EP0908764B1 - Verfahren zur Verarbeitung eines photographischen Schwarzweiss-Silberhalogenidmaterials - Google Patents

Verfahren zur Verarbeitung eines photographischen Schwarzweiss-Silberhalogenidmaterials Download PDF

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Publication number
EP0908764B1
EP0908764B1 EP98203116A EP98203116A EP0908764B1 EP 0908764 B1 EP0908764 B1 EP 0908764B1 EP 98203116 A EP98203116 A EP 98203116A EP 98203116 A EP98203116 A EP 98203116A EP 0908764 B1 EP0908764 B1 EP 0908764B1
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EP
European Patent Office
Prior art keywords
fixer
developer
solution
processing
developing
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EP98203116A
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English (en)
French (fr)
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EP0908764A1 (de
Inventor
André c/o Agfa-Gevaert N.V. Roefs
Benedictus Agfa-Gevaert N.V. Jansen
Frank Agfa-Gevaert N.V. Michiels
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Agfa Gevaert NV
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Agfa Gevaert NV
Agfa Gevaert AG
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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
    • G03C5/38—Fixing; Developing-fixing; Hardening-fixing
    • 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
    • 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
    • G03C5/30—Developers
    • 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
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/0051—Tabular grain emulsions
    • G03C1/0053—Tabular grain emulsions with high content of silver chloride
    • 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
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
    • 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
    • G03C5/30—Developers
    • G03C2005/3007—Ascorbic acid
    • 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
    • G03C2200/00—Details
    • G03C2200/44—Details pH value
    • 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
    • G03C2200/00—Details
    • G03C2200/57—Replenishment rate or conditions
    • 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
    • G03C5/16—X-ray, infrared, or ultraviolet ray processes

Definitions

  • the present invention is related with a method of processing a silver halide light-sensitive photographic material without sludge formation in the fixer solution.
  • the processing time in each step including development, fixing, washing (also called “rinsing") and drying should be shortened.
  • a reduction in development time is generally known to be achieved by enhancing the activity of the developer.
  • a developer activating agent e.g. a hydrazine as in EP-A's 0 679 938 - wherein, besides a method of producing a silver halide photographic light-sensitive material it is suggested to process the said material with i.a.
  • a developing solution that may contain ascorbic acid and a fixing solution that may contain a hardener and have a pH in the range of 4.2 to 5.3 - and 0 789 271 -
  • a method for continuously developing, i.a. with an ascorbic acid as a developing agent, of an exposed silver halide photographic material in an automatic processing machine and wherein fixation of said material proceeds in a fixer solution that may contain hardening agents and compounds aluminum-stabilizing ability such as gluconic, tartaric, citric or oxalic acid in a concentration of 0.001 to 0.3 mol/liter, has a pH of 4.0 or more - preferably from 4.5 to 6.0 and may be replenished at a rate of 30 to 320 ml/m 2 ), in order to enhance the activity of the developer makes the cost of processing rise and/or makes preservation stability of the developer decrease.
  • EP-A 0 712 037 illustrates the combined use of an aminopolycarboxylic acid and a polyphosphonic acid sequestering agent in order to prevent aluminum sludging in hardening fixing baths when pH of the fixing solution is raised by an alkaline developer carried over from the developing solution.
  • the fixing solution moreover shows a reduced sulfur dioxide emission because it is able to work at pH values higher than the well-known values within a classical standard pH range of from about 4.0 up to 4.5.
  • Another composition as described in EP-A 0 726 491 makes use of ⁇ -ketocarboxylic acid compounds in order to reduce sulfur dioxide emission.
  • both the developer and the fixer typically contain a hardening agent, with the hardening agent usually being an aldehyde in the developer and an aluminum salt in the fixer.
  • Boric acid is often incorporated in the fixer used in the aforesaid process in order to prevent the formation of sludge resulting from precipitation of aluminum hydroxide when the fixer is contaminated by developer carry-over.
  • Use of boric acid has been described, e.g., in US-A 4,046,570.
  • the hardening fixer composition described in this patent also contains a 1-hydroxy-alkylidene diphosphonic acid, in which the alkylidene group contains from 2 to 5 carbon atoms in order to retard formation of aluminum hydroxide.
  • the 1-hydroxyalkylidene diphosphonic acid partially or completely replaces boric acid in the hardening fixer composition.
  • Japanese Patent Application 05/323 525 describes a black-and-white fixer solution comprising aminopolycarboxylic acids and/or phosphonic acids as chelating agent, preventing the water fur and odour.
  • the fixer composition is substantially free from ammonium ions and substantially free from aluminum hardener, the amount of the hardener being lower than 0.1 mole/l, which is the minimum amount known in the art to give the fixer composition a hardening activity, as has been described e.g. in Research Disclosure 16768 and in US-A 4,046,570.
  • ammonium thiosulfate acts more rapidly than its alternatives such as sodium thiosulfate, as has been described in GB 1,290,026.
  • a particularly desirable fixer is the one which contains ammonium thiosulfate and which is free from boric acid.
  • crystals are deposited from the fixer on the walls of the fixer tank and on the roller assemblies.
  • the crystalline deposit displays a tendency to absorb additional fixer, thereby resulting in movement of "creep" along processor parts and tank walls.
  • Research Disclosure 18728 discloses a number of agents incorporated in the hardening fixer solution which suppress crystal formation.
  • Useful agents are, for example, aminopolyphosphonic acids, such as diethylenetriaminepenta-methylenephosphonic acid, and aminopolycarboxylic acids, such as 1,3-diamino-2-propanol tetraacetic acid.
  • EP-A 0 486 909 describes a fixing bath free from ammonium ions containing as a complexing agent, e.g., nitrilodiacetic monopropionic acid, useful in the processing of silver halide photographic materials.
  • the bath exhibits good fixing speed and no deposition.
  • the fixer used in US-A 5,300,405 has a pH value generally controlled at a pH of 4.6 or higher, preferably a pH from 4.6 to 6.0, and still more preferably from pH 4.7 to 5.5 as measured in running equilibrium conditions. Minimized odour thereby escapes from the fixer solution and provides minimized corrosion of the processing equipment and the surrounding environment. Since the fixer has a relatively weak hardening effect, increased drying loads are imposed on the photosensitive material being processed therewith. Even so, that invention makes use of a sophisticated drying process as defined above, accomplishing effective drying while eliminating locally uneven drying and drying marks.
  • the pH of common fixer solutions is normally in the range from 4.00-4.50, because at a higher pH value, especially more than 5.00, Al(OH) 3 becomes precipitated.
  • a lower pH value is correlated with an undesired odour of environmentally unwanted sulfur dioxide due to decomposition of sulfites present in the fixer solution at the said lower pH values.
  • Still a further object of the present invention is to provide an environmentally and toxicologically friendly method of processing without deterioration of drying properties of films.
  • a method of processing an exposed black-and-white silver halide light-sensitive photographic material comprising the steps of developing in a developer solution, followed by fixing in a fixer solution, comprising a water-soluble aluminum compound as a hardening agent and buffering compounds, present in a concentration of from 0.2 up to 0.8 mol per litre, said fixer solution being free from an ⁇ -ketocarboxylic acid compound and from any boron compound and wherein, in running equilibrium conditions, said fixer solution has a pH of from 4.6 to 5.5 , further adding to said fixer a fixer replenisher at a rate of from 0 ml/m 2 up to 300 ml/m 2 ; said fixing step followed by rinsing and drying, wherein rinsing between developing and fixing is excluded; wherein a compound having an ⁇ -ketocarboxylic acid structure in an amount from 0 to 3 g per litre is present in the said fixer replenisher; characterized in that said developing step is performed in
  • a developer replenisher having a higher pH value (in an amount of at least 0.5) than its development starting solution has been described in US-A 5,503,965.
  • Addition of starter to developer replenisher in order to reduce pH drop to a value of 0.2 or less has further been described in JP-A 05-289254.
  • Starter tablets and chemical compositions thereof have been described in JP-A 04-032839.
  • JP-A 06-250350 Descriptions of processing methods wherein a starter solution is added to the fixing solution can be found in JP-A 06-250350.
  • JP-A 06-230527 a method for rapid processing a black-and-white silver halide material in an automatic processing machine is disclosed, wherein the fixer replenisher has a higher thiosulfate concentration than the fresh fixer.
  • Addition of a basic starter such as alkali metal hydroxides or carbonates has been described in JP-A 03-068937.
  • Electrolysis can proceed for example by passing the fixer around a circulation loop which includes an electrolytic cell. Electrolytic removal of silver also has the benefit of enabling a lower regeneration rate of fixer to be used. This is fully consistent with recent trends to reduce the volume of treatment liquids used in photographic processing. Electrolysis of the fixer solution, known as most efficient method of chemical recovery of the said fixer solution in order to reduce the slow down effect on fixation rate of increasing amounts of silver ions present in the fixer, however makes pH and sulfite ion concentration decrease.
  • a solution has been proposed as disclosed in EP-A 0_851 286.
  • a method of processing in a processor an image-wise exposed light-sensitive silver halide photographic material is proposed therein, comprising the steps of developing in a developing solution and fixing in a fixer solution, characterized in that upon starting of the processing the said fixer solution comprises a mixture of a fixer starter solution and a fixer replenisher solution and in that said fixer solution is replenished with the said fixer replenishing solution.
  • the particular combination of a developer and a fixer containing aluminum in particular when the pH value of that fixer is increased with respect to the common pH range (4.0 to less than 4.5) wherein said fixer is used at a pH value of from 4.6 up to 5.5 and preferably from 4.8 up to 5.3, admits the use of a decreased amount of fixer replenisher, wherein even the absence of a fixer replenisher is not excluded, even in the absence at the start of the processing of boron compounds in the said fixer.
  • This formula corresponds with (iso)ascorbic acid.
  • iso-ascorbic acid and 1-ascorbic acid are both preferred.
  • the compound(s) according to the formula (I) is(are) present in the developer solution in an amount comprised between 5 g and 100 g per litre, although a preferred amount of from 20 up to 50 g per litre is sufficient in many cases.
  • reducing precursor compounds have, e.g., been described in WO's 94/3834 and 94/16362.
  • ascorbic acid is not merely used in the developer as an antioxidant as, e.g., described in WO 93/12463, in JP-A's 4428673 and 55149936, in GB 1,266,533 and in US-A's 3,865,591; 4,756,997 and 4,839,259 and in the literature as, e.g., J. Am. Chem. Soc., 60 (1938), p. 99 and p. 2084; 61 (1939), p. 442; 64 (1942), p. 1561, 65 (1943), p. 1489; 66 (1944), p. 700 and 104 (1982), p. 6273.
  • said method comprises the step of developing in a developing solution, wherein said solution comprises one or more developing agents.
  • a developing solution comprises one or more developing agents.
  • a preferred phenidone compound used in the method of the present invention is 4,4'-hydroxymethyl-methyl-pyrazolidine-3-one, which is present in amounts of from 0.5 g up to 5 g/litre of developer.
  • said preferred phenidone compound is present in lower amounts as has been disclosed in US-A 5,296,342.
  • said developer is substantially free from any polyhydroxybenzene compound, as e.g. hydroquinone, analogues and/or derivatives therefrom.
  • said developer is substantially free from any hardening agent.
  • said developer solution is free from any boron compound.
  • the method according to the present invention permits use of lower replenisher amounts and even permits the absence thereof.
  • the further advantage of a lower emission level of sulfur dioxide vapours, thus reducing disagreable smell is observed.
  • a fixer replenisher if present, should have a lower pH than the fixer itself in so-called “running equilibrium conditions” in order to compensate for "carry-over" of the alkaline developer to the fixing tank.
  • the pH values in those so-called “running equilibrium conditions” are in the range from 4.6 up to 5.5, and more preferably from 4.8 up to 5.3. This means that at the start of processing said fresh fixer may have a lower pH than 4.6; e.g. in the common range between 4.0 and 4.5.
  • the fixer replenisher should not be extremely low in pH and should preferably be in the pH range from e.g. 4.4 up to 4.9. This pH range makes it unnecessary to separate a part mainly containing a thiosulfate and a part mainly containing an aluminum salt hardener: a single part concentrated replenisher can be used without disadvantages.
  • the fixer replenisher if present, is preferably supplied at a rate of from 50 ml/m 2 up to 300 ml/m 2 , more preferably at a rate of from 50 ml/m 2 up to 150 ml/m 2 and still more preferably from 50 ml/m 2 up to 100 ml/m 2 in running equilibrium conditions.
  • the term "replenishing equilibrium conditions” refers to the condition attained after replacement of a volume equivalent with three times the total tank volume.
  • the term “running equilibrium conditions” refers to the moment the processing solution is exhausted, thus requiring exchange of the said processing solution.
  • the present invention is advantageously applicable to such a reduced replenishment mode and doesn't exclude the absence of a fixer replenisher, especially when, according to the present invention, pH in the fixer solution in running equilibrium conditions is between a value of from 4.6 up to 5.5 and buffering compounds are present in a concentration of from 0.2 up to 0.8 mole per litre and more preferably in a concentration of from 0.3 up to 0.6 mole per litre.
  • buffering compounds in the fixer solution are formed by acetic acid and sodium acetate, forming an acetate buffer.
  • pH in said developer solution is buffered between a value of from 9.0 up to 11.0 by buffering compounds having a concentration of from 0.3 up to 1.0 mole/litre and more preferably from 0.3 up to 0.7 mole/litre.
  • buffering compounds having a concentration of from 0.3 up to 1.0 mole/litre and more preferably from 0.3 up to 0.7 mole/litre.
  • Particularly suitable buffering compounds in the developing solution are carbonates as has also been shown in EP-A 0 565 459 wherein the use of ascorbic acid developers with high concentrations of carbonate buffering is illustrated.
  • the high carbonate level provides a high degree of pH buffering and also provides aeration protection via reduced oxygen solubility in the developing solution.
  • Use of highly buffered ascorbic acid developers has been disclosed e.g.
  • the method of the present invention is particularly applicable when no compound having an ⁇ -ketocarboxylic acid structure is present in the fixer solution, whereas in the fixer replenisher solution, if present, it is present in an amount of from 0 to 3 g per litre.
  • Preferred compounds having such a having an ⁇ -ketocarboxylic acid structure are e.g. oxalic acid, tartaric acid, citric acid, gluconic acid or derivatives thereof in amounts of not more than 3 g per litre at the start of the processing. More preferably the fixer is free from those compounds at the start of the processing. This should be considered as a particular advantage offered by the method of the present invention, especially from the viewpoint of cost price of the processing solutions, as even without the presence of those compounds the object of the present invention to avoid sludge formation is fully attainable.
  • a developer replenisher is preferably supplied at a rate of from 50 ml/m 2 up to 300 ml/m 2 , more preferably at a rate of from 50 ml/m 2 up to 150 ml/m 2 and still more preferably up to 100 ml/m 2 .
  • This reduced replenishing rate is particularly preferred when the developing solution is highly buffered as set forth hereinbefore.
  • the fixer contains a water-soluble aluminum salt as a hardener.
  • aluminum salt hardeners include aluminium chloride, aluminium sulfate and potassium aluminum.
  • the hardener is preferably added in an amount of from 0.01 to 0.2 mole/litre, more preferably 0.03 to 0.08 mole/litre.
  • the fixer contains as preservatives e.g. sulfites and bisulfites, wherein thanks to the preferred pH working range irritating smell or unagreable odour is avoided to a large extent.
  • Further pH adjusting agents as e.g. sulfuric acid and chelating agents are desired.
  • the photosensitive material is processed with washing water or with a stabilizing solution which may be replenished at a rate of up to 3 litres per square meter of the photosensitive material (inclusive of 0, indicating batchwise tank water).
  • a stabilizing solution which may be replenished at a rate of up to 3 litres per square meter of the photosensitive material (inclusive of 0, indicating batchwise tank water).
  • any suitable means for reducing the amount of a washing water replenished can be applied to the invention.
  • One such well-known means is a multistage (e.g. two or three stage) counter-flow system. This system accomplishes efficient washing since the photosensitive material after fixation comes into contact with a series of clearer washing water portions, that is, water portions which are less contaminated with the fixer as the photo-sensitive material proceeds forward.
  • anti-bacterial means is preferably applied to washing water or stabilizing solution.
  • the anti-bacterial means includes irradiation of ultraviolet radiation as disclosed in JP-A 263939 /1985; application of a magnetic field as disclosed in JP-A 263940/1985; blowing of ozone as described in Somiya ed., "Ozone Utilizing Treatment", Kogai Taisaku Gijutu Doyukai, 1989, the methods disclosed in Japanese Patent Application Nos.
  • washing is done with a smaller amount of water in the practice of the present invention, it is preferred to place squeeze roller washing tanks as disclosed in JP-A 18350/1988 or to employ a washing arrangement as disclosed in JP-A 143548/1988.
  • Overflow solution exits from the washing or stabilizing bath as water having any anti-bacterial means applied thereto is replenished with the progress of processing.
  • Part or all of the overflow solution may be used as a processing solution having a fixing function in the preceding step as disclosed in JP-A 235133/1985.
  • the overall process from development to drying should preferably be completed within 90 seconds. More specifically, the time taken from the start point of time when the leading edge of a photosensitive material film or sheet enters the developer, past the fixing, washing (or stabilizing) and drying steps, to the end point of time when the leading edge exits the drying section, which is known as a dry-to-dry time, proceeds within a total processing time of from 30 up to 90 seconds, and more preferably from 35 up to 75 seconds. Comparable desired total processing times have e.g. been set forth in EP-A's 0 678 772, 0 709 730, 0 712 034 and 0 712 036.
  • Developing process time or “developing time” is a duration taken from the point when the leading edge of a photosensitive material is dipped in the developing tank liquid in the processor to the point when it is subsequently dipped in the fixer.
  • Fixing time is a duration taken from the point when the leading edge is dipped in the fixing tank liquid to the point when it is dipped in the washing tank liquid (or stabilizer).
  • Washing time is a duration when the photosensitive material is dipped in the washing tank liquid.
  • Drying time is a duration when the photosensitive material passes through the drying section where hot air at 35° to 100° C, preferably 40° to 80° C, is usually blown.
  • the developing time is generally within 30 seconds, preferably within 25 seconds while the developing temperature ranges from 25° to 50° C, preferably from 30° to 40° C.
  • the fixing time generally ranges from 5 to 20 seconds at temperatures of about 20° to 50° C, preferably from 5 to 15 seconds at temperatures of about 30° to 40° C. Within this range, full fixation is done and the sensitising dye can be leached out to such an extent that no residual colour is left.
  • the time For water washing or stabilizing bath, the time generally ranges from 4 to 20 seconds at temperatures of 0° to 50° C, preferably from 4 to 15 seconds at temperatures of 15° to 40° C.
  • fixer contains a sulfite salt to stabilize the thiosulfate against decomposition with respect to time and temperature.
  • a particularly desirable fixer is one which contains ammonium thiosulfate and a sulfite salt.
  • the sulfite-complexing agent may be an aldehyde e.g., glutaraldehyde, ketone, e.g., acetone, or any compound which forms a relatively stable sulfite complex in aqueous solution in the pH range from 3.0 to 6.0.
  • Japanese Patent Application No. 05-119445 describes a fixer for photographic materials containing specified amounts of ammonium thiosulfate and of sodium thiosulfate which do not generate toxic gases during processing. Japanese Patent Application No.
  • 04-019739 describes a solid fixer for silver halide photographic material containing thiosulphate and sulphite and, opposite to the present invention at the start, at least one of citric , tartaric, maleic, succinic and phenyl acetic acids to prevent sulphur dioxide gas generation just as in EP-A 0 726 491 A1 mentioned above, wherein use of ⁇ -ketocarboxylic acids is described as useful in order to decrease the smell of the fixer solution during processing.
  • Japanese Patent Application No. 05-313,320 describes a fixing liquid containing thiosulfate in concentrated state and diluted at time of use to prevent bad odours from being given off.
  • a fixer composition comprising fixing agents, stabilizing, hardening agents and acids, e.g., succinic or maleic acid, has been disclosed in Japanese Patent Application No. 05-127,323.
  • the apparatus for the processing of photographic material according to the method of the present invention may comprise a plurality of treatment vessels including a developing vessel and a fixing vessel, the apparatus including means for feeding photographic material to be processed along a photographic material path through the developing vessel and the fixing vessel in turn, and an electrolytic cell for removing silver ions from fixer in the fixing vessel.
  • the treatment vessels may be positioned one above the other in a vertical configuration.
  • the developing vessel may be positioned above the fixing vessel. If more than one fixing vessel is present the first fixing vessel may in turn be positioned above the second fixing vessel. This configuration is preferred, in order to prevent fixer from entering the developing vessel. However in such an arrangement, a pump will be required to transfer used fixer upwardly into the first fixing vessel.
  • the vessels may be positioned side by side in an essentially horizontal configuration, especially where fixing vessels, if more than one is present, have a cascade relationship.
  • An electrolytic silver recovery cell may be of known construction.
  • the cell comprises a cylindrical housing fitted with a central anode surrounded by a removable cathode.
  • the housing has inlets and outlets for the liquid to be de-silvered.
  • a glass reference electrode enables control of the de-silvering process, which is carried out either at constant potential, at constant current or according to some other control regime.
  • silver is deposited and builds up on the cathode.
  • the cathode is periodically replaced.
  • Silver can be recovered from the used cathode in a known manner, and usually the cathode can be re-used.
  • the silver recovery cell may be an electrolysis unit from an "ECORAP” processor (trade mark product from Agfa-Gevaert NV) or a Curix "EOSFIX” electrolysis unit (trade marketed product from Agfa-Gevaert NV).
  • An apparatus for the electrolytic recovery of silver from solutions containing silver is known from EP-A 0 611 838 and from EP-A 0 757 120.
  • the fixer is desilvered electrolytically, it may even be possible to use aluminum as (part of the) anode material in the electrolysis unit. Desilvering of the fixer then results in the liberation of aluminum ions due to anodic oxidation, thus providing the hardening component in the fixer.
  • the photographic material is then treated with the first fixer liquid for a period of time less than half that of the fixer treatment time, most preferably less than 25 % that of the fixer treatment time.
  • Treatment with the first fixer liquid for a relatively short period of time can most easily be achieved by providing a shorter photographic material transport path through the intermediate treatment liquid, for example by providing the intermediate treatment liquid in an intermediate vessel having a path length less than that of the vessel containing the fixer, thereby enabling the photographic material to pass through the apparatus at a constant speed.
  • One or more fixing vessels in the method of the present invention are regenerated by addition thereto of replenisher solution.
  • sheet materials such as (medical and industrial) X-ray film materials, pre-sensitized plates, graphic art films and paper, offset plates, can be processed.
  • an X-ray film material is processed according to the method of the present invention.
  • any film for medical diagnostic imaging may be processed, wherein said film may be exposed with a laser directed by digitized data obtained after conversion of information captured by suitable means after exposure to radiation of part of the human body as described e.g.
  • said film may comprise cubic and/or tabular silver halide crystals as described e.g. in EP-Applications Nos. said film and wherein said film may comprise cubic and/or tabular silver halide crystals as described e.g. in EP- A 's 0 862 088 and 0 862 083 and in EP-A 0 890 873.
  • the said materials are composed of at least one light-sensitive silver halide emulsion layer comprising emulsion crystals rich in silver chloride. More preferably said emulsion crystals rich in silver chloride are ⁇ 100 ⁇ cubic or ⁇ 111 ⁇ or ⁇ 100 ⁇ tabular crystals.
  • the materials are X-ray materials, wherein the said X-ray materials are single-side or double-side coated materials.
  • the method comprises the steps of developing, fixing, rinsing and drying, wherein the total processing time of these steps is from 30 up to 90 seconds as set forth hereinbefore.
  • a time of 300 seconds is however required for processing of e.g. industrial X-ray films coated with huge amounts of silver as has e.g. been described in EP-A's 0 620 482, 0 620 483, 0 620 484, 0 621 506, 0 622 668 and in 0 698 817.
  • Developer composition A potassium sulfite 63.9 g ethylene diamine tetra acetic acid (tetra-sodium salt) 2.1 g hydroxyethyl diphosphonic acid (di-sodium salt) 1.0 g diethylene glycol 45.9 g potassium carbonate 30.6 g hydroquinone 29.25 g methyl benzotriazole (mixture of 4- and 5- derivative) 90 mg 1-phenyl-5-mercaptotetrazole 7 mg potassium hydroxide 54 0 g 1-phenyl-pyrazolidine-3-one 1.10 g 5-nitro-indazole 125 mg acetic acid 8.32 g glutardialdehyde 4.9 g potassium metabisulfite 7.5 g Addition of water up to a volume of 1 litre.
  • Example 2 Influence of replenishing amounts on the appearance of precipitation.
  • the developer solution A and the fixer solution A were used.
  • the experiments were performed at standard regeneration rates of 600 ml per square metre of film for the developer.
  • the experiment was performed using the standard regeneration rate for the fixer (750 ml/m 2 ) in one case and without replenishment of the fixer fluid in the other case.
  • Example 3 Influence of buffering of developer solution on pH increase of the fixer solution.
  • Example 4 Appearance of aluminum sludging depending on the developing substance.
  • Example 5 Difference between fresh and oxidized developer solutions.
  • the experiments were performed using a slightly modified Curix 60 automatic developing machine (trademarked product from Agfa Gevaert), using CURIX Ortho HTH film (also trademarked product from Agfa-Gevaert) exposed up to 30 % of the total film surface.
  • the developing solutions A and D and the fixing solution A were used.
  • the experiments were performed at standard replenishment rates of 600 ml /m 2 for the developer.
  • the experiment was performed in one case making use of the standard replenishment rate for the fixer (750 ml/m 2 ) and in the other case without replenishment of the fixer.
  • 525 m 2 of film was processed in 5 blocks of 1,05 m 2 .
  • the seasoned fixer when using developer D moreover clearly shows less unagreable smell or odour than the seasoned fixer used in combination with developer A comprising hydroquinone as a developing agent.
  • Example 7 Processing of a silver halide material having emulsion grains rich in silver chloride.
  • a nucleation step was performed by introducing solution A and solution B1 simultaneously in dispersion medium C both at a flow rate of 30 ml/min during 30 seconds. After a physical ripening time of 15 min. during which the temperature was raised to 70 °C and 97.5 g of gelatin and 1500 ml of water were added and the mixture was stirred for an additional 5 minutes.
  • a growth step was performed by introducing by a double jet during 66 minutes solution A starting at a flow rate of 7.5 ml/min and linearly increasing the flow rate to an end value of 37.5 ml/min, and solution B1 at an increasing flow rate in order to maintain a constant mV-value, measured by a silver electrode versus a saturated calomel electrode (S.C.E.), of +92 mV.
  • S.C.E. saturated calomel electrode
  • the average diameter "d EM ", average thickness "t”, and average aspect ratio “AR” were obtained from electron microscopic photographs: the diameter of the grain was defined as the diameter of the circle having an area equal to the projected area of the grain as viewed in the said photographs.
  • the average sphere equivalent diameter d EM obtained from the measurement of electric reduction currents obtained by reduction of a silver halide grain with a microscopically fine electrode is given: the sphere equivalent diameter was defined as the diameter of a hypothetical spherical grain with the same volume as the corresponding tabular grain. So a value for "dEM” of 1.27 ⁇ m, a value for "t” of 0.14 ⁇ m and for "AR” of 8.8 was found.
  • Ripening agents causing a different composition of the ripening solutions used were: tetramethyl seleno ureum as a source of selenium and sodium thiosulphate as a source of sulfur. Further chemical ripening agents were gold thiocyanate and toluene thiosulphonic acid was used as predigestion agent. Amounts of chemical ripening agents were optimized in order to obtain an optimal fog-sensitivity relationship after 2 hours at 57°C.
  • the emulsion was stabilized with 1-p-carboxyphenyl-5-mercaptotetrazole and after addition of the normal coating additives the solutions were coated simultaneously together with a protective layer containing 1.3 g gelatin per m 2 per side on both sides of a polyethylene terephthalate film support having a thickness of 175 ⁇ m.
  • the resulting photographic material was containing an amount of silver halide corresponding to 4.5 grams of AgNO 3 per m 2 and an amount of gelatin corresponding to 3.55 g/m 2 each expressed per side of the support.
  • Samples of these coatings A, B and C were exposed with green light of 540 nm during 0.1 seconds using a continuous wedge.
  • the density as a function of the light dose was measured and therefrom were determined the following parameters:

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

Claims (10)

  1. Verarbeitungsverfahren für belichtetes lichtempfindliches schwarzweissfotografisches Silberhalogenidmaterial mit den Schritten
    Entwickeln in einer Entwicklerlösung, und anschließendes
    Fixieren in einer Fixierlösung, die ein wasserlösliches Aluminiumsalz als Härtemittel sowie Pufferverbindungen in einer Konzentration von 0,2 bis 0,8 mol pro ℓ enthält, wobei die Fixierlösung frei von einer α-Ketocarbonsäurenverbindung und von irgendeiner Borverbindung ist und bei Gleichgewichtsbetriebsbedingungen einen pH-Wert von 4,6 bis 5,5 aufweist, zusätzliches Zumischen zum Fixiermittel einer Fixiermittelnachfülllösung mit einer Quote von 0 ml/m2 bis 300 ml/m2;
    wobei sich an den Fixierschritt folgende Schritte anschließen
    Spülen und
    Trocknen,
    wobei Spülen zwischen Entwickeln und Fixieren ausgeschlossen ist;
    wobei in der Fixiermittelnachfülllösung eine Verbindung mit einer α-Ketocarbonsäurenstruktur in einer Menge von 0 bis 3 g pro ℓ enthalten ist,
    dadurch gekennzeichnet, dass der Entwickelschritt in einem Entwickler, der eine der nachstehenden Formel (I) entsprechende Entwicklersubstanz, deren Vorläufer und/oder deren Metallsalz in einer Menge von 5 g bis 100 g pro ℓ enthält, durchgeführt wird
    Figure 00410001
    in der A, B und D einzeln je ein Sauerstoffatom oder NR1;
    X ein Sauerstoffatom, ein Schwefelatom, NR2; CR3R4 ; C=O; C=NR5 oder C=S;
    Y ein Sauerstoffatom, ein Schwefelatom, NR'2; CR'3R'4; C=O; C=NR'5 oder C=S;
    Z ein Sauerstoffatom, ein Schwefelatom, NR"2; CR"3R"4 ; C=O; C=NR"5 oder C=S
    bedeuten;
    n gleich 0, 1 oder 2;
    R1 bis R5, R'2 bis R'5 und R"2 bis R"5 einzeln je ein Wasserstoffatom, eine Alkyl-, Aralkyl-, Hydroxyalkyl-, Carboxyalkyl-, Alkenyl-, Alkynyl-, Cycloalkyl-, Cycloalkenyl-, Aryl- oder Heterocyclyl-Gruppe bedeuten; wobei R3 und R4, R'3 und R'4, R"3 und R"4 zusammen zusätzlich einen Ring bilden können; und wobei bei X = CR3R4 und Y = CR'3CR'4, R3 und R'3 und/oder R4 und R'4 einen Ring bilden können, und bei Y = CR'3R'4, Z = CR"3CR"4 und n = 1 oder 2, R3 und R'3 und/oder R4 und R'4 einen Ring bilden können.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass in der Formel (I) A, B und X je ein Sauerstoffatom bedeuten; n = 0; Y = CH-(CHOH)m-CH2-R6, in der m = 1, 2, 3 oder 4, und in der bei m = 1 R6 OH bedeutet und bei m = 2, 3 oder 4 R6 H oder OH bedeutet.
  3. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass in der Formel (I) A und B je ein Sauerstoffatom bedeuten, n = 0, und X und Y je C(CH3)2 bedeuten.
  4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass der Entwickler im wesentlichen frei von irgendeiner Polyhydroxybenzolverbindung ist.
  5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass die Entwicklerlösung frei von irgendeiner Borverbindung ist.
  6. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass der pH-Wert in der Entwicklerlösung unter Verwendung von Pufferverbindungen in einer Konzentration von 0,3 bis 1,0 mol/ℓ zwischen 9,0 und 11,0 gepuffert wird.
  7. Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass der pH-Wert in der Fixierlösung bei Gleichgewichtsbetriebsbedingungen zwischen 4,8 und 5,3 liegt.
  8. Verfahren nach einem der Ansprüche 1 bis 7, wobei dem Entwickler zusätzlich eine Entwicklernachfülllösung mit einer Quote von 50 ml/m2 bis 300 ml/m2 zugemischt wird.
  9. Verfahren nach einem der Ansprüche 1 bis 8, wobei dem Fixiermittel zusätzlich eine Fixiermittelnachfülllösung mit einer Quote von 50 ml/m2 bis 250 ml/m2 zugemischt wird.
  10. Verfahren nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, dass die Verarbeitung in einer Gesamtverarbeitungszeit von 35 bis 75 s durchgeführt wird.
EP98203116A 1997-10-06 1998-09-16 Verfahren zur Verarbeitung eines photographischen Schwarzweiss-Silberhalogenidmaterials Expired - Lifetime EP0908764B1 (de)

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DE102006026422A1 (de) * 2006-06-04 2007-12-06 Orochemie Dürr + Pflug GmbH & Co.KG Entwicklerkonzentrat
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US5582966A (en) * 1994-04-27 1996-12-10 Konica Corporation Method for producing a silver halide photographic light-sensitive material
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EP0789271A1 (de) * 1996-02-07 1997-08-13 Fuji Photo Film Co., Ltd. Verfahren zur Entwicklungsbehandlung photographischer Silberhalogenidmaterialien
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