EP0117227B1 - Photographic material for the silver dye bleach process - Google Patents

Photographic material for the silver dye bleach process Download PDF

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Publication number
EP0117227B1
EP0117227B1 EP84810036A EP84810036A EP0117227B1 EP 0117227 B1 EP0117227 B1 EP 0117227B1 EP 84810036 A EP84810036 A EP 84810036A EP 84810036 A EP84810036 A EP 84810036A EP 0117227 B1 EP0117227 B1 EP 0117227B1
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carbon atoms
formula
alkyl
radical
unsubstituted
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German (de)
French (fr)
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EP0117227A2 (en
EP0117227A3 (en
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Mario Dr. Fryberg
Heinrich Dr. Schaller
Rolf Dr. Steiger
Heinz Dr. Peter
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Cessione ilford AG
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Ciba Geigy 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
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/28—Silver dye bleach processes; Materials therefor; Preparing or processing such materials

Definitions

  • the present invention relates to photographic material for the silver color bleaching process, which contains at least one bleach inhibitor in at least one layer.
  • a negative silver image is first developed in the exposed material with a black and white developer.
  • the material is then bleached, whereby the silver of the silver image is oxidized (bleached) to a silver salt and at the same time the dye is reduced (bleached) according to the original silver image areas.
  • the silver salt still present is then removed by fixing and the material is washed.
  • One or more color bleaching catalysts are usually used for bleaching, e.g. As quinoxalines, pyrazines or phenazines, the z. B. are described in DE-B-1547720 and DE-B-1547759.
  • Recording materials particularly suitable for the silver color bleaching process contain red, green and blue sensitive silver halide emulsion layers on a support which contain bleachable cyan (cyan) dyes, magenta (magenta) dyes and yellow (yellow) dyes.
  • these dyes can also be accommodated in separate layers which are adjacent to the silver halide emulsion layers.
  • the bleach catalysts in the silver image areas are reduced.
  • the bleaching catalysts accelerate dye bleaching in the exposed areas.
  • the dye be bleached only in the silver image areas.
  • reduced bleaching catalysts also diffuse into adjacent layers and can cause bleaching of dyes there. This leads to an undesirable reduction in the dye density in this layer and ultimately to a color falsification in the color image.
  • nitro compounds are used as oxidizing agents in accordance with US Pat. No. 3,782,948.
  • the results achieved with these compounds are unsatisfactory.
  • the nitro compounds cannot be incorporated into the photographic layers in the desired distribution in all cases.
  • Binuclear heterocycles are used according to DE-A-2,949,167. However, these have the disadvantage that they adversely affect the kinetics of silver development.
  • the object of the present invention is now to prevent the undesired bleaching of image dyes by means of diffusing, reduced bleaching catalysts and, at the same time, to overcome the disadvantages of the previously proposed solutions as far as possible.
  • the object is achieved according to the invention by incorporating the 1,4-benzoquinones according to EP-A-0 093 696 in silver color bleaching materials. These compounds are generally resistant to diffusion and are distinguished by a good bleach-inhibiting effect.
  • Q is a group of the formula ⁇ CO 2 R 4 or -CONR 4 R 5 .
  • R 4 is hydrogen or alkyl, preferably having 1 to 20, in particular 1 to 10, carbon atoms. Suitable alkyl radicals are e.g. B. methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl, hexadecyl, octadecyl and eicosyl.
  • the alkyl radicals R 4 can also be in the form of their branched isomers.
  • the alkyl radicals may also contain 1 to 5 oxygen atoms in the carbon chain, such as. B.
  • R 4 are optionally substituted.
  • R 6 means cycloalkyl, preferably having 3 to 12 carbon atoms, e.g. B. cyclopentyl, methylcyclopentyl, cycohexyl, methylcyclohexyl and cyclooctyl.
  • R s is also alkenyl, preferably having 3 to 20 carbon atoms.
  • Suitable alkenyl radicals can be derived from the alkyl radicals mentioned for R 4 .
  • R 6 is aryl preferably having 6 to 10 carbon atoms such as. B. phenyl or naphthyl. These aryl residues can preferably be 1 or 2 further alkyl groups may be substituted, especially alkyl groups having 1 to 4 carbon atoms such as. B. methyl, ethyl, propyl or butyl come into question.
  • R 6 is also aralkyl. Suitable aralkyl radicals contain 7 to 13 carbon atoms such as. B. benzyl, naphthylmethyl, phenylethyl or benzhydryl.
  • R 4 also means alkenyl, suitable alkenyl groups containing 3 to 20 carbon atoms. These can be derived from the alkyl radicals mentioned. In the meaning of cycloalkyl, R 4 contains 3 to 12 carbon atoms, with cyclopropyl, cyclopentyl, cyclohexyl and cyclooctyl being particularly preferred. Suitable aryl groups R 4 are preferably those having 6 to 10 carbon atoms, for example phenyl and naphthyl, these groups having alkyl radicals such as, for. B. methyl, ethyl, propyl, butyl and their isomers may be substituted.
  • R 4 is also an aralkyl group, preferably containing 7 to 13 carbon atoms. Suitable aralkyl groups are those as listed for R 6 .
  • Another meaning of R 4 is a 5- or 6-membered heterocyclic ring which contains an oxygen or nitrogen atom, for example tetrahydrofuranyl or tetrahydropyranyl and piperidinyl or pyrrolidinyl, the rings preferably having 1 to 4 alkyl groups with (each) 1 to 4 Carbon atoms can be substituted.
  • R 4 is also a methyl group which is substituted by one of the heterocyclic rings mentioned.
  • R 4 can mean furfuryl or tetrahydrofurfuryl. These radicals can also be further substituted with preferably 1 or 2 alkyl groups with (each) 1 to 4 carbon atoms.
  • R 5 in the formula ⁇ CONR 4 R 5 is hydrogen or alkyl with preferably 1 to 20 carbon atoms. Suitable alkyl radicals are those as listed for R 4 .
  • R 4 and R 5 together with the nitrogen atom to which they are attached form a 5- or 6-membered heterocyclic ring.
  • Pyrrolidinyl, piperidinyl or morpholinyl can be used, for example.
  • the rings can be substituted with preferably 1 or 2 alkyl groups, the alkyl groups generally containing 1 to 4 carbon atoms.
  • Q is a group of the formula -OX, where X has the meaning of R 5 - as defined above, but in particular alkyl with 3 or 4 carbon atoms or hydrogen, - or -COR 7 .
  • R 7 is alkyl with preferably 1 to 20 carbon atoms. Suitable alkyl radicals are those as listed for R 4 , in particular those with 1 to 4 carbon atoms, methyl being particularly preferred.
  • R 7 is alkenyl, preferably having 3 to 20 carbon atoms. These alkenyl residues can be derived from the alkyl residues mentioned.
  • R 7 is above all cyclopentyl, cyclohexyl or cyclooctyl.
  • Suitable aralkyl groups R 7 which preferably contain 7 to 13 carbon atoms, are those as listed for R 6 .
  • R 7 is also aryl preferably having 6 to 10 carbon atoms, for example phenyl and naphthyl.
  • the aryl groups are optionally substituted with 1 or 2 alkyl groups, preferably with (each) 1 to 4 carbon atoms.
  • Q is also a group of the formula ⁇ NR 8 R 9 , wherein R s in addition to hydrogen alkyl having preferably 1 to 4 carbon atoms such as. B. methyl, ethyl, propyl or butyl or isomers thereof, and Rg is hydrogen or alkyl having preferably 1 to 4 carbon atoms or a radical of the formula ⁇ COR 7 , wherein R 7 has the meaning given.
  • R 8 and Rg together with the nitrogen atom to which they are attached can form a 5- or 6-membered ring which is optionally substituted with 1 or 2 alkyl groups, which preferably (each) contain 1 to 4 carbon atoms.
  • Preferred rings are e.g. B. pyrrolidinyl, piperidinyl or morpholinyl.
  • Q also represents a radical of the formula ⁇ P (O) (OR 10 ) ([O] x R 11 ), where x is 0 or 1.
  • R 10 and R 11 independently of one another denote hydrogen or alkyl having 1 to 20 carbon atoms, the alkyl radicals mentioned for R 4 being particularly suitable.
  • R 10 and R 11 can also form an alkylene chain which preferably contains 2 or 3 carbon atoms, which in turn can be substituted by one of the alkyl radicals mentioned having 1 to 20 carbon atoms.
  • R 10 represents hydrogen or alkyl of 1 to 20 carbon atoms.
  • Suitable alkyl radicals R io are those as mentioned for R 4 .
  • R 11 is alkyl having 1 to 5 carbon atoms, the alkyl radicals preferably being unbranched.
  • Q is a group of the formula ⁇ SO 2 R 12 , wherein R 12 is hydroxyl, halogen such as. B. chlorine, or ⁇ NR 5 R 7 , wherein R 5 and R 7 have the meanings given.
  • R 12 is hydroxyl
  • R 1 is a radical of formula (2).
  • Q also means cyano.
  • R 2 and R 3 in formula (2) are independently alkyl, preferably having 1 to 5 carbon atoms, for example methyl, ethyl, propyl, butyl, pentyl or their isomers, methyl being particularly preferred.
  • Q is ⁇ CO 2 R 4 , either R 2 or R 3 is optionally substituted with -C02R4, the two substituents R 4 having the meanings mentioned independently of one another.
  • R 2 and R 3 can also be bound to the C n H 2n + 1 ⁇ k structure in such a way that a cycloalkyl radical is preferably formed with 5 to 12 carbon atoms, which is substituted by 1 or 2 C0 2 R 4 groups .
  • the two substituents R 4 have, independently of one another, the meanings assigned to them.
  • n is preferably a number from 1 to 20, in particular 3 to 7, and p and k are 1 or 2, but preferably 1.
  • q is 0 or preferably 1.
  • R in formula (1) is alkyl.
  • Suitable alkyl radicals contain 1 to 8 carbon atoms and are e.g. B. Methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl or their isomers.
  • R is also a radical of the formula (2), in which case R and R can be identical or different from one another.
  • Particularly suitable radicals R are alkyl radicals having 1 to 4 carbon atoms, branched isomers, such as. B. t-butyl are preferred.
  • the compounds of formula (1) can also be in the form of salts.
  • Preferred compounds of formula (1) for use in silver color photographic bleaching processes are those in which R occupies the 2- and R, 5-positions.
  • R in the compounds of formula (1) represents a radical of the formula wherein A is alkyl of 1 to 10 carbon atoms.
  • Q in the substituent P of the compound of the formula (1) is preferably ⁇ CO 2 R 4 , ⁇ OCOR 7 or cyano, where R 4 and R 7 have the meanings given.
  • Preferred alkoxy groups Q are those with 1 to 4 carbon atoms.
  • the quinones of formula (1) incorporated in silver color photographic bleaching material are good bleach inhibitors which are capable of reducing, i.e. H. active bleaching catalysts to oxidize.
  • the quinones are incorporated into the photographic material in a known manner in the form of dispersions or emulsions. In most cases they can be dispersed without high-boiling solvents such as di-n-butyl phthalate or tri-o-cresyl phosphate.
  • high-boiling solvents such as di-n-butyl phthalate or tri-o-cresyl phosphate.
  • the amount of quinone depends on the type of photographic layer in which the compounds are to be incorporated. It can vary within wide limits. In general, 0.01 to 5 g per m 2 of quinone are introduced into the corresponding layer.
  • the effectiveness of the quinones according to the invention also depends on the particle size of the dispersion.
  • the quinones can, depending on the desired effect, all layers or only individual layers, e.g. B. silver halide emulsion, dye, silver halide emulsion dye, intermediate or auxiliary layers can be added.
  • the quinones are preferably incorporated into the silver halide and dye-free intermediate gelatin layers in order to prevent diffusion of reduced bleach catalyst from one color layer to another.
  • 0.2 to 0.5 g quinone per m 2 layer area are generally sufficient to completely prevent bleach coupling between two color layers.
  • the quinones used according to the invention also allow the layer thickness of these intermediate gelatin layers to be reduced to a minimum.
  • FIGS. 1 to 3 The color densities determined from color wedges of multicolor materials (see Example 3) are shown in FIGS. 1 to 3.
  • Figures 1 and 2 illustrate results obtained with photographic materials without bleach inhibitors.
  • FIG. 3 relates to the results obtained with a material according to the invention (with bleach inhibitor).
  • Figure 1 shows that the bleaching of the magenta dye can be almost prevented by a sufficiently thick gelatin intermediate layer.
  • the magenta density hardly decreases.
  • FIG. 2 shows that excessively thin gelatin intermediate layers can no longer suppress the diffusion of reduced bleaching catalyst into the layer containing magenta dye.
  • the magenta color density therefore decreases sharply.
  • FIG. 3 shows how the same thin gelatin intermediate layer is sufficient to prevent the magenta dye from fading if it contains the quinones used according to the invention as bleach inhibitors. The magenta density is completely preserved.
  • the quinones of formula (1) play an essential role in the production of negative working silver color bleaching material.
  • a material is e.g. Described, for example, in US-A-2,673,800.
  • the quinones are present in the emulsion layers and barrier layers, and additional gelatin layers which also contain a quinone can optionally be provided, in particular between the silver halide emulsion layers and the dye layers which contain development nuclei for the silver complex diffusion process.
  • the quinones of the formula (1) can also be used with advantage in filter and antihalation layers which contain colloidal particles of silver and in barrier layers which contain colloidal hydrosols or sulfides of noble or heavy metals.
  • the latent silver image created during exposure is developed.
  • the image dye assigned to the silver is bleached out in accordance with the image-based distribution of the silver.
  • the third step is necessary to reoxidize the excess image silver that is still present after the color bleaching.
  • the silver, which is now entirely in the form of halides is removed by leaching out with a complexing agent, in particular a salt of thiosulfuric acid, in order to render the finished image insensitive to further exposure and to clear the pure color image of cloudiness.
  • the second process step, color bleaching is carried out in the customary known processes in a strongly acidic medium, a catalyst being added to accelerate the color bleaching.
  • the bleaching baths also contain a silver complexing agent or ligand. Both components, catalyst and ligand, are necessary in order to transfer the reducing effect of the metallic, non-diffusible image silver to the likewise non-diffusible dye.
  • the reduced form of the catalyst resulting from reduction on the image silver serves as an intermediate support which, after covering a certain diffusion distance, irreversibly reduces the dye and thus bleaches, and is reoxidized itself to the original form.
  • the strong dyebaths and silver bleach baths may contain alkyl or arylsulfonic acids and in particular p-toluenesulfonic acid, sulfuric acid, sulfamic acid or trichloroacetic acid as strong acids (component (a)). If appropriate, mixtures of these acids can also be used.
  • the pH of the bleaching bath is in particular not greater than 2 and preferably not greater than 1.
  • the water-soluble iodides are generally alkali metal iodides, especially sodium and potassium iodide.
  • the oxidizing agent (component (c)) is suitably water-soluble aromatic mononitro and dinitro compounds, as well as anthraquinone sulfonic acid derivatives, such as. B. o- or m-nitrobenzenesulfonic acid or 2,4-dinitrobenzenesulfonic acid.
  • the use of such oxidizing agents serves to influence the color balance and the contrast of the images produced by the color bleaching process and is known from DE 735 672.
  • the compounds of component (c) serve to flatten the gradation.
  • Reductones or water-soluble mercapto compounds are advantageously used as antioxidants (component (d)).
  • Suitable reductones are, in particular, aci reductones with a 3-carbonylenediol (1,2) grouping, such as reductin, triose reductone or preferably ascorbic acid.
  • mercapto compounds come e.g. B. thioglycerol, but especially the compounds of the formula into consideration, in which q is an integer from 2 to 12, B is a sulfonic acid or carboxylic acid group and m is one of the numbers 3 and 4.
  • azines in particular derivatives of quinoxaline, are suitable as bleaching catalysts (c). These are e.g. For example, described in US-A-4,202,698.
  • Suitable bleach accelerators (f) are e.g. B. quaternary ammonium salts as are known from DE-A-2 139401 and DE-A-2 716 136. These are preferably quaternary, optionally substituted piperidine, piperazine, pyrazine, quinoline, pyridine or tetraalkylammonium compounds and water-soluble tertiary phosphines as described in DE-A-2,651,169.
  • All baths can contain other common additives such as. B. contain hardening agents, wetting agents, optical brighteners or UV protection agents.
  • Baths of conventional composition can be used for silver development, e.g. B. such. which contain hydroquinone as developer substance and optionally additionally 1-phenyl-3-pyrazolidinone. If necessary, the silver developing bath already contains a bleaching catalyst or a silver complexing agent such as e.g. B. sodium thiosulfate.
  • the fixing bath can be composed in a known and customary manner.
  • Material A is produced with an intermediate gelatin layer (Z1), which contains 4 g gelatin per m 2 of substrate surface.
  • Material B is produced with an intermediate gelatin layer (Z1) which contains 1 g of gelatin per m 2 of substrate surface.
  • Material C is produced with an intermediate gelatin layer (Z1) consisting of 1 g of gelatin and 0.3 g of a finely divided dispersion of the compound of the formula (100) per m 2 of substrate surface.
  • Material C shows no loss of dye in the magenta layer in spite of the equally thin intermediate layer (Z1) as in material B.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
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Description

Die vorliegende Erfindung betrifft photographisches Material für das Silberfarbbleichverfahren, das in mindestens einer Schicht mindestens einen Bleichhemmer enthält.The present invention relates to photographic material for the silver color bleaching process, which contains at least one bleach inhibitor in at least one layer.

Beim Silberfarbbleichverfahren wird bekanntlich im belichteten Material zunächst mit einem Schwarz-Weiss-Entwickler ein negatives Silberbild entwickelt. Das Material wird dann gebleicht, wobei das Silber des Silberbildes zu einem Silbersalz oxydiert (gebleicht) und gleichzeitig der Farbstoff entsprechend den ursprünglichen Silberbildbezirken (bildweise) reduziert (gebleicht) wird. Anschliessend wird das noch vorhandene Silbersalz durch Fixieren entfernt und das Material gewaschen. Zum Bleichen werden in der Regel ein oder mehrere Farbbleichkatalysatoren verwendet, z. B. Chinoxaline, Pyrazine oder Phenazine, die z. B. in DE-B-1547720 und DE-B-1547759 beschrieben sind.In the silver color bleaching process, it is known that a negative silver image is first developed in the exposed material with a black and white developer. The material is then bleached, whereby the silver of the silver image is oxidized (bleached) to a silver salt and at the same time the dye is reduced (bleached) according to the original silver image areas. The silver salt still present is then removed by fixing and the material is washed. One or more color bleaching catalysts are usually used for bleaching, e.g. As quinoxalines, pyrazines or phenazines, the z. B. are described in DE-B-1547720 and DE-B-1547759.

Für das Silberfarbbleichverfahren besonders geeignete Aufzeichnungsmaterialien enthalten auf einem Schichtträger rot-, grün- und blauempfindliche Silberhalogenidemulsionsschichten, welche bleichbare Blaugrün-(Cyan)Farbstoffe, Purpur-(Magenta) Farbstoffe und Gelb-(Yellow)Farbstoffe enthalten.Recording materials particularly suitable for the silver color bleaching process contain red, green and blue sensitive silver halide emulsion layers on a support which contain bleachable cyan (cyan) dyes, magenta (magenta) dyes and yellow (yellow) dyes.

Gegebenenfalls können diese Farbstoffe auch in separaten Schichten untergebracht werden, die den Silberhalogenidemulsionsschichten benachbart sind.If appropriate, these dyes can also be accommodated in separate layers which are adjacent to the silver halide emulsion layers.

Bei der Bleichung des Silbers werden die Bleichkatalysatoren in den Silberbildbezirken reduziert. In reduzierter Form beschleunigen die Bleichkatalysatoren die Farbstoffbleichung in den belichteten Bezirken. Zur Herstellung eines scharfen und kontrastreichen Bildes ist es erwünscht, dass der Farbstoff nur in den Silberbildbezirken gebleicht wird. Es hat sich jedoch gezeigt, dass reduzierte Bleichkatalysatoren auch in benachbarte Schichten hineindiffundieren und dort eine Bleichung von Farbstoffen verursachen können. Dies führt zu einer unerwünschten Reduzierung der Farbstoffdichte in dieser Schicht und schliesslich zu einer Farbverfälschung im Farbbild.When bleaching the silver, the bleach catalysts in the silver image areas are reduced. In a reduced form, the bleaching catalysts accelerate dye bleaching in the exposed areas. To produce a sharp and high-contrast image, it is desirable that the dye be bleached only in the silver image areas. However, it has been shown that reduced bleaching catalysts also diffuse into adjacent layers and can cause bleaching of dyes there. This leads to an undesirable reduction in the dye density in this layer and ultimately to a color falsification in the color image.

Zur Lösung dieses Problems wird in US-A-3457074 bereits die Verwendung von p-Chinonen mit einer Ballastgruppe vorgeschlagen. Diese diffusionsfesten Oxydationsmittel können die reduzierten Bleichkatalysatoren teilweise oxidieren und damit als solche wirkungslos machen. Der Nachteil dieser Chinone liegt allerdings darin, dass ihre Wirksamkeit gering ist und sie in den üblichen Lösungsmitteln schwer löslich sind. Es muss deshalb eine grosse Menge Lösungsmittel verwendet werden, um eine optimale Verteilung der Chinone in der photographischen Schicht zu erreichen und auch um das Auskristallisieren dieser Verbindungen zu verhindern.To solve this problem, the use of p-quinones with a ballast group is already proposed in US-A-3457074. These diffusion-resistant oxidizing agents can partially oxidize the reduced bleaching catalysts and thus render them ineffective as such. The disadvantage of these quinones, however, is that their effectiveness is low and they are poorly soluble in the usual solvents. A large amount of solvent must therefore be used in order to achieve an optimal distribution of the quinones in the photographic layer and also to prevent these compounds from crystallizing out.

Anstelle von p-Chinonen werden gemäss US-A-3782948 Nitroverbindungen als Oxydationsmittel eingesetzt. Die mit diesen Verbindungen erzielten Resultate sind jedoch unbefriedigend. Ausserdem lassen sich die Nitroverbindungen nicht in allen Fällen in der gewünschten Verteilung in die photographischen Schichten einarbeiten.Instead of p-quinones, nitro compounds are used as oxidizing agents in accordance with US Pat. No. 3,782,948. However, the results achieved with these compounds are unsatisfactory. In addition, the nitro compounds cannot be incorporated into the photographic layers in the desired distribution in all cases.

Zweikernige Heterocyclen finden gemäss DE-A-2.949.167 Verwendung. Diese haben jedoch den nachteil, dass sie die Kinetik der Silberentwicklung in ungünstigem Sinne beeinflussen.Binuclear heterocycles are used according to DE-A-2,949,167. However, these have the disadvantage that they adversely affect the kinetics of silver development.

Aufgabe der vorliegenden Erfindung ist es nun, die unerwünschte Bleichung von Bildfarbstoffen durch diffundierende, reduzierte Bleichkatalysatoren zu verhindern und gleichzeitig die Nachteile der bisher vorgeschlagenen Lösungen möglichst weitgehend zu überwinden. Die Aufgabe wird erfindungsgemäss dadurch gelöst, dass man die 1,4-Benzochinone gemäss EP-A-0 093 696. in Silberfarbbleichmaterialien einarbeitet. Diese Verbindungen sind in der Regel diffusionsfest und zeichnen sich durch eine gute bleichhemmende Wirkung aus.The object of the present invention is now to prevent the undesired bleaching of image dyes by means of diffusing, reduced bleaching catalysts and, at the same time, to overcome the disadvantages of the previously proposed solutions as far as possible. The object is achieved according to the invention by incorporating the 1,4-benzoquinones according to EP-A-0 093 696 in silver color bleaching materials. These compounds are generally resistant to diffusion and are distinguished by a good bleach-inhibiting effect.

Gegenstand der vorliegenden Erfindung ist daher ein photographisches Silberfarbbleichmaterial, das in mindestens einer Schicht mindestens eine Verbindung der Formel

Figure imgb0001
enthält, worin R ein Rest der Formel
Figure imgb0002
ist, worin

  • Q―CO2R4 oder ―CONR4R5 ist, worin
  • R4 Alkyl mit 1 bis 20 Kohlenstoffatomen, welches unsubstituiert oder substituiert ist mit ―OR6, worin R6 Cycloalkyl mit 3 bis 12 Kohlenstoffatomen, Alkenyl mit 3 bis 20 Kohlenstoffatomen, Aryl mit 6 bis 10 Kohlenstoffatomen, welches unsubstituiert oder mit 1 oder 2 Alkylgruppen mit je 1 bis 4 Kohlenstoffatomen substituiert ist, oder Aralkyl mit 7 bis 13 Kohlenstoffatomen ist ; und welches gegebenenfalls 1 bis 5 Sauerstoffatome enthält, oder R4 Alkenyl mit 3 bis 20 Kohlenstoffatomen, Cycloalkyl mit 3 bis 12 Kohlenstoffatomen, Aryl mit 6 bis 10 Kohlenstoffatomen, welches unsubstituiert oder substituiert ist mit Alkyl mit 1 bis 4 Kohlenstoffatomen, Aralkyl mit 7 bis 13 Kohlenstoffatomen, ein heterocyclischer Ring, der ein Sauerstoffatom oder Stickstoffatom enthält und der unsubstituiert oder substituiert ist mit 1 oder 2 Alkylgruppen mit je 1 bis 4 Kohlenstoffatomen, oder Methyl substituiert mit einen 5- oder 6-gliedrigen heterocyclischen Ring, der ein Sauerstoffatom enthält und der unsubstituiert oder substituiert ist mit 1 oder 2 Alkylgruppen mit je 1 bis 4 Kohlenstoffatomen, bedeutet,
  • R5 Wasserstoff oder Alkyl mit 1 bis 20 Kohlenstoffatomen bedeutet, oder
  • R4 und R5 zusammen mit dem Stickstoffatom, an das sie gebunden sind, einen 5- oder 6-gliedrigen Ring bilden, der unsubstituiert oder substituiert ist mit 1 oder 2 Alkylgruppen mit je 1 bis 4 Kohlenstoffatomen,
  • oder Q -OX ist, worin X R5 oder―COR7 ist, worin R5 die angegebene Bedeutung hat, und R7 Alkyl mit 1 bis 20 Kohlenstoffatomen, Alkenyl mit 3 bis 20 Kohlenstoffatomen, Cycloalkyl mit 3 bis 12 Kohlenstoffatomen, Aralkyl mit 7 bis 13 Kohlenstoffatomen oder Aryl mit 6 bis 10 Kohlenstoffatomen bedeutet, welches unsubstituiert oder substituiert ist mit 1 oder 2 Alkylgruppen mit je 1 bis 4 Kohlenstoffatomen, oder Q ―NR8R9 ist, worin
  • R8 Wasserstoff oder Alkyl mit 1 bis 4 Kohlenstoffatomen und Rg Wasserstoff, Alkyl mit 1 bis 4 Kohlenstoffatomen, -COR7, worin R7 die angegebene Bedeutung hat, bedeutet, oder
  • R8 und Rg zusammen mit dem Stickstoffatom, an das sie gebunden sind, einen 5- oder 6-gliedrigen Ring bilden, der unsubstituiert oder substituiert ist mit 1 oder 2 Alkylgruppen mit je 1 bis 4 Kohlenstoffatomen,
  • oder Q ―P(O)(OR10)([O]xR11) ist, worin
  • x 0 oder 1 ist, und wenn x 1 ist, R10 und R11 unabhängig voneinander Wasserstoff oder Alkyl mit 1 bis 20 Kohlenstoffatomen sind, oder
  • R10 und R11 eine Alkylengruppe mit 2 oder 3 Kohlenstoffatomen bilden, die unsubstituiert oder substituiert ist mit einer oder mehreren Alkylgruppen mit je 1 bis 20 Kohlenstoffatomen, oder wenn x 0 ist,
  • R10 Wasserstoff oder Alkyl mit 1 bis 20 Kohlenstoffatomen und R11 unverzweigtes Alkyl mit 1 bis 5 Kohlenstoffatomen bedeutet, oder Q ―SO2R12 ist, worin R,2 Hydroxyl, Chlor oder ―NR5R7 ist, worin R5 und R7 die angegebenen Bedeutungen haben, wobei R1 ein Rest der Formel (2) ist, wenn R12 Hydroxyl ist, oder Q Cyano ist,
  • R2 und R3 unabhängig voneinander Alkyl mit 1 bis 5 Kohlenstoffatomen sind, und, wenn Q ―CO2R4 ist, entweder R2 oder R3 gegebenenfalls mit -C02R4 substituiert ist, oder R2 und R3 können zusammen mit dem Rest der Formel ―CnH2n+1―k einen Cycloalkylrest mit 5 bis 12 Kohlenstoffatomen bilden, der mit 1 oder 2 Gruppen der Formel ―CO2R4 substituiert ist, worin R4 die angegebene Bedeutung hat,
  • R1 Alkyl mit 1 bis 8 Kohlenstoffatomen oder ein Rest der Formel (2) ist,
  • p 1 oder 2, q 0 oder 1, wobei p + q 1 oder 2 sein muss, n 1 bis 20 und k 1 oder 2 ist, oder ein Salz der Verbindung der Formel (1) enthält.
The present invention therefore relates to a photographic silver color bleaching material which contains at least one compound of the formula in at least one layer
Figure imgb0001
 contains, wherein R is a radical of the formula
Figure imgb0002
 is what
  • Q ― CO 2 R 4 or ―CONR 4 R 5 , wherein
  • R 4 alkyl with 1 to 20 carbon atoms, which is unsubstituted or substituted with ―OR 6 , wherein R 6 cycloalkyl with 3 to 12 carbon atoms, alkenyl with 3 to 20 carbon atoms, aryl with 6 to 10 carbon atoms, which is unsubstituted or with 1 or 2 Alkyl groups each having 1 to 4 carbon atoms is substituted, or aralkyl having 7 to 13 carbon atoms; and which optionally contains 1 to 5 oxygen atoms, or R 4 alkenyl with 3 to 20 carbon atoms, cycloalkyl with 3 to 12 carbon atoms, aryl with 6 to 10 carbon atoms, which is unsubstituted or substituted with alkyl with 1 to 4 carbon atoms, aralkyl with 7 to 13 carbon atoms, a heterocyclic ring which contains an oxygen atom or nitrogen atom and which is unsubstituted or substituted by 1 or 2 alkyl groups each having 1 to 4 carbon atoms, or methyl substituted by a 5- or 6-membered heterocyclic ring which contains an oxygen atom and which is unsubstituted or substituted by 1 or 2 alkyl groups each having 1 to 4 carbon atoms,
  • R 5 represents hydrogen or alkyl having 1 to 20 carbon atoms, or
  • R 4 and R 5 together with the nitrogen atom to which they are attached form a 5- or 6-membered ring which is unsubstituted or substituted by 1 or 2 alkyl groups each having 1 to 4 carbon atoms,
  • or Q is -OX, in which XR 5 or ― COR 7 , in which R 5 has the meaning given, and R 7 is alkyl with 1 to 20 carbon atoms, alkenyl with 3 to 20 carbon atoms, cycloalkyl with 3 to 12 carbon atoms, aralkyl with 7 to 13 carbon atoms or aryl having 6 to 10 carbon atoms, which is unsubstituted or substituted by 1 or 2 alkyl groups each having 1 to 4 carbon atoms, or Q is ―NR 8 R 9 , wherein
  • R 8 is hydrogen or alkyl having 1 to 4 carbon atoms and Rg is hydrogen, alkyl having 1 to 4 carbon atoms, -COR 7 , in which R 7 has the meaning given, or
  • R 8 and Rg together with the nitrogen atom to which they are attached form a 5- or 6-membered ring which is unsubstituted or substituted by 1 or 2 alkyl groups each having 1 to 4 carbon atoms,
  • or Q ―P (O) (OR 10 ) ([O] x R 11 ), wherein
  • x is 0 or 1, and when x is 1, R 10 and R 11 are independently hydrogen or alkyl having 1 to 20 carbon atoms, or
  • R 10 and R 11 form an alkylene group having 2 or 3 carbon atoms which is unsubstituted or substituted by one or more alkyl groups each having 1 to 20 carbon atoms, or when x is 0,
  • R 10 is hydrogen or alkyl having 1 to 20 carbon atoms and R 11 is unbranched alkyl having 1 to 5 carbon atoms, or Q is ―SO 2 R 12 , in which R, 2 is hydroxyl, chlorine or ―NR 5 R 7 , in which R 5 and R 7 have the meanings given, where R 1 is a radical of the formula (2) when R 12 is hydroxyl or Q is cyano,
  • R 2 and R 3 are independently alkyl of 1 to 5 carbon atoms, and, if Q is ―CO 2 R 4 , either R 2 or R 3 is optionally substituted with -C02R4, or R 2 and R 3 together with the rest of the formula ―C n H 2n + 1 ― k form a cycloalkyl radical having 5 to 12 carbon atoms which is substituted by 1 or 2 groups of the formula ―CO 2 R 4 , in which R 4 has the meaning given,
  • R 1 is alkyl having 1 to 8 carbon atoms or a radical of the formula (2),
  • p 1 or 2, q 0 or 1, where p + q must be 1 or 2, n is 1 to 20 and k is 1 or 2, or contains a salt of the compound of formula (1).

Weitere Gegenstände der vorliegenden Erfindung sind die Verfahren zur Herstellung des erfindungsgemässen Materials, die Verwendung der 1,4-Benzochinone in photographischem Silberfarbbleichmaterial und das mit diesem Material hergestellte photographische Bild.

  • Im Formel (1) bedeuten R Alkyl, vorzugsweise der Formel
    Figure imgb0003
The present invention further relates to the processes for the preparation of the material according to the invention, the use of the 1,4-benzoquinones in photographic silver color bleaching material and the photographic image produced with this material.
  • In formula (1), R is alkyl, preferably of the formula
    Figure imgb0003

Darin bedeutet Q eine Gruppe der Formel ―CO2R4 oder -CONR4R5. R4 ist Wasserstoff oder Alkyl, vorzugsweise mit 1 bis 20, insbesondere 1 bis 10 Kohlenstoffatomen. Geeignete Alkylreste sind z. B. Methyl, Aethyl, Propyl, Butyl, Pentyl, Hexyl, Octyl, Decyl, Dodecyl, Hexadecyl, Octadecyl und Eicosyl. Die Alkylreste R4 können auch in Form ihrer verzweigten Isomere vorliegen. Die Alkylreste können ferner 1 bis 5 Sauerstoffatome in der Kohlenstoffkette enthalten, wie z. B. ―CH2CH2OCH3, ―CH2CH2OC2H5, ―(C2H4O)2CH3 oder ―(C2H4O)5CH3. Gegebenenfalls sind die Alkylreste R4 substituiert. Als Substituent kommt z. B. die Gruppe der Formel -OR6 in Frage. Darin bedeutet R6 Cycloalkyl, vorzugsweise mit 3 bis 12 Kohlenstoffatomen, z. B. Cyclopentyl, Methylcyclopentyl, Cycohexyl, Methylcyclohexyl und Cyclooctyl. Rs ist ferner Alkenyl, vorzugsweise mit 3 bis 20 Kohlenstoffatomen. Geeignete Alkenylreste lassen sich von den für R4 genannten Alkylresten ableiten. Desweiteren bedeutet R6 Aryl mit vorzugsweise 6 bis 10 Kohlenstoffatomen wie z. B. Phenyl oder Naphthyl. Diese Arylreste können mit vorzugsweise 1 oder 2 weiteren Alkylgruppen substituiert sein, wobei vor allem Alkylgruppen mit 1 bis 4 Kohlenstoffatomen wie z. B. Methyl, Aethyl, Propyl oder Butyl in Frage kommen. R6 ist ferner Aralkyl. Geeignete Aralkylreste enthalten 7 bis 13 Kohlenstoffatome wie z. B. Benzyl, Naphthylmethyl, Phenyläthyl oder Benzhydryl. R4 bedeutet auch Alkenyl, wobei geeignete Alkenylgruppen 3 bis 20 Kohlenstoffatome enthalten. Diese lassen sich von den genannten Alkylresten ableiten. In der Bedeutung von Cycloalkyl enthält R4 3 bis 12 Kohlenstoffatome, wobei Cyclopropyl, Cyclopentyl, Cyclohexyl und Cyclooctyl besonders bevorzugt sind. Als Arylgruppen R4 kommen vorzugsweise solche mit 6 bis 10 Kohlenstoffatomen in Frage, beispielsweise Phenyl und Naphthyl, wobei diese Gruppen mit Alkylreste wie z. B. Methyl, Aethyl, Propyl, Butyl und deren Isomere substituiert sein können. R4 ist ferner eine Aralkylgruppe, die vorzugsweise 7 bis 13 Kohlenstoffatome enthält. Geeignete Aralkylgruppen sind solche, wie sie für R6 aufgezählt sind. Eine weitere Bedeutung von R4 ist ein 5- oder 6-gliedriger heterocyclischer Ring, der ein Sauerstoff- oder Stickstoffatom enthält, beispielsweise Tetrahydrofuranyl oder Tetrahydropyranyl sowie Piperidinyl oder Pyrrolidinyl, wobei die Ringe mit vorzugsweise 1 bis 4 Alkylgruppen mit (je) 1 bis 4 Kohlenstoffatomen substituiert sein können. R4 ist auch eine Methylgruppe, die mit einem der genannten heterocyclischen Ringe substituiert ist. Beispielsweise kann R4 also Furfuryl oder Tetrahydrofurfuryl bedeuten. Auch diese Reste können mit vorzugsweise 1 oder 2 Alkylgruppen mit (je) 1 bis 4 Kohlenstoffatomen weiter substituiert sein.Q is a group of the formula ―CO 2 R 4 or -CONR 4 R 5 . R 4 is hydrogen or alkyl, preferably having 1 to 20, in particular 1 to 10, carbon atoms. Suitable alkyl radicals are e.g. B. methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl, hexadecyl, octadecyl and eicosyl. The alkyl radicals R 4 can also be in the form of their branched isomers. The alkyl radicals may also contain 1 to 5 oxygen atoms in the carbon chain, such as. B. ―CH 2 CH 2 OCH 3 , ―CH 2 CH 2 OC 2 H 5 , - (C 2 H 4 O) 2 CH 3 or - (C 2 H 4 O) 5 CH 3 . The alkyl radicals R 4 are optionally substituted. As a substituent comes e.g. B. the group of formula -OR 6 in question. Therein R 6 means cycloalkyl, preferably having 3 to 12 carbon atoms, e.g. B. cyclopentyl, methylcyclopentyl, cycohexyl, methylcyclohexyl and cyclooctyl. R s is also alkenyl, preferably having 3 to 20 carbon atoms. Suitable alkenyl radicals can be derived from the alkyl radicals mentioned for R 4 . Furthermore, R 6 is aryl preferably having 6 to 10 carbon atoms such as. B. phenyl or naphthyl. These aryl residues can preferably be 1 or 2 further alkyl groups may be substituted, especially alkyl groups having 1 to 4 carbon atoms such as. B. methyl, ethyl, propyl or butyl come into question. R 6 is also aralkyl. Suitable aralkyl radicals contain 7 to 13 carbon atoms such as. B. benzyl, naphthylmethyl, phenylethyl or benzhydryl. R 4 also means alkenyl, suitable alkenyl groups containing 3 to 20 carbon atoms. These can be derived from the alkyl radicals mentioned. In the meaning of cycloalkyl, R 4 contains 3 to 12 carbon atoms, with cyclopropyl, cyclopentyl, cyclohexyl and cyclooctyl being particularly preferred. Suitable aryl groups R 4 are preferably those having 6 to 10 carbon atoms, for example phenyl and naphthyl, these groups having alkyl radicals such as, for. B. methyl, ethyl, propyl, butyl and their isomers may be substituted. R 4 is also an aralkyl group, preferably containing 7 to 13 carbon atoms. Suitable aralkyl groups are those as listed for R 6 . Another meaning of R 4 is a 5- or 6-membered heterocyclic ring which contains an oxygen or nitrogen atom, for example tetrahydrofuranyl or tetrahydropyranyl and piperidinyl or pyrrolidinyl, the rings preferably having 1 to 4 alkyl groups with (each) 1 to 4 Carbon atoms can be substituted. R 4 is also a methyl group which is substituted by one of the heterocyclic rings mentioned. For example, R 4 can mean furfuryl or tetrahydrofurfuryl. These radicals can also be further substituted with preferably 1 or 2 alkyl groups with (each) 1 to 4 carbon atoms.

R5 in der Formel ―CONR4R5 ist Wasserstoff oder Alkyl mit vorzugsweise 1 bis 20 Kohlenstoffatomen. Geeignete Alkylreste sind solche, wie sie für R4 aufgezählt sind.R 5 in the formula ―CONR 4 R 5 is hydrogen or alkyl with preferably 1 to 20 carbon atoms. Suitable alkyl radicals are those as listed for R 4 .

R4 und R5 bilden zusammen mit dem Stickstoffatom, an das sie gebunden sind, einen 5- oder 6- gliedrigen heterocyclischen Ring. Pyrrolidinyl, Piperidinyl oder Morpholinyl kommen beispielsweise in Frage. Die Ringe können mit vorzugsweise 1 oder 2 Alkylgruppen substituiert sein, wobei die Alkylgruppen in der Regel 1 bis 4 Kohlenstoffatome enthalten.R 4 and R 5 together with the nitrogen atom to which they are attached form a 5- or 6-membered heterocyclic ring. Pyrrolidinyl, piperidinyl or morpholinyl can be used, for example. The rings can be substituted with preferably 1 or 2 alkyl groups, the alkyl groups generally containing 1 to 4 carbon atoms.

Des weiteren ist Q eine Gruppe der Formel -OX, worin X die Bedeutung von R5 ― wie oben definiert, insbesondere aber Alkyl mit 3 oder 4 Kohlenstoffatomen oder Wasserstoff, - oder -COR7 hat. R7 ist Alkyl mit vorzugsweise 1 bis 20 Kohlenstoffatomen. Geeignete Alkylreste sind solche, wie sie für R4 aufgezählt sind, insbesondere solche mit 1 bis 4 Kohlenstoffatomen, wobei Methyl besonders bevorzugt ist. Ferner ist R7 Alkenyl, vorzugsweise mit 3 bis 20 Kohlenstoffatomen. Diese Alkenylreste lassen sich von den genannten Alkylresten ableiten. In der Bedeutung von Cycloalkyl mit vorzugsweise 3 bis 12 Kohlenstoffatomen ist R7 vor allem Cyclopentyl, Cyclohexyl oder Cyclooctyl. Geeignete Aralkylgruppen R7, die vorzugsweise 7 bis 13 Kohlenstoffatome enthalten, sind solche, wie sie für R6 aufgezählt sind. R7 ist ferner Aryl mit vorzugsweise 6 bis 10 Kohlenstoffatomen, beispielsweise Phenyl und Naphthyl. Die Arylgruppen sind gegebenenfalls mit 1 oder 2 Alkylgruppen, vorzugsweise mit (je) 1 bis 4 Kohlenstoffatomen substituiert.Furthermore, Q is a group of the formula -OX, where X has the meaning of R 5 - as defined above, but in particular alkyl with 3 or 4 carbon atoms or hydrogen, - or -COR 7 . R 7 is alkyl with preferably 1 to 20 carbon atoms. Suitable alkyl radicals are those as listed for R 4 , in particular those with 1 to 4 carbon atoms, methyl being particularly preferred. Furthermore R 7 is alkenyl, preferably having 3 to 20 carbon atoms. These alkenyl residues can be derived from the alkyl residues mentioned. In the meaning of cycloalkyl with preferably 3 to 12 carbon atoms, R 7 is above all cyclopentyl, cyclohexyl or cyclooctyl. Suitable aralkyl groups R 7 , which preferably contain 7 to 13 carbon atoms, are those as listed for R 6 . R 7 is also aryl preferably having 6 to 10 carbon atoms, for example phenyl and naphthyl. The aryl groups are optionally substituted with 1 or 2 alkyl groups, preferably with (each) 1 to 4 carbon atoms.

Q ist ferner eine Gruppe der Formel ―NR8R9, worin Rs neben Wasserstoff Alkyl mit vorzugsweise 1 bis 4 Kohlenstoffatomen wie z. B. Methyl, Aethyl, Propyl oder Butyl oder Isomere davon, und Rg Wasserstoff oder Alkyl mit vorzugsweise 1 bis 4 Kohlenstoffatomen oder ein Rest der Formel ―COR7, worin R7 die angegebene Bedeutung hat, ist. R8 und Rg können zusammen mit dem Stickstoffatom, an das sie gebunden sind, einen 5- oder 6-gliedrigen Ring bilden, der gegebenenfalls mit 1 oder 2 Alkylgruppen, die vorzugsweise (je) 1 bis 4 Kohlenstoffatome enthalten, substituiert ist. Bevorzugte Ringe sind z. B. Pyrrolidinyl, Piperidinyl oder Morpholinyl.Q is also a group of the formula ―NR 8 R 9 , wherein R s in addition to hydrogen alkyl having preferably 1 to 4 carbon atoms such as. B. methyl, ethyl, propyl or butyl or isomers thereof, and Rg is hydrogen or alkyl having preferably 1 to 4 carbon atoms or a radical of the formula ―COR 7 , wherein R 7 has the meaning given. R 8 and Rg together with the nitrogen atom to which they are attached can form a 5- or 6-membered ring which is optionally substituted with 1 or 2 alkyl groups, which preferably (each) contain 1 to 4 carbon atoms. Preferred rings are e.g. B. pyrrolidinyl, piperidinyl or morpholinyl.

Q bedeutet auch einen Rest der Formel ―P(O)(OR10)([O]xR11), worin x 0 oder 1 ist. Wenn x 1 ist, bedeuten Rio und R11 unabhängig voneinander Wasserstoff oder Alkyl mit 1 bis 20 Kohlenstoffatomen, wobei die für R4 genannten Alkylreste besonders geeignet sind. R10 und R11 können auch, wenn x 1 ist, eine Alkylenkette bilden, die vorzugsweise 2 oder 3 Kohlenstoffatome enthält, wobei diese wiederum mit einem der genannten Alkylreste mit 1 bis 20 Kohlenstoffatome substituiert sein kann. Wenn x 0 ist, bedeutet R10 Wasserstoff oder Alkyl mit 1 bis 20 Kohlenstoffatomen. Geeignete Alkylreste Rio sind solche, wie sie für R4 genannt sind. R11 ist, wenn x 0 bedeutet, Alkyl mit 1 bis 5 Kohlenstoffatomen, wobei die Alkylreste vorzugsweise unverzweigt sind.Q also represents a radical of the formula ―P (O) (OR 10 ) ([O] x R 11 ), where x is 0 or 1. If x is 1, R 10 and R 11 independently of one another denote hydrogen or alkyl having 1 to 20 carbon atoms, the alkyl radicals mentioned for R 4 being particularly suitable. If x is 1, R 10 and R 11 can also form an alkylene chain which preferably contains 2 or 3 carbon atoms, which in turn can be substituted by one of the alkyl radicals mentioned having 1 to 20 carbon atoms. When x is 0, R 10 represents hydrogen or alkyl of 1 to 20 carbon atoms. Suitable alkyl radicals R io are those as mentioned for R 4 . If x is 0, R 11 is alkyl having 1 to 5 carbon atoms, the alkyl radicals preferably being unbranched.

Des weiteren ist Q eine Gruppe der Formel ―SO2R12, worin R12 Hydroxyl, Halogen wie z. B. Chlor, oder ―NR5R7 ist, worin R5 und R7 die angegebenen Bedeutungen haben. Wenn R12 Hydroxyl ist, ist R1 ein Rest der Formel (2).Furthermore, Q is a group of the formula ―SO 2 R 12 , wherein R 12 is hydroxyl, halogen such as. B. chlorine, or ―NR 5 R 7 , wherein R 5 and R 7 have the meanings given. When R 12 is hydroxyl, R 1 is a radical of formula (2).

Q bedeutet ferner Cyano.Q also means cyano.

R2 und R3 in Formel (2) sind unabhängig voneinander Alkyl, vorzugsweise mit 1 bis 5 Kohlenstoffatomen, beispielsweise Methyl, Aethyl, Propyl, Butyl, Pentyl oder deren Isomere, wobei Methyl besonders bevorzugt ist. Falls Q ―CO2R4 bedeutet, ist entweder R2 oder R3 gegebenenfalls mit -C02R4 substituiert, wobei die beiden Substituenten R4 unabhängig voneinander die genannten Bedeutungen haben. R2 und R3 können auch in der Weise an das CnH2n+1―k-Gerüst gebunden sein, dass ein Cycloalkylrest vorzugweise mit 5 bis 12 Kohlenstoffatomen gebildet wird, der mit 1 oder 2 C02R4-Gruppen substituiert ist. Die beiden Substituenten R4 haben unabhängig voneinander die ihnen zugeordneten Bedeutungen.R 2 and R 3 in formula (2) are independently alkyl, preferably having 1 to 5 carbon atoms, for example methyl, ethyl, propyl, butyl, pentyl or their isomers, methyl being particularly preferred. If Q is ―CO 2 R 4 , either R 2 or R 3 is optionally substituted with -C02R4, the two substituents R 4 having the meanings mentioned independently of one another. R 2 and R 3 can also be bound to the C n H 2n + 1 ― k structure in such a way that a cycloalkyl radical is preferably formed with 5 to 12 carbon atoms, which is substituted by 1 or 2 C0 2 R 4 groups . The two substituents R 4 have, independently of one another, the meanings assigned to them.

n ist vorzugsweise eine Zahl von 1 bis 20, insbesondere 3 bis 7, und p und k sind 1 oder 2, vorzugsweise jedoch 1.n is preferably a number from 1 to 20, in particular 3 to 7, and p and k are 1 or 2, but preferably 1.

q ist 0 oder vorzugsweise 1.q is 0 or preferably 1.

R, in Formel (1) ist Alkyl. Geeignete Alkylreste enthalten 1 bis 8 Kohlenstoffatome und sind z. B. Methyl, Aethyl, Propyl, Butyl, Pentyl, Hexyl, Heptyl, Octyl oder deren Isomere. R, ist ferner ein Rest der Formel (2), wobei in diesem Falle R, und R gleich oder verschieden voneinander sein können. Besonders geeignete Reste R, sind Alkylreste mit 1 bis 4 Kohlenstoffatomen, wobei verzweigte Isomere, wie z. B. t-Butyl, bevorzugt sind.R in formula (1) is alkyl. Suitable alkyl radicals contain 1 to 8 carbon atoms and are e.g. B. Methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl or their isomers. R is also a radical of the formula (2), in which case R and R can be identical or different from one another. Particularly suitable radicals R are alkyl radicals having 1 to 4 carbon atoms, branched isomers, such as. B. t-butyl are preferred.

Die Verbindungen der Formel (1) können auch in Form von Salzen vorliegen.The compounds of formula (1) can also be in the form of salts.

Bevorzugte Verbindungen der Formel (1) zur Verwendung in photographischen Silberfarbbleichverfahren sind solche, worin R die 2- und R, die 5-Stellung besetzt.Preferred compounds of formula (1) for use in silver color photographic bleaching processes are those in which R occupies the 2- and R, 5-positions.

In geeigneten Materialien bedeutet R in den Verbindungen der Formel (1) einen Rest der Formel

Figure imgb0004
worin A Alkyl mit 1 bis 10 Kohlenstoffatomen ist.In suitable materials, R in the compounds of formula (1) represents a radical of the formula
Figure imgb0004
 wherein A is alkyl of 1 to 10 carbon atoms.

Vorzugsweise ist Q in dem Substituenten P der Verbindung der Formel (1) ―CO2R4, ―OCOR7 oder Cyano, wobei R4 und R7 die angegebenen Bedeutungen haben.Q in the substituent P of the compound of the formula (1) is preferably ―CO 2 R 4 , ―OCOR 7 or cyano, where R 4 and R 7 have the meanings given.

In besonders bevorzugten Verbindungen der Formel (1) ist R ein Rest der Formel (2), worin Q ―CO2R4, worin R4 Alkyl mit 1 bis 12 Kohlenstoffatomen, welches unsubstituiert oder substituiert ist mit Cycloalkyloxy mit 3 bis 12 Kohlenstoffatomen oder Aryloxy mit 6 bis 10 Kohlenstoffatomen ; Cycloalkyl mit 3 bis 12 Kohlenstoffatomen, Aryl mit 6 bis 10 Kohlenstoffatomen, Aralkyl mit 7 bis 13 Kohlenstoffatomen oder Methyl substituiert mit einem 5- oder 6-gliedrigen heterocyclischen Ring, der ein Sauerstoffatom enthält und unsubstituiert ist, bedeutet, oder Q ―OCOR7 ist, worin R7 Alkyl mit 1 bis 20 Kohlenstoffatomen. Cycloalkyl mit 3 bis 12 Kohlenstoffatomen, Aralkyl mit 7 bis 13 Kohlenstoffatomen oder unsubstituiertes Aryl mit 6 bis 10 Kohlenstoffatomen bedeutet,

  • R1 ein Rest der Formel (2) ist, worin Q die angegebene Bedeutung hat,
  • R2 und R3 unabhängig voneinander Alkyl mit 1 bis 5 Kohlenstoffatomen sind, und
  • p, q, k und n die angegebenen Bedeutungen haben.
  • Eine weitere Gruppe besonders geeigneter Verbindungen der Formel (1) stellen die Verbindungen der Formel
    Figure imgb0005
    dar, worin R ein Rest der Formel (2) ist, worin Q ―CO2R4, worin R4 Alkyl mit 1 bis 8 Kohlenstoffatomen oder Cycloalkyl mit 5 bis 8 Kohlenstoffatomen ist, oder ―OCOR7, worin R7 Alkyl mit 1 bis 4 Kohlenstoffatomen ist, R1 ein Rest der Formel (2) ist, worin Q die angegebene Bedeutung hat, R2 und R3 jeweils Methyl sind, p, q und k jeweils 1 sind und n 1 bis 10 ist, sowie jene Verbindungen der Formel (4) dar, worin R4 Alkyl mit 1 bis 10 Kohlenstoffatomen. Cyclohexyl oder ein Rest der Formel
    Figure imgb0006
    ist, oder ―OCOR7, worin R7 Methyl oder Phenyl ist, oder Alkoxy mit 1 bis 10 Kohlenstoffatomen oder Hydroxyl ist, R1 t-Butyl oder ein Rest der Formel (2) ist, worin Q die angegebene Bedeutung hat, R2 und R3 Methyl sind, p, q und k 1 sind und n 3 bis 7 ist.
In particularly preferred compounds of the formula (1) R is a radical of the formula (2) in which Q ―CO 2 R 4 , in which R 4 is alkyl having 1 to 12 carbon atoms, which is unsubstituted or substituted by cycloalkyloxy having 3 to 12 carbon atoms or Aryloxy of 6 to 10 carbon atoms; Cycloalkyl with 3 to 12 carbon atoms, aryl with 6 to 10 carbon atoms, aralkyl with 7 to 13 carbon atoms or methyl substituted with a 5- or 6-membered heterocyclic ring which contains an oxygen atom and is unsubstituted, or Q is ―OCOR 7 wherein R 7 is alkyl of 1 to 20 carbon atoms. Means cycloalkyl with 3 to 12 carbon atoms, aralkyl with 7 to 13 carbon atoms or unsubstituted aryl with 6 to 10 carbon atoms,
  • R 1 is a radical of the formula (2), in which Q has the meaning given,
  • R 2 and R 3 are independently alkyl of 1 to 5 carbon atoms, and
  • p, q, k and n have the meanings given.
  • Another group of particularly suitable compounds of the formula (1) are the compounds of the formula
    Figure imgb0005
     in which R is a radical of the formula (2) in which Q is ―CO 2 R 4 , in which R 4 is alkyl having 1 to 8 carbon atoms or cycloalkyl in the form of 5 to 8 carbon atoms, or ―OCOR 7 , in which R 7 is alkyl having 1 is to 4 carbon atoms, R 1 is a radical of formula (2) in which Q has the meaning given, R 2 and R 3 are each methyl, p, q and k are each 1 and n is 1 to 10, and those compounds of formula (4) wherein R 4 is alkyl of 1 to 10 carbon atoms. Cyclohexyl or a radical of the formula
    Figure imgb0006
     or ―OCOR 7 , in which R 7 is methyl or phenyl, or alkoxy having 1 to 10 carbon atoms or hydroxyl, R 1 is t-butyl or a radical of the formula (2) in which Q has the meaning given, R 2 and R 3 are methyl, p, q and k are 1 and n is 3 to 7.

Bevorzugte Alkoxygruppen Q sind solche mit 1 bis 4 Kohlenstoffatomen.Preferred alkoxy groups Q are those with 1 to 4 carbon atoms.

Die in photographisches Silberfarbbleichmaterial eingearbeiteten Chinone der Formel (1) stellen gute Bleichhemmer dar, die in der Lage sind, reduzierte, d. h. aktive Bleichkatalysatoren, zu oxidieren.The quinones of formula (1) incorporated in silver color photographic bleaching material are good bleach inhibitors which are capable of reducing, i.e. H. active bleaching catalysts to oxidize.

Die Chinone werden in bekannter Weise in Form von Dispersionen oder Emulsionen in das photographische Material eingearbeitet. In den meisten Fällen können sie ohne hochsiedende Lösungsmittel, wie Di-n-butylphthalat oder Tri-o-kresylphosphat dispergiert werden. Beispielsweise werden 2,5 g Chinon bei etwa 40 °C in 10 ml Aethylacetat gelöst. Diese Lösung gibt man zu einer vorzugsweise ebenfalls 40 °C warmen Lösung aus 2 g Gelatine in etwa 25 ml Wasser und 1 ml Netzmittel, z. B. Natriumsalz der Diisobutylnaphthalinsulfonsäure in Form einer 8 %igen wässrigen Lösung und dispergiert etwa 4 Minuten mittels Ultraschall. Anschliessend wird das Aethylacetat verdampft. Die Menge an Chinon ist jedoch abhängig vom Typ der photographischen Schicht, in die die Verbindungen eingearbeitet werden sollen. Sie kann in weiten Grenzen variieren. Im allgemeinen werden 0,01 bis 5 g pro m2 Chinon in die entsprechende Schicht eingebracht. Die Wirksamkeit der erfindungsgemässen Chinone hängt ausserdem von der Teilchengrösse der Dispersion ab.The quinones are incorporated into the photographic material in a known manner in the form of dispersions or emulsions. In most cases they can be dispersed without high-boiling solvents such as di-n-butyl phthalate or tri-o-cresyl phosphate. For example, 2.5 g Quinone dissolved in 10 ml of ethyl acetate at about 40 ° C. This solution is added to a preferably also 40 ° C warm solution of 2 g of gelatin in about 25 ml of water and 1 ml of wetting agent, e.g. B. sodium salt of diisobutylnaphthalenesulfonic acid in the form of an 8% aqueous solution and dispersed for about 4 minutes using ultrasound. The ethyl acetate is then evaporated. However, the amount of quinone depends on the type of photographic layer in which the compounds are to be incorporated. It can vary within wide limits. In general, 0.01 to 5 g per m 2 of quinone are introduced into the corresponding layer. The effectiveness of the quinones according to the invention also depends on the particle size of the dispersion.

In einem Mehrschichtenmaterial können die Chinone je nach dem gewünschten Effekt allen Schichten oder nur einzelnen Schichten, z. B. Silberhalogenidemulsions-, Farbstoff-, Silberhalogenidemulsionsfarbstoff-, Zwischen- oder Hilfsschichten zugesetzt werden.In a multi-layer material, the quinones can, depending on the desired effect, all layers or only individual layers, e.g. B. silver halide emulsion, dye, silver halide emulsion dye, intermediate or auxiliary layers can be added.

In Mehrfarbenmaterialien werden die Chinone vorzugsweise in die silberhalogenid- und farbstofffreien Gelatinezwischenschichten eingebracht, um eine Diffusion von reduziertem Bleichkatalysator von einer Farbschicht zur anderen zu verhindern. Dies gilt insbesondere für Materialien, die Silberhalogenidemulsionsschichten ohne Farbstoff enthalten. In diesem Fall genügen im allgemeinen 0,2 bis 0,5 g Chinon pro m2 Schichtfläche, um eine Bleichkopplung zwischen zwei Farbschichten völlig zu verhindern. Die erfindungsgemäss verwendeten Chinone erlauben zudem die Schichtdicke dieser Gelatinezwischenschichten auf ein Minimum zu reduzieren.In multicolor materials, the quinones are preferably incorporated into the silver halide and dye-free intermediate gelatin layers in order to prevent diffusion of reduced bleach catalyst from one color layer to another. This applies in particular to materials which contain silver halide emulsion layers without dye. In this case, 0.2 to 0.5 g quinone per m 2 layer area are generally sufficient to completely prevent bleach coupling between two color layers. The quinones used according to the invention also allow the layer thickness of these intermediate gelatin layers to be reduced to a minimum.

In den Figuren 1 bis 3 werden die aus Farbkeilen von Mehrfarbenmaterialien (siehe Beispiel 3) ermittelten Farbdichten dargestellt. Die Figuren 1 und 2 veranschaulichen Ergebnisse, die mit photographischen Materialien ohne Bleichhemmer erhalten werden. Figur 3 betrifft die mit einem erfindungsgemässen Material (mit Bleichhemmer) erhaltenen Ergebnisse.The color densities determined from color wedges of multicolor materials (see Example 3) are shown in FIGS. 1 to 3. Figures 1 and 2 illustrate results obtained with photographic materials without bleach inhibitors. FIG. 3 relates to the results obtained with a material according to the invention (with bleach inhibitor).

Figur 1 zeigt, dass die Bleichung des Magentafarbstoffs durch eine genügend dicke Gelatinezwischenschicht nahezu verhindert werden kann. Die Magentadichte nimmt kaum ab.Figure 1 shows that the bleaching of the magenta dye can be almost prevented by a sufficiently thick gelatin intermediate layer. The magenta density hardly decreases.

Figur 2 zeigt dagegen, dass zu dünne Gelatinezwischenschichten die Diffusion von reduziertem Bleichkatalysator in die Magentafarbstoff enthaltende Schicht nicht mehr unterdrücken können. Die Magentafarbdichte nimmt deshalb stark ab.FIG. 2, on the other hand, shows that excessively thin gelatin intermediate layers can no longer suppress the diffusion of reduced bleaching catalyst into the layer containing magenta dye. The magenta color density therefore decreases sharply.

Figur 3 zeigt, wie dieselbe dünne Gelatinezwischenschicht dann ausreicht, um ein Ausbleichen des Magentafarbstoffs zu verhindern, wenn sie die erfindungsgemäss als Bleichhemmer verwendeten Chinone enthält. Die Magentadichte bleibt vollständig erhalten.FIG. 3 shows how the same thin gelatin intermediate layer is sufficient to prevent the magenta dye from fading if it contains the quinones used according to the invention as bleach inhibitors. The magenta density is completely preserved.

Eine wesentliche Rolle spielen die Chinone der Formel (1) bei der Herstellung von negativ arbeitendem Silberfarbbleichmaterial. Ein solches Material ist z. B. in US-A-2.673.800 beschrieben. Demgemäss liegen die Chinone in den Emulsionsschichten und Sperrschichten vor, und gegebenenfalls können weitere Gelatineschichten, die ebenfalls ein Chinon enthalten, vorgesehen werden, insbesondere zwischen den Silberhalogenidemulsionssichten und den Farbstoffschichten, die Entwicklungskeime für das Silberkomplexdiffusionsverfahren enthalten.The quinones of formula (1) play an essential role in the production of negative working silver color bleaching material. Such a material is e.g. Described, for example, in US-A-2,673,800. Accordingly, the quinones are present in the emulsion layers and barrier layers, and additional gelatin layers which also contain a quinone can optionally be provided, in particular between the silver halide emulsion layers and the dye layers which contain development nuclei for the silver complex diffusion process.

Auf diese Weise kann verhindert werden, dass durch das in den Emulsionsschichten gebildete negative Silberbild und das in den Sperrschichten an Entwicklungskeimen abgeschiedene Silber der Farbstoff in den benachbarten Schichten ausgebleicht wird, den man für die Erzeugung des negativen Farbbildes benötigt.This can prevent the negative silver image formed in the emulsion layers and the silver deposited on development nuclei in the barrier layers from bleaching out the dye in the adjacent layers which is required for producing the negative color image.

Auch in Filter- und Lichthofschutzschichten, die kolloidale Teilchen von Silber enthalten, sowie in Sperrschichten, die kolloidale Hydrosole oder Sulfide von Edel- oder Schwermetallen enthalten, können die Chinone der Formel (1) mit Vorteil verwendet werden.The quinones of the formula (1) can also be used with advantage in filter and antihalation layers which contain colloidal particles of silver and in barrier layers which contain colloidal hydrosols or sulfides of noble or heavy metals.

Die Verarbeitung der belichteten Silberfarbbleichmaterialien erfolgt im allgemeinen in vier aufeinanderfolgenden Schritten :

  • 1. Silberentwicklung
  • 2. Farbbleichung
  • 3. Silberbleichung
  • 4. Fixierung.
The exposed silver color bleaching materials are generally processed in four successive steps:
  • 1. Silver development
  • 2. Color bleaching
  • 3. Silver bleaching
  • 4. Fixation.

Im ersten Schritt wird das bei der Belichtung entstehende latente Silberbild entwickelt. Im zweiten Schritt wird, entsprechend der vorliegenden bildmässigen Verteilung des Silbers, der dem Silber zugeordnete Bildfarbstoff ausgebleicht. Der dritte Schritt ist notwendig, um das nach der Farbbleichung noch vorhandene überschüssige Bildsilber zu reoxidieren. Im vierten Schritt wird das nunmehr gänzlich in Form von Halogeniden vorliegende Silber durch Herauslösen mit einem Komplexbildner, insbesondere einem Salz der Thioschwefelsäure, entfernt, um das fertige Bild gegenüber weiterer Belichtung unempfindlich zu machen, und das reine Farbbild von Trübung zu befreien.In the first step, the latent silver image created during exposure is developed. In the second step, the image dye assigned to the silver is bleached out in accordance with the image-based distribution of the silver. The third step is necessary to reoxidize the excess image silver that is still present after the color bleaching. In the fourth step, the silver, which is now entirely in the form of halides, is removed by leaching out with a complexing agent, in particular a salt of thiosulfuric acid, in order to render the finished image insensitive to further exposure and to clear the pure color image of cloudiness.

Der zweite Verfahrensschritt, die Farbbleichung, erfolgt bei den üblichen bekannten Verfahren in stark saurem Medium, wobei zur Beschleunigung der Farbbleichung ein Katalysator zugesetzt wird. Die Bleichbäder enthalten zudem einen Silber-Komplexbildner oder Liganden. Beide Bestandteile, Katalysator und Ligand, sind notwendig, um die reduzierende Wirkung des metallischen, nicht-diffundierbaren Bildsilbers auf den ebenfalls nicht-diffundierbaren Farbstoff zu übertragen. Die durch Reduktion am Bildsilber entstehende reduzierte Form des Katalysators dient dabei als Zwischenträger, welcher, nach Zurücklegung einer gewissen Diffusionsstrecke, den Farbstoff irreversibel reduziert und damit bleicht, und dabei selbst zur ursprünglichen Form reoxidiert wird.The second process step, color bleaching, is carried out in the customary known processes in a strongly acidic medium, a catalyst being added to accelerate the color bleaching. The bleaching baths also contain a silver complexing agent or ligand. Both components, catalyst and ligand, are necessary in order to transfer the reducing effect of the metallic, non-diffusible image silver to the likewise non-diffusible dye. The reduced form of the catalyst resulting from reduction on the image silver serves as an intermediate support which, after covering a certain diffusion distance, irreversibly reduces the dye and thus bleaches, and is reoxidized itself to the original form.

Eine Vereinfachung des Verarbeitungsprozesses, ergibt sich durch Zusammenlegen der Farbstoffbleichung und der Silberbleichung zu einem einzigen Verfahrensschritt. Die kombinierten Farb- und Silberbleichbäder (Zubereitungen) für die Verarbeitung des belichteten Silberfarbbleichmaterials enthalten in der Regel die Komponenten (a) bis (f) in den folgenden Mengen :

  • (a) starke Säure : 10 bis 200 g/l ;
  • (b) wasserlösliches Jodid : 2 bis 50 g/l, vorzugsweise 5 bis 25 g/l ;
  • (c) wasserlösliches Oxydationsmittel : 1 bis 30 g/l ;
  • (d) Oxydationsschutzmittel : 0,5 bis 10 g/I ;
  • (e) Bleichkatalysatoren : 0,05 bis 10 g/I, und gegebenenfalls
  • (f) Bleichbeschleuniger : 1 bis 5 g/I.
The processing process is simplified by folding the dye together bleaching and silver bleaching in a single process step. The combined color and silver bleaching baths (preparations) for processing the exposed silver color bleaching material generally contain components (a) to (f) in the following amounts:
  • (a) strong acid: 10 to 200 g / l;
  • (b) water-soluble iodide: 2 to 50 g / l, preferably 5 to 25 g / l;
  • (c) water soluble oxidizer: 1 to 30 g / l;
  • (d) antioxidant: 0.5 to 10 g / l;
  • (e) bleaching catalysts: 0.05 to 10 g / l, and optionally
  • (f) Bleach accelerator: 1 to 5 g / l.

Als starke Säuren (Komponente (a)), können die kombinierten Farb- und Silberbleichbäder Alkyl, oder Arylsulfonsäuren und insbesondere p-Toluolsulfonsäure, Schwefelsäure, Sulfaminsäure oder Trichloressigsäure enthalten. Gegebenenfalls können auch Gemische dieser Säuren eingesetzt werden. Der pH-Wert des Bleichbades ist insbesondere nicht grösser als 2 und vorzugsweise nicht grösser als 1.The strong dyebaths and silver bleach baths may contain alkyl or arylsulfonic acids and in particular p-toluenesulfonic acid, sulfuric acid, sulfamic acid or trichloroacetic acid as strong acids (component (a)). If appropriate, mixtures of these acids can also be used. The pH of the bleaching bath is in particular not greater than 2 and preferably not greater than 1.

Die wasserlöslichen Jodide (Komponente (b)) sind in der Regel Alkalimetalliodide, insbesondere Natrium- und Kaliumiodid.The water-soluble iodides (component (b)) are generally alkali metal iodides, especially sodium and potassium iodide.

Als Oxydationsmittel (Komponente (c)) verwendet man zweckmässig wasserlösliche aromatische Mononitro- und Dinitroverbindungen, sowie Anthrachinonsulfonsäurederivate, wie z. B. o- oder m-Nitrobenzolsulfonsäure oder 2,4-Dinitrobenzolsulfonsäure. Die Verwendung solcher Oxydationsmittel dient zur Beeinflussung des Farbgleichgewichts und des Kontrasts der im Farbbleichverfahren hergestellten Bilder und ist aus DE 735 672. GB 539190 und GB 539 509 bekannt.The oxidizing agent (component (c)) is suitably water-soluble aromatic mononitro and dinitro compounds, as well as anthraquinone sulfonic acid derivatives, such as. B. o- or m-nitrobenzenesulfonic acid or 2,4-dinitrobenzenesulfonic acid. The use of such oxidizing agents serves to influence the color balance and the contrast of the images produced by the color bleaching process and is known from DE 735 672. GB 539190 and GB 539 509.

Die Verbindungen der Komponente (c) dienen neben ihrer Funktion als Silber-Bleichmittel zur Gradationsverflachung.In addition to their function as silver bleaching agents, the compounds of component (c) serve to flatten the gradation.

Als Oxydationsschutzmittel (Komponente (d)) werden mit Vorteil Reduktone oder wasserlösliche Mercaptoverbindungen verwendet. Geeignete Reduktone sind insbesondere aci-Reduktone mit einer 3-Carbonylendiol-(1,2)-Gruppierung, wie Reduktin, Triose-Redukton oder vorzugsweise Ascorbinsäure. Als Mercaptoverbindungen kommen z. B. Thioglycerin, insbesondere jedoch die Verbindungen der Formel

Figure imgb0007
in Betracht, worin q eine ganze Zahl im Wert von 2 bis 12, B eine Sulfonsäure- oder Carbonsäuregruppe und m eine der Zahlen 3 und 4 bedeuten.Reductones or water-soluble mercapto compounds are advantageously used as antioxidants (component (d)). Suitable reductones are, in particular, aci reductones with a 3-carbonylenediol (1,2) grouping, such as reductin, triose reductone or preferably ascorbic acid. As mercapto compounds come e.g. B. thioglycerol, but especially the compounds of the formula
Figure imgb0007
 into consideration, in which q is an integer from 2 to 12, B is a sulfonic acid or carboxylic acid group and m is one of the numbers 3 and 4.

Als Bleichkatalysatoren (c) kommen vor allem Azine, insbesondere Derivate des Chinoxalins in Frage. Diese sind z. B. in US-A-4.202.698 beschrieben.Above all, azines, in particular derivatives of quinoxaline, are suitable as bleaching catalysts (c). These are e.g. For example, described in US-A-4,202,698.

Geeignete Bleichbeschleuniger (f) sind z. B. quaternäre Ammoniumsalze wie sie aus DE-A-2 139401 und DE-A-2 716 136 bekannt sind. Bevorzugt handelt es sich dabei um quaternäre, gegebenenfalls substituierte Piperidin-, Piperazin-, Pyrazin-, Chinolin-, Pyridin- oder Tetraalkylammoniumverbindungen, sowie wasserlösliche tertiäre Phosphine wie sie in DE-A-2.651.169 beschrieben sind.Suitable bleach accelerators (f) are e.g. B. quaternary ammonium salts as are known from DE-A-2 139401 and DE-A-2 716 136. These are preferably quaternary, optionally substituted piperidine, piperazine, pyrazine, quinoline, pyridine or tetraalkylammonium compounds and water-soluble tertiary phosphines as described in DE-A-2,651,169.

Die Wiederholung einzelner Behandlungen (jeweils in einem weiteren Tank mit einem Bad gleicher Zusammensetzung wie das vorangehende) ist möglich, wodurch in manchen Fällen eine bessere Badausnützung erreicht werden kann.The repetition of individual treatments (in each case in a further tank with a bath of the same composition as the previous one) is possible, whereby in some cases better use of the bath can be achieved.

Alle Bäder können weitere übliche Zusätze wie z. B. Härtungsmittel, Netzmittel, optische Aufheller oder UV-Schutzmittel enthalten.All baths can contain other common additives such as. B. contain hardening agents, wetting agents, optical brighteners or UV protection agents.

Zur Silberentwicklung können Bäder üblicher Zusammensetzung angewendet werden z. B. solche. die als Entwicklersubstanz Hydrochinon und gegebenenfalls zusätzlich 1-Phenyl-3-pyrazolidinon enthalten. Gegebenenfalls enthält bereits das Silberentwicklungsbad einen Bleichkatalysator oder einen Silberkomplexbildner wie z. B. Natriumthiosulfat.Baths of conventional composition can be used for silver development, e.g. B. such. which contain hydroquinone as developer substance and optionally additionally 1-phenyl-3-pyrazolidinone. If necessary, the silver developing bath already contains a bleaching catalyst or a silver complexing agent such as e.g. B. sodium thiosulfate.

Das Fixierbad kann in bekannter und üblicher Weise zusammengesetzt sein. Als Fixiermittel dient z. B. Natriumthiosulfat oder mit Vorteil Ammoniumthiosulfat, gewünschtenfalls mit Zusätzen wie Natriumbisulfit und/oder Natriummetabisulfit.The fixing bath can be composed in a known and customary manner. As a fixing agent z. B. sodium thiosulfate or advantageously ammonium thiosulfate, if desired with additives such as sodium bisulfite and / or sodium metabisulfite.

Beispiel 1example 1

Auf einen opaken Cellulosetriacetatträger wird eine Schicht aufgetragen, die pro m2 :

  • 8,2 g Gelatine
  • 0,27 g Farbstoff der Formel

(Siehe Formel Seite 8 f.)
Figure imgb0008
  • 0,69 g Silber (als Silberbromiddispersion),
  • 0,43 g 2-Amino-4-hydroxy-6-(4-methyl-morpholinium)-1,3,5-triazintetrafluoroborat
  • 0,43 g einer feinteiligen Dispersion der Verbindung der Formel
    Figure imgb0009
    als Bleichhemmer enthält.
  • Ein gleiches photographisches Element wird hergestellt, jedoch ohne Zusatz des Bleichhemmers.
  • Je zwei Streifen dieser Elemente werden hinter einem Stufenkeil während zwei Sekunden mit 200 Lux belichtet. Anschliessend wird je 1 Streifen der Elemente bei 30 °C folgendermassen behandelt :
    Figure imgb0010
  • Die beiden übrigen Streifen werden wie folgt verarbeitet:
    Figure imgb0011
  • Die Bäder haben die folgende Zusammensetzung : Bad 1 : Entwickler
    Figure imgb0012
    Bad 3 : Bleichbad
    Figure imgb0013
    Figure imgb0014
    Bad 5 : Fixierbad
    Figure imgb0015
  • Man erhält nach (A) für beide Elemente einen klaren, scharfen Cyankeil und nach (B) jeweils einen Silberkeil, der vom eingegossenen Farbstoff überlagert ist.
  • Die Cyandichten der nach (A) erhaltenen Keile werden mittels eines Remissionsdensitometers im roten Spektralbereich gemessen. Die maximale Cyandichte beträgt 2,5.
  • Die Silberdichten werden mit dem gleichen Instrument im blauen Spektralbereich bestimmt.
  • Im Element ohne Bleichhemmer wird an den Stellen mit einer Silberdichte von 0,5 der Cyanfarbstoff bis zu einer Dichte von etwa 0,4 ausgebleicht. Enthält das Element dagegen einen Bleichhemmer, wird mit derselben Silbermenge der Cyanfarbstoff nur bis auf eine Dichte von etwa 0,9 ausgebildet (die Farbbleichung wird durch die Verbindung der Formel (100) gehemmt).
  • Verwendet man anstelle der Verbindung der Formel (100) als Bleichhemmer Verbindungen der Formeln
    Figure imgb0016
    Figure imgb0017
    Figure imgb0018
    Figure imgb0019
    Figure imgb0020
    Figure imgb0021
    Figure imgb0022
    Figure imgb0023
    Figure imgb0024
    Figure imgb0025
    Figure imgb0026
    Figure imgb0027
    Figure imgb0028
    oder
    Figure imgb0029
    so ergeben sich nach Belichtung und Verarbeitung folgende Farbstoffdichten :
    Figure imgb0030
A layer is applied to an opaque cellulose triacetate support, per m 2 :
  • 8.2 g gelatin
  • 0.27 g of dye of the formula

(See formula on page 8 f.)
Figure imgb0008
  • 0.69 g of silver (as a silver bromide dispersion),
  • 0.43 g of 2-amino-4-hydroxy-6- (4-methylmorpholinium) -1,3,5-triazine tetrafluoroborate
  • 0.43 g of a finely divided dispersion of the compound of the formula
    Figure imgb0009
     contains as a bleach inhibitor.
  • The same photographic element is produced, but without the addition of the bleach inhibitor.
  • Two strips of each of these elements are exposed to 200 lux behind a step wedge for two seconds. Then treat 1 strip of the elements at 30 ° C as follows:
    Figure imgb0010
  • The two remaining strips are processed as follows:
    Figure imgb0011
  • The baths have the following composition: Bath 1: developer
    Figure imgb0012
    Bath 3: bleach bath
    Figure imgb0013
    Figure imgb0014
    Bath 5: fixing bath
    Figure imgb0015
  • According to (A), a clear, sharp cyan wedge is obtained for both elements and, according to (B), a silver wedge, which is overlaid by the poured-in dye.
  • The cyan densities of the wedges obtained according to (A) are measured in the red spectral range using a reflectance densitometer. The maximum cyan density is 2.5.
  • The silver densities are determined with the same instrument in the blue spectral range.
  • In the element without bleach inhibitor, the cyan dye is bleached to a density of about 0.4 at the points with a silver density of 0.5. On the other hand, if the element contains a bleaching inhibitor, the same amount of silver is used to form the cyan dye only to a density of about 0.9 (the color bleaching is inhibited by the compound of the formula (100)).
  • If compounds of the formulas are used as bleach inhibitors instead of the compound of the formula (100)
    Figure imgb0016
    Figure imgb0017
    Figure imgb0018
    Figure imgb0019
    Figure imgb0020
    Figure imgb0021
    Figure imgb0022
    Figure imgb0023
    Figure imgb0024
    Figure imgb0025
    Figure imgb0026
    Figure imgb0027
    Figure imgb0028
     or
    Figure imgb0029
     the following dye densities result after exposure and processing:
    Figure imgb0030

Beispiel 2Example 2

Es werden vier photographische Elemente hergestellt, die ein negatives Cyanbild nach dem Silberfarbbleichverfahren ergeben :

  • Element A: Auf einen transparenten Polyesterträger werden folgende Schichten aufgetragen : eine Schicht, die pro m2 1,6,g Gelatine, 0,135 g blaugrünen Farbstoff der Formel (I) gemäss Beispiel 1,
  • 0,05 mg rote, kolloidale Goldteilchen als Entwicklungskeime und 40 mg 2-Amino-4-hydroxy-6-(4-methylmorpholinium)-1,3,5-triazintetrafluoroborat als Härter enthält ;
  • eine Schicht, die pro m2 1 g Gelatine, 0,5 g Verbindung der Formel (100) und 20 mg besagten Härters enthält, und
  • eine Schicht, die pro m2 1,8 g Gelatine, 0,4 g Silber als rotempfindliche Silberchlorobromidemulsion mit 25 Mol% Silberchlorid und einer mittleren Teilchengrösse von 0,3 µm, und 40 mg besagten Härters enthält.
  • Element B wird wie Element A hergestellt, jedoch ohne Bleichhemmer in der zweiten Schicht.
  • Element C wird wie Element A hergestellt, jedoch ohne die zweite Schicht.
  • Element D wird wie Element C hergestellt, in der dritten Schicht sind jedoch 1 g/m2 der Verbindung der Formel (100) enthalten.
Four photographic elements are produced which give a negative cyan image using the silver color bleaching process:
  • Element A: The following layers are applied to a transparent polyester support: a layer containing 1.6 g gelatin, 0.135 g blue-green dye of the formula (I) according to Example 1 per m 2 ,
  • Contains 0.05 mg of red, colloidal gold particles as development nuclei and 40 mg of 2-amino-4-hydroxy-6- (4-methylmorpholinium) -1,3,5-triazine tetrafluoroborate as hardener;
  • a layer containing 1 g of gelatin, 0.5 g of compound of formula (100) and 20 mg of said hardener per m 2 , and
  • a layer containing 1.8 g of gelatin, 0.4 g of silver as a red-sensitive silver chlorobromide emulsion with 25 mol% of silver chloride and an average particle size of 0.3 μm, and 40 mg of said hardener per m 2 .
  • Element B is made like Element A, but without bleach inhibitors in the second layer.
  • Element C is made like Element A, but without the second layer.
  • Element D is produced like element C, but the third layer contains 1 g / m 2 of the compound of formula (100).

Proben der Elemente A bis D werden in einem Sensitometer mit rotem Licht belichtet und anschliessend wie folgt verarbeitet:

  • 1. Silberentwicklung während 3 Minuten bei 30 °C im Bad 1 gemäss Beispiel 1.
  • Es entsteht ein negatives Silberbild in der dritten Schicht und durch Silberkomplexdiffusion und Silberabscheidung an den Entwicklungskeimen ein positives Silberbild in der ersten Schicht.
  • 2. Wässern während 1 Minute.
  • 3. Gleichzeitige Farbstoff- und Silberbleichung während 3 Minuten bei 30 °C im Bad 3 gemäss Beispiel 1.
  • 4. Wässern während 1 Minute.
  • 5. Fixieren während 3 Minuten bei 30 °C im Bad 5 gemäss Beispiel 1.
  • 6. Wässern während 4 Minuten und trocknen der Elemente.
Samples of elements A to D are exposed to red light in a sensitometer and then processed as follows:
  • 1. Silver development for 3 minutes at 30 ° C. in bath 1 according to example 1.
  • A negative silver image is formed in the third layer, and silver complex diffusion and silver deposition on the development nuclei result in a positive silver image in the first layer.
  • 2. Soak for 1 minute.
  • 3. Simultaneous dye and silver bleaching for 3 minutes at 30 ° C. in bath 3 according to example 1.
  • 4. Soak for 1 minute.
  • 5. Fix for 3 minutes at 30 ° C in bath 5 according to example 1.
  • 6. Soak for 4 minutes and dry the elements.

Alle vier Elemente ergeben ein negatives, d. h. zum Belichtungskeil gegenläufiges Farbbild. Misst man darin die maximale Farbstoffdichte, so erhält man die folgenden Werte :

Figure imgb0031
All four elements result in a negative color image, ie in the opposite direction to the exposure wedge. If you measure the maximum dye density, you get the following values:
Figure imgb0031

Vergleicht man die Maximaldichten der vier Elemente mit der Maximaldichte von entsprechenden Proben, die direkt nach der Entwicklung fixiert werden (100 %), so ergibt sich für A bis D demgegenüber folgender Farbstoffverlust :

Figure imgb0032
If you compare the maximum densities of the four elements with the maximum density of corresponding samples that are fixed immediately after development (100%), the following dye loss results for A to D:
Figure imgb0032

Beispiel 3Example 3

Es werden drei weitere Materialien A, B und C hergestellt, die für die Herstellung positiver Aufsichtskopien nach dem Silberfarbbleichverfahren geeignet sind :

  • Auf einen weissopaken Träger werden in der angegebenen Reihenfolge die folgenden Schichten aufgetragen :
    • 1. Ein rotempfindliches Schichtenpaar, bestehend aus einer Silberhalogenidemulsionsschicht, die 2 g Gelatine, 0,16 g Silber als Silberbromojodid und 0,15 g des blaugrünen Farbstoffs der Formel (I) und einer von Bildfarbstoff freien Silberhalogenidemulsionsschicht die 2 g Gelatine und 0,30 g Silber als Silberbromojodidemulsion pro m2 Schichtträgerfläche enthält ;
    • 2. Eine Gelatinezwischenschicht (Z1) ;
    • 3. Ein grünempflindliches Schichtenpaar, bestehend aus einer Silberhalogenidemulsionsschicht. die 2,5 g Gelatine, 0,17 g Silber als Silberbromojodid und 0,18 g des Magentafarbstoffs der Formel
      Figure imgb0033
      und einer von Bildfarbstoff freien Silberhalogenidemulsionsschicht, die 2 g Gelatine und 0,30 g Silber als Silberbromojodid pro m2 Schichtträgerfläche enthält ;
    • 4. Eine zweite Gelatinezwischenschicht (Z2) aus 4 g Gelatine und 10 mg Kolloidsilber pro m2 Schichtträgerfläche ;
    • 5. Ein blauempfindliches Schichtenpaar, bestehend aus einer Silberhalogenidemulsionsschicht, die 3 g Gelatine und 0,45 g Silber als Silberbromid und 0,14 g des gelben Farbstoffs der Formel
      Figure imgb0034
      und einer Bildfarbstoff freien Silberhalogenidemulsionsschicht, die 2 g Gelatine und 0,36 g Silber als Silberbromid pro m2 Schichtträgerfläche enthält.
    • 6. Eine Gelatineschutzschicht aus 1,5 g Gelatine und 0,4 g des Härtungsmittels 2-Amino-4-hydroxy-6-(4-methyl-morpholinium)-1,3.5-triazintetrafluoroborat pro m2 Schichtträgerfläche enthält.
Three further materials A, B and C are produced, which are suitable for the production of positive top-up copies using the silver color bleaching process:
  • The following layers are applied to a white opaque support in the order given:
    • 1. A pair of layers sensitive to red, consisting of a silver halide emulsion layer, the 2 g gelatin, 0.16 g silver as silver bromoiodide and 0.15 g of the blue-green dye of the formula (I) and a silver halide emulsion layer free of image dye, the 2 g gelatin and 0.30 g contains silver as a silver bromoiodide emulsion per m 2 of substrate surface;
    • 2. An intermediate gelatin layer (Z1);
    • 3. A pair of layers sensitive to green, consisting of a silver halide emulsion layer. the 2.5 g of gelatin, 0.17 g of silver as silver bromoiodide and 0.18 g of the magenta dye of the formula
      Figure imgb0033
       and an image dye-free silver halide emulsion layer containing 2 g of gelatin and 0.30 g of silver as silver bromoiodide per m 2 of the substrate surface;
    • 4. A second intermediate layer of gelatin (Z2) composed of 4 g of gelatin and 10 mg of colloidal silver per m 2 of substrate surface;
    • 5. A blue-sensitive layer pair consisting of a silver halide emulsion layer, the 3 g of gelatin and 0.45 g of silver as silver bromide and 0.14 g of the yellow dye of the formula
      Figure imgb0034
       and an image dye-free silver halide emulsion layer containing 2 g of gelatin and 0.36 g of silver as silver bromide per m 2 of substrate surface.
    • 6. A protective gelatin layer comprising 1.5 g of gelatin and 0.4 g of the hardening agent 2-amino-4-hydroxy-6- (4-methyl-morpholinium) -1,3,5-triazine tetrafluoroborate per m 2 of substrate surface.

Material A wird hergestellt mit einer Gelatinezwischenschicht (Z1), die 4g Gelatine pro m2 Schichtträgerfläche enthält.Material A is produced with an intermediate gelatin layer (Z1), which contains 4 g gelatin per m 2 of substrate surface.

Material B wird hergestellt mit einer Gelatinezwischenschicht (Z1), die 1 g Gelatine pro m2 Schichtträgerfläche enthält.Material B is produced with an intermediate gelatin layer (Z1) which contains 1 g of gelatin per m 2 of substrate surface.

Material C wird hergestellt mit einer Gelatinezwischenschicht (Z1), bestehend aus 1 g Gelatine und 0,3 g einer feinteiligen Dispersion der Verbindung der Formel (100) pro m2 Schichtträgerfläche.Material C is produced with an intermediate gelatin layer (Z1) consisting of 1 g of gelatin and 0.3 g of a finely divided dispersion of the compound of the formula (100) per m 2 of substrate surface.

Die Materialien A, B und C werden in einem Sensitometer mit rotem Licht belichtet und wie in Beispiel 2 verarbeitet. Man erhält Farbkeile, deren Farbe von Rot nach Schwarz verläuft. Misst man die Farbdichten der Keile mit einem Densitometer und berechnet daraus die analytischen Farbdichten der drei Farbkanäle, so erhält man die in den Abbildungen 1 bis 3 wiedergegebenen Farbkurven. (Die Farbdichten sind in « Unity neutral normalized analytical densities UNNAD, vgl. A.J. Sant, Phot. Sci. Eng. 14.356 (1970) angegeben).Materials A, B and C are exposed to red light in a sensitometer and processed as in Example 2. Color wedges are obtained whose color runs from red to black. If you measure the color densities of the wedges with a densitometer and use them to calculate the analytical color densities of the three color channels, you get the color curves shown in Figures 1 to 3. (The color densities are given in «Unity neutral normalized analytical densities UNNAD, see A.J. Sant, Phot. Sci. Eng. 14.356 (1970)).

Man sieht deutlich, dass im Material A die Zwischenschicht (Z1) gerade dick genug ist, um eine Ausbleichung des Magentafarbstoffs zu verhindern. Material B (Figur 2) mit dünner Gelatinezwischenschicht (Z1) zeigt etwa 30 % Farbstoffverlust in der Magentaschicht, was einer sehr deutlich sichtbaren Farbverschiebung entspricht.It can clearly be seen that in the material A the intermediate layer (Z1) is just thick enough to prevent the magenta dye from bleaching. Material B (Figure 2) with a thin gelatin intermediate layer (Z1) shows about 30% loss of dye in the magenta layer, which corresponds to a very clearly visible color shift.

Material C (Figur 3) dagegen zeigt trotz gleich dünner Zwischenschicht (Z1) wie im Material B keinerlei Farbstoffverlust in der Magentaschicht.Material C (FIG. 3), on the other hand, shows no loss of dye in the magenta layer in spite of the equally thin intermediate layer (Z1) as in material B.

Claims (15)

1. A photographic silver dye bleach material which, in at least one layer, contains at least one compound of the formula
Figure imgb0041
in which R is a radical of the formula
Figure imgb0042
in which
Q is -C02R4 or -CONR4R5, in which
R4 is alkyl having 1 to 20 carbon atoms, which is unsubstituted or is substituted by ―OR6, in which R6 is cycloalkyl having 3 to 12 carbon atoms, alkenyl having 3 to 20 carbon atoms, aryl having 6 to 10 carbon atoms, which is unsubstituted or is monosubstituted or disubstituted by alkyl groups having 1 to 4 carbon atoms each, or aralkyl having 7 to 13 carbon atoms, and which may contain 1 to 5 oxygen atoms, or R4 is alkenyl having 3 to 20 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, aryl having 6 to 10 carbon atoms, which is unsubstituted or is substituted by alkyl having 1 to 4 carbon atoms, or is aralkyl having 7 to 13 carbon atoms, a heterocyclic ring which contains an oxygen atom or a nitrogen atom and is unsubstituted or substituted by 1, 2, 3 or 4 alkyl groups having 1 to 4 carbon atoms each, or is methyl substituted by a 5-membered or 6-membered heterocyclic ring which contains an oxygen atom and is unsubstituted or is monosubstituted or disubstituted by alkyl groups having 1 to 4 carbon atoms each,
R5 is hydrogen or alkyl having 1 to 20 carbon atoms or
R4 and R5, together with the nitrogen atom to which they are linked, form a 5-membered or 6- membered ring which is unsubstituted or is monosubstituted or disubstituted by alkyl groups having 1 to 4 carbon atoms each,
or Q is -OX, in which X is Rs or―COR7, in which R5 is as defined and R7 is alkyl having 1 to 20 carbon atoms, alkenyl having 3 to 20 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, aralkyl having 7 to 13 carbon atoms or aryl having 6 to 10 carbon atoms, which is unsubstituted or is monosubstituted or disubstituted by alkyl groups having 1 to 4 carbon atoms each,
or Q is ―NR8R9, in which
R8 is hydrogen or alkyl having 1 to 4 carbon atoms and Rg is hydrogen, alkyl having 1 to 4 carbon atoms or ―COR7, in which R7 has the meaning given, or
R8 and Rg, together with the nitrogen atom to which they are linked, form a 5-membered or 6- membered ring which is unsubstituted or is monosubstituted or disubstituted by alkyl groups having 1 to 4 carbon atoms each,
or Q is ―P(O)(OR10)([O]xR11), in which
x is 0 or 1, and, if x = 1, R10 and R11 independently of one another are hydrogen or alkyl having 1 to 20 carbon atoms, or
Rio and R11 form an alkylene group having 2 or 3 carbon atoms, which is unsubstituted or is monosubstituted or polysubstituted by alkyl groups having 1 to 20 carbon atoms each, or, if x = 0,
R10 is hydrogen or alkyl having 1 to 20 carbon atoms and R11 is unbranched alkyl having 1 to 5 carbon atoms,
or Q is ―SO2R12, in which R12 is hydroxy, chlorine or ―NR5R7, in which R5 and R7 are as defined, R, being a radical of the formula (2) if R12 is hydroxy,
or Q is cyano,
R2 and R3 independently of one another are alkyl having 1 to 5 carbon atoms and, if Q is ―CO2R4, R2 or R3 may be substituted by -C02R4, or R2 and R3 can, together with the radical of the formula ―CnH2n+1―k, form a cycloalkyl radical having 5 to 12 carbon atoms, which is monosubstituted or disubstituted by groups of the formula ―CO2R4, in which R4 is as defined,
R, is alkyl having 1 to 8 carbon atoms or a radical of the formula (2),
p is 1 or 2, q is 0 or 1, p + q having to be 1 or 2, n is 1 to 20 and k is 1 or 2,
or a salt of the compound of the formula (1).
2. A material according to Claim 1, wherein R in the compound of the formula (1) occupies the 2- position and R1 occupies the 5-position.
3. A material according to Claim 1, wherein R1 in the compound of the formula (1) is a radical of the formula
Figure imgb0043
in which A is alkyl having 1 to 10 carbon atoms.
4. A material according to Claim 3, wherein R, is t-butyl.
5. A material according to Claim 1, wherein R in the compound of the formula (1) is a radical of the formula (2), in which Q is ―CO2R4, ―OCOR7 or cyano, R4 and R7 being as defined in claim 1 and R1, R2, R3, p, q, k and n being as defined in claim 1.
6. A material according to Claim 5, wherein R in the compound of the formula (1) is a radical of the formula (2), in which Q is ―CO2R4, in which R4 is alkyl having 1 to 12 carbon atoms, which is unsubstituted or is substituted by cycloalkyloxy having 3 to 12 carbon atoms or aryloxy having 6 to 10 carbon atoms, or is cycloalkyl having 3 to 12 carbon atoms, aryl having 6 to 10 carbon atoms, aralkyl having 7 to 13 carbon atoms or methyl substituted by a 5-membered or 6-membered heterocyclic ring which contains an oxygen atom and is unsubstituted, or Q is ―OCOR7, in which R7 is alkyl having 1 to 20 carbon atoms, cycloalkyl having 3 to 12 carbon atoms, aralkyl having 7 to 13 carbon atoms or unsubstituted aryl having 6 to 10 carbon atoms,
R, is a radical of the formula (2), in which Q is as defined,
R2 and R3 independently of one another are alkyl having 1 to 5 carbon atoms and
p, q, k and n are as defined in claims 5.
7. A material according to Claim 6, wherein the compound is of the formula
Figure imgb0044
in which R is a radical of the formula (2), in which Q is -C02R4, in which R4 is alkyl having 1 to 8 carbon atoms or cycloalkyl having 5 to 8 carbon atoms, or ―OCOR7, in which R7 is alkyl having 1 to 4 carbon atoms, R1 is a radical of the formula (2), in which Q is as defined, R2 and R3 are each methyl and p, q and k are each 1 and n is 1 to 10.
8. A material according to Claim 1, wherein the compound is of the formula
Figure imgb0045
in which R is a radical of the formula (2), in which Q is -C02R4, in which R4 is alkyl having 1 to 10 carbon atoms, cyclohexyl or a radical of the formula
Figure imgb0046
or is -OCOR7, in which R7 is methyl or phenyl, or is alkoxy having 1 to 10 carbon atoms or hydroxyl, R1 is t-butyl or a radical of the formula (2), in which Q is a defined, R2 and R3 are methyl, p, q and k are 1 and n is 3 to 7.
9. A material according to Claim 1, wherein the compound of the formula (1) is present in a layer between a silver halide emulsion layer and a dye-containing layer associated therewith.
10. A material according to Claim 1, wherein the compound of the formula (1) is present in the silver halide emulsion layer.
11. A material according to Claim 1, wherein the compound of the formula (1) is present in a layer in an amount of 0.01 to 5 g/m2.
12. A process for the preparation of the photographic silver dye bleach material according to Claim 1, which comprises incorporating at least one compound of the formula (1) into at least one layer of the material.
13. The use of a compound of the formula (1) as a bleach inhibitor in layers of photographic silver dye bleach materials.
14. A process for the production of a photographic image, which comprises using a material according to Claim 1.
15. The photographic image produced with the silver photographic dye bleach material according to Claim 1.
EP84810036A 1983-01-26 1984-01-20 Photographic material for the silver dye bleach process Expired EP0117227B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH425/83A CH656725A5 (en) 1983-01-26 1983-01-26 PHOTOGRAPHIC MATERIAL FOR SILVER COLORING METHOD.
CH425/83 1983-01-26

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EP0117227A2 EP0117227A2 (en) 1984-08-29
EP0117227A3 EP0117227A3 (en) 1985-08-21
EP0117227B1 true EP0117227B1 (en) 1988-03-23

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EP (1) EP0117227B1 (en)
JP (1) JPS59139030A (en)
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CN87105999A (en) * 1987-01-06 1988-07-20 希巴-盖吉股份公司 The purging method of the photographic silver dye bleach materials of exposure
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CH466036A (en) * 1965-08-19 1968-11-30 Kodak Sa Process for producing a color image and photographic product for the implementation of this process
US3457074A (en) * 1966-04-22 1969-07-22 Eastman Kodak Co Silver dye bleach element containing ballasted para-quinone as diffusion inhibitor
CH507536A (en) * 1968-04-09 1971-05-15 Ciba Geigy Ag Photographic material containing nitro compounds for the silver dye bleaching process
JPS5227637A (en) * 1975-08-11 1977-03-02 Fuji Photo Film Co Ltd One bath type dye and silver bleaching solution
JPS5820424B2 (en) * 1976-10-12 1983-04-22 富士写真フイルム株式会社 Color image forming method
JPS58203935A (en) * 1982-05-05 1983-11-28 チバ・ガイギ−・アクチエンゲゼルシヤフト Novel 1,4-benzoquinones

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DE3470102D1 (en) 1988-04-28
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CH656725A5 (en) 1986-07-15
EP0117227A3 (en) 1985-08-21

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