Photographic developing process
First Claim
1. Process for developing a photographic material, which contains a silver halide and has been exposed image-wise, using an aqueous preparation which contains (a) a developer for the silver halide, (b) a water-soluble solvent for the silver halide selected from the group consisting of thioethers, thioamides and salts of thiocyanic, sulphurous and thiosulphuric acid or mixtures of these compounds containing as one component a salt of sulphurous acid and (c) as a compounds which avoids the deposition of metallic silver, a compound of divalent sulphur in solution, wherein this sulphur compound corresponds to the formula ##STR46## in which B1 and D1 each denote ##STR47## wherein R1 is hydrogen, alkyl or hydroxyalkyl with 1 to 6 carbon atoms, phenyl, tolyl, cycloalkyl of 5 to 6 carbon atoms, or a five-membered to six-membered hetero-ring which contains 1 to 3 nitrogen atoms or 1 oxygen atom or 1 sulphur atom, or is a carboxylic acid group, R2 is a direct bond or alkylene of 1 to 4 carbon atoms or phenylene, R3 is hydrogen or alkyl of 1 to 2 carbon atoms or B1 and D1 each denote a cycloaliphatic radical of 5 to 6 carbon atoms, phenylene or a heterocyclic 5-membered or 6-membered ring and such ring fused with a further benzene ring, and the hetero-ring contains 1 to 3 nitrogen atoms, an oxygen atom or a sulphur atom, m1 and n1 each represent one of the numbers 1, 2 and 3, p represents 1 or 2 and A2 and E2 independently of one another each represent a radical of the formulae ##STR48## in which X and Y in each case are hydrogen or alkyl of at most 8 carbon atoms and is optionally substituted by hydroxyl groups, carboxylic acid groups or sulphonic acid groups and Y also represents a phenylsulphonic acid group, a lower alkylsulphonyl group or a phenylsulphonyl group and M represents a monovalent cation and Z has the meaning of X and Y with the exception of hydrogen.
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Accused Products
Abstract
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.
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Citations
18 Claims
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1. Process for developing a photographic material, which contains a silver halide and has been exposed image-wise, using an aqueous preparation which contains (a) a developer for the silver halide, (b) a water-soluble solvent for the silver halide selected from the group consisting of thioethers, thioamides and salts of thiocyanic, sulphurous and thiosulphuric acid or mixtures of these compounds containing as one component a salt of sulphurous acid and (c) as a compounds which avoids the deposition of metallic silver, a compound of divalent sulphur in solution, wherein this sulphur compound corresponds to the formula ##STR46## in which B1 and D1 each denote ##STR47## wherein R1 is hydrogen, alkyl or hydroxyalkyl with 1 to 6 carbon atoms, phenyl, tolyl, cycloalkyl of 5 to 6 carbon atoms, or a five-membered to six-membered hetero-ring which contains 1 to 3 nitrogen atoms or 1 oxygen atom or 1 sulphur atom, or is a carboxylic acid group, R2 is a direct bond or alkylene of 1 to 4 carbon atoms or phenylene, R3 is hydrogen or alkyl of 1 to 2 carbon atoms or B1 and D1 each denote a cycloaliphatic radical of 5 to 6 carbon atoms, phenylene or a heterocyclic 5-membered or 6-membered ring and such ring fused with a further benzene ring, and the hetero-ring contains 1 to 3 nitrogen atoms, an oxygen atom or a sulphur atom, m1 and n1 each represent one of the numbers 1, 2 and 3, p represents 1 or 2 and A2 and E2 independently of one another each represent a radical of the formulae ##STR48## in which X and Y in each case are hydrogen or alkyl of at most 8 carbon atoms and is optionally substituted by hydroxyl groups, carboxylic acid groups or sulphonic acid groups and Y also represents a phenylsulphonic acid group, a lower alkylsulphonyl group or a phenylsulphonyl group and M represents a monovalent cation and Z has the meaning of X and Y with the exception of hydrogen.
- View Dependent Claims (2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17)
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4. Process according to claim 3, wherein the developer preparation contains a sulphur compound of the formula ##STR51## in which m2 and A3 have the meanings indicated in claim 5, R4 is a direct bond or alkylene of 1 to 4 carbon atoms, R5 is hydrogen, --CH3, --CH2 OH, --COOH, --CH2 COOH, cyclopentyl, cyclohexyl, phenyl, tolyl, furyl or thienyl and R6 is hydrogen, methyl or ethyl.
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5. Process according to claim 3, wherein the developer preparation contains a sulphur compound of the formula ##STR52## in which M is a monovalent cation, t is an integer from 1 to 4, R7 is hydrogen, --CH3, --CH2 COOH, phenyl, p-tolyl or p-benzenesulphonamide and R8 is hydrogen or --CH3.
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6. Process according to claim 3, wherein the developer preparation contains a sulphur compound of the formula ##STR53## in which t an integer from 1 to 4.
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7. Process according to claim 6, wherein the developer preparation contains a sulphur compound of the formula ##STR54##
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8. Process according to claim 3, wherein the developer preparation contains a sulphur compound of the formula ##STR55## in which t is an integer from 1 to 4.
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9. Process according to claim 8, wherein the developer preparation contains a sulphur compound of the formula ##STR56##
- 10. Process according to claim 2, wherein the developer preparation contains a sulphur compound of the formula ##STR57## in which m2 denotes 1 or 2, B2 denotes a cycloaliphatic radical of 5 to 6 carbon atoms or phenyl or an N-aromatic-heterocyclic six-membered ring and A3 denotes a radical of the formulae
- space="preserve" listing-type="equation">--CO--0--M and --SO.sub.2 --O--M
in which M is a monovalent cation.
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11. Process according to claim 10, wherein the developer preparation contains a sulphur compound of the formula ##STR58## in which M is a monovalent cation and B3 is cyclopentyl which in the 1-position is bonded to the sulphur atom and in the 5-position is bonded via --CH2 -- to the C0 group, cyclohexyl which in the 1-position is bonded to the sulphur atom and in the 3-position or 4-position is bonded to the CO group, or phenyl which in the 1-position is bonded to the sulphur atom and in the 2-position or 4-position is bonded to the CO group.
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12. Process according to claim 10, wherein the developer preparation contains a sulphur compound of the formula ##STR59## in which M is a monovalent cation and B4 is optionally substituted pyrimidyl which in the 2-position is bonded to the sulphur atom and in the 5-position or 6-position is bonded to the CO group, or optionally substituted pyrindyl which in the 2-position is bonded to the sulphur atom and in the 4-position or 5-position is bonded to the CO group.
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13. Process according to claim 1, wherein the developer preparation contains a sulphur compound of the formula ##STR60## in which R8 and R9 independently of one another are hydrogen or methyl.
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14. Process according to claim 1, wherein the developer preparation contains a sulphur compound of the formula ##STR61## in which A4 denotes a radical of the formulae --CO--O--M or SO2 --O--M, in which M is a monovalent cation and, B5 denotes a cyclohexane radical which is bonded in the 1-position to the sulphur atom and in the 3- or 4-position to the --CO-- group, and m2 denotes the numbers 1 2.
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15. Process according to claim 1, wherein the developer preparation contains a sulphur compound of the formula ##STR62## in which A5 is a radical of the formula ##STR63## and M and has the meanings indicated in claim 1.
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16. Process according to claim 7, wherein the developer preparation contains, as the solvent for the silver halide, a sulphite in a concentration of more than 20 g per liter, or a water soluble thiocyanate or thiosulphate.
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17. Process according to claim 1, wherein silver dye-bleach material which has a composition suitable for reducing undesirable secondary colour densities is developed with a developer formulation of the indicated composition.
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18. Preparation for developing a silver halide photographic material which has been exposed image-wise, which preparation contains (a) a developer substance for the silver halide, (b) a water-soluble solvent for the silver halide and (c) a compound of divalent sulphur in solution, wherein this sulphur compound corresponds to the formula ##STR64## in which B1 and D1 each denote ##STR65## wherein R1 is hydrogen, alkyl or hydroxyalkyl with 1 to 6 carbon atoms, phenyl, tolyl, cycloalkyl of 5 to 6 carbon atoms or a five-membered to six-membered hetero-ring which contains 1 to 3 nitrogen atoms or 1 oxygen atom or 1 sulphur atom, or is a carboxylic acid group, R2 is a direct bond or alkylene of 1 to 4 carbon atoms or phenylene, R3 is hydrogen or alkyl of 1 to 2 carbon atoms or B1 and D1 each denote a cycloaliphatic radical of 5 to 6 carbon atoms, phenylene or a heterocyclic 5-membered or 6-membered ring and such ring fused with a further benzene ring, and the hetero-ring contains 1 to 3 nitrogen atoms, an oxygen atom or a sulphur atom, m1 and n1 each represents one of the numbers 1, 2 and 3, p represents 1 or 2 and A2 and E2 independently of one another each represent a radical of the formulae ##STR66## in which X and y in each case are hydrogen or alkyl of at most 8 carbon atoms and is optionally substituted by hydroxyl groups, carboxylic acid groups or sulphonic acid groups and Y also represents a phenylsulphonic acid group, a lower alkylsulphonyl group or a phenylsulphonyl group and M represents a monovalent cation and Z has the the meaning of X and Y with the exception of the hydrogen.
Specification