EP0584665A2 - Solutions de traitement pour matériaux photographiques à l'halogénure d'argent - Google Patents

Solutions de traitement pour matériaux photographiques à l'halogénure d'argent Download PDF

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Publication number
EP0584665A2
EP0584665A2 EP93112951A EP93112951A EP0584665A2 EP 0584665 A2 EP0584665 A2 EP 0584665A2 EP 93112951 A EP93112951 A EP 93112951A EP 93112951 A EP93112951 A EP 93112951A EP 0584665 A2 EP0584665 A2 EP 0584665A2
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EP
European Patent Office
Prior art keywords
represent
solution
processing
bleach
processing solution
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP93112951A
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German (de)
English (en)
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EP0584665A3 (en
Inventor
Kenji Kuwae
Yutaka Ueda
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Konica Minolta Inc
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Konica Minolta Inc
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Publication of EP0584665A2 publication Critical patent/EP0584665A2/fr
Publication of EP0584665A3 publication Critical patent/EP0584665A3/en
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    • 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
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/407—Development processes or agents therefor
    • G03C7/413—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
    • 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
    • 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
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/3046—Processing baths not provided for elsewhere, e.g. final or intermediate washings
    • 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
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/42—Bleach-fixing or agents therefor ; Desilvering processes
    • 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
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/42—Bleach-fixing or agents therefor ; Desilvering processes
    • G03C7/421—Additives other than bleaching or fixing agents

Definitions

  • the present invention relates to improvements in a processing solution for processing exposed silver halide photographic light-sensitive materials. More particularly, the present invention relates to a photographic processing solution for silver halide photographic light-sensitive materials containing a new photographic chelating agent for the purpose of sequestering metal ions which exert adverse effects or using the chelating agent as a bleaching agent.
  • processing solutions used in such processes contain a variety of components; therefore, when water used for the preparation of the relevant solutions contains metal ions such as calcium, magnesium or iron ions, the components in the solution react with such metal ions to form precipitates or sludges, causing troubles such as clogging of the filter mounted on an automatic processor and staining on a light-sensitive material under processing due to adhesion of these deposits.
  • metal ions such as calcium, magnesium or iron ions
  • chelating agent for sequestering the metal ions to a photographic processing composition.
  • chelating agents include polyphosphates such as sodium hexametaphosphate proposed in British Pat. No. 520,593, alkylidene diphosphonic acids proposed in U.S. Pat. No. 3,214,454, and aminopolycarboxylic acids represented by aminopolymethylene phosphonic acids and ethylenediaminetetraacetic acid proposed in U.S. Pat. No. 3,201,246.
  • polyphosphates are low in capabilities of blocking metal ions, particularly poor in blocking heavy metal ions and therefore cannot be put into practical use.
  • the alkylidene diphosphonic acids have a problem of forming solid precipitates and thereby impairing automatic processors when a calcium ion and a sodium ion coexist at a certain concentration or above.
  • the conventional aminopolycarboxylic acids represented by ethylenediaminetetraacetic acid and aminopolymethylenephosphonic acid represented by aminotrimethylenephosphonic acid though high in metal ion blocking capabilities, have problems that when used in a color developer containing hydroxylamine, they decompose the hydroxylamine in the presence of the metal ion and thereby cause fogs on a light-sensitive material processed in the color developer, and that when used in a black-and-white developer, they accelerate oxidation and degrade storage stability of developing agents, which causes heavy fogs on a high-sensitivity photographic film.
  • the chelating agents proposed up to the present more or less have disadvantages and cannot necessarily produce satisfactory results when used in a photographic processing composition. Further, with the recent tendency to decrease a replenishing amount of photographic processing solutions due to socio-environmental requirements toward lower pollution as well as economical requirements toward lower processing costs, the amount of metal ions including a calciumion, which are dissolved out while processing photographic light-sensitive materials and accumulated in the processing solutions, is increasing steadily.
  • the above aminopolycarboxylic acids are widely used in large amounts, in the form of metal complex salts, in bleaches and bleach-fixers as bleaching agents to remove image silver.
  • the metal complex salts of the above aminopolycarboxylic acids include a ferric complex salt of ethylenediaminetetraacetic acid, a ferric complex salt of 1,3-propylenediaminetetraacetic acid, and a ferric complex salt of diethylenetriaminepentaacetic acid.
  • the ferric complex salt of 1,3-propylenediaminetetraacetic acid have a high oxidizing power, so that this is used in bleaches particularly for rapid processing of high-sensitive silver halide color photographic light-sensitive materials.
  • the ferric complex salt of 1,3-propylenediaminetetraacetic acid has a disadvantage attributable to the high oxidizing power; that is, this salt oxidizes a color developing agent brought from the preceding bath and enable it to form dyes through coupling with unreacted couplers in a light-sensitive material, causing the so-called bleach fogging.
  • the ferric complex salt of ethylenediaminetetraacetic acid though inferior to the ferric complex salt of 1,3-polypylenediaminetetraacetic acid in oxidizing power, is widely used as a bleaching agent in the bleach-fixing process which carries out bleaching and fixing in a single bath, for purposes of simplifying the process and performing the processing rapidly.
  • the oxidizing agent decomposes the thiosulfate ion to sulfur by oxidation.
  • a bleach-fixer usually contains a sulfite ion as a preservative.
  • ferric complex salt of ethylenediaminetetraacetic acid when used in a bleach-fixing bath, the complex salt always keeps the ferric state in the bath because of very fast oxidation speed from the ferrous state to the ferric state, and continues decomposing the sulfite ion used as a preservative. As a result, the oxidation of the thiosulfate ion to sulfur is accelerated, lowering the preservability of the processing solution.
  • Japanese Pat. O.P.I. Pub. Nos. 149358/1984, 151154/1984 and 166977/1984 disclose techniques which use ferric complex salt of diethylenetriaminepentaacetic acid.
  • Bleach-fixers based on these techniques are certainly superior in solution preservability to those using a ferric complex salt of ethylenediaminetetraacetic acid. But, when color paper is processed using a ferric complex salt of diethylenetriaminepentaacetic acid, stains are often observed at the edges of the paper, and a trouble called edge penetration is liable to occur.
  • a first object of the present invention is to provide a processing solution with bleaching capability for a silver halide photographic light-sensitive material which is excellent in rapid desilverizing capability, less in fogging in edge portions and high in solution preservability.
  • a second object of the present invention is to provide a processing solution for a silver halide photographic light-sensitive material which can give a stable processing bath free from formation of precipitates or sludges caused by metal ions present therein.
  • a third object of the present invention is to provide a processing solution for a silver halide photographic light-sensitive material which allows stable processing over a long period and causes no filter clogging when used in processing with an automatic processor.
  • a fourth object of the present invention is to provide a processing solution for a silver halide photographic light-sensitive material which is excellent in biodegradability and thereby fits for global environmental protection.
  • a 1 to A4 may be the same or different and each represent -COOM 1 , -OH, -PO 3 M 1 M 2 or -CONH 2 .
  • M 1 and M 2 each represent a hydrogen ion, an alkali metal ion such as a sodium, potassium or lithium ion, or another cation such as an ammonium, methylammonium or tetramethylammonium ion.
  • n 1 to n 4 each represent an integer of 0 to 2 and may be the same or different, but preferably n 1 is zero and n 3 is zero.
  • X represents a substituted or unsubstituted alkylene group of 2 to 6 carbon atoms or -(B 1 O) m -B 2 -, in which B 1 and B 2 may be the same or different and each represent a substituted or unsubstituted alkylene group of 1 to 5 carbon atoms.
  • the alkylene group represented by X includes an ethylene, trimethylene and tetramethylene group; the alkylene group represented by B 1 or B 2 includes a methylene, ethylene and trimethylene group.
  • the substituent of the alkylene group represented by X, B 1 or B 2 includes a hydroxyl group and an alkyl group of 1 to 3 carbon atoms such as a methyl or ethyl group.
  • m is an integer of 1 to 4, and preferably 1 to 2.
  • Exemplified compound A-1 was synthesized by the method described in Bulletin of the chemical society of Japan, Vol. 46,844 (1973).
  • Exemplified compound A-2 was synthesized by the following method with reference to Inorganic Chemistry Vol. 7,2405 (1968).
  • the precipitate thus obtained was dissolved in an aqueous solution of sodium hydroxide and adjusted to pH 3.0 by adding 6N hydrochloric acid to precipitate crystal to be purified.
  • the crystal was washed with water, ethanol and ether and then was dried for 5 hours at 60 ° C under reduced pressure.
  • the yield was 96 g (30%), and the structure thereof was checked by means of NMR, IR and mass-spectra.
  • the bleach or the bleach-fixer contain the compound represented by formula (A) in the form of a ferric complex salt.
  • the addition amount of the compound to the processing solution having bleaching capability is preferably 0.05 to 2.0 moles per liter, more preferably 0.1 to 1.0 mole per liter.
  • the bleach or the bleach-fixer according to the invention may contain ferric complex salts of the following compounds besides ferric complex salts of the compound represented by formula (A):
  • organic acid ferric complex salts are used in an amount of preferably 0.05 to 2.0 moles, more preferably 0.1 to 1.5 mole per liter of bleach or bleach-fixer.
  • the rapid processing capability of the bleach or the bleach-fixer can be enhanced by adding thereto at least one of the compounds selected from imidazole and its derivatives disclosed in Japanese Pat. O.P.I. Pub. No. 295258/1989, the compounds represented by formula (I) to (IX) described in the same specification and the exemplified compounds thereof.
  • the bleach and the bleach-fixer are used at temperatures of 20 to 50 ° C, preferably 25 to 45 ° C.
  • the pH of the bleach is preferably not more than 6.0, more preferably within the range of 1.0 to 5.5.
  • the pH of the bleach-fixer is preferably within the range of 5.0 to 9.0, more preferably 6.0 to 8.5. These pH values are those at which a silver halide photographic light-sensitive material is processed and are clearly distinguished from those of the so-called replenishers.
  • the bleacher or the bleach-fixer may contain halides such as ammonium bromide, potassium bromide, sodium bromide, various optical whitening agents, defoamers and surfactants besides the above compounds.
  • the replenishing amount of the bleach or the bleach-fixer is preferably not more than 500 ml, more preferably 20 to 400 ml and most preferably 40 to 350 ml per square meter of light-sensitive material. The effect of the invention is brought out more apparently as the replenishing amount decreases.
  • air or oxygen may be blown into a processing bath or a replenisher tank of the bleach or the bleach-fixer, if desired, for enhancing the activities of these processing solutions.
  • suitable oxidizing agents such as hydrogen peroxide, bromates or persulfates, is also effective as an alternative measure.
  • thiocyanates and thiosulfates are preferred.
  • the content of thiocyanates is usually not less than 0.1 mol/I and, in processing color negative films, it is preferably not less than 0.5 mol/I and more preferably not less than 1.0 mol/I.
  • the content of thiosulfates is usually not less than 0.2 mol/I and, in processing color negative films, it is preferably not less than 0.5 mol/I.
  • the bleach-fixer of the invention may contain, singly or in combination of two or more types, pH buffers comprising a variety of salts. Further, it is preferred that rehalogenating
  • the compounds expressed by formula [FA] in the above specification can be synthesized by general methods described, for example, in U.S. Pat. Nos. 3,335,161 and 3,260,718.
  • the compounds represented by formula (FA) may be used singly or in combination of two or more types.
  • the processing times with the bleach and the bleach-fixer can be arbitrarily selected; but, these are preferably not more than 3 minutes and 30 seconds, more preferably 10 seconds to 2 minutes and 20 seconds, and most preferably 20 seconds to 1 minute and 20 seconds, respectively.
  • the processing time with the bleach-fixer is preferably not more than 4 minutes, more preferably within the range of 10 seconds to 2 minutes and 20 seconds.
  • the amount of ammonium ions contained in the processing solution of the invention for silver halide color photographic light-sensitive materials is not more than 50 mol% of the total cations contained therein, the effect of the invention is well brought out and, further, smelling can be minimized. Accordingly, this is one of the preferable embodiments of the invention. Much better results can be obtained when the amount of ammonium ions is not more than 30 mol%, especially not more than 10 mol%.
  • the processing solution of the invention is a processing solution other than the bleach or the bleach-fixer
  • favorable results can be obtained when the compound of formula (A) are added in an amount of 0.1 to 50 g, preferably 0.5 to 10 g per liter of processing solution.
  • two or more compounds of formula (A) may be combined, or these may be used jointly with other types of chelating agents. These may be incorporated into the processing solution together with other components at the time of preparing the processing solution, or these may be incorporated, together with other components, into a powdery kit without being dissolved, or into a kit of concentrated solutions.
  • the photographic processing solution according to the invention can be applied to any other processing solution for silver halide photographic light-sensitive materials.
  • processing solution include usual black-and-white developer, infection developer for lith films, color developer, fixer, stopping solution, a hardening solution, stabilizer, fogging solution and a toning solution, but the embodiment of the invention is not limited to them.
  • the developers, color developer, fixer, stopping solution, hardening solution, stabilizer, fogging solution and toning solution above-described contain a developing agent, a color developing agent, a fixing agent, a stopping agent, a hardening agent, a stabilizing agent, a fogging agent and a toning agent, respectively.
  • the processing solution according to the invention can be used in processing all types of silver halide photographic light-sensitive materials including color films, color photographic paper, black-and-white films for popular uses, X-ray photographic films, lith films for printing, and microfilms.
  • a multilayer silver halide color photographic light-sensitive material was prepared by forming the following component layers on a paper support laminated with polyethylene on one side and with titanium- oxide-containing polyethylene on the first layer of the other side.
  • the coating solutions were prepared as follows:
  • Coating solutions for 2nd to 7th layers were prepared in a similar manner as above.
  • hardener H-1 was used in the 2nd and 4th layers and hardener H-2 in the 7th layer.
  • coating aides surfactants SU-2 and SU-3 were employed to adjust the surface tension.
  • the control of the pAg was performed by the procedure described in Japanese Pat. O.P.I. Pub. No. 45437/1984, and the pH was controlled with sulfuric acid or an aqueous solution of sodium hydroxide.
  • Emulsion EMP-1 thus obtained comprises monodispersed cubic grains having an average grain size of 0.85 am, a coefficient of variation of grain size distribution of 7% and a silver chloride content of 99.5 mol%.
  • Emulsion EMP-1 was then chemically ripened for 90 minutes at 50°C in the presence of the following compounds to obtain a blue-sensitive silver halide emulsion (Em-A).
  • Emulsion EMP-2 comprising monodispersed cubic grains having an average grain size of 0.43 ⁇ m, a coefficient of variation of grain size distribution of 8% and a silver chloride content of 99.5 mol% was prepared in the same manner as in emulsion EMP-1, except that the addition time of solutions A and B as well as that of solutions C and D were changed.
  • Emulsion EMP-2 was chemically ripened at 55°C for 120 minutes using the following compounds.
  • a green-sensitive silver halide emulsion (Em-B) was so prepared.
  • Emulsion EMP-3 comprising monodispersed cubic grains having an average grain size of 0.50 ⁇ m, a coefficient of variation of grain size distribution of 8% and a silver chloride content of 99.5 mol% was prepared in the same manner as in emulsion EMP-1, except that the addition time of solutions A and B as well as that of solutions C and D were changed.
  • Emulsion EMP-3 was then chemically ripened at 60 °C for 90 minutes using the following compounds, so that a red-sensitive silver halide emulsion (Em-C) was obtained.
  • This light-sensitive material sample was exposed in the usual manner and then processed using the following processes and processing solutions.
  • the pH was adjusted to 7.0 with aqueous ammonia, potassium hydroxide or acetic acid, and then the total volume was made up to 1 liter.
  • Each bleach-fixer component was used at a concentration 1.25 times that in the bleach-fixer to obtain a bleach-fixing replenisher.
  • the pH was adjusted to 5.8.
  • the pH was adjusted to 7.8 with aqueous ammonia or sulfuric acid, and water was added to 1 liter.
  • an automatic processor was filled with the above color developing tank solution, bleach-fixing tank solution and stabilizing tank solution, and then the color paper was processed while the above color developing replenisher, bleach-fixing replenisher and stabilizing replenisher were replenished at 3-minute intervals through constant delivery pumps.
  • the continuous processing was run till the volume of the bleach-fixing replenisher fed to the bleach-fixing tank reached three times the capacity of the bleach-fixing tank (3R).
  • the term "1 R" which will appear later means that the bleach-fixing replenisher is replenished up to a volume equal to the capacity of the bleach-fixing tank.
  • the exposed portion of the color paper was divided into two portions; the one portion was used to measure the residual amount of silver by fluorescent X-ray analysis. Further, the processed color paper was checked for staining at the edge portion. In addition, the bleach-fixing bath after the continuous processing was visually examined if there were formed sulfides. The evaluation results are shown in Tables 3 and 4.
  • EDTA ⁇ Fe means a ferric complex salt of ethylenediaminetetraacetic acid
  • PDTA ⁇ Fe a ferric complex salt of diethylenetriaminepentaacetic acid
  • NTA ⁇ Fe a ferric complex salt of nitrilotriacetic acid
  • A-1)-Fe a ferric complex salt of exemplified compound (A-1)
  • A-2)-Fe a ferric complex salt of exemplified compound (A-2)
  • A-3) ⁇ Fe a ferric complex salt of exemplified compound (A-3).
  • a 60- ⁇ m thick triacetyl cellulose film support was subbed on one side. Then, layers of the following compositions were formed in order on the unsubbed side (reverse side) of the support.
  • the color photographic light-sensitive material contained compounds Su-1, Su-2, viscosity modifier, hardeners H-1, H-2, stabilizer ST-1, antifoggants AF-1, AF-2 having average molecular weights of 10,000 and 1,100,000, respectively, dyes AI-1, AI-2, and compound DI-1 (9.4 mg/m 2 ).
  • the silver iodobromide emulsion used in the 10th layer was prepared by the double-jet method using monodispersed silver iodobromide grains having an average grain size of 0.33 ⁇ m and a silver iodide content of 2 mol% as seed grains; details of the procedure were as follows:
  • the pAg and the pH were controlled with an aqueous solution of potassium bromide and 56% aqueous acetic acid. After forming grains, the grains were subjected to washing treatment according to the usual flocculation method and redispersed by adding gelatin. The resulting emulsion was adjusted to pH 5.8 and pAg 8.06 at 40 ° C.
  • the emulsion was a monodispersed emulsion comprising octahedral silver iodobromide grains having an average grain size of 0.80 ⁇ m, a coefficient of variation of grain size distribution of 12.4% and a silver iodide content of 9.0 mol%.
  • the other emulsions different in average grain size and silver iodide content were prepared in similar manners by changing the average grain size of seed grains, temperature, pAg, pH, flow rate, addition time and halide composition.
  • Each of the emulsions was monodispersed emulsion comprising core/shell type grains having a coefficient of variation of grain size distribution not larger than 20 mol%.
  • Each emulsion was subjected to optimum chemical ripening in the presence of sodium thiosulfate, chloroauric acid and ammonium thiocyanate, and then sensitizing dyes, 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene and 1-phenyl-5-mercaptotetrazole were added thereto.
  • the light-sensitive material sample prepared as above was exposed wedgewise by the usual method and subjected to continuous processing according to the following processes. This continuous processing was carried out till the volume of bleach-fixer replenished reached twice the capacity of the bleach-fixing tank (2R).
  • the pH was adjusted to 4.5 with aqueous ammonia or acetic acid, and the total volume was made up to 1 liter with water.
  • the components of the above bleach were each used at a concentration 1.2 times that in the bleach, and the pH was adjusted to 3.5.
  • the pH was adjusted to 8.0 with potassium hydroxide and water was added to 1 liter.
  • Example 1 The continuous processing in Example 1 was repeated. Then, the magenta transmission density (green light density) in the unexposed portion of the film sample was determined and, at the same time, the amount of residual silver in the exposed portion was measured by X-ray fluorescence analysis.
  • magenta transmission density green light density
  • a color developer of the following composition was prepared.
  • sample A a developer prepared by adding exemplified compound A-1 to sample A at a proportion of 2 g/I was designated as sample B.
  • sample B a developer prepared by adding exemplified compound A-1 to sample A at a proportion of 2 g/I was designated as sample B.
  • sample C a developer prepared by adding exemplified compound A-1 was designated as sample B.
  • sample C a developer prepared by adding exemplified compound A-1 was designated as sample B.
  • sample C a developer prepared by adding exemplified compound A-2
  • sample C a developer prepared by adding exemplified compound A-2
  • sample D a developer prepared by adding exemplified compound A-3
  • sample E containing 2 g/I of exemplified compound A-4
  • sample F one containing 2 g/I of exemplified compound A-23 as sample F
  • HMP sodium hexametaphosphate
  • sample G one containing 3.3 g/I of 1-hydroxyethylidene
  • Example 2 The light-sensitive material used in Example 2 was exposed stepwise to white light using a sensitometer and, then, subjected to color development under the following conditions. In the color developing, developer samples A to J aged for 7 days as in Example 1 were used by turns.
  • compositions of the processing solutions used in the above processes except color developing are compositions of the processing solutions used in the above processes except color developing:
  • the fog density of blue reflection density in the unexposed portion was measured for each sample with a Konica PDA-65 photoelectric densitometer.
  • each developer sample After adding 210 ppm of calcium ions and 3000 ppm of sodium ions (calcium ions and sodium ions to concentrations of 210 ppm and 3000 ppm, respectively,) to each of developer samples A to J, each developer sample was allowed to stand for 7 days at room temperature and, then, checked for precipitation.
  • developer samples B to F according to the invention are lower in hydroxylamine decomposition, less in fogging and less in formation of precipitates due to the metal ions added.
  • comparative sample H though a little effective in preventing hydroxylamine decomposition and fogging, is not effective at all in preventing formation of precipitates due to metal ions present therein and impractical for use.
  • Comparative sample I is as effective as the chelating agent of the invention in preventing precipitation, but it accelerates decomposition of hydroxylamine and causes heavy fogs; therefore, it is also impractical for use. Further, samples A, G and J cannot be used practically, either, because these not only decompose hydroxylamine and cause fogs but are low in capability of preventing precipitation in the presence of metal ions.
  • a first developer for reversal films of the following composition (black-and-white developer) was prepared as a photographic processing composition.
  • sample K The above developer was designated as sample K, and a developer prepared by adding ethylenediaminetetraacetic acid (EDTA) to sample K at a proportion of 2 g/I was designated as sample L. Similarly, one containing 2g/1 of exemplified compound A-1 was designated as sample M, and one containing 2 g/I of ethylenediaminetetramethylene-phosphonic acid (EDTP) as sample N. These four samples were each adjusted to pH 9.90 with potassium hydroxide or 20% sulfuric acid.
  • EDTA ethylenediaminetetraacetic acid
  • comparative sample L accelerates decomposition of Phenidone, a developing agent, though effective in preventing precipitation caused by metal ions.
  • sample M containing the chelating agent of the invention effectively inhibits formation of precipitates and well prevents decomposition of Phenidone.
  • a fixer and a bleach-fixer of the following compositions were prepared as photographic processing compositions to examine the deterrent effect of the exemplified compound upon formation of precipitates due to metal ions.
  • the fixer and the bleach-fixer were partially used as they were for comparison.
  • To the other portions were independently added exemplified compounds A-1, A-2, A-3 and A-23 at proportions of 4 g/I respectively, so that eight samples were prepared.
  • the fixers were adjusted to pH 6.8, and the bleach-fixers to pH 7.1, with aqueous ammonia or acetic acid.
  • 200 ppm of calcium ions were added to each solution (calcium ions were added to a concentration of 200 ppm to each solution).
  • a stabilizer of the following compositions were prepared as photographic processing compositions (also referred to as a stabilizer for non-water washing) to examine the exemplified compound's deterrent effect upon formation of floating matter caused by sulfuration.
  • This stabilizer was partially used as it was for comparison, and exemplified compounds A-1, A-2 and A-3 were independently added to the rest of the stabilizer at proportions of 3 g/I, so that three samples were prepared.
  • each stabilizer After adjusting each stabilizer to pH 8.0 with potassium hydroxide or 20% sulfuric acid, 100 ppm of calcium ions were added thereto, and each stabilizer was allowed to stand. While a floating matter was formed in 2 days on the surface of the comparative one containing no exemplified compound, the stabilizer containing exemplified compound A-1, A-2 or A-3 showed no abnormal change even in a 10-day period and prevented growth of fungi.
  • EDTA ethylenediaminetetraacetic acid
  • DTPA diethylenetriaminepentaacetic acid
  • HEDTA N-hydroxyethylethylenediaminetriaceticacid

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
EP19930112951 1992-08-21 1993-08-12 Processing solution for silver halide photographic light-sensitive materials Withdrawn EP0584665A3 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP222865/92 1992-08-21
JP04222865A JP3116194B2 (ja) 1992-08-21 1992-08-21 ハロゲン化銀写真感光材料用処理液

Publications (2)

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EP0584665A2 true EP0584665A2 (fr) 1994-03-02
EP0584665A3 EP0584665A3 (en) 1994-07-27

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JP (1) JP3116194B2 (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5569443A (en) * 1994-11-18 1996-10-29 The Dow Chemical Company Method for removing hydrogen sulfide from a gas using polyamino disuccinic acid
US5585226A (en) * 1995-08-30 1996-12-17 Eastman Kodak Company Polyamino monoesuccinates for use in photographic processes
US5652085A (en) * 1995-08-30 1997-07-29 Eastman Kodak Company Succinic acid derivative degradable chelants, uses and composition thereof
EP0795782A2 (fr) * 1996-03-11 1997-09-17 Konica Corporation Composition développatrice pour matériau photographique à l'halogénure d'argent sensible à la lumière
US5741555A (en) * 1995-05-22 1998-04-21 The Dow Chemical Company Succinic acid derivative degradable chelants, uses and compositions thereof
EP0783034A3 (fr) * 1995-12-22 1998-07-08 Nitto Chemical Industry Co., Ltd. Agent chélateur et détergent le contenant
EP0907104A2 (fr) * 1997-09-26 1999-04-07 Fuji Photo Film Co., Ltd. Composition et méthode de traitement photographique
US7160674B2 (en) 2003-08-29 2007-01-09 A&O Imagining Solutions Gmbh Photographic chemicals bundle

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE60121068T3 (de) 2000-01-18 2011-05-12 Tosoh Corp., Shinnanyo Aminopolycarboxylate, ihre Herstellung und Verwendung
JP4742419B2 (ja) * 2000-12-25 2011-08-10 東ソー株式会社 エチレンジアミン−ｎ，ｎ’−ジマロン酸錫（ｉｉ）錯体、その製造法およびその用途

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0532003A1 (fr) * 1991-09-11 1993-03-17 Konica Corporation Solution de traitement pour un matériau photographique couleur à l'halogénure d'argent sensible à la lumière

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0532003A1 (fr) * 1991-09-11 1993-03-17 Konica Corporation Solution de traitement pour un matériau photographique couleur à l'halogénure d'argent sensible à la lumière

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5569443A (en) * 1994-11-18 1996-10-29 The Dow Chemical Company Method for removing hydrogen sulfide from a gas using polyamino disuccinic acid
US5741555A (en) * 1995-05-22 1998-04-21 The Dow Chemical Company Succinic acid derivative degradable chelants, uses and compositions thereof
US5585226A (en) * 1995-08-30 1996-12-17 Eastman Kodak Company Polyamino monoesuccinates for use in photographic processes
US5652085A (en) * 1995-08-30 1997-07-29 Eastman Kodak Company Succinic acid derivative degradable chelants, uses and composition thereof
US6221834B1 (en) 1995-12-22 2001-04-24 Mitsubishi Rayon Co., Ltd. Chelating agent and detergent comprising the same
EP0783034A3 (fr) * 1995-12-22 1998-07-08 Nitto Chemical Industry Co., Ltd. Agent chélateur et détergent le contenant
US6426229B1 (en) 1995-12-22 2002-07-30 Mitsubishi Rayon Co., Ltd. Chelating agent and detergent comprising the same
US6451757B2 (en) 1995-12-22 2002-09-17 Mitsubishi Rayon Co., Ltd. Chelating agent and detergent comprising the same
EP0795782A3 (fr) * 1996-03-11 1997-11-05 Konica Corporation Composition développatrice pour matériau photographique à l'halogénure d'argent sensible à la lumière
EP0795782A2 (fr) * 1996-03-11 1997-09-17 Konica Corporation Composition développatrice pour matériau photographique à l'halogénure d'argent sensible à la lumière
EP0907104A2 (fr) * 1997-09-26 1999-04-07 Fuji Photo Film Co., Ltd. Composition et méthode de traitement photographique
EP0907104A3 (fr) * 1997-09-26 2000-02-02 Fuji Photo Film Co., Ltd. Composition et méthode de traitement photographique
US7160674B2 (en) 2003-08-29 2007-01-09 A&O Imagining Solutions Gmbh Photographic chemicals bundle

Also Published As

Publication number Publication date
JPH0667370A (ja) 1994-03-11
JP3116194B2 (ja) 2000-12-11
EP0584665A3 (en) 1994-07-27

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