EP0742481A1 - Procédé de traitement de matériaux photographiques en noir et blanc - Google Patents

Procédé de traitement de matériaux photographiques en noir et blanc Download PDF

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Publication number
EP0742481A1
EP0742481A1 EP96201165A EP96201165A EP0742481A1 EP 0742481 A1 EP0742481 A1 EP 0742481A1 EP 96201165 A EP96201165 A EP 96201165A EP 96201165 A EP96201165 A EP 96201165A EP 0742481 A1 EP0742481 A1 EP 0742481A1
Authority
EP
European Patent Office
Prior art keywords
tank
fixer
wash
silver
stabiliser
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.)
Withdrawn
Application number
EP96201165A
Other languages
German (de)
English (en)
Inventor
Christopher Barrie Rider
Mark Joseph Devaney
Paul W Wagner
Andrew Michael Wyner
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.)
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 EP0742481A1 publication Critical patent/EP0742481A1/fr
Withdrawn legal-status Critical Current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
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/395—Regeneration of photographic processing agents other than developers; Replenishers therefor
    • G03C5/3958—Replenishment processes or compositions, i.e. addition of useful photographic processing agents
    • 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
    • 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

Definitions

  • This invention relates to the processing of photographic materials and particularly to the fixing and washing of said materials.
  • replenisher solution containers and effluent containers are housed within the processor.
  • no external plumbing e.g. to a water supply or drain, is required for these machines.
  • replenisher solutions and effluent are brought to and from the machine in suitable containers.
  • the replenishment rates be as low as possible.
  • Washing photographic materials is necessary to remove any processing chemicals from the processed material which might, in time, degrade the image. This degradation may happen though destruction of the image - i.e. a lowering of density - or it may happen through an increase in density as coloured substances are formed within the film or paper. Temperature, humidity and light all have a strong effect in accelerating these processes. To preserve an image adequately, the level of residual chemicals in the processed film must be kept low. In particular, the fixing agent and by-products of the fixing reaction are known to cause image degradation if they are retained in significant amounts in the film.
  • Stabiliser solutions may also be used instead of water for the wash section of a processor.
  • Stabilisers usually contain additives such as a wetting agent to enhance washing and drying, a biocide to guard against biogrowth in the solution or on tank and roller surfaces, hardening agents and possibly other additives to retard the effects of ageing in the processed photographic material.
  • Soluble complexes of silver with fixing agent are by-products from the fixing reaction. These complexes are produced in the photographic material as the fixing agent reacts with undeveloped silver in the form of silver halide. The complexes diffuse out of the material and into the bulk of the fixing solution. Without silver recovery on the fixing bath, the concentration of complexed silver may build up to quite high levels, especially when low replenishment rates are used for the fixer (ie there is no substantial dilution of fixing by-products due to the addition of replenisher) and when the level of silver in the photosensitive material is high. Since fixing rate shows an inverse dependence on silver concentration in the fixer bath, the time required to clear the film will also depend on the silver level.
  • a particular problem for graphic arts films is a rise in the optical density in the ultra-violet region of the spectrum of the non-image areas, referred to as "UV D min ", upon ageing of processed film.
  • UV D min ultra-violet contact exposures are used to copy a graphic arts film onto a printing plate or another piece of film and very high contrast images are needed for accurate copying.
  • the contrast of the image is effectively lowered.
  • inaccuracies may result.
  • the minimum density of the image increases, the overall exposure time for the copying process increases.
  • changes in the tone scale and contrast of the image upon ageing are also detrimental even if no further copying process is involved because the quality of the image is reduced.
  • Fixing is a two-part process: first undeveloped silver is converted to a soluble silver salt within the film (i.e. clearing) and then the soluble salt is washed out.
  • fixing times have been reduced so that the "washing out” part of the fixing process has significantly less time allocated than the "solubilisation” part of the process. If a fixed film does not have sufficient time to equilibrate with the fixer bath, with the result that the washing out of the soluble silver salts is substantially incomplete, it will carry over into the wash section a greater quantity of silver than expected, thus making more demands on the wash section. It is therefore preferable both to maintain a low level of silver in the fixer, and also to allow enough time so that the "washing-out" part of the fixing process is virtually complete.
  • US patent 5,019,850 (Ishikawa et al) describes a photographic processor for colour paper in which the bleach/fixing bath is replenished with a mixture of concentrated processing liquid and liquid extracted from the wash section.
  • One example describes a processor in which the bleach-fix bath is replaced by a separate bleach and fix followed by 3 wash baths where some of the wash solution in the first wash bath is pumped into the fixer bath together with some fixer concentrate. There is no reference to black-and-white materials.
  • coated silver weights of around 3 grams per square metre or more are typical whereas for a colour paper, the coated silver weight will typically be less than 1 gram per square metre. The demands placed upon the fix and wash baths are therefore very different.
  • the problem to be solved by the present invention is how to efficiently fix and wash black and white silver halide photographic materials, for example graphic arts (very high contrast) or radiographic materials, using the minimum amount of water for washing while retaining adequate image stability, the materials having been processed in a processor in which the fixer tank contains high levels of silver, for example, one which is not equipped with any means of silver recovery.
  • concentrated fixer solution may be used as replenisher to be diluted by the addition of wash water so that the volume of fixer solution used is reduced compared with the case when working strength replenisher is used.
  • Washing performance is improved either by enabling a reduction in wash water used or by enabling a reduction in washing time or both.
  • a further effect of lowering of the silver level in the fixer is that the carry-out of silver from the fixer solution by the photographic material being processed is lowered. This results in lower concentrations of silver in the wash bath(s) with the consequence that the level of residual silver in the processed film also reduces. This advantage may be traded for a reduction in wash replenishment rates or washing time.
  • Figures 1, 2 3 and 4 show embodiments of the present invention and Figure 5 is a graph showing the results of the Example below.
  • the total submersion time in the tank(s) having fixing ability is no more than 20 seconds.
  • the preferred method of operation is to use the entire outflow of the wash/stabiliser tank nearest the fixer tank to dilute concentrated fixer replenisher solution added to said fixer tank.
  • the concentration of silver in at least one of the baths with fixing ability is greater than 10 g/l, more preferably greater than 15 g/l.
  • the fixer replenishment rate is below 125 ml/m 2 , particularly below 75 ml/m 2 and especially below 65 ml/m 2 of material processed.
  • the wash or stabiliser replenishment rate is preferably below 250 ml/m 2 , especially below 150 ml/m 2 and particularly below 125 ml/m 2 of material processed.
  • fixing times should be short. Fixing time is normally set for a given material type and processor by determining the time required to adequately fix the material under the worst conditions for fixing, i.e. when there is a high concentration of silver and other seasoning products in the fixer. This situation will arise when the film has received a low average exposure level.
  • a common rule-of-thumb has been used for many years in black-and-white processing: namely that fixing time should be twice the clearing time, i.e. double the time at which all the silver has been solubilised.
  • a preferred fixing time can be defined as one where 80% of the silver is removed from a non-image area of the material being processed in 80% of the fixer submersion time when the fixer bath has been seasoned with substantially unexposed film. This definition removes all the safety margins associated with the old rule-of-thumb and can therefore be considered as defining an acceptable "short" fixer submersion time.
  • a simple formula may be used to provide a good estimate of the concentration of a fixer bath which has been seasoned with unexposed film in the case where the processor is operated in the manner of the present invention, i.e. where all the outflow of the wash section is passed into the fixer bath.
  • F is the volume of fixer replenisher added to the fixing bath per unit area of film processed
  • W is the volume of wash solution taken out of the first wash bath and added to the fixer bath per unit area of film processed
  • A is the coated weight of silver in the film per unit area (which is all assumed to be solubilised in the fixing bath)
  • ⁇ is the difference in volume between the carryout per unit area of film from the last wash bath and the last fixer bath (taking account of small gelatin swell changes)
  • a is the residual silver remaining in the film after leaving the last wash bath
  • C fmax is the maximum silver concentration in the first fixer bath (i.e. the fixer effluent concentration)
  • Fig 1 shows a conventional processor which includes a developer tank (1), a fixer tank (2) and two wash tanks (3 & 4).
  • the developer tank (1) is replenished from a holding tank (5) of previously mixed working strength developer replenisher, which is pumped into the developer tank at an appropriate rate by means of pump (10).
  • the fixer tank (2) is replenished by means of pump (11), passing fixer concentrate from the holding vessel (26) into the fixer tank (2) at an appropriate rate.
  • Wash tanks (3) and (4) are arranged such that when fresh wash solution is pumped from holding tank (15) by pump (16) into wash tank (4), the overflow so produced passes into wash tank (3), forming a conventional counter-flow wash section.
  • Overflow (25) from the wash tank(s) passes out of the processor as effluent as does fixer overflow (14) and developer overflow (13).
  • FIG. 2 shows one embodiment of the present invention.
  • the processor includes a developer tank (1), a fixer tank (2) and two wash tanks (3 & 4).
  • the developer tank (1) is replenished from a holding tank (5) of previously mixed working strength developer replenisher, which is pumped into the developer tank at an appropriate rate by means of pump (10).
  • the fixer tank (2) is replenished by means of pump (11), passing working strength fixer replenisher from the holding vessel (6) and pump (12) passing wash water from wash tank (3) into the fixer tank (2) at an appropriate rate.
  • the rates of replenishment of the solutions supplied by pumps (11) and (12) are maintained in a predetermined ratio.
  • Wash tanks (3) and (4) are arranged such that when fresh wash solution is pumped from holding tank (15) by pump (16) into wash tank (4), the overflow so produced passes into wash tank (3), forming a conventional counter-flow wash section.
  • Level sensor (9) detects when the level of wash solution in wash tank (3) drops below a certain predetermined level. When the level drops below this predetermined level, a signal produced by the level sensor control means (7) sends a signal to pump (16) to add fresh wash solution to wash tank (4).
  • the level sensor control means ends the flow of fresh wash solution into wash tank (4).
  • Extra level sensors may also be provided so that evaporation losses may be controlled and appropriate extra solution replenishment may be made in any of the tanks.
  • Figure 3 shows a processor similar to that described in figure 2 except that it is provided with two fixer tanks (21 & 22) and only one wash tank (23).
  • the fixer tanks are arranged so that replenisher solutions are pumped into fixer tank (22) and the overflow thereby produced passes into fixer tank (21).
  • the wash tank (23) is provided with a sump (17) from which wash solution is recirculated by pump (16) which continually pumps solution from the sump (17) into the wash tank (23).
  • the overflow from the wash tank (23) passes down a pipe (20) back into the sump.
  • a float valve (24) senses the level in the sump. If the level drops sufficiently to open the valve (18), fresh water from the mains supply (19) passes into the sump under pressure.
  • Fixer replenishment is accomplished by taking wash solution either from the sump (17) (as shown) or by withdrawing it directly from the wash tank (not shown) and pumping it into fixer tank (22) by means of pump (12).
  • pump (11) withdraws fixer concentrate from the holding vessel (6) and supplies it to fixer tank (22) in a predetermined ratio compared with that supplied by (12).
  • Extra level sensors may also be provided so that evaporation losses may be controlled and appropriate extra solution replenishment may be made in any of the tanks.
  • FIG. 4 shows another embodiment of the present invention.
  • the processor is provided with single developer (1), fixer (2) and two wash tanks (3 & 4). Wash water pump (16) and fixer concentrate pump (11) are operated simultaneously to deliver solutions from tanks (15) and (6) respectively in a predetermined ratio of volumes. The action of pump (16) replenishing the wash tank (4) causes the overflow to cascade into the fixer tank (2). Extra level sensors (not shown) may also be provided so that evaporation losses may be controlled and appropriate extra solution replenishment may be made in any of the tanks.
  • Figure 5 is a graph showing the silver carried out of the fixing solution by the photographic material as a function of submersion time in the fixer solution. The data plotted resulted from the following example which is included for a better understanding of the invention.
  • Black-and-white photographic materials in particular graphic arts high contrast materials and radiographic materials, are well known. They may have silver coating weights in the range 1 to 15 g/m 2 , typically 2 to 8 g/m 2 , and most typically 2.5 to 6 g/m 2 .
  • Exposure was about 2% by area (in order to produce a very high level of silver in the fixer since 98% of the coated silver would not result in a developed image and would therefore need to be fixed), wash replenishment rate was 125 ml/m 2 , and fixer replenishment rate was also 125 ml/m 2 .
  • the fixer replenisher was made from a concentrate (formula A as shown in Table 1 below) diluted at 2 parts by volume water to 1 part by volume concentrate. Development and fixing times were both 25 seconds at 35°C and the wash time was 30 seconds in total at 20°C. A fixing time of 25 seconds corresponded to a fixer submersion time of 20 seconds in the processor used for the experiment since the ratio of air time to submersion time was 1:4. Several hundred square metres of film were processed to ensure that the fix and wash baths were fully seasoned.
  • the processing times include the time taken to travel through the air between processing tanks. So, for example, the development time is defined as the time taken from when the front edge of a piece of film just touches the developer solution in the developer tank to when it just touches the solution in the fixing tank. This range of processing times corresponds to a range of fixer submersion times from 12 seconds to 32 seconds).
  • the wet film samples were not washed, being removed from the processor after they had passed out of the last roller pair nip at the exit of the fixer bath.
  • the processor was then converted to be able to implement the present invention in the form shown in figure 2 (case B). Processing and exposure conditions were unchanged, except that a re-balanced fixer concentrate (formula B as shown in Table 1 above) was used directly to replenish the fixer tank at a replenishment rate of 62 ml/m 2 . The wash replenishment rate remained at 125 ml/m 2 .
  • a re-balanced fixer concentrate (formula B as shown in Table 1 above) was used directly to replenish the fixer tank at a replenishment rate of 62 ml/m 2 .
  • the wash replenishment rate remained at 125 ml/m 2 .
  • case B gives a very significantly greater benefit than might be expected from a simple consideration of the fixer silver concentrations in the two cases: at the end of the case A experiment, the fixer silver level was 21 g/l, whereas at the end of the case B experiment, the fixer silver level was 18.5 g/l. Thus, the fixer silver level for case B was 88% of that for case A.
  • wash replenishment rate should not be so low that sufficient dilution of the fixing agent in the washing bath is not achieved and residual fixing agent in the processed material becomes the key determinant of image stability upon ageing.
  • fixing rate may be increased by raising the temperature of the fixing bath. This is not generally desirable since evaporation from the fixer bath is thereby increased and problems of crystallisation of fixer on rollers and creep of fixing agent over tank walls to adjacent tanks is increased. Furthermore, energy required to heat the solutions is increased and warm-up time is also increased.
  • Most graphic arts processors are run at fixing temperatures of 35°C which is sufficient to be above ambient temperature in most parts of the world. It is known for radiographic processors to use fixer temperatures of 38°C.
  • Fixer submersion times under consideration are less than 24 seconds. Greater benefit would be seen with submersion times less than or equal to 20 seconds.
  • Maximum expected silver concentrations under consideration are preferably greater than 10 g/l and most preferably greater than 15 grams/litre.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Photographic Processing Devices Using Wet Methods (AREA)
EP96201165A 1995-05-04 1996-04-29 Procédé de traitement de matériaux photographiques en noir et blanc Withdrawn EP0742481A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9509079 1995-05-04
GBGB9509079.1A GB9509079D0 (en) 1995-05-04 1995-05-04 Method of processing black-and-white photographic materials

Publications (1)

Publication Number Publication Date
EP0742481A1 true EP0742481A1 (fr) 1996-11-13

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EP96201165A Withdrawn EP0742481A1 (fr) 1995-05-04 1996-04-29 Procédé de traitement de matériaux photographiques en noir et blanc

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EP (1) EP0742481A1 (fr)
JP (1) JPH08304970A (fr)
GB (1) GB9509079D0 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2318189A (en) * 1996-10-09 1998-04-15 Eastman Kodak Co Photographic fixer
US7001085B2 (en) 2001-05-18 2006-02-21 Eastman Kodak Company Method and system for processing of photographic materials

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57157243A (en) * 1981-03-24 1982-09-28 Konishiroku Photo Ind Co Ltd Processing method for photographic sensitive silver halide material
JPS60235133A (ja) * 1984-05-08 1985-11-21 Konishiroku Photo Ind Co Ltd ハロゲン化銀写真感光材料の処理方法
US4839273A (en) * 1986-10-02 1989-06-13 Fuji Photo Film Co., Ltd. Process for the development of silver halide photographic material
US4855218A (en) * 1987-02-13 1989-08-08 Fuji Photo Film Co., Ltd. Method for processing silver halide photographic lightsensitive materials
US4960683A (en) * 1987-06-29 1990-10-02 Fuji Photo Film Co., Ltd. Method for processing a black-and-white photosensitive material

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57157243A (en) * 1981-03-24 1982-09-28 Konishiroku Photo Ind Co Ltd Processing method for photographic sensitive silver halide material
JPS60235133A (ja) * 1984-05-08 1985-11-21 Konishiroku Photo Ind Co Ltd ハロゲン化銀写真感光材料の処理方法
US4839273A (en) * 1986-10-02 1989-06-13 Fuji Photo Film Co., Ltd. Process for the development of silver halide photographic material
US4855218A (en) * 1987-02-13 1989-08-08 Fuji Photo Film Co., Ltd. Method for processing silver halide photographic lightsensitive materials
US4960683A (en) * 1987-06-29 1990-10-02 Fuji Photo Film Co., Ltd. Method for processing a black-and-white photosensitive material

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 8602, Derwent World Patents Index; Class G06, AN 86-010682, XP002012300 *
PATENT ABSTRACTS OF JAPAN vol. 6, no. 262 (P - 164)<1140> 21 December 1982 (1982-12-21) *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2318189A (en) * 1996-10-09 1998-04-15 Eastman Kodak Co Photographic fixer
US5882848A (en) * 1996-10-09 1999-03-16 Eastman Kodak Company Photographic fixing composition
GB2318189B (en) * 1996-10-09 2000-09-06 Eastman Kodak Co Photographic fixing composition
US7001085B2 (en) 2001-05-18 2006-02-21 Eastman Kodak Company Method and system for processing of photographic materials

Also Published As

Publication number Publication date
GB9509079D0 (en) 1995-06-28
JPH08304970A (ja) 1996-11-22

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