Ciba-geigy Ag

Ciba-geiby Ag

John Lenoir

Gerald Jan

Remon Hagen

Paul Tschopp

Max Marthaler

Thomas Stauner

Bernhard Piller

Ekkehard Kramp

Alfred Froehlich

Mario Fryberg

De Montmollin: Rene

Robert Schaller

Hansrolf Loeffel

Photographic materials which comprise, on a base, at least one layer containing an azo dyestuff of the formula ##STR1## in which R.sub.1 is hydrogen, an alkylsulfone, halogen, cyano or nitro, R.sub.2 is hydrogen, halogen, cyano or nitro, R.sub.3 is hydrogen, alkyl, halogen, cyano or nitro, B.sub.1 is an aromatic ring system, K.sub.1 is an aromatic amine and m.sub.1 is 1 or 2.

Photographic silver dye bleach materials containing formyl-substituted

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

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 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

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 process is described for the prevention of darkening and the formation of a sediment in photographic developer solutions which contain a silver halide developer, a water-soluble silver halide solvent and organic sulfur compounds. The organic sulfur compounds are a combination of (a) an organic thiol compound or thione compound capable of tautomerism and (b) a Bunte salt which contains groups conferring solubility in water. Developer solutions which contain the indicated combination of sulfur compounds are outstandingly stable.

Process for the prevention of darkening and the formation of a sediment

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.

A process for developing photographic silver halide material, which has been exposed image-wise is provided. The aqueous developer preparation used contains a developer compound for the silver halide, a water-soluble solvent for the silver halide and an aliphatic, cycloaliphatic, aromatic or heterocyclic di- or trisulphide. These preparations remain clear over a long period of time during which they do not lose their effectiveness by becoming turbid or by sedimentation of silver. They are of special advantage in continuously operated photographic developing processes.

Photographic developing process

The invention is directed essentially to photographic material containing, on a carrier, a layer with azo dyestuffs of the formula ##STR1## wherein A, B, X and Y are certain substituents, in a second main aspect azo dyestuffs of the formula ##STR2## wherein B' represents certain substituents and in a third main aspect azo deystuffs of the formula

Photographic material containing sulphonic acid group containing disazo

In a first main aspect azo dyestuffs of the formula ##STR1## wherein A, B, X and Y are certain substituents, in a second main aspect azo dyestuffs of the formula ##STR2## wherein B' represents certain substituents and in a third main aspect azo dyestuffs of the formula

Sulfonic-acid-group containing disazo dyestuffs

The invention relates to a dye bleach preparation which contains in addition to an acid, a water-soluble iodide and optionally a dye bleach catalyst at least one bifunctional sulphur compound having a sufficient solubility in the preparation and a low vapor pressure and containing at least one HS-group and at least one oxygen, nitrogen, phosphorus or additional sulphur atom, the sulphur atom of each HS-group being separated from the next oxygen, sulphur, nitrogen and phosphorus atom present in the molecule by at least three carbon atoms.

Dye bleach preparation for the photographic silver dye bleach process

This invention relates to a process for the manufacture sulphonated compounds. Aromatically unsaturated amines are reacted with sulphamic acid or its derivatives at temperatures between 20.degree. and 250.degree.C in the presence of an aprotic solvent and a catalyst.

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Marly, Switzerland

John Lenoir