EP0189604B1 - Procédé pour la production d'une image argentique comprenant un traitement de stabilisation-fixage - Google Patents

Procédé pour la production d'une image argentique comprenant un traitement de stabilisation-fixage Download PDF

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Publication number
EP0189604B1
EP0189604B1 EP85200096A EP85200096A EP0189604B1 EP 0189604 B1 EP0189604 B1 EP 0189604B1 EP 85200096 A EP85200096 A EP 85200096A EP 85200096 A EP85200096 A EP 85200096A EP 0189604 B1 EP0189604 B1 EP 0189604B1
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EP
European Patent Office
Prior art keywords
process according
silver halide
thiosulphate
silver
mole
Prior art date
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
EP85200096A
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German (de)
English (en)
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EP0189604A1 (fr
Inventor
Antonius Albertus Rutges
Robert Joseph Pollet
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Agfa Gevaert NV
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Agfa Gevaert NV
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Publication date
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Priority to DE8585200096T priority Critical patent/DE3565014D1/de
Priority to EP85200096A priority patent/EP0189604B1/fr
Priority to JP1462286A priority patent/JPS61183645A/ja
Publication of EP0189604A1 publication Critical patent/EP0189604A1/fr
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Publication of EP0189604B1 publication Critical patent/EP0189604B1/fr
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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
    • G03C5/39—Stabilising, i.e. fixing without washing out

Definitions

  • the present invention relates to a process for the production of a silver image including a stabilisation-fixing treatment of an image-wise exposed and developed photographic silver halide emulsion material to obtain an image having improved heat and/or light stability.
  • Stabilising baths for exposed and developed photographic silver halide emulsion layers which contain a large variety of organic mercapto compounds are state of the art and particulars concerning such baths are described, e.g. in the book "Modern Photographic Processing” Vol. 2 of Grant Haist - A Wiley Interscience Publication - (1979) New York - p. 210-227.
  • the stabilising agent forms an insoluble non-lightsensitive silver compound while the fixing agent forms a soluble silver complex.
  • solubility of said compounds in a given medium varies inter alia with the pH-value of the medium.
  • one compound may be effective as stabilising agent as well as a fixing agent depending on the pH-value of the processing bath.
  • Compound (A) is an iodide of alkali metals and ammonium.
  • Compound (B) corresponds to the following general formula: wherein:
  • Z represents the non-metallic atoms necessary to form a 5- or 6-membered heterocyclic nucleus.
  • R 2 represents a C,-C s alkyl group, preferably a C,-C 3 alkyl group or carboxyl group.
  • JP-A-58 122 536 fixation speed of a silver halide photosensitive material is enhanced by a fixation solution containing (NH 4 ) Z S 2 0 3 as principal agent and a compound according to one of the or wherein R 1 , R are each H, amino, lower alkyl, hydroxyalkyl or aryl, or each may combine to form a hetero ring;
  • a process for the production of a silver image including a stabilising-fixing treatment of said image formed by development of an imagewise exposed photographic silver halide emulsion material is provided wherein the imagewise exposed and developed silver halide emulsion material is treated with an aqueous solution containing thiosulphate ions and a cyclic thiourea compound corresponding to the following general formula (X) or a corresponding tautomeric structure thereof: wherein:
  • Table 1 contains a list of specific compounds within the scope of the above general formula (X) with a literature reference for their preparation.
  • the specified heterocyclic compounds are simply dissolved in water together with the other ingredients.
  • the pH of the treating liquid is in the acidic range, e.g. in the range of 6 to 4.
  • Small amounts of water-soluble solvents, e.g. acetic acid and water-miscible alcohols may be added to improve the dissolution of the cyclic thiourea compound.
  • the treating liquids used according to the present invention contain an anti-oxidizing agent to shield the cyclic thiourea compound from aerial oxidation.
  • Suitable anti-oxidizing agents are ascorbic acid and compounds yielding sulphite ions such as sodium sulphite and potassium metabisulphite.
  • the present image-stabilising process makes it possible to eliminate the customary washing procedure and yet to obtain a satisfactory stable print.
  • the treatment of the developed silver image with the above aqueous solution containing alkali metal thiosulphate ions and the cyclic thiourea compound corresponding to the general formula (X) may be preceded by a rinsing treatment but such is not strictly necessary.
  • the image-stabilising liquids used according to the present invention do not alter the binding properties of gelatin, so that no sticky gelatin silver halide emulsion layers are obtained as is the case when using stabilising liquids based on thiocyanates. Further no particular odour is produced and toxicity and corrosivity are very low.
  • the stabilising-fixing treatment according to the present invention is particularly effective for the stabilisation of silver images obtained by means of silver halide emulsion layers wherein the silver halide is for at least 50 mole% silver chloride.
  • the present stabilising-fixing treatment is very effective when used in conjunction with silver halide emulsion layers having a silver halide coverage, the silver halide being expressed in an equivalent amount of silver nitrate, not higher than 4 g per sq.m.
  • the treatment according to the present invention provides image stabilisation in a short time.
  • Stabilising treatment according to the present invention may be terminated in 30 s at room temperature (20°C) and may be terminated in 15 s at 35°C.
  • the stabilising-fixing treatment can be used for photographic black-and-white papers and films, e.g. graphic art film materials, but is likewise applicable for the image stabilisation of photographic colour materials wherein residual silver halide may not remain.
  • the photographic materials may contain already before the exposure some or all of the developing agent(s) used in the development step.
  • the developing agents When the developing agents are present already in the photographic material during the exposure the development may be carried out with a so-called activator bath which is an alkaline aqueous liquid being free from developing agents and activates these agents already present in the photographic material.
  • the silver images stabilised according to the present invention show a very low darkening in the non- image area under circumstances of heat, humidity and/or light-exposure.
  • the washing liquid likewise incorporates a said cyclic thiourea compound, e.g. in an amount up to 1 x 10 ⁇ 1 mole per liter.
  • the application of the treating liquids used in the processing of photographic silver halide emulsion materials may proceed by immersion but more advantageously proceeds by meniscus coating using a lick- roller, sponge or resilient roller to limit the volume of applied liquid.
  • an image-wise exposed silver halide emulsion material according to the present invention it is in favour of effective stabilisation to keep the pH of the liquid(s) containing said cyclic thiourea compound in the acidic range and therefore to eliminate as much as possible of the alkaline developing or development activating liquid from the material before applying the stabilising liquid.
  • Such may proceed by squeegee, e.g. with rollers or by applying an intermediate rinsing step.
  • the developed material was led between squeegee rollers to remove the major part of adhering alkaline liquid and was then dipped for 5 s at 20°C into a fixing or stabilising-fixing liquid as defined in the following Table 2.
  • Liquid no. 1 contained per liter 198.5 g (0.80 mole) of sodium thiosulphate.5 water and 25 g of potassium metabisulphite.
  • Liquid no. 2 had the same composition as liquid no. 1 but included in addition thereto per liter 10 g of 2-thio-hexahydropyrimidone-2.
  • the fixing-stabilisation was followed by rinsing.
  • the rinsing was effected by conveying the material for 10 s at 20°C through a tray containing plain water.
  • the efficiency of the stabilisation was determined by measuring the change in optical density (AD) obtained after keeping one strip (i) of the processed material for 3 days in the dark at 35°C at 80% relative humidity and another strip (ii) for 4 h in a XENOTEST (trade name) exposure apparatus wherein the strip was subjected to a white light illumination of 180,000 lux.
  • AD optical density

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)

Claims (11)

1. Procédé pour la formation d'une image argentique, ce procédé comprenant un traitement de stabilisation-fixage de cette image formée par développement d'un matériau d'émulsion photographique à l'halogénure d'argent exposé sous forme d'une image, procédé dans lequel ce matériau exposé et développé sous forme d'une image est traité avec une solution aqueuse contenant des ions thiosulfate et un composé de thiourée cyclique répondant à la formule générale (X) ci-après ou une structure tautomère correspondante de ce composé:
Figure imgb0013
où
R représente un atome d'hydrogène, un groupe d'hydrocarbure non substitué ou un groupe ―CH2―CH2OH, et
Z représente un groupe d'hydrocarbure saturé bivalent, y compris ce même groupe sous forme substituée, formant un noyau hétérocyclique pentagonal ou hexagonal avec le groupe
Figure imgb0014
caractérisé en ce que les ions thiosulfate proviennent d'un thiosulfate d'un métal alcalin, tandis qu'il n'y a pas d'ions ammonium.
2. Procédé selon la revendication 1, caractérisé en ce que Z représente―CH2―CH2―CH2―.
3. Procédé selon la revendication 1 ou 2, caractérisé en ce que le composé de thiourée cyclique est la 2-thio-hexahydro-pyrimidone-2.
4. Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce que le thiosulfate d'un métal alcalin est le thiosulfate de sodium.
5. Procédé suivant l'une quelconque des revendications 1 à 4, caractérisé en ce que la solution précitée contient le composé de thiourée cyclique en une concentration de 1 x 10-4 mole à 1 x 10-' mole par litre en présence du thiosulfate d'un métal alcalin en une concentration de 0,1 mole à 1,5 mole par litre.
6. Procédé selon l'une quelconque des revendications 1 à 5, caractérisé en ce que le traitement est suivi d'un traitement de rinçage avec de l'eau.
7. Procédé selon la revendication 6, caractérisé en ce que l'eau contient le mercapto-triazole à l'état dissous en une quantité allant jusqu'à 1 x 10-' mole par litre.
8. Procédé selon l'une quelconque des revendications 1 à 7, caractérisé en ce que la solution a un pH se situant dans l'intervalle allant de 6 à 4.
9. Procédé selon l'une quelconque des revendications 1 à 8, caractérisé en ce que la solution contient un agent antioxydant..
10. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que l'halogénure d'argent du matériau d'émulsion à l'halogénure d'argent contient au moins 50% molaires de chlorure d'argent.
11. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que le matériau d'émulsion à l'halogénure d'argent contient 4 g/m2 maximum d'halogénure d'argent, exprimé en une quantité équivalente de nitrate d'argent.
EP85200096A 1985-01-29 1985-01-29 Procédé pour la production d'une image argentique comprenant un traitement de stabilisation-fixage Expired EP0189604B1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
DE8585200096T DE3565014D1 (en) 1985-01-29 1985-01-29 Process for the production of a silver image including a stabilisation-fixing treatment
EP85200096A EP0189604B1 (fr) 1985-01-29 1985-01-29 Procédé pour la production d'une image argentique comprenant un traitement de stabilisation-fixage
JP1462286A JPS61183645A (ja) 1985-01-29 1986-01-24 安定化定着処理を含む銀像の製造方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP85200096A EP0189604B1 (fr) 1985-01-29 1985-01-29 Procédé pour la production d'une image argentique comprenant un traitement de stabilisation-fixage

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EP0189604A1 EP0189604A1 (fr) 1986-08-06
EP0189604B1 true EP0189604B1 (fr) 1988-09-14

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EP (1) EP0189604B1 (fr)
JP (1) JPS61183645A (fr)
DE (1) DE3565014D1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07119974B2 (ja) * 1987-12-16 1995-12-20 富士写真フイルム株式会社 ハロゲン化銀感光材料の現像処理方法
EP0356581B1 (fr) * 1988-08-09 1993-07-14 Agfa-Gevaert N.V. Méthode de traitement d'un matériau photographique à émulsion d'halogénure d'argent

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0189603A1 (fr) * 1985-01-29 1986-08-06 Agfa-Gevaert N.V. Procédé pour la production d'une image argentique comprenant un traitement de stabilisation-fixage

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1285696A (en) * 1968-09-19 1972-08-16 Kodak Ltd Processing method for photodevelopable silver halide recording materials
SE375162B (fr) * 1970-01-15 1975-04-07 Agfa Gevaert Ag
US3854947A (en) * 1973-05-16 1974-12-17 E Ritchey Process and solution for fixing an image on silver halide prints

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0189603A1 (fr) * 1985-01-29 1986-08-06 Agfa-Gevaert N.V. Procédé pour la production d'une image argentique comprenant un traitement de stabilisation-fixage

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Publication number Publication date
JPS61183645A (ja) 1986-08-16
EP0189604A1 (fr) 1986-08-06
DE3565014D1 (en) 1988-10-20

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