Ciba-geigy Ag

Ciba-geigy Corporation

Gerald Jan

John Lenoir

Remon Hagen

Mario Fryberg

Matthias Schellenberg

Christoph Chylewski

Max Meier

Roland Kurzen

Eddy Forte

Max Marthaler

Compounds of the formula ##STR1## in which X.sub.1 is hydrogen, alkyl, alkoxy, --NL.sub.1 COM.sub.1, in which L.sub.1 is hydrogen or alkyl and M.sub.1 is alkyl or alkoxy, or is --NL.sub.1 P(O)(OG.sub.1).sub.2, in which G.sub.1 is alkyl, or is alkylsulfonamide or hydroxyl, Y.sub.1 is hydrogen, alkyl, alkoxy, carbalkoxy, N-alkyl-substituted or N,N-dialkyl-substituted amino or --NL.sub.2 COM.sub.2, in which L.sub.2 is hydrogen or alkyl and M.sub.2 is alkyl or alkoxy, Z.sub.1 is hydrogen, alkyl, alkoxy, --NL.sub.2 COM.sub.3, in which M.sub.3 is alkyl, or is carbalkoxy or halogen or represents those atoms which are required to form a ring with Y.sub.1, W.sub.1 is hydrogen, alkyl or alkoxy, R.sub.1 and R.sub.2 independently of one another are hydrogen, halogen, cyano, nitro or --SO.sub.2 U.sub.3, in which U.sub.3 is alkyl or phenyl, R.sub.3 is hydrogen or alkyl or, if R.sub.4 is a direct chemical bond, the two radicals R.sub.3 together are a link member and R.sub.4 is a direct chemical bond or a link member, and at least two of the substituents W.sub.1, X.sub.1, Y.sub.1 and Z.sub.1 are other than hydrogen. The compounds can be used with particular advantage as image dyes, for example in photographic materials for the silver dye bleach process. Color images with excellent color reproduction are obtained.

Oil-soluble disazo dyes and their use in color-photographic recording

A process for the production of photographic color images by the silver dye bleach process, by exposure, silver development, dye formation, dye bleach, silver bleach and fixing of a photographic material which, in a light-sensitive silver halide emulsion layer or in an adjacent layer, contains, dispersed in oil, an oil-soluble triazene of the formula ##STR1## and an oil-soluble coupling component of the formula ##STR2## in which Ar.sub.1 is aryl or an aromatic heterocyclic radical, R.sub.1 is hydrogen, alkyl, aryl, hydroxyl, --(CH.sub.2 CH.sub.2 O).sub.r --L.sub.1 or --OL.sub.1, in which L.sub.1 is alkyl and r is 1, 2 or 3, or R.sub.1 is ##STR3## in which V is hydrogen or alkyl, and R.sub.2 is alkyl, aryl or --(CH.sub.2 CH.sub.2 O).sub.r --L.sub.1, or R.sub.1 and R.sub.2, conjointly with the nitrogen atom to which they are bonded, form a ring, A.sub.1 and A.sub.2 independently of one another are an amine of the formula --NT.sub.1 T.sub.2, in which T.sub.1 and T.sub.2 independently of one another are hydrogen, alkyl or aryl, and X.sub.1 and X.sub.2 independently of one another are hydrogen or alkyl, X.sub.3 is hydrogen, alkyl, alkoxy, --O(C.sub.2 H.sub.4 O).sub.n --H, --O(CH.sub.2).sub.m --OH, --O(CH.sub.2).sub.m --OZ.sub.1 or --O(CH.sub.2 CH.sub.2 O).sub.n --Z.sub.1, in which Z.sub.1 is alkyl, n is 1 to 5 and m is 2 to 4, or X.sub.3 is aryloxy, hydroxyl, halogen, --NHCOY.sub.1, --NHCOH, --NHCOOY.sub.1, --NHP(O)(OY.sub.1).sub.2 or --NHSO.sub.2 Y.sub.1, in which Y.sub.1 is alkyl, --O(CH.sub.2).sub.m --OH, --O(CH.sub.2 CH.sub.2 O).sub.n --H, --O(CH.sub.2).sub.m --OZ.sub.1 or --O(CH.sub.2 CH.sub.2 O).sub.n --Z.sub.1, or is aryl, and X.sub.4 is hydrogen, alkyl, --O(CH.sub.2).sub.m --OH, --O(CH.sub.2 CH.sub.2 O).sub.n --H, --O(CH.sub.2).sub.m --OZ.sub.1 or --O(CH.sub.2 CH.sub.2 O).sub.n --Z.sub.1, alkoxy, aryloxy or halogen, and the total of the carbon atoms in the substituents X.sub.1, X.sub.2, X.sub.3 and X.sub.4 is at least 10. The material which has an enhanced sensitivity is treated, after developing the image silver, with an acid processing solution which contains a phase transfer catalyst capable of transferring cations. The material used in this process exhibits a clearly increased sensitivity.

Process for the production of photographic color images by the silver

Azo dyes of the formula ##STR1## in which X.sub.1 and X.sub.2 independently of one another are alkyl, cycloalkyl, alkenyl, aryl or aralkyl, Y.sub.1 is hydrogen or alkyl, Y.sub.2 is hydrogen, alkyl, alkenyl or aryl or together with Y.sub.1 stands for the atoms required to complete a ring, Z.sub.1 is hydrogen, alkyl, alkenyl, alkoxy, aryl, aryloxy, alkylmercapto, arylmercapto, halogen, cyano, carbalkoxy or stands for the atoms which together with Y.sub.1 form a ring, and D.sub.1 is the radical of a heterocyclic azo component such as a thienyl, thiazolyl, benzthiazolyl, pyrazolyl or imidazolyl radical, or is phenyl optionally substituted by alkyl, cycloalkyl, alkoxy, alkenyl, electronegative substituents such as halogen, cyano, nitro or carboxylic acyl, alkyl- or phenylsulfone or N-alkyl or N,N-dialkyl-substituted sulfonamido, can be used as image dyes in photographic silver dye-bleach materials, or for dyeing textile materials.

Azo dyes containing phosphamic acid diester groups

Azo dyes of the formula in which X.sub.1 and X.sub.2 independently of one another are alkyl, cycloalkyl, alkenyl, aryl or aralkyl, Y.sub.1 is hydrogen or alkyl, Y.sub.2 is hydrogen, alkyl, alkenyl or aryl or together with Y.sub.1 stands for the atoms required to complete a ring, Z.sub.1 is hydrogen, alkyl, alkenyl, alkoxy, aryl, aryloxy, alkylmercapto, arylmercapto, halogen, cyano, carbalkoxy or stands for the atoms which together with Y.sub.1 form a ring, and D.sub.1 is the radical of a heterocyclic azo component such as a thienyl, thiazolyl, benzthiazolyl, pyrazolyl or imidazolyl radical, or is phenyl optionally substituted by alkyl, cycloalkyl, alkoxy, alkenyl, electronegative substituents such as halogen, cyano, nitro or carboxylic acid, alkyl- or phenylsulfone or N-alkyl or N,N-dialkyl-substituted sulfonamido, can be used as image dyes in photographic silver dye-bleach materials, or for dyeing textile materials.

Monoazo dyes containing phosphamic acid diester groups

A process for the production of photographic color images by the silver dye bleach process, by exposure, silver development, dye formation, dye bleach, silver bleach and fixing of a photographic material which, in a light-sensitive silver halide emulsion layer or in an adjacent layer, contains, dispersed in oil, an oil-soluble triazene of the formula ##STR1## and an oil-soluble coupling component of the formula ##STR2## in which Ar.sub.1 is aryl or an aromatic heterocyclic radical, R.sub.1 is hydrogen, alkyl, aryl, hydroxyl, --(CH.sub.2 CH.sub.2 O).sub.r --L.sub.1 or --OL.sub.1, in which L.sub.1 is alkyl and r is 1, 2 or 3, or R.sub.1 is ##STR3## in which V is hydrogen or alkyl, and R.sub.2 is alkyl, aryl or --(CH.sub.2 CH.sub.2 O).sub.r --L.sub.1, or R.sub.1 and R.sub.2, conjointly with the nitrogen atom to which they are bonded, form a ring, A.sub.1 and A.sub.2 independently of one another are an amine of the formula --NT.sub.1 T.sub.2, in which T.sub.1 and T.sub.2 independently of one another are hydrogen, alkyl or aryl, and X.sub.1 and X.sub.2 independently of one another are hydrogen or alkyl, X.sub.3 is hydrogen, alkyl, alkoxy, --O(C.sub.2 H.sub.4 O).sub.n, --H, --O(CH).sub.2).sub.m --OH, --O(CH.sub.2).sub.m --OZ.sub.1 or --O(CH.sub.2 CH.sub.2 O).sub.n --Z.sub.1, in which Z.sub.1 is alkyl, n is 1 to 5 and m is 2 to 4, or X.sub.3 is aryloxy, hydroxyl, halogen, --NHCOY.sub.1, --NHCOH, --NHCOOY.sub.1, --NHP(O)(OY.sub.1).sub.2 or --NHSO.sub.2 Y.sub.1, in which Y.sub.1 is alkyl, --O(CH.sub.2).sub.m --OH, --O(CH.sub.2 CH.sub.2 O).sub.n --H, --O(CH.sub.2).sub.m --OZ.sub.1 or --O(CH.sub.2 CH.sub.2 O).sub.n --Z.sub.1, or is aryl, and X.sub.4 is hydrogen, alkyl, --O(CH.sub.2).sub.m --OH, --O(CH.sub.2 CH.sub.2 O).sub.n --H, --O(CH.sub.2).sub.m --OZ.sub.1 or --O(CH.sub.2 CH.sub.2 O).sub.n Z.sub.1, alkoxy, aryloxy or halogen, and the total of the carbon atoms in the substituents X.sub.1, X.sub.2, X.sub.3 and X.sub.4 is at least 10. The material which has an enhanced sensitivity is treated, after developing the image silver, with an acid processing solution which contains a phase transfer catalyst capable of transferring cations. The material used in this process exhibits a clearly increased sensitivity.

A color-photographic recording material for the silver dye bleach process, which contains oil-soluble azo dyes of the formula ##STR1## in which R.sub.1 is hydrogen, alkyl, alkoxy, alkenyl, acyl, carbalkoxy, acylamino, carbamide, sulfonamide, alkylsulfone, arylsulfone, aryloxy, arylsulfonic acid ester, hydroxyl, cyano, nitro or halogen, R.sub.2 is hydrogen, alkyl, alkoxy, carbalkoxy, carbamide, sulfonamide, alkylsulfone, arylsulfone, aryloxy, cyano, nitro or halogen, R.sub.3 is hydrogen, alkyl, alkoxy, phenoxy, sulfonamide, alkylsulfone, sulfonic acid ester, cyano, nitro, halogen, carbalkoxy, carbamide or phosphoric acid diester, R.sub.4 is hydrogen, alkyl, alkoxy, carbalkoxy, carbamide, sulfonamide, acylamino, alkylsulfone, arylsulfone, hydroxyl, cyano, nitro or halogen, R.sub.5 is hydrogen, alkyl or carbalkoxy, X.sub.1 is hydrogen, alkyl, alkoxy, acylamino, alkylsulfonamide or hydroxyl, Y.sub.1 is hydrogen, alkyl, alkoxy, amino, carbalkoxy, arylsulfonamide, acylamino, halogen, hydroxyl or phosphamic acid ester, Z.sub.1 is hydrogen, alkyl, alkoxy, acylamino, acyl, carbalkoxy, alkylsulfonamide or halogen or forms a ring with Y.sub.1, and W.sub.1 is hydrogen, alkyl, alkoxy or halogen. The substituents mentioned can, where relevant, themselves be further substituted. The oil-soluble azo dyes are easily incorporated into silver halide gelatin emulsions and are very stable therein. Because of the good oil-solubility of the azo dyes, very thin layers can be cast in producing photographic materials, and this has an advantageous effect on, for example, the image sharpness.

Color-photographic recording material for the silver dye bleach process

A process for the production of colored photographic images by the silver dye-bleach process by image-wise exposure and subsequent processing by developing the silver image, dye-bleaching and silver bleaching, it being possible, optionally, for the last two steps to be combined, silver fixing and washing, in which process dye-bleaching and/or silver bleaching is carried out in the presence of at least one bleach catalyst of the formula ##STR1## In the formula, A and B are in each case the non-metallic atoms necessary to complete a benzene or pyridine ring, R.sub.1 and R.sub.3 are each hydrogen, hydroxyl, halogen, alkyl, carboxyl, carbalkoxy, carbalkoxyalkoxy, --CH.sub.2 OH, --O(CH.sub.2).sub.n OH, --O(CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH, --CH.sub.2 Cl, --CH.sub.2 Br, --NR.sub.5 R.sub.6, --CH.sub.2 NR.sub.5 R.sub.6, --O(CH.sub.2).sub.n NR.sub.5 R.sub.6, --CH.sub.2 SO.sub.3 M, --O(CH.sub.2).sub.n SO.sub.3 M or --SO.sub.3 M, R.sub.2 and R.sub.4 are each hydrogen, hydroxyl, alkyl or alkoxy and R.sub.5 and R.sub.6 are each hydrogen or alkyl, M is hydrogen, an alkali metal, ammonium and alkylammonium and n is an integer from 2 to 4.

Process for the production of colored photographic images by the silver

A method of processing photographic silver dye bleach materials which have been exposed imagewise is provided. The process steps are (1) silver developing, (2) dye bleaching, (3) silver bleaching and (4) fixing. The treatment baths for the process steps (2), (3) and (4), or the combined treatment baths useful for process step (3) with at least one the process steps (2) or (4) contain water-soluble tertiary phosphines as silver ligands. These phosphines effect an acceleration of the dye and silver bleaching and they are further suitable stabilizers and optionally antioxidants which yield stable treatment baths.

Use of tertiary phosphines in photographic silver dye bleach materials

Quinoxalines of the formula ##STR1## are provided, in which R.sub.1 and R.sub.2 independently are lower alkyl R.sub.3 is lower alkyl, --CH.sub.2 OR.sub.5, --CH.sub.2 NRR', --CH.sub.2 OCOR, --CH.sub.2 Cl, --CH.sub.2 Br, --CH.sub.2 SR, --CH.sub.2 O(CH.sub.2).sub.p OR, --CH.sub.2 PO(OR.sub.5).sub.2, --CH.sub.2 PO(OR.sub.6).sub.2, --CH.sub.2 SO.sub.3 R.sub.6, --O(CH.sub.2).sub.m OR, --O(CH.sub.2).sub.p SO.sub.3 R.sub.6 or --(OCH.sub.2 CH.sub.2).sub.n OAr, R.sub.4 is hydrogen, lower alkyl or alkoxy when R.sub.3 is other than lower alkyl, or R.sub.4 is --OH, --NRR', --NHCOR, --NHCOAr', --NHSO.sub.2 R.sub.5 or --NHSO.sub.2 Ar', R and R' independently are hydrogen or lower alkyl, R.sub.5 is lower alkyl, R.sub.6 is hydrogen, an alkali metal cation or --N.sym.(R).sub.4, Ar is aryl or sulphonated aryl, Ar' is aryl or substituted aryl, m is 3 or 4, n is 1 to 3 and p is 2 to 4. The quinoxalines are useful as bleach catalysts, especially as dye bleach catalysts, for the photographic silver dye bleach process.

Quinoxalines and their use in photographic processes

A method for processing exposed silver dye-bleach materials using novel preparations for combined dye bleaching and silver bleaching is described. In addition to a strong acid, a water-soluble iodide, a water-soluble oxidizing agent, an antioxidant and, if desired, a bleaching accelerator, these preparations also contain a mixture of 1,4- or 1,2-diazines as bleach catalysts. This mixture consists either of at least two bleach catalysts with redox potentials between +105 mV and -30 mV, the difference between the redox potentials of the catalysts being at least 15 mV, or of at least one bleach catalyst with a redox potential between +60 mV and -30 mV and at least one bleach catalyst with a redox potential between -30 mV and -100 mV, the difference between the redox potentials of the catalysts likewise being at least 15 mV. When exposed dye-bleach materials are processed using these preparations, images with improved color quality are obtained.

Method for processing silver dye-bleach materials

A process for the production of colored photographic images by the silver dye-bleach process by image-wise exposure and subsequent processing by developing the silver image, dye-bleaching and silver bleaching, it being possible, optionally, for the last two steps to be combined, silver fixing and washing, in which process dye-bleaching and/or silver bleaching is carried out in the presence of at least one bleach catalyst of the formula ##STR1## In the formula, A and B are in each case the non-metallic atoms necessary to complete a benzene or pyridine ring, R.sub.1 and R.sub.3 are each hydrogen, hydroxyl, halogen, alkyl, carboxyl, carbalkoxy, carbalkoxyalkoxy, --CH.sub.2 OH, --O(CH.sub.2).sub.n OH, --O(CH.sub.2).sub.2 O(CH.sub.2).sub.2 OH, --CH.sub.2 Cl, --CH.sub.2 Br, --NR.sub.5 R.sub.6, --CH.sub.2 NR.sub.5 R.sub.6, --O(CH.sub.2).sub.n NR.sub.5 R.sub.6, --CH.sub.2 SO.sub.3 M, --O(CH.sub.2).sub.n SO.sub.3 M or --SO.sub.3 M, R.sub.2 and R.sub.4 are each hydrogen, hydroxyl, alkyl or alkoxy and R.sub.5 and R.sub.6 are each hydrogen or alkyl, M is hydrogen, an alkali metal, ammonium or alkylammonium and n is an integer from 2 to 4.

Quinoxalines of the formula ##STR1## are provided, in which R.sub.1 is hydrogen if R.sub.3 and R.sub.4 conjointly are --O(CH.sub.2).sub.p O--, or is --CH.sub.2 OR, --CH.sub.2 NRR', --CH.sub.2 OCOR, --CH.sub.2 Cl, --CH.sub.2 Br, --CH.sub.2 CN, --CH.sub.2 SR, --CH.sub.2 SCN, --CH.sub.2 O(CH.sub.2).sub.m OR, --CH.sub.2 (OCH.sub.2 CH.sub.2).sub.n OR, --CH.sub.2 SO.sub.2 R.sub.5, --CH.sub.2 PO(OR.sub.5).sub.2, --CH.sub.2 SO.sub.3 R.sub.6 or --CH.sub.2 PO(OR.sub.6).sub.2 and R.sub.2 is lower alkyl, --CH.sub.2 PO(OR.sub.5).sub.2, --CH.sub.2 PO(OR.sub.6).sub.2 or CH.sub.2 SO.sub.3 R.sub.6, R.sub.3 and R.sub.4 independently are lower alkyl, lower alkoxy, RO(CH.sub.2).sub.m O-- or RO(CH.sub.2 CH.sub.2 O).sub.n -- or R.sub.3 and R.sub.4 conjointly are --O(CH.sub.2).sub.p O--, R and R' independently are hydrogen or lower alkyl, R.sub.5 is lower alkyl, R.sub.6 is hydrogen, an alkali metal cation or --N.sup..sym. (R).sub.4, m is 3 or 4, n is 1 to 3 and p is 1 or 2. The quinoxalines are useful as bleach catalysts, especially as dye bleach catalysts, in processing baths for the photographic silver dye bleach process.

Quinoxaline bleach catalysts

Quinoxalines of the formula ##STR1## are provided, in which R.sub.1 and R.sub.2 independently are lower alkyl R.sub.3 is lower alkyl, --CH.sub.2 OR.sub.5, --CH.sub.2 NRR', --CH.sub.2 OCOR, --CH.sub.2 Cl, --CH.sub.2 Br, --CH.sub.2 SR, --CH.sub.2 O(CH.sub.2).sub.p OR, --CH.sub.2 PO(OR.sub.5).sub.2, --CH.sub.2 PO(OR.sub.6).sub.2, --CH.sub.2 SO.sub.3 R.sub.6, --O(CH.sub.2).sub.m OR, --O(CH.sub.2).sub.p SO.sub.3 R.sub.6 or --(OCH.sub.2 CH.sub.2).sub.n OAr, R.sub.4 is hydrogen, lower alkyl or alkoxy when R.sub.3 is other than lower alkyl, or R.sub.4 is --OH, --NRR', --NHCOR, --NHCOAr', --NHSO.sub.2 R.sub.5 or --NHSO.sub.2 Ar', R and R' independently are hydrogen or lower alkyl, R.sub.5 is lower alkyl, R.sub.6 is hydrogen, an alkali metal cation or --N.sup..sym. (R).sub.4, Ar is aryl or sulphonated aryl, Ar' is aryl or substituted aryl, m is 3 or 4, n is 1 to 3 and p is 2 to 4. The quinoxalines are useful as bleach catalysts, especially as dye bleach catalysts, for the photographic silver dye bleach process.

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Marly, Switzerland

Gerald Jan