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GB2303931A - Forming a photographic colour image - Google Patents

Forming a photographic colour image Download PDF

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Publication number
GB2303931A
GB2303931A GB9515515A GB9515515A GB2303931A GB 2303931 A GB2303931 A GB 2303931A GB 9515515 A GB9515515 A GB 9515515A GB 9515515 A GB9515515 A GB 9515515A GB 2303931 A GB2303931 A GB 2303931A
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United Kingdom
Prior art keywords
bleach
image
processing
silver
hydrogen peroxide
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
GB9515515A
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GB9515515D0 (en
GB2303931B (en
Inventor
John Richard Fyson
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
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Kodak Ltd
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Filing date
Publication date
Application filed by Kodak Ltd filed Critical Kodak Ltd
Priority to GB9515515A priority Critical patent/GB2303931B/en
Publication of GB9515515D0 publication Critical patent/GB9515515D0/en
Priority to JP19923396A priority patent/JPH09106053A/en
Publication of GB2303931A publication Critical patent/GB2303931A/en
Priority to US08/953,941 priority patent/US5925504A/en
Application granted granted Critical
Publication of GB2303931B publication Critical patent/GB2303931B/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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Classifications

    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/3017Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials with intensification of the image by oxido-reduction
    • G03C7/302Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials with intensification of the image by oxido-reduction using peroxides
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/3017Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials with intensification of the image by oxido-reduction
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/42Bleach-fixing or agents therefor ; Desilvering processes
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/42Bleach-fixing or agents therefor ; Desilvering processes
    • G03C7/421Additives other than bleaching or fixing agents

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)

Abstract

A method of forming a photographic image in an imagewise exposed photographic silver halide material includes a redox amplification dye image-forming step in a combined developer/amplifier solution (devamp) and a bleach step wherein: (a) the bleach solution comprises hydrogen peroxide or a compound which releases hydrogen peroxide during processing, (b) the bleach solution contains an alkali metal halide, (c) the bleach step follows the image-forming step without any intermediate processing bath, and (d) image formation by redox amplification continues in the bleach solution. The method may be used in low-volume, thin-tank processors.

Description

METHOD OF FORMING A PHOTOGRAPHIC COLOUR IMAGE Field of the Invention The invention relates to a method of forming a colour photographic image by a redox amplification method. In particular, this invention relates to processing low silver photographic materials in a redox amplifying developer followed by a bleach.
Background of the Invention Redox amplification processes have been described, for example in British Specification Nos.
1,268,126, 1,399,981, 1,403,418 and 1,560,572. In such processes colour materials are developed to produce a silver image (which may contain only small amounts of silver) and then treated with a redox amplifying solution (or a combined developeramplifier) to form a dye image.
The developer-amplifier solution contains a colour developing agent and an oxidising agent which will oxidise the colour developing agent in the presence of the silver image which acts as a catalyst.
Oxidised colour developer reacts with a colour coupler to form the image dye. The amount of dye formed depends on the time of treatment or the availability of colour coupler and is less dependent on the amount of silver in the image as is the case in conventional colour development processes.
Examples of suitable oxidising agents include peroxy compounds including hydrogen peroxide and compounds which provide hydrogen peroxide, eg addition compounds of hydrogen peroxide; cobalt (III) complexes including cobalt hexammine complexes; and periodates.
Mixtures of such compounds can also be used.
The image-forming step can be followed by a stop bath, bleach and fix, although the bleach and/or fix may be omitted if the silver coating weight of the material processed is low enough. Recently it has been proposed that the bleach bath may contain a peroxide as sole bleaching agent. Such proposals have carried the warning that rede amplification has to be stopped before bleaching otherwise colour staining will occur due to image formation continuing in the peroxide bleach solution.
Problem to be Solved by the Invention There is a continuing need to reduce photographic processing times. This is desirable as it means that processing throughput can be increased.
Summary of the Invention According to the present invention there is provided a method of forming a photographic image in an imagewise exposed photographic silver halide material which includes a redox amplification dye image-forming step in a combined developer/amplifier solution (devamp) and a bleach step wherein: (a) the bleach solution comprises hydrogen peroxide or a compound which releases hydrogen peroxide during processing, (b) the bleach solution contains an alkali metal halide, (c) the bleach step follows the image-forming step without any intermediate processing bath, and (d) image formation by redox amplification continues in the bleach solution.
Advantageous Effect of the Invention The processing time can be reduced while at the same time better colours are obtained.
The effluent from the process contains no iron as it would if a conventional ferric EDTA bleaching agent were used.
The overall chemical oxygen demand of the process is reduced.
Without the alkali metal halide in the bleach solution the emulsion layers of the treated material are destroyed by the formation of oxygen bubbles. In addition stain is formed without the halide.
Detailed Description of the Invention Preferably the time of treatment in the bleach step is less than the time of treatment in the devamp step. In one embodiment the time of treatment in the bleach step is less than half the time of treatment in the devamp step and particularly less than one third the time of treatment in the devamp step.
Preferably the oxidant of the redox amplification step is hydrogen peroxide or a compound which releases hydrogen peroxide during processing.
The present bleach solutions preferably contain an alkali metal halide at a concentration of 0.25 to 50g, preferably 0.5 to 35g, more preferably 1 to 30g (as sodium chloride) . In the absence of halide the bleach solution forms oxygen bubbles in the material being processed and removes the emulsion layers of the material from the support.
The present bleach baths preferably contain 30% hydrogen peroxide solution at concentrations of from 10 to 300 ml/l, preferably from 20 to 100 ml/l.
Preferably peroxide is the sole oxidant of the bleach.
The present bleach baths preferably have a pH of from 8 to 11.5, preferably from 9 to 11.
A particular application of this technology is in the processing of silver chloride colour paper, for example paper comprising at least 85 mole percent silver chloride, especially such paper with low silver levels, for example total silver levels below 130 mg/m2, eg from 25 to 120 mg/m2, preferably below 60 mg/m2 and particularly in the range 20 to 60 mg/m2.
Within these total ranges the blue sensitive emulsion layer unit may comprise 20 to 60 mg/m2, preferably 25 to 50 mg/m2 with the remaining silver divided between the red and green-sensitive layer units, preferably more or less equally between the red and greensensitive layer units.
The photographic materials can be black-andwhite, single colour elements or multicolour elements.
Multicolour elements contain dye image-forming units sensitive to each of the three primary regions of the spectrum. Each unit can be comprised of a single emulsion layer or of multiple emulsion layers sensitive to a given region of the spectrum. The layers of the element, including the layers of the image-forming units, can be arranged in various orders as known in the art. In a alternative format, the emulsions sensitive to each of the three primary regions of the spectrum can be disposed as a single segmented layer.
A typical multicolour photographic element comprises a support bearing a cyan dye image-forming unit comprised of at least one red-sensitive silver halide emulsion layer having associated therewith at least one cyan dye-forming coupler, a magenta dye image-forming unit comprising at least one greensensitive silver halide emulsion layer having associated therewith at least one magenta dye-forming coupler, and a yellow dye image-forming unit comprising at least one blue-sensitive silver halide emulsion layer having associated therewith at least one yellow dye-forming coupler. The element can contain additional layers, such as filter layers, interlayers, overcoat layers, subbing layers, and the like.
Suitable materials for use in the emulsions and elements processed by the method of this invention, are described in Research Disclosure Item 36544, September 1994, published by Kenneth Mason Publications, Emsworth, Hants, United Kingdom.
The present processing method is preferably carried out by passing the material to be processed through a tank containing the processing solution which is recirculated through the tank at a rate of from 0.1 to 10 tank volumes per minute.
The preferred recirculation rate is from 0.5 to 8, especially from 1 to 5 and particular from 2 to 4 tank volumes per minute.
The recirculation, with or without replenishment, is carried out continuously- or intermittently. In one method of working both could be carried out continuously while processing was in progress but not at all or intermittently when the machine was idle.
Replenishment may be carried out by introducing the required amount of replenisher into the recirculation stream either inside or outside the processing tank.
It is advantageous to use a tank of relatively small volume. Hence in a preferred embodiment of the present invention the ratio of tank volume to maximum area of material accomodatable therein (ie maximum path length x width of material) is less than 11 dm3/m2, preferably less than 3 dm3/m2.
The shape and dimensions of the processing tank are preferably such that it holds the minimum amount of processing solution while still obtaining the required results. The tank is preferably one with fixed sides, the material being advanced therethrough by drive rollers. Preferably the photographic material passes through a thickness of solution less than 11 mm, preferably less than 5 mm and especially about 2 mm. The shape of the tank is not critical but it could be in the shape of a shallow tray or, preferably U-shaped. It is preferred that the dimensions of the tank be chosen so that the width of the tank is the same or only just wider than the width of the material to be processed.
The total volume of the processing solution within the processing channel and recirculation system is relatively smaller as compared to prior art processors. In particular, the total amount of processing solution in the entire processing system for a particular module is such that the total volume in the processing channel is at least 40 percent of the total volume of processing solution in the system.
Preferably, the volume of the processing channel is at least about 50 percent of the total volume of the processing solution in the system.
In order to provide efficient flow of the processing solution through the opening or nozzles into the processing channel, it is desirable that the nozzles/opening that deliver the processing solution to the processing channel have a configuration in accordance with the following relationship: 0.6 1 F/A S 23 wherein: F is the flow rate of the solution through the nozzle in litres/minute; and A is the cross-sectional area of the nozzle provided in square centimetres.
Providing a nozzle in accordance with the foregoing relationship assures appropriate discharge of the processing solution against the photosensitive material. Such Low Volume Thin Tank systems are described in more detail in the following patent specifications: US 5,294,956, US 5,179,404, US 5,270,762, EP 559,025, EP 559,026, EP 559,027, WO 92/10790, WO 92/17819, WO 93/04404, WO 92/17370, WO 91/19226, WO 91/12567, WO 92/07302, WO 93/00612, WO 92/07301, and WO 92/09932 The following Example is included for a better understanding of the invention.
EXAMPLE The following processing solutions were made up.
RX developer/amplifier l-hydroxyethylidene-l, 1 '-diphosphonic acid 0.6g diethyltriamine-pentaacetic acid 2.0g Dipotassium hydrogen phosphate 40.0g Hydroxylamine sulphate 0.5g 4-N-ethyl-N-(ss-methanesulphonamido- ethyl)-Q-toluidine sesquisulphate 4.5g Hydrogen Peroxide (30% w/w) 2ml Water to 1 litre pH adjusted to 11.7 Fix/stop Sodium thiosulphate pentahydrate 20g Sodium sulphite anhydrous 30g Sodium acetate 40g Water to 1 litre pH adjusted to 5.0 with sulphuric acid at 250C Bleach-fix Sodium iron(III) EDTA 75g Sodium thiosulphate pentahydrate 75g Acetic acid lolls Water to 1 litre pH adjusted to 6.0 at 20 C with 10% sodium carbonate solution Bleach 1 30% hydrogen peroxide somas sodium chloride lg sodium hydrogen carbonate 20g Water to 1 litre pH adjusted to 10.0 at 20 C with 3M sodium hydroxide Bleach 2 30% hydrogen peroxide sodium hydrogen carbonate 20g Water to 1 litre pH adjusted to 10.0 at 20 C with 3M sodium hydroxide The solutions described above were use to process a low silver paper containing l9mg/m2 Ag in red and green sensitive layers and 30mg/m2 in the blue sensitive layer, exposed to 21 step colour wedges for 0.ls.The processes carried out were as follows: Process 1 (Comparison) Develop 45s 350C Fix/Stop 45s 35 C Bleach-Fix 45s 35 C Wash 45s 35 C Dry Process 2 (Comparison) Develop 45s 35 C Fix/Stop 45s 35 C Wash 45s 35 C Dry Process 3 (Invention) Develop 35s 35 C Bleach 1 10s 350C Fix/Stop 45s 350C Wash 45s 35 C Dry Process 4 (Comparison) Develop 35s 35 C Bleach 2 10s 35 C Fix/Stop 45s 35 C Wash 45s 35 C Dry Process 5 (Comparison) Develop 35s 35"C Fix/Stop 45s 35 C Wash 45s 35 C Dry After processing the steps were read and sensitometric parameters calculated.
The following Table 1 summarises the sensitometry read on the neutral exposed wedge.
TABLE 1
Process Dmin Dmax Speed Inertia Speed Contrast Shoulder Toe No. Contrast R G B R G B R G B R G B R G B R G B R G B 1 .095 .101 .086 2.95 2.66 2.29 133 123 125 150 144 151 4.83 3.79 3.08 2.27 2.01 1.76 .196 .229 .228 1 .097 .104 .088 2.91 2.71 2.53 137 129 130 153 147 154 4.81 4.23 3.47 2.23 2.09 1.89 .196 .238 .235 3 .101 .104 .086 2.90 2.66 2.28 142 131 129 162 154 160 4.65 4.07 3.16 2.17 2.01 1.84 .197 .230 .230 4 .143 .125 .120 - - - - - .214 .253 ..241 5 .092 .092 .082 2.61 2.46 1.81 129 119 119 148 142 147 4.24 3.65 2.86 1.99 1.85 1.55 .192 .223 .221 The results show that the sensitometry of the invention, Process 3 is similar to the bleach-fixed process but took 45 seconds less time to process.
Process 2 shows increased density and contrast due to retained silver. The sensitometry of Process 4 was not complete as the paper was destroyed in high density area by the formation of oxygen bubbles in the film. At low densities without chloride in the bleach, stain was observed. The shorter development time(35s) without the bleach following the developer showed low density particularly in the blue sensitive layer, demonstrating that formation of the dye image was continuing in the bleach The following Table 2 summarises the Dmin and Dmax read on the blue exposed wedge. This shows the amount unwanted colour contamination due to retained silver.
TABLE 2
Process No. Dmin Dmax G G B R G B 1 .089 .098 .084 0.14 0.54 2.20 2 .094 .104 .091 0.28 0.68 2.31 3 .090 .102 .085 0.16 0.57 2.20 4 .143 . .120 .121 - - 5 .087 .098 .082 0.27 0.69 2.12 In the Dmax area of Processes 2 and 5 without bleach (comparative) high red and green densities are observed in the blue exposed patches due to retained silver which results in colour degradation of the yellow layer particularly at high densities. Most of this increased grey density is removed by process 3 (the invention), in which the result is similar to the long process time Process 1 (comparative). Processes 1 and 3 give 'brighter' yellows.

Claims (11)

CLAIMS:
1. A method of forming a photographic image in an imagewise exposed photographic silver halide material which includes a redox amplification dye image-forming step in a combined developer/amplifier solution (devamp) and a bleach step wherein: (a) the bleach solution comprises hydrogen peroxide or a compound which releases hydrogen peroxide during processing, (b) the bleach solution contains an alkali metal halide, (c) the bleach step follows the image-forming step without any intermediate processing bath, and (d) image formation by redox amplification continues in the bleach solution.
2. A method as claimed in claim 1 in which the time of treatment in the bleach step is less than the time of treatment in the devamp step.
3. A method as claimed in claim 1 in which the oxidant of the redox amplification step is hydrogen peroxide or a compound which releases hydrogen peroxide during processing.
4. A method as claimed in claim 1 or 2 in which the bleach solution contains an alkali metal halide at a concentration of 0.25 to 50g, preferably 0.5 to 35g (as sodium chloride).
5. A method as claimed in claim 3 in which the bleach solution contains an alkali metal halide at a concentration of 1 to 30g (as sodium chloride).
6. A method as claimed in any of claims 1-4 in which the bleach bath preferably has a pH of from 8 to 11.5, preferably from 9 to 11.
7. A method as claimed in any of claims 1-5 in which the photographic silver halide material is a silver chloride colour paper whose silver halide comprises at least 85 mole percent silver chloride.
8. A method as claimed in claim 6 in which the total silver halide coating weight of the photographic material is under 30 mg/m2 as silver.
9. A method as claimed in claim 7 in which the total silver halide coating weight is from 1 to 20 mg/m2 as silver.
10. A method as claimed in any of claims 1-8 in which the processing is carried out by passing the material to be processed through a tank containing the processing solution which is recirculated through the tank at a rate of from 0.1 to 10 tank volumes per minute.
11. A method as claimed in any of claims 1-9 in which the processing is carried out in a machine wherein the ratio of tank volume to maximum area of material accomodatable therein (ie maximum path length x width of material) is less than 11 dm3/m2, preferably less than 3 dm3/m2.
GB9515515A 1995-07-28 1995-07-28 Method of forming a photographic colour image Expired - Fee Related GB2303931B (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
GB9515515A GB2303931B (en) 1995-07-28 1995-07-28 Method of forming a photographic colour image
JP19923396A JPH09106053A (en) 1995-07-28 1996-07-29 Formation method of photographic color image
US08/953,941 US5925504A (en) 1995-07-28 1997-10-20 Method of forming a photographic color image

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB9515515A GB2303931B (en) 1995-07-28 1995-07-28 Method of forming a photographic colour image

Publications (3)

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GB9515515D0 GB9515515D0 (en) 1995-09-27
GB2303931A true GB2303931A (en) 1997-03-05
GB2303931B GB2303931B (en) 1999-03-24

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GB (1) GB2303931B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5925504A (en) * 1995-07-28 1999-07-20 Eastman Kodak Company Method of forming a photographic color image

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992001524A1 (en) * 1990-07-23 1992-02-06 Davy (Distington) Limited Method of manufacturing metal strip

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992001524A1 (en) * 1990-07-23 1992-02-06 Davy (Distington) Limited Method of manufacturing metal strip

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5925504A (en) * 1995-07-28 1999-07-20 Eastman Kodak Company Method of forming a photographic color image

Also Published As

Publication number Publication date
GB9515515D0 (en) 1995-09-27
JPH09106053A (en) 1997-04-22
GB2303931B (en) 1999-03-24

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Effective date: 20040728