EP0500764B1 - Replenishment system for colour paper developer - Google Patents
Replenishment system for colour paper developer Download PDFInfo
- Publication number
- EP0500764B1 EP0500764B1 EP91900015A EP91900015A EP0500764B1 EP 0500764 B1 EP0500764 B1 EP 0500764B1 EP 91900015 A EP91900015 A EP 91900015A EP 91900015 A EP91900015 A EP 91900015A EP 0500764 B1 EP0500764 B1 EP 0500764B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- developer
- replenishment
- colour
- exchange resin
- components
- 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
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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
- G03C7/44—Regeneration; Replenishers
Definitions
- This invention relates to a method of processing photographic silver halide colour material and in particular to the replenishment of a developer solution system for colour paper.
- replenishment systems of the prior art liquid replenisher is added to the developer solution and spent developer is removed by allowing overflow. A stable condition in which chemicals used up during processing are replenished to maintain a working concentration may thus be maintained.
- replenishment systems which involve overflow are environmentally undesirable and the objective of the present invention is to provide a replenishment system without overflow.
- a system for replenishing a colour paper processing system is described in European Specification No. 0,173,203.
- Using 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. This is a major operation and is best avoided if a simpler option as is described in our invention is available.
- Another special case is where even though seasoning products do build-up with use, they do not affect sensitometry because the developer used already contains a more powerful inhibitor.
- 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 method of processing a photographic silver halide colour paper including the steps of replenishing the colour developer solution with a sufficiently small volume of replenishment components such that substantially no overflow is produced and removing by an in-line ion exchange resin system components which build up to an excessive concentration.
- 'In-line' means that the ion exchange system is contained in an integrated facility connected or connectable with the tank in which the processing takes place.
- the overall volume of replenishment added is approximately equal to the volume loss caused by take-off by the paper and evaporation.
- the build-up in the liquid system of halides, principally chlorides, and to some extent sulphates is controlled by an on-line ion exchange system which is operated from time to time to remove these undesirable ions and return the processed solution back to the vessel in which the liquid system is contained.
- a replenishment system for a colour paper development solution system essentially comprises two components:
- the colour developing agent e.g. ⁇ methane sulphonamide-ethyl ethyl aminotoluidine sesquisulphate hydrate known as CD3, and an activator/replenisher for the other elements of the system as will subsequently be explained.
- the CD3 component can be added in solid form or as a liquid concentrate.
- the salt is essentially acid so is readily dissolved in the basic development solution with no substantial increase in volume.
- the activator/replenisher is added as a liquid.
- 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 in-line 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.
- a replenishment assembly comprises: (a) Solid CD3 addition in an amount calculated at 5.76 mg/dm2 of photographic colour paper having substantially pure chloride emulsions.
- This solid additive may be in the form of an acidic pellet which dissolves readily with the evolution of carbon dioxide in the basic developer solution. As alternatives the solid additive may be on a coated tape or in some kind of perforated container. However, the simple pellet method has been found to work quite effectively.
- This activator/replenishment solution was preferably kept in, and dispensed from a collapsible container. If the volume drops due to carry out on the developed paper the level is topped up with water.
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
- Liquid Developers In Electrophotography (AREA)
- Wet Developing In Electrophotography (AREA)
- Developing Agents For Electrophotography (AREA)
Abstract
Description
- This invention relates to a method of processing photographic silver halide colour material and in particular to the replenishment of a developer solution system for colour paper.
- In the replenishment systems of the prior art liquid replenisher is added to the developer solution and spent developer is removed by allowing overflow. A stable condition in which chemicals used up during processing are replenished to maintain a working concentration may thus be maintained. However, replenishment systems which involve overflow are environmentally undesirable and the objective of the present invention is to provide a replenishment system without overflow.
- A system for replenishing a colour paper processing system is described in European Specification No. 0,173,203. Using 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. This is a major operation and is best avoided if a simpler option as is described in our invention is available. Another special case is where even though seasoning products do build-up with use, they do not affect sensitometry because the developer used already contains a more powerful inhibitor. For example, if a sensitized material containing a high silver chloride content is processed in a developer containing soluble sodium bromide (0.7 g/l), then the increase in chloride level during use would only have a small effect on sensitometry. This is similar to the method employed in EP-A-0,173,203 for a colour paper developer. To some extent this is an artificial case because high silver chloride coatings are best processed with much lower levels of bromide (about 20 mg/l) to allow for rapid processing (e.g. the RA-4 process). If seasoning products such as chloride are allowed to build up in the RA-4 process, then sensitometry and processing rapidity are detrimentally affected.
- Whilst it is known to remove seasoning products from developers using ion-exchange resin, such resins have never been used in a system having such low replenishment rates as are achieved by the present invention. For example, in "Developer Recycling - A New Generation" Meckl, Journal of Imaging Technology, 13, (1987), 3, 85-89 there is described a system in which the overflow from the colour developer tank is passed to a holding tank and then through ion-exchange resin to remove bromide ions. The so treated solution is then passed to a mixing tank where replenisher components are added and the newly formed solution is then passed to the replenisher tank ready for use. The replenishment rate for a paper process is said to be 325 ml/m².
- 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.
- In accordance with the present invention there is provided a method of processing a photographic silver halide colour paper including the steps of replenishing the colour developer solution with a sufficiently small volume of replenishment components such that substantially no overflow is produced and removing by an in-line ion exchange resin system components which build up to an excessive concentration.
- 'In-line' (or on-line) means that the ion exchange system is contained in an integrated facility connected or connectable with the tank in which the processing takes place.
- The overall volume of replenishment added is approximately equal to the volume loss caused by take-off by the paper and evaporation. The build-up in the liquid system of halides, principally chlorides, and to some extent sulphates is controlled by an on-line ion exchange system which is operated from time to time to remove these undesirable ions and return the processed solution back to the vessel in which the liquid system is contained.
- A replenishment system for a colour paper development solution system essentially comprises two components:
- The colour developing agent,e.g.β methane sulphonamide-ethyl ethyl aminotoluidine sesquisulphate hydrate known as CD3, and an activator/replenisher for the other elements of the system as will subsequently be explained.
- Preferably the CD3 component can be added in solid form or as a liquid concentrate. The salt is essentially acid so is readily dissolved in the basic development solution with no substantial increase in volume. The activator/replenisher is added as a liquid.
- The ion-exchange resin may comprise anionic (for the exchange of anions) or amphoteric types or mixtures thereof. A preferred type of 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
- Dorvex l-X8
- Dow Chemical, and
- Duolite All3
- Diamond Shamrock
- The in-line 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 invention will be described by way of Example and with reference to the accompanying drawings wherein:-
- Figure 1 is a diagram of the development tank and in-line ion-exchange; and
- Figure 2 is a control plot.
- The example given is for colour paper having substantially pure silver chloride emulsions however the principle is valid for chlorobromide emulsions or any other silver halide or mixed silver halide emulsions used with the appropriate processing solutions.
-
- The approximate replenishment rates for the above 3 part replenisher would be:
- Part A
- 3 ml/m²
- Part B
- 1.6 ml/m²
- Part C
- 1.6 ml/m²
- A replenishment assembly comprises: (a) Solid CD3 addition in an amount calculated at 5.76 mg/dm² of photographic colour paper having substantially pure chloride emulsions. This solid additive may be in the form of an acidic pellet which dissolves readily with the evolution of carbon dioxide in the basic developer solution. As alternatives the solid additive may be on a coated tape or in some kind of perforated container. However, the simple pellet method has been found to work quite effectively. (b) A solution of replenisher/activator which is added at 3.06 mls per sq.ft.(0.33 mg/dm²) and comprises:
The pH of the solution is 11.30 - This activator/replenishment solution was preferably kept in, and dispensed from a collapsible container. If the volume drops due to carry out on the developed paper the level is topped up with water.
- With the above system an in-line, recirculatory ion exchange system is incorporated as shown in Figure 1. This system uses IRA400 resin and the developer solution is pumped through the resin intermittently at a rate of about 3.7 ml per sq.ft. (0.40 mg/dm²) of processed paper and then returned directly to the tank. This procedure essentially removes all the chloride and sulphate from the volume of developer that passes through and the above rate is calculated so that the total chloride and sulphate removal is equivalent to the build up rate. The control plot in Figure 2 of the accompanying drawings shows that the CD3 level was maintained within the defined limits through the course of a run of 5 months.
- Reference is made to the International Application of even date claiming priority from G.B. Application No. 8925311.6.
Claims (3)
- A method of processing a photographic silver halide colour paper including the steps of replenishing the colour developer solution with a sufficiently small volume of replenishment components such that substantially no overflow is produced and removing by an in-line ion exchange resin system components which build up to an excessive concentration.
- A method according to Claim 1 wherein the small volume replenishment components comprises the developer in the form of a solid or liquid concentrate and other components in the form of a liquid.
- A method according to either Claim 1 or Claim 2 wherein the ion exchange resin is an ionic and based on a cross-linked polystyrene matrix.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT91900015T ATE96234T1 (en) | 1989-11-09 | 1990-10-31 | REPLENISHMENT AND REFILL SYSTEM FOR COLOR IMAGE DEVELOPERS. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB8925276 | 1989-11-09 | ||
GB898925276A GB8925276D0 (en) | 1989-11-09 | 1989-11-09 | Replenishment system for colour paper developer |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0500764A1 EP0500764A1 (en) | 1992-09-02 |
EP0500764B1 true EP0500764B1 (en) | 1993-10-20 |
Family
ID=10665969
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP91900015A Expired - Lifetime EP0500764B1 (en) | 1989-11-09 | 1990-10-31 | Replenishment system for colour paper developer |
Country Status (6)
Country | Link |
---|---|
EP (1) | EP0500764B1 (en) |
JP (1) | JP2944205B2 (en) |
AT (1) | ATE96234T1 (en) |
DE (1) | DE69004100T2 (en) |
GB (1) | GB8925276D0 (en) |
WO (1) | WO1991007699A1 (en) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
WO2004095130A1 (en) * | 2003-04-23 | 2004-11-04 | Konica Minolta Photo Imaging, Inc. | Method of processing silver halide photographic lightsensitive material |
WO2004095131A1 (en) * | 2003-04-23 | 2004-11-04 | Konica Minolta Photo Imaging, Inc. | Silver halide photographic lightsensitive material and method of processing the same |
WO2004095132A1 (en) * | 2003-04-23 | 2004-11-04 | Konica Minolta Photo Imaging, Inc. | Silver halide photographic lightsensitive material and method of processing the same |
WO2004095129A1 (en) * | 2003-04-23 | 2004-11-04 | Konica Minolta Photo Imaging, Inc. | Silver halide photographic lightsensitive material and method of processing the same |
WO2004095128A1 (en) * | 2003-04-23 | 2004-11-04 | Konica Minolta Photo Imaging, Inc. | Method of processing silver halide photographic lightsensitive material |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5674247A (en) * | 1979-11-22 | 1981-06-19 | Konishiroku Photo Ind Co Ltd | Method for continuously processing silver halide photographic material |
DE3431860A1 (en) * | 1984-08-30 | 1986-03-06 | Agfa-Gevaert Ag, 5090 Leverkusen | METHOD FOR PRODUCING COLOR PHOTOGRAPHIC IMAGES |
JPH0830881B2 (en) * | 1988-11-10 | 1996-03-27 | 富士写真フイルム株式会社 | Processing method of silver halide color photographic light-sensitive material |
-
1989
- 1989-11-09 GB GB898925276A patent/GB8925276D0/en active Pending
-
1990
- 1990-10-31 DE DE91900015T patent/DE69004100T2/en not_active Expired - Fee Related
- 1990-10-31 AT AT91900015T patent/ATE96234T1/en not_active IP Right Cessation
- 1990-10-31 EP EP91900015A patent/EP0500764B1/en not_active Expired - Lifetime
- 1990-10-31 WO PCT/EP1990/001837 patent/WO1991007699A1/en active IP Right Grant
- 1990-10-31 JP JP3500624A patent/JP2944205B2/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
JP2944205B2 (en) | 1999-08-30 |
WO1991007699A1 (en) | 1991-05-30 |
ATE96234T1 (en) | 1993-11-15 |
DE69004100D1 (en) | 1993-11-25 |
JPH05502115A (en) | 1993-04-15 |
DE69004100T2 (en) | 1994-03-17 |
EP0500764A1 (en) | 1992-09-02 |
GB8925276D0 (en) | 1989-12-28 |
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