Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
  • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
  • G03C5/29—Development processes or agents therefor
  • G03C5/305—Additives other than developers
  • G03C5/3053—Tensio-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)

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Publications (2)

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• 1985
  • 1985-11-26 DE DE8585201959T patent/DE3568377D1/de not_active Expired
  • 1985-11-26 EP EP19850201959 patent/EP0223883B1/en not_active Expired
• 1986
  • 1986-11-25 JP JP61280531A patent/JPH07119972B2/ja not_active Expired - Lifetime

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