EP0223883B1 - Method for developing an exposed photographic silver halide emulsion material - Google Patents

Method for developing an exposed photographic silver halide emulsion material Download PDF

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Publication number
EP0223883B1
EP0223883B1 EP19850201959 EP85201959A EP0223883B1 EP 0223883 B1 EP0223883 B1 EP 0223883B1 EP 19850201959 EP19850201959 EP 19850201959 EP 85201959 A EP85201959 A EP 85201959A EP 0223883 B1 EP0223883 B1 EP 0223883B1
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Prior art keywords
mercapto
compound
liquid
heterocyclic
surface active
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EP19850201959
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German (de)
French (fr)
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EP0223883A1 (en
Inventor
Antoine Roberta Van Rossen
André Cornelius Roefs
Robert Joseph Pollet
Etienne Adrianus Van Thillo
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Agfa Gevaert NV
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Agfa Gevaert NV
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Priority to DE8585201959T priority patent/DE3568377D1/en
Priority to JP61280531A priority patent/JPH07119972B2/en
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    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C5/00Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/29Development processes or agents therefor
    • G03C5/305Additives other than developers
    • G03C5/3053Tensio-active agents or sequestering agents, e.g. water-softening or wetting agents

Definitions

  • the present invention relates to a method for developing an exposed photographic silver halide emulsion material and a liquid used therein by means of which the formation of silver sludge is effectively reduced.
  • finely divided metallic silver so-called silver sludge
  • the formation of silver sludge is particularly disturbing in automatic processing apparatus wherein it results in deposits of black silver on conveyor and transport rollers and smudging of photographic material conducted therewith.
  • the emulsion layer may contain auxiliary coating agents such as saponin, sodium lauryl sulphate, dodecylphenol polyethylene oxide ether and hexadecyltrimethyl ammonium bromide.
  • a method for developing an exposed photographic silver halide emulsion material comprises the treating of said material with an aqueous alkaline liquid in the presence of (i) a developing agent, (ii) a heterocyclic mercapto compound including an aliphatic group of at least 3 carbon atoms and (iii) a surface active agent, characterized in that said surface active agent is an anionic alkylphenoxy polyalkyleneoxy phosphate ester surfactant, and the mercapto compound is a heterocyclic mercapto compound corresponding to the following tautomeric general formulae (A) and (B): wherein:
  • the said anionic surfactant is preferably an alkylphenoxy(ethyleneoxy) n phosphoric acid mono- and/or di-ester compound in salt form, e.g. sodium salt, wherein n is a positive integer of at least 4, e.g. n is 4 to 25, and the alkyl group is a C8 to C20 alkyl group.
  • Heterocyclic mercapto-compounds that are within the scope of said general formulae (A) and (B) belong e.g. to the classes of mercapto-tetrazoles, mercapto-triazoles, mercapto-thiadiazoles, mercapto-oxadiazoles, mercapto-benzimidazoles, mercapto-benzoxazoles and mercapto-benzthiazoles.
  • Preferred mercapto-tetrazoles correspond to the following general formula: wherein:
  • Compound 12 of the above Table 2 can be prepared starting from n-hexadecylisothiocyanate and sodium azide in a mixture of dioxan and water.
  • Compounds 13 and 14 of the above Table 2 can be prepared by a condensation reaction using the corresponding amino-phenyl-5-mercapto-tetrazole compounds and acid chlorides.
  • alkylphenoxy polyoxyalkylene phosphoric acid mono- and/or diester surfactants The preparation of anionic alkylphenoxy polyoxyalkylene phosphoric acid mono- and/or diester surfactants is described e.g. in the book Anionic Surfactants, part II, edited by Warner M. Linfield, Marcel Dekker Inc. - New York and Basel, 509-511 (1976).
  • Alkylphenoxy polyalkyleneoxy mono- and diester phosphates are commercially available under the trade name GAFAC, e.g. GAFAC RM-710, of Antara Chemicals-General Aniline & Film Corporation, New York - USA (see Chem. Eng. News 40 (1962) No. 16, p. 87).
  • the liquid according to the present invention for use in the development of a photo-exposed photographic silver halide emulsion material is an aqueous alkaline liquid containing a heterocyclic mercapto compound including an aliphatic group of at least 3 carbon atoms and a surface active agent, characterized in that said surface active agent is an anionic alkylphenoxy polyalkyleneoxy phosphate ester surfactant, and the mercapto compound is a heterocyclic mercapto compound corresponding to the following tautomeric general formulae (A) and (B): wherein:
  • Said liquid used for the development of a photo-exposed photographic silver halide emulsion material does not necessarily contain a developing agent before its use since the developing agent(s) may be present already in the photographic material. In that case the liquid is called an activator liquid.
  • the mercapto compound (ii) is present preferably in an amount of from 10- 4 to 10- 3 mole per liter and the surface active agent (iii) is present in said liquid preferably in an amount of 50 mg to 200 mg per liter.
  • the surfactant (iii) is applied in the photographic material in a water-permeable layer wherefrom it can diffuse into the developing liquid.
  • the surface active agent (iii) is present in a hydrophilic colloid layer of the photographic material at the rear side of its support with respect to the photographic silver halide emulsion layer(s), e.g. in an anti-curl or anti-halation layer.
  • a suitable coverage of surface active agent (iii) in the photographic material is e.g. in the range of 0.01 to 0.20 g per m 2 .
  • the developer liquid may contain any type of developing agent known for use in the development of exposed photographic silver halide.
  • developer compounds may be utilized hydroquinone, p-methylaminophenol, 1-phenyl-3-pyrazolidinone, p-phenylene diamine derivatives and the like.
  • the developer may contain antioxidants such as alkali-metal sulphites, bisulphites, metasulphites or metahydrogen sulphites.
  • the developer solution can be alkalized with alkali-metal hydroxides, phosphates, borates, carbonates and the like.
  • the developer liquid or activator liquid may contain still other ingredients, e.g. metal complexing agents, an anti-fogging agent, e.g.
  • potassium bromide a benzotriazole, a benzothiazole, a tetrazole, e.g. up to 0.03 g per liter of 1-phenyl-5-mercapto-tetrazole, solvents improving the dissolution of the developing agents, e.g. alcohols, polyethylene glycols and esters thereof and alkanolamines, surface active agents other than the above mentioned compound (iii), development retarding or activating compounds, e.g. quaternary ammonium salts, and gelatin hardening agents, e.g. dialdehyde compounds such as glutardialdehyde.
  • solvents improving the dissolution of the developing agents e.g. alcohols, polyethylene glycols and esters thereof and alkanolamines
  • surface active agents other than the above mentioned compound (iii) e.g. quaternary ammonium salts
  • gelatin hardening agents e.g. dialdehyde compounds such as glutardialdeh
  • the pH of the alkaline activator or developer solution is generally in the range of 8.5 to 11.
  • the present invention includes the development by means of the above defined liquid of any type of photographic silver halide emulsion layer material, e.g. a graphic art and X-ray recording material.
  • any type of photographic silver halide emulsion layer material e.g. a graphic art and X-ray recording material.
  • the silver halide used in the silver halide emulsion layer(s) may be of any type or composition used in silver halide photography.
  • the liquid according to the present invention may be applied in the development of black-and-white materials as well as in colour development.
  • the development proceeds advantageously in conjunction with the silver halide complex diffusion transfer reversal process (DTR-process) described in detail in the already mentioned book of A.Rott and E.Weyde.
  • the development process according to the present invention is advantageously applied in automatic processing equipment containing conveyer rollers as described, e.g. in US-P 3 025 779 and 3 545 971.
  • a filter may be used wherethrough the liquid is pumped in a closed circuit.
  • a cartridge filter wherefrom the filter medium, e.g. cellulose yarn, can be removed from the filter housing and burned without leaving ashes.
  • the filter medium e.g. cellulose yarn
  • filter media comprising a mercapto-compound (ii) as defined herein intercept colloidal noble metal even when the pores of the filter medium are rather large and by their diameter are not contributing to an absolute interception.
  • the flow-through speed or pump pressure may be increased so that larger volumes of liquid can be freed from noble metal within the same period of time.
  • Photosensitive paper sheet materials containing a silver halide emulsion layer incorporating silver bromoiodide grains (containing 99 mole % of bromide) at a coverage of 2.85 g per m 2 expressed as silver nitrate were exposed through a graphic original so that about 10% of the total surface of each sheet material had been exposed.
  • These sheet materials were developed in a developer containing the following ingredients in 1000 ml of demineralized water. The development was carried out at 35 ° C in a developer tank containing 24 liters of developer regenerated at a rate of 250 ml per h with fresh developer.
  • the sheet materials were conveyed by rollers at a daily throughput of 30 m 2 through the developer in a developing machine PAKO 24 S (trade name).
  • the speed values defined as log exposure values at optical density 1.00 above fog were expressed as percentual values with respect to the speed 100 given arbitrarily to the result obtained in Test 1.
  • the fog values are the optical density values in the non-exposed area.
  • Compound is compound 3 of Table 1.
  • Compound 11 is an equimolar mixture of alkylphenoxy(OH 2 -CH 2 -O)n-PO-(OH) 2 and [alkylphenoxy(CH 2 -CH2-0)n)]2-PO-OH, wherein the alkyl group is a n-hexadecyl group and n is 15.
  • Compound III is 1-phenyl-5-mercaptotetrazole.
  • test 2 the developer liquid was completely free of 1-phenyl-5-mercapto-tetrazole.

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

Description

  • The present invention relates to a method for developing an exposed photographic silver halide emulsion material and a liquid used therein by means of which the formation of silver sludge is effectively reduced. It is known that finely divided metallic silver, so-called silver sludge, is formed in the developer (ref. e.g. Photographic Silver Halide Diffusion Processes by A.Rott and E.Weyde - The Focal Press, (1972), p. 67). The formation of silver sludge is particularly disturbing in automatic processing apparatus wherein it results in deposits of black silver on conveyor and transport rollers and smudging of photographic material conducted therewith.
  • In order to prevent the formation of silver sludge it has been proposed to add particular compounds forming sparingly soluble and non-reducible silver salts to the developer, e.g. 5,5'-bis-1,2,4-triazolin-3-thiones or derivatives of 1,3,4-thiadiazole-2-thiols as described, e.g. in BE-P 606 550 and GB-P 1 120 963, 2-mercapto-1,3,4-thiadiazoles described in US-P 3 212 892, a great variety of other mercapto compounds described in FR-P 1 470 235 and 1-phenyl-5-mercapto-tetrazole compounds having a -NHX substituent on the phenyl nucleus as described in GB-P 1 471 554. In the latter document it has been described that the emulsion layer may contain auxiliary coating agents such as saponin, sodium lauryl sulphate, dodecylphenol polyethylene oxide ether and hexadecyltrimethyl ammonium bromide.
  • It is generally known that even small amounts of 1-phenyl-5-mercaptotetrazole are highly effective in preventing fog.
  • It has been found experimentally by us that when in the developer liquid 1-phenyl-5-mercaptotetrazole is used for anti-sludge purposes in an amount higher than necessary for reducing fog the photographic sensitivity, i.e. speed is markedly reduced. Such is probably due to the penetrating of the 1-phenyl-5-mercaptotetrazole from the developer liquid into the exposed photographic silver halide emulsion layer and its interaction with latent image nuclei.
  • It is an object of the present invention to provide a method for developing a photographic silver halide emulsion material wherein the formation of silver sludge is reduced effectively without adversely affecting photographic speed.
  • It is another object of the present invention to provide an aqueous alkaline liquid for use in the development of an exposed photographic silver halide emulsion material and by means of which the formation of silver sludge is reduced effectively without adversely affecting the photographic speed of the silver halide emulsion material.
  • Other objects and advantages of the present invention will become clear from the further description.
  • In accordance with the present invention a method for developing an exposed photographic silver halide emulsion material is provided, wherein said method comprises the treating of said material with an aqueous alkaline liquid in the presence of (i) a developing agent, (ii) a heterocyclic mercapto compound including an aliphatic group of at least 3 carbon atoms and (iii) a surface active agent, characterized in that said surface active agent is an anionic alkylphenoxy polyalkyleneoxy phosphate ester surfactant, and the mercapto compound is a heterocyclic mercapto compound corresponding to the following tautomeric general formulae (A) and (B):
    Figure imgb0001
    wherein:
    • Z represents the necessary atoms to close a 5- or 6-membered heterocyclic nitrogen containing ring and includes a hydrocarbon group of at least 7 carbon atoms in straight line.
  • The said anionic surfactant is preferably an alkylphenoxy(ethyleneoxy)n phosphoric acid mono- and/or di-ester compound in salt form, e.g. sodium salt, wherein n is a positive integer of at least 4, e.g. n is 4 to 25, and the alkyl group is a C8 to C20 alkyl group.
  • Heterocyclic mercapto-compounds that are within the scope of said general formulae (A) and (B) belong e.g. to the classes of mercapto-tetrazoles, mercapto-triazoles, mercapto-thiadiazoles, mercapto-oxadiazoles, mercapto-benzimidazoles, mercapto-benzoxazoles and mercapto-benzthiazoles.
  • Preferred mercapto-tetrazoles correspond to the following general formula:
    Figure imgb0002
    wherein:
    • R represents a substituent comprising a hydrocarbon chain containing at least 7 C-atoms in straight line, preferably at least 9 C-atoms in straight line.
  • Examples of 1-phenyl-5-mercaptotetrazole compounds suited for use according to the present invention are listed in the following Table 1.
    Figure imgb0003
  • Other suitable heterocyclic mercapto or thione compounds according to general formulae (A) and (B) are listed in the following Table 2.
    Figure imgb0004
    Figure imgb0005
  • Compound 12 of the above Table 2 can be prepared starting from n-hexadecylisothiocyanate and sodium azide in a mixture of dioxan and water.
  • Compounds 13 and 14 of the above Table 2 can be prepared by a condensation reaction using the corresponding amino-phenyl-5-mercapto-tetrazole compounds and acid chlorides.
  • By the presence of the long chain R group (at least 7 -C in straight line) in the mercapto compounds there is almost no diffusion of these compounds from the processing liquid into the hydrophilic silver halide gelatin emulsion layer(s) of the photographic material and no interaction with the latent silver image resulting in a lowering of the photographic speed can take place.
  • The preparation of anionic alkylphenoxy polyoxyalkylene phosphoric acid mono- and/or diester surfactants is described e.g. in the book Anionic Surfactants, part II, edited by Warner M. Linfield, Marcel Dekker Inc. - New York and Basel, 509-511 (1976). Alkylphenoxy polyalkyleneoxy mono- and diester phosphates are commercially available under the trade name GAFAC, e.g. GAFAC RM-710, of Antara Chemicals-General Aniline & Film Corporation, New York - USA (see Chem. Eng. News 40 (1962) No. 16, p. 87).
  • The liquid according to the present invention for use in the development of a photo-exposed photographic silver halide emulsion material is an aqueous alkaline liquid containing a heterocyclic mercapto compound including an aliphatic group of at least 3 carbon atoms and a surface active agent, characterized in that said surface active agent is an anionic alkylphenoxy polyalkyleneoxy phosphate ester surfactant, and the mercapto compound is a heterocyclic mercapto compound corresponding to the following tautomeric general formulae (A) and (B):
    Figure imgb0006
    wherein:
    • Z represents the necessary atoms to close a 5- or 6-membered heterocyclic nitrogen containing ring and includes a hydrocarbon group of at least 7 carbon atoms in straight line.
  • Said liquid used for the development of a photo-exposed photographic silver halide emulsion material does not necessarily contain a developing agent before its use since the developing agent(s) may be present already in the photographic material. In that case the liquid is called an activator liquid.
  • In a developer or activator liquid according to the present invention the mercapto compound (ii) is present preferably in an amount of from 10-4 to 10-3 mole per liter and the surface active agent (iii) is present in said liquid preferably in an amount of 50 mg to 200 mg per liter.
  • According to a particular embodiment the surfactant (iii) is applied in the photographic material in a water-permeable layer wherefrom it can diffuse into the developing liquid. For example, the surface active agent (iii) is present in a hydrophilic colloid layer of the photographic material at the rear side of its support with respect to the photographic silver halide emulsion layer(s), e.g. in an anti-curl or anti-halation layer. A suitable coverage of surface active agent (iii) in the photographic material is e.g. in the range of 0.01 to 0.20 g per m2.
  • The developer liquid may contain any type of developing agent known for use in the development of exposed photographic silver halide. For example as developer compounds may be utilized hydroquinone, p-methylaminophenol, 1-phenyl-3-pyrazolidinone, p-phenylene diamine derivatives and the like. The developer may contain antioxidants such as alkali-metal sulphites, bisulphites, metasulphites or metahydrogen sulphites. The developer solution can be alkalized with alkali-metal hydroxides, phosphates, borates, carbonates and the like. The developer liquid or activator liquid may contain still other ingredients, e.g. metal complexing agents, an anti-fogging agent, e.g. potassium bromide, a benzotriazole, a benzothiazole, a tetrazole, e.g. up to 0.03 g per liter of 1-phenyl-5-mercapto-tetrazole, solvents improving the dissolution of the developing agents, e.g. alcohols, polyethylene glycols and esters thereof and alkanolamines, surface active agents other than the above mentioned compound (iii), development retarding or activating compounds, e.g. quaternary ammonium salts, and gelatin hardening agents, e.g. dialdehyde compounds such as glutardialdehyde.
  • The pH of the alkaline activator or developer solution is generally in the range of 8.5 to 11.
  • The present invention includes the development by means of the above defined liquid of any type of photographic silver halide emulsion layer material, e.g. a graphic art and X-ray recording material.
  • The silver halide used in the silver halide emulsion layer(s) may be of any type or composition used in silver halide photography. The liquid according to the present invention may be applied in the development of black-and-white materials as well as in colour development. The development proceeds advantageously in conjunction with the silver halide complex diffusion transfer reversal process (DTR-process) described in detail in the already mentioned book of A.Rott and E.Weyde.
  • The development process according to the present invention is advantageously applied in automatic processing equipment containing conveyer rollers as described, e.g. in US-P 3 025 779 and 3 545 971.
  • In order to remove sludge that may be formed, e.g. in developing liquids wherein the mercapto-compound (ii) has reacted substantially with colloidal silver and has lost its activity a filter may be used wherethrough the liquid is pumped in a closed circuit.
  • A survey of filters and filter media is given by Kirk-Othmer in Encyclopedia of Chemical Technology, 3rd ed., Vol. 10 (1980) - A Wiley-Interscience Publication - John Wiley & Sons, New York, p. 298-334.
  • Particular preference is given to a cartridge filter wherefrom the filter medium, e.g. cellulose yarn, can be removed from the filter housing and burned without leaving ashes. Such makes it much easier to separate the solid residue containing noble metal without interference with solid material the filter is made of.
  • It has been established in practice that filter media comprising a mercapto-compound (ii) as defined herein intercept colloidal noble metal even when the pores of the filter medium are rather large and by their diameter are not contributing to an absolute interception. By the consequence of the improved interception of the colloidal noble metal particles the flow-through speed or pump pressure may be increased so that larger volumes of liquid can be freed from noble metal within the same period of time.
  • The present invention is illustrated by the following example without, however, limiting it thereto. All ratios and percentages are by weight unless otherwise indicated.
  • EXAMPLE
  • Photosensitive paper sheet materials containing a silver halide emulsion layer incorporating silver bromoiodide grains (containing 99 mole % of bromide) at a coverage of 2.85 g per m2 expressed as silver nitrate were exposed through a graphic original so that about 10% of the total surface of each sheet material had been exposed. These sheet materials were developed in a developer containing the following ingredients in 1000 ml of demineralized water.
    Figure imgb0007
    The development was carried out at 35°C in a developer tank containing 24 liters of developer regenerated at a rate of 250 ml per h with fresh developer. The sheet materials were conveyed by rollers at a daily throughput of 30 m2 through the developer in a developing machine PAKO 24 S (trade name).
  • In comparison tests compounds I, II and III as described hereinafter were added to the alkaline developer liquid in the amounts given. The obtained results in the counteraction of sludge deposition being defined as m2 of photographic material passed through the developing machine before visual appearance of a black deposit on the white area of the photographic material are listed in Table 3. In that Table 3 also fog values and sensitivity values (photographic speed values) obtained before detectable sludge deposition are listed.
  • The speed values defined as log exposure values at optical density 1.00 above fog were expressed as percentual values with respect to the speed 100 given arbitrarily to the result obtained in Test 1.
  • The fog values are the optical density values in the non-exposed area.
  • From the obtained results can be learned that there is a superadditive effect in the counteraction of sludge by using in the developer liquid according to the present invention the combination of compounds I and II which combination does not result in a loss of speed.
    Figure imgb0008
  • Compound is compound 3 of Table 1. Compound 11 is an equimolar mixture of alkylphenoxy(OH2-CH2-O)n-PO-(OH)2 and [alkylphenoxy(CH2-CH2-0)n)]2-PO-OH, wherein the alkyl group is a n-hexadecyl group and n is 15. Compound III is 1-phenyl-5-mercaptotetrazole.
  • In test 2 the developer liquid was completely free of 1-phenyl-5-mercapto-tetrazole.
  • In replacing compound II in the above test 4 by a 08-alkylphenoxy(CH2-CH2-O)n-PO-(OH)2 compound having n = 4 a still valuable anti-sludge activity without drop in sensitivity was obtained.

Claims (15)

1. A method for developing an exposed photographic silver halide emulsion material, wherein said method comprises the treating of said material with an aqueous alkaline liquid in the presence of (i) a developing agent, (ii) a heterocyclic mercapto compound including an aliphatic group of at least 3 carbon atoms and (iii) a surface active agent, characterized in that said surface active agent is an anionic alkylphenoxy polyalkyleneoxy phosphate ester surfactant, and the mercapto compound is a heterocyclic mercapto compound corresponding to the following tautomeric general formulae (A) and (B):
Figure imgb0009
wherein:
Z represents the necessary atoms to close a 5- or 6-membered heterocyclic nitrogen containing ring and includes a hydrocarbon group of at least 7 carbon atoms in straight line.
2. A method according to claim 1, wherein the heterocyclic mercapto compound is selected from the group of mercapto-tetrazoles, mercapto-triazoles, mercapto-thiadiazoles, mercapto-oxadiazoles, mercapto-benzimidazoles, mercapto-benzoxazoles and mercapto-benzthiazoles.
3. A method according to claim 1 or 2, wherein the heterocyclic mercapto compound is a mercaptotetrazole corresponding to the following general formula:
Figure imgb0010
wherein:
R represents a substituent comprising a hydrocarbon chain containing at least 7 C-atoms in straight line.
4. A method according to any of claims 1 to 3, wherein the anionic surfactant is an alkylphenoxy(ethyleneoxy)n phosphoric acid mono- or di-ester compound in salt form, wherein n is a positive integer of at least 4, and the alkyl group is a C8 to C20 alkyl group.
5. A method according to any of the preceding claims, wherein said compound (ii) is used in the aqueous alkaline liquid in an amount of from 10-4 to 10-3 mole per liter.
6. A method according to any of the preceding claims, wherein the compound (iii) is used in the aqueous alkaline liquid in an amount of from 50 to 200 mg per liter.
7. A method according to any of the preceding claims, wherein the treating is carried out in the presence of an anti-fogging agent.
8. A method according to any of the claims 1 to 5, wherein the exposed photographic material contains in a water-permeable layer already before exposure said compound (iii).
9. Aqueous alkaline developer or activator liquid for use in the development of a photo-exposed photographic silver halide emulsion material containing a heterocyclic mercapto compound including an aliphatic group of at least 3 carbon atoms and a surface active agent, characterized in that said surface active agent is an anionic alkylphenoxy polyalkyleneoxy phosphate ester surfactant, and the mercapto compound is a heterocyclic mercapto compound corresponding to the following tautomeric general formulae (A) and (B):
Figure imgb0011
wherein:
Z represents the necessary atoms to close a 5- or 6-membered heterocyclic nitrogen containing ring and includes a hydrocarbon group of at least 7 carbon atoms in straight line.
10. A liquid according to claim 9, wherein the heterocyclic mercapto compound is selected from the group of mercapto-tetrazoles, mercapto-triazoles, mercapto-thiadiazoles, mercapto-oxadiazoles, mercapto-benzimidazoles, mercapto-benzoxazoles and mercapto-benzthiazoles.
11. A liquid according to claim 9 or 10, wherein the heterocyclic mercapto compound is a mercapto-tetrazole corresponding to the following general formula:
Figure imgb0012
wherein:
R represents a substituent comprising a hydrocarbon chain containing at least 7 C-atoms in straight line.
12. A liquid according to any of claims 9 to 11, wherein the anionic surface active agent is an alkylphenoxy(ethyleneoxy)n phosphoric acid mono- or di-ester compound in salt form, wherein n is a positive integer of at least 4, and the alkyl group is a C8 to C20 alkyl group.
13. A liquid according to any of claims 9 to 12, wherein said mercapto compound is present in an amount of from 10-4 to 10-3 mole per liter.
14. A liquid according to any of claims 9 to 13, wherein said surface active agent is present in an amount of from 50 to 200 mg per liter.
15. A liquid according to any of the claims 9 to 14, wherein the liquid contains an anti-fogging agent.
EP19850201959 1985-11-26 1985-11-26 Method for developing an exposed photographic silver halide emulsion material Expired EP0223883B1 (en)

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EP19850201959 EP0223883B1 (en) 1985-11-26 1985-11-26 Method for developing an exposed photographic silver halide emulsion material
DE8585201959T DE3568377D1 (en) 1985-11-26 1985-11-26 Method for developing an exposed photographic silver halide emulsion material
JP61280531A JPH07119972B2 (en) 1985-11-26 1986-11-25 Method for developing exposed photographic silver halide emulsion material

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JP2704287B2 (en) * 1989-03-24 1998-01-26 コニカ株式会社 Image forming method for silver halide photographic material
US5215873A (en) * 1989-11-21 1993-06-01 E. I. Du Pont De Nemours And Company Process for developing silver halide recording materials
EP0518627A1 (en) * 1991-06-10 1992-12-16 International Paper Company Reducing silver sludging during photographic processing
EP0620483A1 (en) * 1993-04-13 1994-10-19 Agfa-Gevaert N.V. Processing of silver halide photographic industrial X-ray films
EP0621506A1 (en) * 1993-04-13 1994-10-26 Agfa-Gevaert N.V. Processing of silver halide photographic industrial X-ray films
EP0620484B1 (en) * 1993-04-13 1997-02-05 Agfa-Gevaert N.V. Silver halide photographic industrial X-ray films
EP0620482A1 (en) * 1993-04-13 1994-10-19 Agfa-Gevaert N.V. Method of processing forehardened silver halide photographic industrial X-ray films
US5506092A (en) * 1993-12-06 1996-04-09 Konica Corporation Method of processing black and white silver halide photographic compositions with a developer containing an anti sludgant
US5457011A (en) * 1993-12-27 1995-10-10 Eastman Kodak Company Photographic developing composition containing a sludge inhibiting agent and use thereof in the high contrast development of nucleated photographic elements

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1314087A (en) * 1960-12-29 1963-01-04 Gevaert Photo Prod Nv Process for improving the physical properties of photographic material
DE1801330A1 (en) * 1968-10-04 1970-04-23 Eastman Kodak Co Counter-acting diffusion transfer-delaying action of - mercapto tetrazols
JPS495334A (en) * 1972-04-28 1974-01-18
JPS56142529A (en) * 1980-04-07 1981-11-06 Fuji Photo Film Co Ltd Developing method for silver halide photographic sensitive material
JPS5711341A (en) * 1980-06-25 1982-01-21 Fuji Photo Film Co Ltd Photographic sensitive material
JPS5822734A (en) * 1981-08-04 1983-02-10 Nissan Motor Co Ltd Elevational adjustment parcel shelf
JPS58171036A (en) * 1982-03-25 1983-10-07 Konishiroku Photo Ind Co Ltd Formation of photographic image
JPS5968732A (en) * 1982-10-13 1984-04-18 Fuji Photo Film Co Ltd Photosensitive silver halide material
IT1175017B (en) * 1983-09-20 1987-07-01 Minnesota Mining & Mfg DEVELOPMENT COMPOSITIONS FOR PHOTOGRAPHIC MATERIALS WITH SILVER HALIDES

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JPH07119972B2 (en) 1995-12-20
JPS62131252A (en) 1987-06-13
DE3568377D1 (en) 1989-03-30
EP0223883A1 (en) 1987-06-03

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