EP0500592B1 - Systeme de regeneration a effluent lent pour revelateurs de negatifs en couleur - Google Patents

Systeme de regeneration a effluent lent pour revelateurs de negatifs en couleur Download PDF

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Publication number
EP0500592B1
EP0500592B1 EP90915970A EP90915970A EP0500592B1 EP 0500592 B1 EP0500592 B1 EP 0500592B1 EP 90915970 A EP90915970 A EP 90915970A EP 90915970 A EP90915970 A EP 90915970A EP 0500592 B1 EP0500592 B1 EP 0500592B1
Authority
EP
European Patent Office
Prior art keywords
developer
processing
ion
exchange resin
solution
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.)
Expired - Lifetime
Application number
EP90915970A
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German (de)
English (en)
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EP0500592A1 (fr
Inventor
Peter Jeffery ''woodside'' Lee Common Twist
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
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Publication date
Application filed by Kodak Ltd, Eastman Kodak Co filed Critical Kodak Ltd
Priority to AT90915970T priority Critical patent/ATE94659T1/de
Publication of EP0500592A1 publication Critical patent/EP0500592A1/fr
Application granted granted Critical
Publication of EP0500592B1 publication Critical patent/EP0500592B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • G03C7/44—Regeneration; Replenishers

Definitions

  • This invention relates to a method of processing photographic silver halide colour materials and in particular to the replenishment of colour developer for colour negative film.
  • Colour negative films are processed in an industry standard process called C-41.
  • C-41 systems are run on the basis that a replenisher solution is added to the developer and excess developer is removed by letting it overflow.
  • the developer solution thus achieves a stable condition in which chemicals used up during processing are replenished to maintain a working concentration and seasoning products e.g. bromide and iodide ions and antifoggant fragments from DIR couplers entering the developer solution from the film are kept at an acceptable level.
  • Recent C-41 systems are run on a developer replenishment rate of from 500 to 1800 ml/m2 of film processed.
  • Colour paper is also processed in a replenished system but current colour paper is based on silver chloride emulsions containing very little bromide or iodide. This permits a replenishment regime in which there is little or no need to remove bromide and iodide hence the developer can be replenished with a more than usually concentrated replenisher which does not cause overflow.
  • a concentrated source of replenishment can result in zero-overflow from the developer tank and a build-up of seasoning products which is not significantly detrimental to sensitometry. This could involve rebalancing the sensitized coating to match aim sensitometry in the presence of higher levels of seasoning products.
  • Japanese application 62/019842 describes a method of reducing the bromide ion concentration of colour developer for silver bromide colour paper by coating an ion-exchange resin on the back of the colour paper. This then takes up bromide ions as it passes through the developer solution. Clearly this process is undesirable because a special and more costly photographic paper has to be used thus rendering the paper more expensive and the process non-universal. The process wastes otherwise regeneratable ion-exchange resin. A coating of such a material on film (having a transparent base) is likely to result in an unacceptably degraded image.
  • the combination of very low replenishment rates and the use of in-line ion-exchange resin has a cooperative or synergistic effect in that the more effective the removal of seasoning products by the ion-exchange resin, the less is the replenisher that is needed.
  • the ion-exchange resin not only removes bromide ions but also undesirable levels of other seasoning products such as antifoggants released from DIR couplers in the film being processed.
  • the present invention can be configured to remove halide ions at the rate at which they are generated. In addition, antifoggant fragments are similarly removed.
  • This invention therefore, uses both in-line ion-exchange and concentrated replenisher addition to enable the theoretical minimum chemical input for a C-41 developer solution in a single developer tank configuration.
  • the normal developer replenishment rate for Kodak VR400 film in C-41 is 1675 ml/m2 for 35 mm film although this has now been lowered to about 841 ml/m2 with the new C-41 LORR (Low Replenishment Rate) process.
  • the present invention lowers this rate to between 56.0 and 117 ml/m2 for 35 mm film. Since the volume added is very much reduced so is the volume that is expelled. In fact, no overflow is generated and the only effluent comes from that volume of developer carried over into the bleach tank. This is about 18.7 to 56.0 ml/m2 for 35 mm film.
  • the chemical effluent is the same concentration as in a normally replenished process but its volume has been reduced from about 841 ml/m2 to about 56.0 ml/m2.
  • a further advantage of the present invention is the reduced chemical input that is necessary by virtue of the reduced effluent and the greater proportion of the chemicals being used to generate image.
  • the chemical input is 70% less than the current C-41 LORR replenisher. This offers advantages in terms of the cost of the photofinishing operation and in manufacturing cost.
  • An additional advantage of this invention is the ability of this system to cope with a wide range of utilisation conditions.
  • a low utilisation condition can be tolerated more readily because colour developing agent can be added independently of the other components and does not depend for its level in the working tank on the level of the anti-oxidant.
  • the bromide level, CD4 level and anti-oxidant level can be controlled independently of each other, the correct tank chemistry can be maintained for any utilisation condition. This is not possible with the conventional method which has all these components in the same replenisher solution. Because of these reasons a process that is replenished with the system described in this invention need never suffer from process collapse.
  • the system in the present invention is also ideally suited to be controlled by a replenisher management unit that could adjust the chemical input to account for different film types and utilisation conditions.
  • Fig 1 shows a developer tank to which additions of activator solution and solid CD4 colour developing agent are made. There is a carry-out of developer solution on the film and, should the volume drop, due to evaporation, the level is made up with water.
  • the ion-exchange cartridge is attached to the tank as shown and developer is circulated through it, eg with a pump, preferably only when there is film being processed.
  • the ion-exchange resin may comprise anionic (for the exchange of anions) or amphoteric types or mixtures thereof.
  • anionic resin is based on a polystyrene matrix cross-linked, for example, with 3% to 5% of divinylbenzene. Its strongly basic character is derived from quaternary ammonium groups. Examples of suitable anionic exchange resins are:
  • the ion-exchange resin is preferably located in a cartridge through which the contents of the colour developer tank are pumped either continuously or when required. When it has been exhausted it may be discarded or regenerated as will be well understood.
  • the replenisher may be in the form of a solution or a solid. However, its exact form must be such that at normal replenishment rates under normal working conditions substantially no overflow is caused.
  • the replenisher components are added as an activator solution and a solution of colour developing agent; in another, the colour developer is added as a solid.
  • the replenisher components may be added as three separate solutions having the following compositions:
  • the present invention can also be used to deliberately control tank chemical levels to some values other than those in normal working tank chemistry. This might be desirable for special uses where non-standard sensitometry, e.g. higher speed is needed.
  • the film to be processed may be any camera-speed colour negative film such as those commercially available or as described in Research Disclosure Item 17643 December 1978 pages 22-31 published by Kenneth Mason Publications of Emsworth, Hampshire, United Kingdom.
  • a seasoning run was carried out for several months to establish the basic operating procedure and the chemical addition and ion-exchange rates.
  • the three elements of the replenishment system are:
  • This solution was kept in a closed container namely a 'bag-in-the-box' collapsible plastic vessel often used for wine and other fluids sensitive to degradation by the atmosphere.
  • a conventional replenisher tank is acceptable for short times (days) but for longer times (weeks) it was found that carbon dioxide absorption from the air caused the pH of the activator to drop so that it was then unable to maintain developer tank pH.
  • These problems were prevented by the use of a collapsible container.
  • This activator was added at a rate of between 37.4 and 117 ml/m2 of 35 mm film processed depending on the average throughput rate of film on a weekly basis. The overall average film throughput was about 62 linear metres per day of VR400 which was exposed to average customer density.
  • the rate of addition of solid CD4 was estimated from a computer model of the replenishment system. In practice this was modified slightly to account for some losses of CD4 on the ion-exchange resin. The addition rates were: 1.4 - 1.9 g/m2 VR400 0.65 - 0.94 g/m2 VR100
  • Solid CD4 was added at the above rates in proportion to the amount of film processed. In practice this was done by removing some developer solution, adding a weighed amount of solid CD4 to this and replacing the same into the developer tank.
  • IRA400 a strong anion resin available from Rohm and Haas was used.
  • the ion-exchange rate was 196 ml/m2 for VR400 film.
  • the resin was regenerated with 5% potassium carbonate, washed with demineralised water and then connected in-line with the developer tank.
  • Approximately 400g of resin was contained in a simple flow through cell of about 500 ml volume.
  • the flow through the resin cell was controlled by a conventional replenishment pump which is switched on along with the replenishment pump for the activator when film passes through the processor.
  • the flow of solution from the developer tank through the cartridge occurs only when film is passing through the processor.
  • the treated solution is then returned directly back to the developer tank. This ensures a controlled rate of removal of bromide ions and other seasoning products.
  • Film was put through the processor at approximately 62 metres of 35 mm film per day.
  • a resin cell of the size described here lasts about one week or for 300 to 385 linear metres of 35 mm VR400 seasoning film

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Treatment Of Water By Ion Exchange (AREA)

Abstract

Procédé de traitement d'une pellicule photographique de négatifs en couleur d'halogénure d'argent, dans lequel la solution de développement est: (i) traitée à l'aide d'une résine d'échange d'ions en ligne, permettant d'éliminer les produits vieillissants du révélateur, et (ii) régénérée à l'aide d'un volume suffisamment faible de constituants de solution de redosage, pour qu'aucun débordement ne se produise.

Claims (8)

  1. Méthode de traitement d'un film aux halogénures d'argent pour la photographie en couleur dans laquelle la solution de développement est :
    (i) traitée avec une résine échangeuse d'ion en ligne pour éliminer les produits de saisonnement du révélateur, et
    (ii) renouvelée avec un volume suffisamment faible de constituants de renouvellement pour éviter en pratique un débordement de solution.
  2. Méthode de traitement de la revendication 1, dans laquelle la solution de révélateur traitée est renvoyée directement la cuve de développement.
  3. Méthode de traitement de la revendication 1 ou 2, dans laquelle les constituants de renouvellement sont ajoutés sous forme d'une ou plusieurs substances solides ou solutions concentrées.
  4. Méthode de traitement selon l'une des revendications 1 à 3, dans laquelle la résine échangeuse d'ions est du type anionique.
  5. Méthode de traitement selon l'une des revendications 1 à 4, dans laquelle la solution en provenance de la cuve de développement est pompée à travers un réservoir contenant une résine échangeuse d'ion et renvoyée directement dans la cuve de développement.
  6. Méthode de traitement selon l'une des revendications 1 à 5, dans laquelle la solution de développement est traitée seulement avec de la résine échangeuse d'ion pendant que le film est traité.
  7. Méthode de traitement selon l'une des revendications 1 à 6, dans laquelle la solution de développement est traitée avec la résine échangeuse d'ion quand cela est nécessaire.
  8. Méthode de traitement selon l'une des revendications 1 à 7, dans laquelle la résine échangeuse d'ion comprend essentiellement une matrice de polystyrène réticulé et contient des groupes ammonium quaternaire.
EP90915970A 1989-11-09 1990-10-31 Systeme de regeneration a effluent lent pour revelateurs de negatifs en couleur Expired - Lifetime EP0500592B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT90915970T ATE94659T1 (de) 1989-11-09 1990-10-31 Abwasserarmes regeneriersystem fuer farbnegativentwickler.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8925311 1989-11-09
GB898925311A GB8925311D0 (en) 1989-11-09 1989-11-09 Low effluent replenishment system for colour negative developers

Publications (2)

Publication Number Publication Date
EP0500592A1 EP0500592A1 (fr) 1992-09-02
EP0500592B1 true EP0500592B1 (fr) 1993-09-15

Family

ID=10665992

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90915970A Expired - Lifetime EP0500592B1 (fr) 1989-11-09 1990-10-31 Systeme de regeneration a effluent lent pour revelateurs de negatifs en couleur

Country Status (5)

Country Link
EP (1) EP0500592B1 (fr)
JP (1) JP2944204B2 (fr)
DE (1) DE69003396T2 (fr)
GB (1) GB8925311D0 (fr)
WO (1) WO1991007698A1 (fr)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4120867A1 (de) * 1991-06-25 1993-01-07 Agfa Gevaert Ag Fotografisches verarbeitungsverfahren und vorrichtung dafuer
US5780189A (en) * 1991-08-01 1998-07-14 Eastman Kodak Company Apparatus and method for controlling the chemical activity of processing solution in a photographic processing apparatus
GB9118007D0 (en) * 1991-08-21 1991-10-09 Kodak Ltd Method for replenishing photographic developer solutions
DE69310769T2 (de) * 1992-12-30 1998-01-22 Cultor Oy Rücktgewinnung von erythorbaten aus photographischen lösungen
GB9301852D0 (en) * 1993-01-30 1993-03-17 Kodak Ltd Method of processing photographic silver halide material
GB9301857D0 (en) * 1993-01-30 1993-03-17 Kodak Ltd Method of processing photographic silver halide material
US5556736A (en) * 1993-11-11 1996-09-17 Konica Corporation Method for processing a silver halide color photographic light-sensitive material and producing a color image
USH1648H (en) * 1995-06-07 1997-05-06 Kim; Hongzoon Method for storing and regenerating photographic processing solutions
GB2306686A (en) * 1995-10-18 1997-05-07 Kodak Ltd Processing system for developing photographic materials
FR2754360A1 (fr) * 1996-10-08 1998-04-10 Eastman Kodak Co Procede de renouvellement d'un revelateur a l'acide ascorbique

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3431860A1 (de) * 1984-08-30 1986-03-06 Agfa-Gevaert Ag, 5090 Leverkusen Verfahren zur herstellung farbfotografischer bilder
DE3437631A1 (de) * 1984-10-13 1986-04-24 Agfa-Gevaert Ag, 5090 Leverkusen Aufbereitung von gebrauchten entwicklern
EP0252185A1 (fr) * 1986-07-11 1988-01-13 Agfa-Gevaert N.V. Procédé et appareil pour enlever des anions complexes d'argent dissous de solutions aqueuses
US4857950A (en) * 1987-02-13 1989-08-15 Fuji Photo Film Co., Ltd. Wash water reservoiring method and apparatus therefore
JPH01267649A (ja) * 1988-04-20 1989-10-25 Fuji Photo Film Co Ltd 感光材料処理装置
GB8909577D0 (en) * 1989-04-26 1989-06-14 Kodak Ltd A method of recovering silver from photographic processing solutions
JPH03141352A (ja) * 1989-10-27 1991-06-17 Fuji Photo Film Co Ltd ハロゲン化銀感光材料の処理方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Journal of Imaging Technology, Vol. 13, No. 3, March 1987, Heinz Meckl: "Developer Recycling-A New Generation", pp. 85-89 *
SMPTE Journal, Vol. 93, No. 11, November 1984, Brian C. Barbo: "Advanced Chemical Methods Improve Film Processing and Control Pollution", p. 1064 *

Also Published As

Publication number Publication date
DE69003396T2 (de) 1994-05-11
WO1991007698A1 (fr) 1991-05-30
JP2944204B2 (ja) 1999-08-30
GB8925311D0 (en) 1989-12-28
JPH05505244A (ja) 1993-08-05
DE69003396D1 (de) 1993-10-21
EP0500592A1 (fr) 1992-09-02

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