EP0609939A1 - Verfahren zur Verarbeitung eines photographischen Silberhalogenidmaterials - Google Patents

Verfahren zur Verarbeitung eines photographischen Silberhalogenidmaterials Download PDF

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Publication number
EP0609939A1
EP0609939A1 EP94200183A EP94200183A EP0609939A1 EP 0609939 A1 EP0609939 A1 EP 0609939A1 EP 94200183 A EP94200183 A EP 94200183A EP 94200183 A EP94200183 A EP 94200183A EP 0609939 A1 EP0609939 A1 EP 0609939A1
Authority
EP
European Patent Office
Prior art keywords
developer
ion
bromide ion
bromide
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.)
Granted
Application number
EP94200183A
Other languages
English (en)
French (fr)
Other versions
EP0609939B1 (de
Inventor
Peter Jeffrey C/O Kodak Limited Twist
Paul Mary C/O Kodak Limited Magee
Nigel Richard C/O Kodak Limited Wildman
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 EP0609939A1 publication Critical patent/EP0609939A1/de
Application granted granted Critical
Publication of EP0609939B1 publication Critical patent/EP0609939B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • 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
    • G03C5/31—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
    • G03C7/44—Regeneration; Replenishers

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 method of processing photographic silver halide material 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 replenisher developer 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 can be used in the low effluent replenishment system for colour negative developers which is described and claimed in our PCT/EP 90/01854.
  • 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 replenisher which is added to the development solution may be in the form of a solution, having a pH of 10.09, of the following composition: Potassium carbonate 37.5 g/l Sodium bromide 0.45 g/l Anti-cal 6.5 ml/l Sodium sulphite 4.85 g/l Hydroxylamine sulphate 3.4 g/l CD4 5.9 g/l where Anti-cal is the penta sodium salt of diethylene triamine penta acetic acid.
  • 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.
  • 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, e.g. with a pump, preferably only when there is film being processed.
  • the ion-exchange resin used is preferably anionic as described above and is preferably located in a cartridge also as described above.
  • the replenisher 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.
  • Analysis of the solution after the ion-exchange treatment gave the results which are summarised in Figure 2, which shows plots for concentrations of (1) sodium bromide, (2) sodium sulphite, (3) sodium sulphate and (4) CD4 against the number of bed volumes.
  • One bed volume is equal to the volume of resin beads in the column and was about 50 ml.
  • the resin used was IRA 400 ( Rohm and Haas ). This was regenerated with ten bed volumes of potassium carbonate solution,(5%) and then washed with five bed volumes of water.
  • a series of single layer coatings with a fast magenta emulsion and a magenta coupler (Iso 400 speed) were processed in standard C-41 developer (a) and in an experimental developer containing zero bromide ion and half the CD4 level of C-41 (b) to (d).
  • the compositions of the developers were as follows: Standard 4.5 g/L CD4 developer, 1.3 g/L NaBr Experimental 2.25 g/L CD4 developer, 0.0 g/L NaBr Using the experimental developer processing took place at 3 different development times i.e. 0.5 minutes (b), 0.75 minutes (c) and 1.0 minutes (d).
  • the development time for the standard was 2.5 minutes. In all cases the development temperature was 37.8 o C.
  • Curve a) is for standard C-41 developer containing 1.3 g/l sodium bromide
  • Curve b) is for experimental developer containing 1.125 g/l CD-4 and zero bromide ion
  • Curve c) is for experimental developer containing 1.125 g/l CD-4, zero bromide ion and 0.002 g/l of 5-methyl benzotriazole. Development times were a) 2.5 minutes and b) and c) 2.08 minutes each.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
EP19940200183 1993-01-30 1994-01-27 Verfahren zur Verarbeitung eines photographischen Silberhalogenidmaterials Expired - Lifetime EP0609939B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9301852 1993-01-30
GB939301852A GB9301852D0 (en) 1993-01-30 1993-01-30 Method of processing photographic silver halide material

Publications (2)

Publication Number Publication Date
EP0609939A1 true EP0609939A1 (de) 1994-08-10
EP0609939B1 EP0609939B1 (de) 1999-11-03

Family

ID=10729568

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19940200183 Expired - Lifetime EP0609939B1 (de) 1993-01-30 1994-01-27 Verfahren zur Verarbeitung eines photographischen Silberhalogenidmaterials

Country Status (4)

Country Link
EP (1) EP0609939B1 (de)
JP (1) JPH06242559A (de)
DE (1) DE69421424T2 (de)
GB (1) GB9301852D0 (de)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5643399A (en) 1994-05-17 1997-07-01 Carlisle Corporation Composite roofing product and apparatus and method for cleaning vulcanized rubber and for making a composite roofing product
US5456785A (en) 1994-05-17 1995-10-10 Venable; Jesse S. Composite roofing product and method and apparatus for making a composite roofing product

Citations (4)

* 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
EP0368340A1 (de) * 1988-11-10 1990-05-16 Fuji Photo Film Co., Ltd. Verarbeitungsverfahren für silberhalogenidhaltende lichtempfindliche Farbmaterialien
WO1991007698A1 (en) * 1989-11-09 1991-05-30 Kodak Limited Low effluent replenishment system for colour negative developers
US5051342A (en) * 1988-03-22 1991-09-24 Fuji Photo Film Co., Ltd. Silver halide photographic materials and method for color development thereof

Patent Citations (4)

* 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
US5051342A (en) * 1988-03-22 1991-09-24 Fuji Photo Film Co., Ltd. Silver halide photographic materials and method for color development thereof
EP0368340A1 (de) * 1988-11-10 1990-05-16 Fuji Photo Film Co., Ltd. Verarbeitungsverfahren für silberhalogenidhaltende lichtempfindliche Farbmaterialien
WO1991007698A1 (en) * 1989-11-09 1991-05-30 Kodak Limited Low effluent replenishment system for colour negative developers

Also Published As

Publication number Publication date
EP0609939B1 (de) 1999-11-03
GB9301852D0 (en) 1993-03-17
DE69421424D1 (de) 1999-12-09
DE69421424T2 (de) 2000-05-25
JPH06242559A (ja) 1994-09-02

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