxidation-sensitive free p-phenylenediamines can be prepared by preparing the free base from the corresponding salt by adding sodium acetate to the reaction solution during the reaction.
  • the compounds to be used according to the invention are outstandingly suitable for increasing the stability of the latent image nuclei in light-sensitive photographic materials with at least one silver halide emulsion layer.
  • the stability of the latent image nuclei is prolonged while preserving all the usual photographic properties, which of course are largely determined by the structure of the silver halide emulsion, even when the materials are stored: time at normal temperature or at elevated temperature in the heating cabinet is achieved excellently.
  • the compounds to be used according to the invention are added to the photographic material, in particular after the emulsion has been physically ripened.
  • the derivatives are preferably added in dissolved form to the light-sensitive silver halide emulsion during or after chemical ripening or the finished casting solution.
  • Lower aliphatic alcohols, tetrahydrofuran, acetone or mixtures thereof are particularly suitable as solvents.
  • the concentration of the compounds in the photographic materials can vary within wide limits. It depends on the desired effect, the type of reproduction process and the structure of the photographic material.
  • Amounts of at most 10 to 2 mol, in particular at most 10 to 3 mol, per mol of silver halide have proven to be suitable.
  • Particularly preferred concentrations between 10 mg and 1000 mg per mole of silver are Halo a enid.
  • the compounds to be used according to the invention can be used in conventional light-sensitive materials for stabilizing the latent image nuclei, which are suitable for the production of black and white images, for.
  • color couplers can be contained in the material without affecting the stabilization.
  • These materials are primarily developable silver halide materials with common silver halide emulsions that give a negative image on development, including the reversal materials where the first development after fogging is followed by a second development.
  • hydrophilic film-forming agents are suitable as protective colloid or binder for the silver halide emulsion layer, e.g. B. proteins, especially gelatin, alginic acid or their derivatives such as esters, amides or salts, cellulose derivatives such as carboxymethyl cellulose and cellulose sulfates, starch or their derivatives or hydrophilic synthetic binders such as polyvinyl alcohol, partially saponified polyvinyl acetate, polyvinyl pyrrolidone and others.
  • proteins especially gelatin, alginic acid or their derivatives such as esters, amides or salts, cellulose derivatives such as carboxymethyl cellulose and cellulose sulfates, starch or their derivatives or hydrophilic synthetic binders such as polyvinyl alcohol, partially saponified polyvinyl acetate, polyvinyl pyrrolidone and others.
  • the layers can also contain other synthetic binders in dissolved or dispersed form, such as homopolymers or copolymers of acrylic or methacrylic acid or their derivatives, such as esters, amides or nitriles, and also vinyl polymers, such as vinyl esters or vinyl ethers.
  • synthetic binders in dissolved or dispersed form, such as homopolymers or copolymers of acrylic or methacrylic acid or their derivatives, such as esters, amides or nitriles, and also vinyl polymers, such as vinyl esters or vinyl ethers.
  • the usual substrates can be used for the materials according to the invention, e.g. B. carriers made of cellulose esters such as cellulose acetate or cellulose acetobutyrate, further polyester, in particular polyethylene terephthalate or polycarbonates, in particular based on bisphenylol propane.
  • cellulose esters such as cellulose acetate or cellulose acetobutyrate
  • polyester in particular polyethylene terephthalate or polycarbonates, in particular based on bisphenylol propane.
  • paper supports which are optionally impermeable polyolefin layers, e.g. B. of polyethylene or polypropylene, can also contain supports made of glass or metal.
  • silver halide emulsions are suitable for the present invention.
  • these can contain silver chloride, silver bromide or mixtures thereof, possibly with a low content of silver iodide up to 10 Mo 1 - ofo.
  • the emulsions can also be chemically sensitized, e.g. B. by adding sulfur-containing compounds during chemical ripening, for example allyl isothiocyanate, allyl thiourea and sodium thiosulfate or by adding selenium compounds.
  • Reducing agents e.g. B. the tin compounds described in Belgian patents 493464 or 568 687, also polyamines such as diethylenetriamine or aminomethylsulfinic acid derivatives, e.g. B. according to Belgian patent 547 323 used.
  • Precious metals or noble metal compounds such as gold, platinum, palladium, iridium, ruthenium or rhodium are also suitable as chemical sensitizers.
  • polyalkylene oxide derivatives e.g. B. with polyethylene oxide having a molecular weight between 1000 and 20,000, also with condensation products of alkylene oxides and alcohols, aliphatic carboxylic acids, aliphatic amines, aliphatic diamines and amides.
  • the emulsions can also be optically sensitized, e.g. B. 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.
  • Such sensitizers are described in the work of F. M. Hamer, "The Cyanine Dyes and related Compounds" (1964).
  • the materials can contain in combination with the further stabilizers to be used according to the invention, e.g. B. azaindenes, preferably tetra- or pentaazaindenes, especially those which are substituted with hydroxyl or amino groups.
  • B. azaindenes preferably tetra- or pentaazaindenes, especially those which are substituted with hydroxyl or amino groups.
  • suitable stabilizers are u. a. heterocyclic mercapto compounds, e.g. B. phenyl mercaptotetrazole, quaternary benzothiazole derivatives, benzotriazole and the like.
  • the layers of the photographic material 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.
  • the photographic layers can be hardened with hardeners of the epoxy type, the heterocyclic ethylene imine or the acryloyl type.
  • hardeners of the diazine, triazine or 1,2-dihydroquinoline series are alkyl or arylsulfonyl group-containing diazine derivatives, derivatives of hydrogenated diazines or triazines, such as. B. 1,3,5-hexahydrotriazine, fluorine-substituted diazine derivatives, such as. B. fluoropyrimidine, esters of 2-substituted 1,2-dihydroquinoline or 1,2-dihydroisoquinoline-N-carboxylic acids.
  • vinyl sulfonic acid hardeners such as. B. in German laid-open publications 2 263 602, 2 225 230 and 1 808 685, French patent 1 491 807, German patent 872 153 and DD-A-7218.
  • Other useful hardeners are described, for example, in British Patent 1,268,550.
  • Colored photographic images can e.g. B. according to the known principle of chromogenic development in the presence of color couplers, which react with the oxidation product of coloring p-phenylenediamine developers to form dyes.
  • the color couplers can be added to the color developer, for example, according to the principle of the so-called development process.
  • the photographic material itself contains the usual color couplers, which are usually incorporated into the silver halide layers.
  • the red-sensitive layer can contain a non-diffusing color coupler for producing the blue-green partial color image, generally a coupler of the phenol or ⁇ -naphthol type.
  • the green-sensitive layer can contain, for example, at least one non-diffusing color coupler for producing the purple partial color image, color couplers of the 5-pyrazolone or imidazolone type usually being used.
  • the blue-sensitive layer can contain, for example, a non-diffusing color coupler for generating the yellow partial color image, usually a color coupler with an open-chain ketomethylene grouping.
  • Color couplers of this type are known in large numbers and are described in a large number of patents. Examples include the publication "Color coupler” by W. Pelz in “Messages from the research laboratories of Agfa, Leverkusen / Kunststoff", Volume 111 (1961), and K. Venkataraman in “The Chemistry of Synthetic Dyes", Vol. 4, 341 to 387, Academic Press, 1971.
  • 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, optionally with the addition of water-miscible organic solvents such as ethanol, acetone or dimethylformamide. Insofar as the non-diffusing color couplers and coloring compounds are water- or alkali-insoluble compounds, they can be emulsified in a known manner, e.g.
  • a highly sensitive silver bromide iodide emulsion with 6 mol% silver iodide is prepared in the usual way, flocculated and freed from the soluble salts. It is then redispersed, mixed with gelatin and ripened with sulfur and gold compounds in a known manner.
  • the emulsion had a silver nitrate / gelatin ratio of 1: 1 and contained 95 g of silver per kg, calculated as silver nitrate.
  • the emulsions were then poured onto a cellulose acetate support in such a way that the silver coating, calculated as silver nitrate, was 5.5 g per m 2 .
  • the samples were dried in the customary manner, exposed in a sensitometer behind a gray-scale wedge and, after the treatments shown in Table 2, were developed at 20 ° C. for 7 or 16 minutes in a developer I of the following composition: Make up to 1 liter with water.
  • the evaluation of the sensitivity in Table 2 is carried out relative to the test drawn as a type. Differences in sensitivity are thus indicated. An increase of this value by three units means a doubling of the sensitivity.
  • the sensitivity itself is determined at a density of 0.2 over fog.
  • Color photographic materials for reverse processing are produced by successively applying the layers listed below to a cellulose triacetate support provided with an adhesive layer.
  • the sample is prepared as described for sample I, except that 100 mg / kg of compound 1, dissolved in methanol, are added to the yellow layer (layer 5).

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  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
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Description

Die Erfindung betrifft ein fotografisches Material mit einem Latentbildstabilisator, ein Verfahren zur Herstellung dieses Materials und ein Verfahren zur Herstellung fotografischer Bilder.The invention relates to a photographic material with a latent image stabilizer, a method for producing this material and a method for producing photographic images.

Es ist bekannt, daß die latenten Bildkeime belichteter Silberhalogenidemulsionen bei der Lagerung nicht stabil sind. Diese Erscheinung ist beispielsweise beschrieben in »The Theory of the Photographic Process«, 4. Auflage, Macmillan Publishing Co., New York, 1977, Seiten 167 ff.It is known that the latent image nuclei of exposed silver halide emulsions are not stable during storage. This phenomenon is described, for example, in "The Theory of the Photographic Process", 4th edition, Macmillan Publishing Co., New York, 1977, pages 167 ff.

Die Rückbildung des latenten Bildes (fading) macht sich gewöhnlich dadurch bemerkbar, daß ein belichtetes Material, das vor der Entwicklung gelagert wurde, unempfindlicher ist als ein Material, das nach der Belichtung nicht gelagert wurde. Die Gründe für die Rückbildung des latenten Bildes sind noch nicht vollständig geklärt, jedoch wird angenommen, daß sie durch Substanzen in der Emulsion, z. B. Verunreinigungen oder Zusätze, ausgelöst wird, die einen Teil des Silbers, aus dem das latente Bild besteht, oxidieren. Die Rückbildung des latenten Bildes ist in der Praxis außerordentlich störend, und zwar nicht nur für die Aufnahmematerialien, die gewöhnlich vor dem Entwickeln längere Zeit in belichtetem Zustand gelagert werden, sondern auch für Kopiermaterialien, wenn letztere nicht sofort nach dem Belichten entwickelt werden. Insbesondere bei der Verarbeitung von Rollenkopiermaterialien werden diese oft erst einige Tage nach dem Belichten entwickelt.The fading of the latent image is usually noticeable in that an exposed material that was stored before development is less sensitive than a material that was not stored after exposure. The reasons for the regression of the latent image have not yet been fully clarified, but it is believed that they are caused by substances in the emulsion, e.g. B. impurities or additives, which oxidize part of the silver that makes up the latent image. The regression of the latent image is extremely troublesome in practice, not only for the recording materials, which are usually stored in the exposed state for a long time before development, but also for copying materials if the latter are not developed immediately after exposure. Especially when processing roll copy materials, these are often only developed a few days after exposure.

Es ist bekannt, fotografischen Silberhalogenidemulsionen zur Stabilisierung der Latentbildkeime sogenannte Latentbildstabilisatoren zuzusetzen. Latentbildstabilisatoren werden beispielsweise beschrieben in der deutschen Offenlegungsschrift 2 827 937 sowie in den britischen Patentschriften 1 343 904, 1412294, 1 378 354, 1 386 630, 1453388 sowie in den US-Patentschriften 3 386 831 und 3 881 939.It is known to add so-called latent image stabilizers to photographic silver halide emulsions to stabilize the latent image nuclei. Latent image stabilizers are described, for example, in German Offenlegungsschrift 2,827,937 and in British Patents 1,343,904, 1,412,294, 1,378,354, 1,386,630, 1453388 and in U.S. Patents 3,386,831 and 3,881,939.

Eine Aufgabe der Erfindung ist es, eine verbesserte Latentbildstabilisierung zu erreichen.An object of the invention is to achieve improved latent image stabilization.

Es wurde nun gefunden:

Figure imgb0001
Figure imgb0002
worin bedeuten
Figure imgb0003
Figure imgb0004
Figure imgb0005
 It has now been found:
Figure imgb0001
Figure imgb0002
 in what mean
Figure imgb0003
Figure imgb0004
Figure imgb0005

Die erfindungsgemäß zu verwendenden Verbindungen sind sogenannte Schiffsche Basen. Es ist bereits bekannt, derartige Verbindungen fotografischen Aufzeichnungsmaterialien als verkappte Entwicklersubstanzen zuzufügen. Hierbei sind aber naturgemäß Konzentrationen in der gleichen Größenordnung wie die des verwendeten Silberhalogenids zu verwenden. So ist aus der US-A-3 342 599 bekannt, Schiffsche Basen in einer Menge von vorzugsweise 0,5 bis 2,5 Mol pro Mol Silberhalogenid als Entwicklungsvorläufer in fotografischen Aufzeichnungsmaterialien zu verwenden. Es findet sich aber überhaupt kein Hinweis darauf, daß die erfindungsgemäß zu verwendenden Verbindungen bei einer Konzentration von maximal 10-2 Mol pro Mol Silberhalogenid als Latentbildstabilisator wirken. Ferner folgt aus Spalte 2, Zeile 10, der US-A-3 342 599, daß die angegebenen Verbindungen erst bei einem pH-Wert oberhalb von 9 hydrolysieren und aktiv sind. Ein derartiger pH-Wert liegt in üblichen fotografischen Aufzeichnungsmaterialien in der Zeit zwischen Belichtung und Entwicklung nicht vor. Dieser Zeitraum ist gerade aber der, in welchem die zugefügten Latentbildstabilisatoren den Rückgang des latenten Bildes verhindern sollen. Somit hätte erwartet werden müssen, daß die erfindungsgemäß zu verwendenden Verbindungen als Latentbildstabilisator unwirksam sind. Dieses ist aber, wie aus den Beispielen der vorliegenden Anmeldung hervorgeht, nicht der Fall. Aus den US-Patentschriften 3 227 552, 3 227 550 und 3 243 294 ist weiterhin bekannt, für die Herstellung direkt positiver Bilder als Entwickler Schiffsche Basen zu verwenden. Es findet sich wiederum kein Hinweis darauf, daß die erfindungsgemäß zu verwendenden Verbindungen in den angegebenen Konzentrationen als Latentbildstabilisator wirken können. Aus der US-Patentschrift 2507 114 ist bekannt, Schiffsche Basen, die mit einer Carboxyl- oder Sulfonsäuregruppe substituiert sind, in fotografischen Materialien als Entwicklersubstanz zu verwenden. Auch in dieser Patentschrift findet sich kein Hinweis auf die erfindungsgemäße Verwendung.The compounds to be used according to the invention are so-called Schiff bases. It is already known to add such compounds to photographic recording materials as masked developer substances. However, concentrations of the same order of magnitude as that of the silver halide used are naturally to be used. It is known from US-A-3,342,599 to use Schiff bases in an amount of preferably 0.5 to 2.5 moles per mole of silver halide as a development precursor in photographic recording materials. There is, however, absolutely no indication that the present invention as the compounds to be used at a concentration of up to 10- 2 mol per mol of silver halide Latent image stabilizer act. It also follows from column 2, line 10, of US Pat. No. 3,342,599 that the compounds indicated only hydrolyze and are active at a pH above 9. Such a pH value does not exist in the usual time between exposure and development in conventional photographic recording materials. However, this period is exactly the one in which the added latent image stabilizers are intended to prevent the decline in the latent image. Thus, the compounds to be used according to the invention should have been expected to be ineffective as a latent image stabilizer. However, as is evident from the examples of the present application, this is not the case. From US Pat. Nos. 3,227,552, 3,227,550 and 3,243,294 it is also known to use Schiff bases as developers for the production of directly positive images. Again, there is no indication that the compounds to be used according to the invention can act as latent image stabilizers in the stated concentrations. From US Pat. No. 2,507,114 it is known to use Schiff bases which are substituted with a carboxyl or sulfonic acid group in photographic materials as developer. In this patent there is also no reference to the use according to the invention.

Die in der folgenden Tabelle (1) aufgeführten Verbindungen der Formel (1) haben sich als besonders geeignet erwiesen.

Figure imgb0006
The compounds of the formula (1) listed in the following table (1) have proven to be particularly suitable.
Figure imgb0006

Die in der erfindungsgemäßen Weise zu verwendenden Schiffschen Basen können nach bekannten Methoden durch Kondensation der entsprechenden aromatischen Aldehyde und p-Phenylendiaminderivate in Gegenwart eines inerten Lösungsmittels hergestellt werden. Die Herstellung der oxydationsempfindlichen freien p-Phenylendiamine kann durch Herstellung der freien Base aus dem entsprechenden Salz durch Zusatz von Natriumacetat zur Reaktionslösung während der Umsetzung erfolgen.The Schiff bases to be used in the manner according to the invention can be prepared by known methods by condensation of the corresponding aromatic aldehydes and p-phenylenediamine derivatives in the presence of an inert solvent. The oxidation-sensitive free p-phenylenediamines can be prepared by preparing the free base from the corresponding salt by adding sodium acetate to the reaction solution during the reaction.

Die Herstellung einiger Verbindungen wird im folgenden im einzelnen beschrieben, die übrigen werden in analoger Weise erhalten.The preparation of some compounds is described in detail below, the others are obtained in an analogous manner.

Herstellung der Verbindung 2Establishing connection 2

53,2 g (0,25 Mol) 4-N,N-Diethylamino-2-toluidinhydrochlorid, 34 g Natriumacetat x 3H20 und 25,3 ml Benzaldehyd werden in 300 ml Toluol unter Rühren am Wasserabscheider unter Rückfluß so lange erhitzt, bis die Wasserabscheidung beendet ist. Nach dem Abkühlen wird das ausgefallene Salz abfiltriert und die Reaktionslösung mehrmals mit Bleicherde und Aktivkohle behandelt. Anschließend wird das Lösungsmittel im Vakuum abdestilliert und der Rückstand im Ether gelöst. Die etherische Lösung wird mit Natriumhydrogencarbonat und Wasser neutral gewaschen, mit Bleicherde und Aluminiumoxid behandelt, getrocknet und der Ether abdestilliert. Ausbeute: 38 g eines dunkelbraunen Ois.

Figure imgb0007
53.2 g (0.25 mol) of 4-N, N-diethylamino-2-toluidine hydrochloride, 34 g of sodium acetate x 3H 2 0 and 25.3 ml of benzaldehyde are refluxed in 300 ml of toluene with stirring on a water separator, until the water separation is finished. After cooling, the precipitated salt is filtered off and the reaction solution is treated several times with bleaching earth and activated carbon. The solvent is then distilled off in vacuo and the residue is dissolved in ether. The ethereal solution is washed neutral with sodium hydrogen carbonate and water, treated with bleaching earth and aluminum oxide, dried and the ether is distilled off. Yield: 38 g of a dark brown oil.
Figure imgb0007

Herstellung der Verbindung 11Establishing connection 11

131,1 g 4-N,N-Diethylaminoanilin-sulfat, 136,1 g Natriumacetat x 3 H20 und 61 g 2-Hydroxybenzaldehyd werden in 500 ml Benzol unter Rühren am Wasserabscheider unter Rückfluß so lange erhitzt, bis die Wasserabscheidung beendet ist. Nach dem Abkühlen wird das Reaktionsprodukt abgesaugt und zweimal aus Aceton umkristallisiert. Ausbeute: 94,3 g, Schmelzpunkt:102-103°C.131.1 g of 4-N, N-diethylaminoaniline sulfate, 136.1 g of sodium acetate x 3 H 2 O and 61 g of 2-hydroxybenzaldehyde are refluxed in 500 ml of benzene with stirring on a water separator until the water separation has ended . After cooling, the reaction product is filtered off and recrystallized twice from acetone. Yield: 94.3 g, melting point: 102-103 ° C.

Die erfindungsgemäß zu verwendenden Verbindungen sind in hervorragender Weise geeignet, in lichtempfindlichen fotografischen Materialien mit wenigstens einer Silberhalogenidemulsionsschicht die Stabilität der Latentbildkeime zu erhöhen. Die Stabilität der Latentbildkeime wird unter Erhaltung aller üblichen fotografischen Eigenschaften, die selbstverständlich weitgehend vom Aufbau der Silberhalogenidemulsion bestimmt werden, auch bei der Lagerung der Materialien über iängert: Zeit bei Normaltemperatur oder bei erhöhter Temperatur im Heizschrank in hervorragender Weise erreicht.The compounds to be used according to the invention are outstandingly suitable for increasing the stability of the latent image nuclei in light-sensitive photographic materials with at least one silver halide emulsion layer. The stability of the latent image nuclei is prolonged while preserving all the usual photographic properties, which of course are largely determined by the structure of the silver halide emulsion, even when the materials are stored: time at normal temperature or at elevated temperature in the heating cabinet is achieved excellently.

Die erfindungsgemäß zu verwendenden Verbindungen werden dem fotografischen Material insbesondere nach der physikalischen Reifung der Emulsion zugegeben. Vorzugsweise werden die Derivate in gelöster Form der lichtempfindlichen Silberhalogenidemulsion während oder nach der chemischen Reifung oder der fertigen Gießlösung zugesetzt. Als Lösungsmittel sind insbesondere niedere aliphatische Alkohole, Tetrahydrofuran, Aceton oder Mischungen davon geeignet. Die Konzentration der Verbindungen in den fotografischen Materialien kann innerhalb weiter Grenzen schwanken. Sie richtet sich nach dem gewünschten Effekt, der Art des Reproduktionsprozesses und dem Aufbau des fotografischen Materials.The compounds to be used according to the invention are added to the photographic material, in particular after the emulsion has been physically ripened. The derivatives are preferably added in dissolved form to the light-sensitive silver halide emulsion during or after chemical ripening or the finished casting solution. Lower aliphatic alcohols, tetrahydrofuran, acetone or mixtures thereof are particularly suitable as solvents. The concentration of the compounds in the photographic materials can vary within wide limits. It depends on the desired effect, the type of reproduction process and the structure of the photographic material.

Mengen von maximal 10-2 Mol, insbesondere maximal 10-3 Mol pro Mol Silberhalogenid haben sich als geeignet erwiesen. Besonders bevorzugt sind Konzentrationen zwischen 10 mg und 1000 mg pro Mol Silberhaloaenid.Amounts of at most 10 to 2 mol, in particular at most 10 to 3 mol, per mol of silver halide have proven to be suitable. Particularly preferred concentrations between 10 mg and 1000 mg per mole of silver are Halo a enid.

Die erfindungsgemäß zu verwendenden Verbindungen können in üblichen lichtempfindlichen Materialien zur Stabilisierung der Latentbildkeime verwendet werden, die für die Herrstellung von Schwarz/Weiß-Bildern geeignet sind, z. B. Schwarz/Weiß-Aufnahme- oder -Kopiermaterialien oder Umkehrmaterialien. Weiterhin können ohne Beeinträchtigung der Stabilisierung Farbkuppler im Material enthalten sein.The compounds to be used according to the invention can be used in conventional light-sensitive materials for stabilizing the latent image nuclei, which are suitable for the production of black and white images, for. B. Black and white recording or copying materials or reversal materials. Furthermore, color couplers can be contained in the material without affecting the stabilization.

Bei diesen Materialien handelt es sich in erster Linie um ausentwickelbare Silberhalogenidmaterialien mit üblichen Silberhalogenidemulsionen, die bei der Entwicklung ein negatives Bild ergeben, einschließlich der Umkehrmaterialien, bei denen auf die erste Entwicklung nach einer Verschleierung eine zweite Entwicklung folgt.These materials are primarily developable silver halide materials with common silver halide emulsions that give a negative image on development, including the reversal materials where the first development after fogging is followed by a second development.

Als Schutzkolloid bzw. Bindemittel für die Silberhalogenidemulsionsschicht sind die üblichen hydrophilen filmbildenden Mittel geeignet, z. B. Proteine, insbesondere Gelatine, Alginsäure oder deren Derivate wie Ester, Amide oder Salze, Cellulose-Derivate wie Carboxymethylcellulose und Cellulosesulfate, Stärke oder deren Derivate oder hydrophile synthetische Bindemittel wie Polyvinylalkohol, teilweise verseiftes Polyvinylacetat, Polyvinylpyrrolidon und andere. Die Schichten können im Gemisch mit den hydrophilen Bindemitteln auch andere synthetische Bindemittel in gelöster oder dispergierter Form enthalten wie Homo- oder Copolymerisate von Acryl- oder Methacrylsäure oder deren Derivaten wie Estern, Amiden oder Nitrilen, ferner Vinylpolymerisate wie Vinylester oder Vinylether.The usual hydrophilic film-forming agents are suitable as protective colloid or binder for the silver halide emulsion layer, e.g. B. proteins, especially gelatin, alginic acid or their derivatives such as esters, amides or salts, cellulose derivatives such as carboxymethyl cellulose and cellulose sulfates, starch or their derivatives or hydrophilic synthetic binders such as polyvinyl alcohol, partially saponified polyvinyl acetate, polyvinyl pyrrolidone and others. In a mixture with the hydrophilic binders, the layers can also contain other synthetic binders in dissolved or dispersed form, such as homopolymers or copolymers of acrylic or methacrylic acid or their derivatives, such as esters, amides or nitriles, and also vinyl polymers, such as vinyl esters or vinyl ethers.

Für die erfindungsgemäßen Materialien können die üblichen Schichtträger verwendet werden, z. B. Träger aus Celluloseestern wie Celluloseacetat oder Celluloseacetobutyrat, ferner Polyester, insbesondere Polyethylenterephthalat oder Polycarbonate, insbesondere auf Basis von Bisphenylolpropan. Geeignet sind ferner Papierträger, die gegebenenfalls wasserundurchlässige Polyolefinschichten, z. B. aus Polyethylen oder Polypropylen, enthalten können, ferner Träger aus Glas oder Metall.The usual substrates can be used for the materials according to the invention, e.g. B. carriers made of cellulose esters such as cellulose acetate or cellulose acetobutyrate, further polyester, in particular polyethylene terephthalate or polycarbonates, in particular based on bisphenylol propane. Also suitable are paper supports, which are optionally impermeable polyolefin layers, e.g. B. of polyethylene or polypropylene, can also contain supports made of glass or metal.

Für die vorliegende Erfindung sind die üblichen Silberhalogenidemulsionen geeignet. Diese können als Silberhalogenid Silberchlorid, Silberbromid oder Gemische davon, eventuell mit einem geringen Gehalt an Silberjodid bis zu 10 Mol -Ofo, enthalten.The usual silver halide emulsions are suitable for the present invention. As silver halide, these can contain silver chloride, silver bromide or mixtures thereof, possibly with a low content of silver iodide up to 10 Mo 1 - ofo.

Die Emulsionen können auch chemisch sensibilisiert werden, z. B. durch Zusatz schwefelhaltiger Verbindungen bei der chemischen Reifung, beispielsweise Allylisothiocyanat, Allylthioharnstoff und Natriumthiosulfat oder durch Zusatz von Selenverbindungen. Als chemische Sensibilisatoren können ferner auch Reduktionsmittel, z. B. die in den belgischen Patentschriften 493464 oder 568 687, beschriebenen Zinnverbindungen, ferner Polyamine wie Diethylentriamin oder Aminomethylsulfinsäurederivate, z. B. gemäß der belgischen Patentschrift 547 323, verwendet werden. Geeignet als chemische Sensibilisatoren sind auch Edelmetalle bzw. Edelmetallverbindungen wie Gold, Platin, Palladium, Iridium, Ruthenium oder Rhodium. Es ist ferner möglich, die Emulsionen mit Polyalkylenoxidderivaten zu sensibilisieren, z. B. mit Polyethylenoxid eines Molekulargewichtes zwischen 1000 und 20000, ferner mit Kondensationsprodukten von Alkylenoxiden und Alkoholen, aliphatischen Carbonsäuren, aliphatischen Aminen, aliphatischen Diaminen und Amiden.The emulsions can also be chemically sensitized, e.g. B. by adding sulfur-containing compounds during chemical ripening, for example allyl isothiocyanate, allyl thiourea and sodium thiosulfate or by adding selenium compounds. Reducing agents, e.g. B. the tin compounds described in Belgian patents 493464 or 568 687, also polyamines such as diethylenetriamine or aminomethylsulfinic acid derivatives, e.g. B. according to Belgian patent 547 323 used. Precious metals or noble metal compounds such as gold, platinum, palladium, iridium, ruthenium or rhodium are also suitable as chemical sensitizers. It is also possible to sensitize the emulsions with polyalkylene oxide derivatives, e.g. B. with polyethylene oxide having a molecular weight between 1000 and 20,000, also with condensation products of alkylene oxides and alcohols, aliphatic carboxylic acids, aliphatic amines, aliphatic diamines and amides.

Die Emulsionen können auch optisch sensibilisiert sein, z. B. mit den üblichen Polymethinfarbstoffen, wie Neutrocyaninen, 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. B. 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 of F. M. Hamer, "The Cyanine Dyes and related Compounds" (1964).

Die Materialien können in Kombination mit den erfindungsgemäß zu verwendenden weitere Stabilisatoren enthalten, 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, 2-58 (1952), beschrieben. Weitere geeignete Stabilisatoren sind u. a. heterocyclische Mercaptoverbindungen, z. B. Phenylmercaptotetrazol, quaternäre Benzthiazolderivate, Benzotriazol und ähnliche.The materials can contain in combination with the further stabilizers to be used according to the invention, e.g. B. azaindenes, preferably tetra- or pentaazaindenes, especially those which are substituted with hydroxyl or amino groups. Such connections are described in the article by Birr, Z. wiss. Phot. 47, 2-58 (1952). Other suitable stabilizers are u. a. heterocyclic mercapto compounds, e.g. B. phenyl mercaptotetrazole, quaternary benzothiazole derivatives, benzotriazole and the like.

Die Schichten des fotografischen Materials können in der üblichen Weise gehärtet sein, beispielsweise mit Formaldehyd oder halogensubstituierten Aldehyden, die eine Carboxylgruppe enthalten, wie Mucobromsäure, Diketonen, Methansulfonsäureester, Dialdehyden und dergleichen. Weiterhin können die fotografischen Schichten mit Härtern des Epoxidtyps, des heterocyclischen Ethylenimins oder des Acryloyltyps gehärtet werden. Weiterhin ist es auch möglich, die Schichten gemäß dem Verfahren der deutschen Offenlegungsschrift 2218009 zu härten, um fotografische Materialien zu erzielen, die für eine Hochtemperaturverarbeitung geeignet sind. Es ist ferner möglich, die fotografischen Schichten bzw. die farbfotografischen Mehrschichtenmaterialien mit Härtern der Diazin-, Triazin- oder 1,2-Dihydrochinolin-Reihe zu härten. Beispiele derartiger Härter sind Alkyl- oder Arylsulfonylgruppen-haltige Diazinderivate, Derivate von hydrierten Diazinen oder Triazinen, wie z. B. 1,3,5-Hexahydrotriazin, Fluor-substituierte 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 2 263 602, 2 225 230 und 1 808 685, der französischen Patentschrift 1 491 807, der deutschen Patentschrift 872 153 und der DD-A-7218, beschrieben. Weitere brauchbare Härter sind beispielsweise in der britischen Patentschrift 1 268 550 beschrieben.The layers of the photographic material 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. Furthermore, the photographic layers can be hardened with hardeners of the epoxy type, the heterocyclic ethylene imine or the acryloyl type. Furthermore, it is also possible to harden the layers in accordance with the process of German laid-open specification 2218009 in order to obtain photographic materials which are suitable for high-temperature processing. 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. Examples of such hardeners are alkyl or arylsulfonyl group-containing diazine derivatives, derivatives of hydrogenated diazines or triazines, such as. B. 1,3,5-hexahydrotriazine, fluorine-substituted diazine derivatives, such as. B. fluoropyrimidine, esters of 2-substituted 1,2-dihydroquinoline or 1,2-dihydroisoquinoline-N-carboxylic acids. Also useful are vinyl sulfonic acid hardeners, carbodiimide or carbamoyl hardeners, such as. B. in German laid-open publications 2 263 602, 2 225 230 and 1 808 685, French patent 1 491 807, German patent 872 153 and DD-A-7218. Other useful hardeners are described, for example, in British Patent 1,268,550.

Die vorliegende Erfindung kann sowohl für die Herstellung schwarz-weißer als auch farbiger fotografischer Bilder angewendet werden. Farbige fotografische Bilder können z. B. nach dem bekannten Prinzip der chromogenen Entwicklung in Anwesenheit von Farbkupplern, die mit dem Oxidationsprodukt von farbgebenden p-Phenylendiamin-Entwicklern unter Bildung von Farbstoffen reagieren, hergestellt werden.The present invention can be applied to both black and white and color photographic images. Colored photographic images can e.g. B. according to the known principle of chromogenic development in the presence of color couplers, which react with the oxidation product of coloring p-phenylenediamine developers to form dyes.

Die Farbkuppler können beispielsweise dem Farbentwickler nach dem Prinzip des sogenannten Einentwicklungsverfahrens zugesetzt werden. In einer bevorzugten Ausführungsform enthält das fotografische Material selbst die üblichen Farbkuppler, die in der Regel den Silberhalogenidschichten einverleibt sind. So kann die rotempfindliche Schicht beispielsweise einen nicht-diffundierenden Farbkuppler zur Erzeugung des blaugrünen Teilfarbenbildes enthalten, in der Regel einen Kuppler vom Phenol- oder α-Naphtholtyp. Die grünempfindliche Schicht kann beispielsweise mindestens einen nicht-diffundierenden Farbkuppler zur Erzeugung des purpurnen Teilfarbenbildes enthalten, wobei üblicherweise Farbkuppler vom Typ des 5-Pyrazolons oder des Imidazolons Verwendung finden. Die blauempfindliche Schicht kann beispielsweise einen nicht-diffundierenden Farbkuppler zur Erzeugung des gelben Teilfarbenbildes, in der Regel einen Farbkuppler mit einer offenkettigen Ketomethylengruppierung enthalten.The color couplers can be added to the color developer, for example, according to the principle of the so-called development process. In a preferred embodiment, the photographic material itself contains the usual color couplers, which are usually incorporated into the silver halide layers. For example, the red-sensitive layer can contain a non-diffusing color coupler for producing the blue-green partial color image, generally a coupler of the phenol or α-naphthol type. The green-sensitive layer can contain, for example, at least one non-diffusing color coupler for producing the purple partial color image, color couplers of the 5-pyrazolone or imidazolone type usually being used. The blue-sensitive layer can contain, for example, a non-diffusing color coupler for generating the yellow partial color image, usually a color coupler with an open-chain ketomethylene grouping.

Farbkuppler dieser Art 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, hingewiesen.Color couplers of this type are known in large numbers and are described in a large number of patents. Examples include the publication "Color coupler" by W. Pelz in "Messages from the research laboratories of Agfa, Leverkusen / Munich", Volume 111 (1961), and K. Venkataraman in "The Chemistry of Synthetic Dyes", Vol. 4, 341 to 387, Academic Press, 1971.

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 Ethanol, Aceton oder Dimethylformamid, zugesetzt werden. Soweit es sich bei den nicht-diffundierenden Farbkupplern und farbgebenden Verbindungen um wasser- bzw. alkaliunlösliche 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 Gelatineemulgat der jeweiligen Verbindung wird anschließend mit der Silberhalogenidemulsion 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, optionally with the addition of water-miscible organic solvents such as ethanol, acetone or dimethylformamide. Insofar as the non-diffusing color couplers and coloring compounds are water- or alkali-insoluble compounds, they can be emulsified in a known manner, e.g. by 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 mixed, after which 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 compounds in the form of oily droplets which release non-diffusing color couplers and development inhibitors to be emulsified 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.

Die fotografischen Materialien können mit üblichen Schwarz-Weiß-Entwicklern, z. B. Hydrochinon, Brenzkatechin, p-Methylaminophenol und 1-Phenyl-3-pyrazolidon und mit Farbentwicklersubstanzen, insbesondere vom Typ des p-Phenylendiamins, entwickelt werden, z. B. mit

  • N,N-Dimethyl-p-phenylendiamin,
  • 4-Amino-3-methyl-N-ethyl-N-methoxyethylanilin,
  • 2-Amino-5-diethylaminotoluol,
  • N-Butyl-N-ω-sulfobutyl-p-phenylendiamin,
  • 2-Amino-5-(N-ethyl-N-ß-methansulfonamidethyl-amino)-toluol,
  • N-Ethyl-N-ß-hydroxyethyl-p-phenylendiamin,
  • N,N-Bis-(ß-hydroxyethyl)-p-phenylendiamin,
  • 2-Amino-5-(N-ethyl-N-ß-hydroxyethylamino)-toluol.

Weitere brauchbare Farbentwickler sind beispielsweise beschrieben in J. Amer. Chem. Soc. 73, 3100 (1951).The photographic materials can be processed with conventional black and white developers, e.g. As hydroquinone, pyrocatechol, p-methylaminophenol and 1-phenyl-3-pyrazolidone and with color developer substances, in particular of the p-phenylenediamine type, are developed, e.g. B. with
  • N, N-dimethyl-p-phenylenediamine,
  • 4-amino-3-methyl-N-ethyl-N-methoxyethylaniline,
  • 2-amino-5-diethylaminotoluene,
  • N-butyl-N-ω-sulfobutyl-p-phenylenediamine,
  • 2-amino-5- (N-ethyl-N-ß-methanesulfonamidethyl-amino) -toluene,
  • N-ethyl-N-β-hydroxyethyl-p-phenylenediamine,
  • N, N-bis (ß-hydroxyethyl) -p-phenylenediamine,
  • 2-amino-5- (N-ethyl-N-β-hydroxyethylamino) toluene.

Other useful color developers are described, for example, in J. Amer. Chem. Soc. 73, 3100 (1951).

Besonders vorteilhaft an den erfindungsgemäß zu verwendenden Verbindungen ist, daß die Stabilisierung der Latentbildkeime nicht gebunden ist an die gleichzeitige Verwendung von bestimmten Härtungsmitteln für die Gelatine.It is particularly advantageous about the compounds to be used according to the invention that the stabilization of the latent image nuclei is not linked to the simultaneous use of certain hardening agents for the gelatin.

Beispiel 1example 1

Eine hochempfindliche Silberbromidjodidemulsion mit 6 Mol-% Silberjodid wird in der üblichen Weise hergestellt, geflockt und von den löslichen Salzen befreit. Anschließend wird redispergiert, mit Gelatine versetzt und mit Schwefel- und Goldverbindungen in bekannter Weise gereift. Die Emulsion hatte ein Silbernitrat/Gelatine-Verhältnis von 1 : 1 und enthielt pro kg 95 g Silber, berechnet als Silbernitrat.A highly sensitive silver bromide iodide emulsion with 6 mol% silver iodide is prepared in the usual way, flocculated and freed from the soluble salts. It is then redispersed, mixed with gelatin and ripened with sulfur and gold compounds in a known manner. The emulsion had a silver nitrate / gelatin ratio of 1: 1 and contained 95 g of silver per kg, calculated as silver nitrate.

Die Emulsion wird vor dem Vergießen in 11 gleiche Teile geteilt. Vor dem Beguß wird diesen Teilen jeweils pro kg zugesetzt:

  • 200 mg 4-Hydroxy-6-methyl-1,3,3a,7-tetraazainden in Form einer 1%igen wäßrig-alkalischen Lösung;
    Figure imgb0008
    sowie ein erfindungsgemäß zu verwendender Stabilisator in Form einer 1%igen alkoholischen Lösung in den aus Tabelle (2) ersichtlichen Mengen.
The emulsion is divided into 11 equal parts before pouring. Before the sprue, these parts are added per kg:
  • 200 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene in the form of a 1% aqueous alkaline solution;
    Figure imgb0008
    and a stabilizer to be used according to the invention in the form of a 1% alcoholic solution in the amounts shown in table (2).

Die Emulsionen wurden dann derart auf einen Celluloseacetatträger vergossen, daß der Silberauftrag, berechnet als Silbernitrat, 5,5 g pro m2 betrug. Die Proben wurden in üblicher Weise getrocknet, in einem Sensitometer hinter einem Graustufenkeil belichtet und nach den aus Tabelle 2 ersichtlichen Behandlungen bei 20°C 7 bzw. 16 Minuten lang in einem Entwickler I der folgenden Zusammensetzung entwickelt:

Figure imgb0009
mit Wasser auf 1 I auffüllen.The emulsions were then poured onto a cellulose acetate support in such a way that the silver coating, calculated as silver nitrate, was 5.5 g per m 2 . The samples were dried in the customary manner, exposed in a sensitometer behind a gray-scale wedge and, after the treatments shown in Table 2, were developed at 20 ° C. for 7 or 16 minutes in a developer I of the following composition:
Figure imgb0009
 Make up to 1 liter with water.

Die Ergebnisse der sensitometrischen Auswertung sind aus der folgenden Tabelle 2 ersichtlich.

Figure imgb0010
The results of the sensitometric evaluation are shown in Table 2 below.
Figure imgb0010

Die Auswertung der Empfindlichkeit in Tabelle 2 erfolgt relativ zu dem als Typ gezogenen Versuch. Somit werden Empfindlichkeitsdifferenzen angegeben. Eine Steigerung dieses Wertes um drei Einheiten bedeutet eine Verdoppelung der Empfindlichkeit. Die Empfindlichkeit selbst wird bestimmt bei einer Dichte von 0,2 über Schleier.The evaluation of the sensitivity in Table 2 is carried out relative to the test drawn as a type. Differences in sensitivity are thus indicated. An increase of this value by three units means a doubling of the sensitivity. The sensitivity itself is determined at a density of 0.2 over fog.

Beispiel 2Example 2

Farbfotografische Materialien für Umkehrverarbeitung werden hergestellt, indem auf einen mit einer Haftschicht versehenen Schichtträger aus Cellulosetriacetat nacheinander die im folgenden aufgeführten Schichten aufgetragen werden.Color photographic materials for reverse processing are produced by successively applying the layers listed below to a cellulose triacetate support provided with an adhesive layer.

I. KontrollprobeI. Control sample

  • 1. Eine rotsensibilisierte Silberhalogenidemulsion, enthaltend pro kg 70 g Gelatine, 60 g Silber (davon 96% in Form des Bromids und 4% in Form des Jodids) und 55 g des Blaugrün-Kupplers der folgenden Formel
    Figure imgb0011
    Der Silberauftrag beträgt 1,0 g pro m2, berechnet als Silbernitrat.    1. A red-sensitized silver halide emulsion containing 70 g of gelatin, 60 g of silver (thereof 96% in the form of the bromide and 4% in the form of the iodide) and 55 g of the cyan coupler of the following formula per kg
    Figure imgb0011
     The silver coating is 1.0 g per m 2 , calculated as silver nitrate.
  • 2. Eine 2%ige wäßrige Gelatinelösung, enthaltend pro kg 4 g des in der DE-A-2 304 319 beschriebenen polymeren Weißkupplers folgender Formel
    Figure imgb0012
         2. A 2% aqueous gelatin solution containing 4 g of the polymeric white coupler of the following formula described in DE-A-2 304 319 per kg
    Figure imgb0012
  • 3. Eine grünsensibilisierte Silberhalogenidemulsion, enthaltend pro kg 70 g Gelatine, 60 g Silber (davon 96% in Form des Bromids und 4% in Form des Jodids) und 60 g des Purpurkupplers der folgenden Formel
    Figure imgb0013
    Der Silberauftrag beträgt 0,9 g pro m2, berechnet als Silbernitrat.    3. A green-sensitized silver halide emulsion containing 70 g of gelatin, 60 g of silver (thereof 96% in the form of the bromide and 4% in the form of the iodide) and 60 g of the purple coupler of the following formula per kg
    Figure imgb0013
     The silver coating is 0.9 g per m 2 , calculated as silver nitrate.
  • 4. Eine Silberdispersion, enthaltend 1,8 g Silber, berechnet als Silbernitrat, und 12 g Gelatine pro Liter. Die farbdichte der Gelbfilterschicht, gemessen hinter einem Blaufilter, beträgt 0,6; der Silberauftrag beträgt 0,2 g/m2, berechnet als Silbernitrat.4. A silver dispersion containing 1.8 g of silver, calculated as silver nitrate, and 12 g of gelatin per liter. The color density of the yellow filter layer, measured behind a blue filter, is 0.6; the silver coating is 0.2 g / m 2 , calculated as silver nitrate.
  • 5. Eine unsensibilisierte Silberhalogenidemulsion, enthaltend pro kg 70 g Gelatine, 60 g Silber (davon 95% in Form des Bromids und 5% in Form des Jodids) und 140 g des folgenden Gelbkupplers
    Figure imgb0014
    Der Silberauftrag beträgt 1,5 g pro m2, berechnet als Silbernitrat.    5. An unsensitized silver halide emulsion containing 70 g of gelatin, 60 g of silver (thereof 95% in the form of the bromide and 5% in the form of the iodide) and 140 g of the following yellow coupler per kg
    Figure imgb0014
     The amount of silver applied is 1.5 g per m 2 , calculated as silver nitrate.
  • 6. Eine 1%ige Gelatinelösung mit einem Naßauftrag von 60 g pro m2. 6. A 1% gelatin solution with a wet application of 60 g per m 2.
  • 7. Eine 1%ige wäßrige Lösung des Härters der folgenden Formel mit einem Naßauftrag von 60 g pro m2:
    Figure imgb0015
         7. A 1% aqueous solution of the hardener of the following formula with a wet application of 60 g per m 2 :
    Figure imgb0015
Il. Erfindungsgemäße Probe mit Verbindung 1Il. Sample according to the invention with compound 1

Die Herstellung der Probe erfolgt wie bei Probe I beschrieben, nur werden der Gelbschicht (Schicht 5) 100 mg/kg von der Verbindung 1, gelöst in Methanol, zugegeben.The sample is prepared as described for sample I, except that 100 mg / kg of compound 1, dissolved in methanol, are added to the yellow layer (layer 5).

Jede der Proben I und II wird hinter einem grauen Verlaufskeil belichtet, 8 Wochen bei Zimmertemperatur gelagert und anschließend folgender Umkehrverarbeitung bei 30°C unterworfen:

Figure imgb0016
Each of samples I and II is exposed behind a gray gradient wedge, stored for 8 weeks at room temperature and then subjected to the following reverse processing at 30 ° C:
Figure imgb0016

Es werden dabei Bäder folgender Zusammensetzung verwendet:Baths of the following composition are used:

Entwickler IIDeveloper II

Figure imgb0017
mit Wasser auf 1000 ml auffüllen und auf pH 10,0 einstellen.
Figure imgb0017
 Make up to 1000 ml with water and adjust to pH 10.0.

StoppbadStop bath

Figure imgb0018
mit Wasser auf 1000 ml auffüllen und auf pH 4,1 einstellen.
Figure imgb0018
 Make up to 1000 ml with water and adjust to pH 4.1.

Entwickler IIIDeveloper III

Figure imgb0019
mit Wasser auf 1000 ml auffüllen und auf pH 12,0 einstellen.
Figure imgb0019
 Make up to 1000 ml with water and adjust to pH 12.0.

BleichbadBleach bath

Figure imgb0020
mit Wasser auf 1000 ml auffüllen, mit Essigsäure auf pH 5 einstellen.
Figure imgb0020
 make up to 1000 ml with water, adjust to pH 5 with acetic acid.

FixierbadFixer

Figure imgb0021
mit Wasser auf 1000 ml auffüllen und auf pH 5,0 einstellen.
Figure imgb0021
 Make up to 1000 ml with water and adjust to pH 5.0.

Die sensitometrische Auswertung in der Tabelle 3 zeigt, daß das fotografische Material, welches die Verbindung 1 enthält (Probe 11), wesentlich geringere Empfindlichkeitsrückgänge des latenten Bildes im Gelbguß aufweist als die Vergleichsprobe. Mit den Verbindungen 9, 10 und 11 werden analoge Ergebnisse erhalten.

Figure imgb0022
The sensitometric evaluation in Table 3 shows that the photographic material which contains the compound 1 (sample 11) has significantly lower sensitivity decreases in the latent image in the brass than the comparative sample. Analogous results are obtained with compounds 9, 10 and 11.
Figure imgb0022

Eine Steigerung der angegebenen Werte um 3 Einheiten entspricht einer Verdoppelung der Empfindlichkeit.An increase of the specified values by 3 units corresponds to a doubling of the sensitivity.

Claims (8)

1. Light-sensitive photographic material containing at least one light-sensitive silver halide emulsion layer and optionally other layers, characterised in that it contains in at least one layer a compound of the formula (I)
Figure imgb0027
wherein
RI denotes H, OH or halogen;
R2 and R3, which may be the same or different, denote H, an optionally substituted alkyl group having 1 -4 C atoms or acyl; and
R4 denotes H or alkyl having 1 to 4 C atoms,
in a quantity of at the most 10-2 mol per mol of silver halide.
2. Material according to Claim 1, characterised in that
R1 denotes H or OH;
R2 denotes an optionally substituted alkyl group having 1 to 3 C atoms or acetyl;
R3 denotes an optionally substituted alkyl group having 1 to 3 C atoms or H; and
R4 denotes H or methyl.
3. Material according to Claim 1, characterised in that
R1 denotes H or OH;
R2 and R3, which may be the same or different, denote ethyl or hydroxyethyl, and
R4 denotes H.
4. Material according to Claim 1, characterised in that it contains the compound of the formula (I) in a quantity of 10 mg to 1000 mg per mol of silver halide.
5. Material according to Claim 1, characterised in that it contains at least one of the following compounds:
Figure imgb0028
Figure imgb0029
Figure imgb0030
6. Process for the preparation of light-sensitive photographic materials containing silver halide by precipitation of the silver halide, ripening and application to a layer support, characterised in that a compound of the formula (1) according to Claim 1 is added to the silver halide emulsion before its application.
7. Process according to Claim 6, characterised in that the addition is carried out before chemical ripening.
8. Process for the production of photographic images by image-wise exposure and development of the material according to Claim 1.
EP81107953A 1980-10-16 1981-10-06 Photographic material, process for its production and method for the production of photographic pictures Expired EP0050260B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3039168 1980-10-16
DE19803039168 DE3039168A1 (en) 1980-10-16 1980-10-16 PHOTOGRAPHIC MATERIAL, PRODUCTION METHOD AND METHOD FOR PRODUCING PHOTOGRAPHIC IMAGES

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EP0050260A1 EP0050260A1 (en) 1982-04-28
EP0050260B1 true EP0050260B1 (en) 1983-10-19

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EP (1) EP0050260B1 (en)
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DE (2) DE3039168A1 (en)

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US2507114A (en) * 1946-08-21 1950-05-09 Du Pont Aryl azo methine sulfonic acids
DE1199612B (en) * 1964-03-05 1965-08-26 Agfa Ag Process for stabilizing photographic silver halide emulsions
USB342599I5 (en) * 1965-06-07
US3982044A (en) * 1970-12-10 1976-09-21 Fuji Photo Film Co., Ltd. Silver halide photographic emulsions used for electron beam recording
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EP0050260A1 (en) 1982-04-28
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US4358531A (en) 1982-11-09
JPS57100425A (en) 1982-06-22

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