EP0609940A1 - Procédé de traitement d'un matériau photographique à l'halogénure d'argent - Google Patents

Procédé de traitement d'un matériau photographique à l'halogénure d'argent Download PDF

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Publication number
EP0609940A1
EP0609940A1 EP94200184A EP94200184A EP0609940A1 EP 0609940 A1 EP0609940 A1 EP 0609940A1 EP 94200184 A EP94200184 A EP 94200184A EP 94200184 A EP94200184 A EP 94200184A EP 0609940 A1 EP0609940 A1 EP 0609940A1
Authority
EP
European Patent Office
Prior art keywords
bromide
solution
developer
ion
bromide ion
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.)
Granted
Application number
EP94200184A
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German (de)
English (en)
Other versions
EP0609940B1 (fr
Inventor
Peter Jeffery C/O Kodak Limited 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
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
Application filed by Kodak Ltd, Eastman Kodak Co filed Critical Kodak Ltd
Publication of EP0609940A1 publication Critical patent/EP0609940A1/fr
Application granted granted Critical
Publication of EP0609940B1 publication Critical patent/EP0609940B1/fr
Anticipated expiration legal-status Critical
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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
    • G03C5/29—Development processes or agents therefor
    • G03C5/31—Regeneration; Replenishers
    • 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

Definitions

  • This invention relates to a method of processing photographic silver halide material such as photographic film and paper. In particular it relates to a method of processing 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 papers and black and white photographic materials can also be processed by replenishment systems.
  • CD4 (4-(N-ethyl-N-2-hydroxyethyl)-2-methylphenylenediamine sulphate) effluent produced during the development of colour negative films.
  • One way to achieve this is to lower the CD4 concentration in the developer and to compensate somewhere else in the overall system to restore the necessary development activity.
  • a lower bromide ion level in the development solution can help in this regard.
  • a low effluent replenishment system for colour negative developers is described and claimed in our PCT/EP/ 90/01854.
  • This system provides a very low replenishment rate. The only loss to drain is the chemistry carried over in the film into the next tank. However a difficulty in this system is maintaining the desired bromide level by balancing the removal rate with the input rate from the film.
  • a method of processing photographic silver halide material in which developing solution is treated to remove developer seasoning products and is replenished with a sufficiently small volume of replenisher components that substantially no overflow is produced characterised in that it includes a step in which a developing solution is treated with means to remove continuously substantially all bromide ion from the solution and to maintain the solution substantially free from bromide ion during operation of the method.
  • bromide ion is substantially absent from the developer or developer replenisher used in the method of the invention and bromide ion formed by the reduction of silver bromide during development is removed substantially completely as it is formed so that bromide ion effectively takes no part in the development reaction.
  • the method of the invention is applicable to the processing of any form of silver halide photographic material such as colour negative film, colour paper and black and white materials. It is very suitable for processing colour negative film, particularly by the C-41 process.
  • Colour negative films which may be processed include for example films that are commercially available and films described in Research Disclosure Item 17643, December 1978, pages 22-31, Published by Kenneth Mason Publications of Emsworth, Hampshire, United Kingdom.
  • bromide ion produced during development is removed from development solution which is continuously withdrawn from a development tank into a treatment loop with the treated solution being thereafter returned to the tank.
  • Bromide ion removal can be effected by any suitable means including ion-exchange, electrodialysis, dialysis and reverse osmosis, with ion-exchange removal being preferred. Whatever the removal means, it has suitably sufficient capacity to achieve removal of substantially all potential bromide.
  • the method of the present invention is an extension of the low effluent replenishment system for colour negative developers which is described and claimed in our PCT/EP 90/01854. It comprises the use of a reformulated developer solution which does not contain bromide ions, in addition to removal of bromide. Any bromide generated by the film is removed by means having sufficient capacity to remove bromide completely as it passes into the solution. This is easy to achieve and eliminates any need to balance exactly the removal and generation rates found to be necessary in our earlier system.
  • the ion-exchange resin is preferably anionic (for the exchange of anions).
  • 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: IRA 400 Rohm and Haas Dowex 1-X8 Dow Chemical, and Duolite A113 Diamond Shamrock.
  • the ion-exchange resin is preferably located in a cartridge through which the contents of the 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 small amount of replenisher which is added to the development solution may be in the form of a solution or a solid. It may be added in a variety of ways. In a first way of addition, the replenisher components are added as an activator solution and a solution of colour developing agent.
  • the replenisher components may be added as three separate solutions having the following compositions: PART A Potassium carbonate 470 g/l Potassium hydroxide 11 g/l Diethylenetriamine-pentaacetic acid pentasodium salt 106 g/l Sodium metabisulphite 43 g/l PART B Hydroxylamine sulphate 272 g/l PART C Sodium metabisulphite 16.5 g/l CD4 472 g/l
  • activator solution and solid CD4 colour developing agent may be made, the activator composition being suitably as follows: Potassium sulphate 24.0 g/l Hydroxylamine sulphate 13.4 g/l Anti-cal 6.5 g/l Potassium carbonate 37.5 g/l where Anti-cal is the penta sodium salt of diethylene triamine penta acetic acid and the pH is 11.6.
  • Approximate replenishment rates for the above 3 part replenisher are as follows: Part A 16.8 to 49.5 ml/m2 of film Part B 1.87 to 6.5 ml/m2 of film Part C 3.5 to 6.5 ml/m2.of film.
  • the method of the invention allows developer solutions to be used which contain lower levels of colour developers compared with the solutions used in the standard C-41 process.
  • the levels which can be used suitably are between 10% and 100% of those used in the standard process and preferably in the range 25% to 50% of those used in the standard C-41 process.
  • a zero-sulphite developer can be used with advantage since sulphite ions are removed to some extent during its operation. This adds the advantage that any variability in sulphite level introduced by operation of the method will be eliminated.
  • Figure 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.
  • the ion-exchange resin used is preferably anionic as described above and is preferably located in a cartridge also as described above.
  • the small amount of replenisher necessary may be a solution or a solid and may be added by one of the ways described above.
  • bromide ion was removed from C-41 developer solution as shown in Figure 1. Bromide removal was by ion-exchange and the resin used in the experiment was IRA 400 regenerated with potassium carbonate (5%). The complete removal of bromide ion at the same time as replenishing with the minimum volume might at first sight be thought to need a large column or frequent renewal of a smaller column thereby making the method impractical. A simple consideration shows that this is not the case. In the earlier zero-overflow replenishment system ( PCT/EP 90/01854 ) all excess bromide is removed to maintain a tank level of 1.3 g/l sodium bromide.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
EP19940200184 1993-01-30 1994-01-27 Procédé de traitement d'un matériau photographique à l'halogénure d'argent Expired - Lifetime EP0609940B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9301857 1993-01-30
GB939301857A GB9301857D0 (en) 1993-01-30 1993-01-30 Method of processing photographic silver halide material

Publications (2)

Publication Number Publication Date
EP0609940A1 true EP0609940A1 (fr) 1994-08-10
EP0609940B1 EP0609940B1 (fr) 1999-11-10

Family

ID=10729573

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19940200184 Expired - Lifetime EP0609940B1 (fr) 1993-01-30 1994-01-27 Procédé de traitement d'un matériau photographique à l'halogénure d'argent

Country Status (4)

Country Link
EP (1) EP0609940B1 (fr)
JP (1) JPH06242560A (fr)
DE (1) DE69421555T2 (fr)
GB (1) GB9301857D0 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0729066A1 (fr) * 1995-02-21 1996-08-28 Eastman Kodak Company Séparation de l'étain de développeurs photographiques couleurs utilisés
US5843629A (en) * 1996-08-21 1998-12-01 Eastman Kodak Company Method of treating a seasoned ascorbic acid developer
US5869223A (en) * 1996-10-08 1999-02-09 Eastman Kodak Company Method for replenishing an ascorbic acid developer

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019216830A (ja) 2018-06-15 2019-12-26 株式会社トライテック 硬性内視鏡のカバーおよび内視鏡ユニット

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4529687A (en) * 1982-10-07 1985-07-16 Fuji Photo Film Co., Ltd. Method to form color image
EP0325277A2 (fr) * 1988-01-21 1989-07-26 Fuji Photo Film Co., Ltd. Procédé de traitement d'un matériau photographique couleur à l'halogénure d'argent
EP0368340A1 (fr) * 1988-11-10 1990-05-16 Fuji Photo Film Co., Ltd. Procédé de traitement de matériaux photosensibles à l'halogénure d'argent pour photographie en couleurs
WO1991007698A1 (fr) * 1989-11-09 1991-05-30 Kodak Limited Systeme de regeneration a effluent lent pour revelateurs de negatifs en couleur
US5063144A (en) * 1988-02-24 1991-11-05 Agfa Gevaert Aktiengesellschaft Photographic color developer solution and a process for the development of a color photographic material

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4529687A (en) * 1982-10-07 1985-07-16 Fuji Photo Film Co., Ltd. Method to form color image
EP0325277A2 (fr) * 1988-01-21 1989-07-26 Fuji Photo Film Co., Ltd. Procédé de traitement d'un matériau photographique couleur à l'halogénure d'argent
US5063144A (en) * 1988-02-24 1991-11-05 Agfa Gevaert Aktiengesellschaft Photographic color developer solution and a process for the development of a color photographic material
EP0368340A1 (fr) * 1988-11-10 1990-05-16 Fuji Photo Film Co., Ltd. Procédé de traitement de matériaux photosensibles à l'halogénure d'argent pour photographie en couleurs
WO1991007698A1 (fr) * 1989-11-09 1991-05-30 Kodak Limited Systeme de regeneration a effluent lent pour revelateurs de negatifs en couleur

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0729066A1 (fr) * 1995-02-21 1996-08-28 Eastman Kodak Company Séparation de l'étain de développeurs photographiques couleurs utilisés
US5843629A (en) * 1996-08-21 1998-12-01 Eastman Kodak Company Method of treating a seasoned ascorbic acid developer
US5869223A (en) * 1996-10-08 1999-02-09 Eastman Kodak Company Method for replenishing an ascorbic acid developer

Also Published As

Publication number Publication date
DE69421555D1 (de) 1999-12-16
JPH06242560A (ja) 1994-09-02
GB9301857D0 (en) 1993-03-17
DE69421555T2 (de) 2000-05-31
EP0609940B1 (fr) 1999-11-10

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