Photographic developing process

• US 4,141,734 A
• Filed: 12/01/1977
• Issued: 02/27/1979
• Est. Priority Date: 09/11/1975
• Status: Expired due to Term

• Current Assignee: Ilford AG
• Original Assignee: Ciba-Geigy AG (Novartis Ag)
• Inventors: Lenoir, John, Marthaler, Max
• Primary Examiner(s): Kelley, Mary F.
• Application Number:
  US05/856,389
• Time in Patent Office: 453 Days
• Field of Search: 96/61 M, 96/53, 96/66, 96/66.3, 96/66.4, 96/66.5, 96/50, 96/29 R
• US Class Current: 430/445
• CPC Class Codes: C07C 323/00 Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
• CPC Class Codes: C07D 239/47 One nitrogen atom and one oxygen or sulfur atom, e.g. cytosine
• CPC Class Codes: C07D 307/54 Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
• CPC Class Codes: C07D 333/24 Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
• CPC Class Codes: G03C 5/305 Additives other than developers G03C5/264 takes precedence
• CPC Class Codes: G03C 5/383 Developing-fixing, i.e. mono-baths
• CPC Class Codes: G03C 5/50 Reversal development; Contact processes G03C5/315, G03C8/00 take precedence

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.

Claims

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.

2. Process according to claim 1, wherein the developer preparation contains a sulphur compound of the formula ##STR49## in which m₁, A₂ and B₁ have the meanings indicated in claim 1.

3. Process according to claim 2, wherein the developer preparation contains a sulphur compound of the formula ##STR50## in which m₂ is 1 or 2, R₁ is hydrogen, alkyl or hydroxyzlkyl with at most 6 carbon atoms, phenyl, tolyl, cycloalkyl of 5 to 6 carbon atoms or a five-membered to six-membered heero-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, alkylene of 1 to 4 carbon atoms or phenylene, R₃ is hydrogen or alkyl of 1 to 2 carbon atoms and A₃ is a radical of the formulae

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.

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.

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.

7. Process according to claim 6, wherein the developer preparation contains a sulphur compound of the formula ##STR54##

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.

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

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.

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.

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.

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.

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.

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.

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.

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.