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WO1993012463A1 - Procede de stabilisation de revelateur photographique - Google Patents

Procede de stabilisation de revelateur photographique Download PDF

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Publication number
WO1993012463A1
WO1993012463A1 PCT/EP1992/002849 EP9202849W WO9312463A1 WO 1993012463 A1 WO1993012463 A1 WO 1993012463A1 EP 9202849 W EP9202849 W EP 9202849W WO 9312463 A1 WO9312463 A1 WO 9312463A1
Authority
WO
WIPO (PCT)
Prior art keywords
developer
developing agent
sulphite
developing
agent
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.)
Ceased
Application number
PCT/EP1992/002849
Other languages
English (en)
Inventor
Anthony Malcolm Barnett
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.)
Kodak Ltd
Eastman Kodak Co
Original Assignee
Kodak Ltd
Eastman Kodak Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=10706113&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO1993012463(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Kodak Ltd, Eastman Kodak Co filed Critical Kodak Ltd
Priority to EP93901673A priority Critical patent/EP0571616B1/fr
Priority to DE69222153T priority patent/DE69222153T2/de
Priority to JP51060093A priority patent/JP3249521B2/ja
Publication of WO1993012463A1 publication Critical patent/WO1993012463A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/29—Development processes or agents therefor
    • G03C5/30—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
    • 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

Definitions

  • This invention relates to a method of stabilising photographic silver halide developer solutions and, in particular, to stabilising them against pH changes brought about by aerial oxidation.
  • Photographic silver halide developer solutions are usually alkaline and contain a developing agent (which is a reducing agent) which reduces photoexposed silver halide to silver. Inherently therefore developing agents can react with oxygen in the air to become oxidised and thus ineffective for development purposes. Most developing solutions, however, contain considerable amounts of sulphite whose primary purpose is to protect the developing agent against aerial oxidation. This is effective but will not stabilise a developer over long periods of exposure to the air, eg a day or two if there is a significant surface area exposed to air. Certain developer solutions in the graphic arts area (not widely used now) produce images of extremely high contrast by a process known as "infectious development".
  • Infectious development can only take place where there is a very low concentration of sulphite ions, equivalent to some 3 to 5 grams anhydrous sodium sulphite per litre. Under such circumstances, the developing agent is very prone to aerial oxidation making the solution unstable. Infectious developers contain a single developing agent, usually hydroquinone or similar dihydroxybenzene compounds. US Patent Specification 3 512 981 describes the use of ascorbic acid or an analogue thereof in such developing solutions to protect them against aerial oxidation ("tray life”) .
  • US Patent 3,865,591 describes developer compositions containing a dihydroxybenzene developing agent, a 3-pyrazolidone developing agent, an ene-diol developing agent including ascorbic acid and sodium or potassium thiocyanate as a silver halide solvent.
  • the advantage is said to be that the developer is capable of increasing the exposure index (speed) of the film that is developed.
  • US Patent 3,022,168 describes ascorbic acid based developers having a pH of from 8 to 9.
  • Example 3 describes such a developer also containing Metol and hydroquinone.
  • US Patent 3,938,997 describes developers comprising an iron chelate developer, an ascorbic acid and a third developing agent which are said to form a ternary superadditive combination at pH 6.
  • Example 1 it is shown that the activity of the developer becomes less with ageing and ascorbic acid is said to stabilise it. This is clearly a protection against aerial oxidation of the developing agents which are subject thereto.
  • the present invention has as its object the solution to problems associated with dihydroxybenzene- containing developer solutions and their pH fluctuations due to aerial oxidation.
  • a method of controlling the pH of photographic silver halide developer solutions which contain a dihydroxybenzene developing agent and a secondary developing agent which together form a super-additive combination and an amount of sulphite ions sufficient to protect the developing agents from aerial oxidation by producing in the working solution a concentration of at least lOg/litre (as anhydrous sodium sulphite) wherein there is added to the developer solution a reducing agent which releases hydrogen ions during aerial oxidation of the developer solution and which is different from any developing agent of the superadditive combination.
  • the reducing agent which releases hydrogen ions is a compound of the formula:
  • n 0, 1, 2, 3 or 4 and
  • the preferred reducing agents are also silver halide developing agents.
  • the developer solution contains hydroquinone as the polyhydroxybenzene developing agent.
  • the superadditive developing agents for use with the dihydroxybenzene developing agent may be either N- methyl-p-amino ⁇ henol or a pyrazolidone, for example 1- phenyl-3-pyrazolidone, 4-hydroxymethyl-4-methyl-l- phenyl-3-pyrazolidone, or 4,4-dimethyl-l-phenyl-3- pyrazolidone.
  • the developer preferably contains sulphite in the working strength solution at above 20 g/1, preferably above 25 g/1 and more preferanly above 40 g/1 (as anhydrous sodium sulphite) .
  • the present invention also provides silver halide developer composition having a pH above 9 and which is substantially free from a thiosulphate or thiocyanate silver halide solvent, contains a dihydroxybenzene developing agent and a secondary developing agent which together form a super-additive combination and an amount of sulphite ions sufficient to protect the developing agents from aerial oxidation by producing in the working solution a concentration of at least lOg/litre (as anhydrous sodium sulphite) wherein the developer solution contains a reducing agent, different from any developing agent of the super ⁇ additive combination, which releases hydrogen ions during aerial oxidation of the developer solution.
  • the preferred developers have a pH in the range from 9 to 13, preferably from 10 to 12.
  • the developer solutions may be suitable for use in the graphic arts area, especially to obtain very high contrast images with developers which are designed for use with silver halide materials containing an incorporated hydrazide as nucleating agent.
  • Such developer solutions may also contain an amine which helps to provide the desired very high contrast as described in European Patent 0 032 456.
  • Such materials often form a so-called “pepper fog” which is due to the spontaneous development of unexposed grains. The production of "pepper fog” is increased dramatically when the developer is exposed to the air and is often particularly bad in processors where the cross-over from the developer to the fixer is of a long duration.
  • the beakers were then exposed to air for 6 days and the pH levels measured.
  • the resulting pH's are recorded below in Table 1.
  • the surface area per ml was 0.27 c 2.
  • Example 1 was repeated using 100 ml of developer in a 250 ml beaker thus creating a higher suface to volume ratio of 0.44 cm 2 per ml. This time ascorbic acid additions are compared to polyethylene glycol (PEG) or sugar. The results are shown in Table 2 below. Table 2
  • the strips were developed for 30 seconds or 60 seconds and then held in the air to simulate long "cross-overs". They were then placed in a stop bath of 4% acetic acid and then fixed in Kodak Fixer 3000 (1+3) . The developed strips were examined for the presence of "pepper fog” and rated on a scale of 1-10 (10 worst) . The results are shown in Table 3 below.
  • Example 3 was repeated using 0, 5, 10, 15, 20 and 40 g/1 of ascorbic acid and adjusting the pH of the solution back to that of the control.
  • the samples were developed for 30 or 60 seconds at 35°C and then held in the air for 15, 30 or 60 seconds before stopping in 4% acetic acid.
  • the samples were developed in 250ml of solution in a 250ml measuring cylinder which was then left exposed to air.
  • the processing was repeated after 2, 3, 4 and 7 days. The results are shown below in Table 4 below.
  • C means that the sample was clear of pepper fog.
  • Example 3 was repeated but in this case the processing was done in an INTERPRO AR10 machine using solutions at 35°C.
  • the speed of the processor was adjusted so that the cross-over from the developer to the fixer varied from 10 to 20 to 34 seconds while the development time also increased from 30 to 60 to 102 seconds. These are referred to as fast, medium and slow in Table 5 below.
  • Two solutions were used, these were the developer of Example 3 with 0 and then 10 g/1 ascorbic acid both at the same pH. Samples were processed on days 1, 2 and 3 and then evaluated for pepper fog. The results are shown in Tables 5 and 6 below.

Landscapes

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

Abstract

Procédé servant à réguler le pH de solutions de révélateurs photographiques à base d'halogénure d'argent qui contiennent un agent de développement à base de dihydroxybenzène et un agent de développement secondaire qui constituent ensemble une combinaison additive secondaire, ainsi qu'une quantité d'ions sulfite suffisante pour protéger les agents de développement contre l'oxydation à l'air en produisant dans la solution active une concentration d'au moins 10g/litre (sous forme de sulfite de sodium anhydre); un agent réducteur étant ajouté à la solution révélatrice, cet agent réducteur libèrant les ions hydrogène au cours de l'oxydation à l'air de la solution révélatrice et étant différent de tout autre agent de développement de la combinaison additive secondaire.
PCT/EP1992/002849 1991-12-12 1992-12-10 Procede de stabilisation de revelateur photographique Ceased WO1993012463A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP93901673A EP0571616B1 (fr) 1991-12-12 1992-12-10 Procede de stabilisation de revelateur photographique
DE69222153T DE69222153T2 (de) 1991-12-12 1992-12-10 Stabilisierung photographischer entwickler
JP51060093A JP3249521B2 (ja) 1991-12-12 1992-12-10 写真現像液の安定化

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9126362.4 1991-12-12
GB919126362A GB9126362D0 (en) 1991-12-12 1991-12-12 Photographic developer stabilisation

Publications (1)

Publication Number Publication Date
WO1993012463A1 true WO1993012463A1 (fr) 1993-06-24

Family

ID=10706113

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1992/002849 Ceased WO1993012463A1 (fr) 1991-12-12 1992-12-10 Procede de stabilisation de revelateur photographique

Country Status (5)

Country Link
EP (1) EP0571616B1 (fr)
JP (1) JP3249521B2 (fr)
DE (1) DE69222153T2 (fr)
GB (1) GB9126362D0 (fr)
WO (1) WO1993012463A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5385811A (en) * 1993-04-27 1995-01-31 Fuji Photo Film Co., Ltd. Method for processing silver halide photographic materials
USH1508H (en) * 1993-06-18 1995-12-05 Fuji Photo Film Co., Ltd. Image-forming process
EP0732619A1 (fr) * 1995-02-21 1996-09-18 Agfa-Gevaert N.V. Solution et méthode pour le développement d'un matériau photographique à l'halogénure d'argent exposé
US6379877B1 (en) 1995-02-21 2002-04-30 Agfa-Gevaert Method for developing an exposed photographic silver halide material

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3022168A (en) * 1958-06-28 1962-02-20 Pharmacia Ab Photographic developer
US3865591A (en) * 1973-05-10 1975-02-11 Delaware Photographic Products General purpose developer
US3867151A (en) * 1973-05-10 1975-02-18 Delaware Photographic Products General purpose monobath

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3022168A (en) * 1958-06-28 1962-02-20 Pharmacia Ab Photographic developer
US3865591A (en) * 1973-05-10 1975-02-11 Delaware Photographic Products General purpose developer
US3867151A (en) * 1973-05-10 1975-02-18 Delaware Photographic Products General purpose monobath

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPIL Week 9023, Derwent Publications Ltd., London, GB; AN 90-175471 (23) *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5385811A (en) * 1993-04-27 1995-01-31 Fuji Photo Film Co., Ltd. Method for processing silver halide photographic materials
USH1508H (en) * 1993-06-18 1995-12-05 Fuji Photo Film Co., Ltd. Image-forming process
EP0732619A1 (fr) * 1995-02-21 1996-09-18 Agfa-Gevaert N.V. Solution et méthode pour le développement d'un matériau photographique à l'halogénure d'argent exposé
US6379877B1 (en) 1995-02-21 2002-04-30 Agfa-Gevaert Method for developing an exposed photographic silver halide material

Also Published As

Publication number Publication date
EP0571616A1 (fr) 1993-12-01
GB9126362D0 (en) 1992-02-12
JP3249521B2 (ja) 2002-01-21
EP0571616B1 (fr) 1997-09-10
DE69222153D1 (de) 1997-10-16
JPH06508226A (ja) 1994-09-14
DE69222153T2 (de) 1998-04-09

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