EP1273968A1 - Herstellungsmethode eines photographischen Bildes - Google Patents

Herstellungsmethode eines photographischen Bildes Download PDF

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Publication number
EP1273968A1
EP1273968A1 EP01202563A EP01202563A EP1273968A1 EP 1273968 A1 EP1273968 A1 EP 1273968A1 EP 01202563 A EP01202563 A EP 01202563A EP 01202563 A EP01202563 A EP 01202563A EP 1273968 A1 EP1273968 A1 EP 1273968A1
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EP
European Patent Office
Prior art keywords
sulphite
oxidant
solution
developing agent
solutions
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Withdrawn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
EP01202563A
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English (en)
French (fr)
Inventor
John Richard Fyson
Louis E. Friedrich
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
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 Eastman Kodak Co filed Critical Eastman Kodak Co
Priority to EP01202563A priority Critical patent/EP1273968A1/de
Publication of EP1273968A1 publication Critical patent/EP1273968A1/de
Withdrawn legal-status Critical Current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
    • 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
    • G03C7/3046—Processing baths not provided for elsewhere, e.g. final or intermediate washings
    • 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
    • G03C5/268—Processing baths not provided for elsewhere, e.g. pre-treatment, stop, intermediate or rinse baths
    • 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
    • G03C7/3017—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials with intensification of the image by oxido-reduction

Definitions

  • This invention relates to the processing of photographic materials.
  • the invention simplifies the chemical processing of silver halide materials and reduces the volumes of liquid processing solutions employed.
  • silver halide materials are processed in equipment with deep tanks containing processing solutions.
  • the solutions need to be maintained in a chemically stable state to the extent that uniformity and consistency of photographic results are assured.
  • Low silver materials have been described which use small fractions of the amount of silver needed to provide the oxidation of developer resulting from development of the silver halide crystals when that oxidised developer is used to provide the image dye via reaction with colour-forming couplers.
  • These low silver materials are processed in the presence of oxidising agents such as hydrogen peroxide in development amplification processes commonly referred to as Redox Amplification or RX processes.
  • oxidising agents such as hydrogen peroxide in development amplification processes commonly referred to as Redox Amplification or RX processes.
  • the developed silver image is used to catalyse in an image-wise manner, the production of oxidised developer and hence, image dye.
  • Such materials are appropriate for print production.
  • the silver halide can be stabilised to degradation by light, for example, by destroying the silver halide spectral sensitising dyes by exposure to light ( US Patent No. 5 441 843 ) or by converting the silver halide to a more stable form such as silver iodide ( US Patent No. 5 246 822).
  • the material After processing, the material has to be washed to remove materials generated during the processing and to remove excess colour developing agent and hydrogen peroxide which would cause coloration of the material with time.
  • a method of removal of organic materials, which does not involve washing the processed materials has been described in PCT GB99/04319.
  • the method involves the use of carbon coated in a gelatin layer on a suitable support. The coating is laminated with the processed material and the carbon used to adsorb the undesirable chemicals which are consequently extracted from the processed material. The amounts of soluble dyes used for sharpness control and the unused colour developer were reduced to low levels by this method.
  • the present invention provides a method of producing a photographic image in an imagewise exposed photographic material comprising one or more silver halide emulsion layers which method comprises developing the material with a developer solution containing a silver halide developing agent, applying to the surface of the developed material a solution of a sulphite compound that reacts with oxidised developing agent and prevents further development, and applying to the surface of the developed material a solution of an oxidant that oxidises any remaining developing agent, wherein said sulphite compound is present in an amount sufficient to react with all the oxidised developing agent and said solutions of sulphite and oxidant are applied to the material by means other than immersion in a tank.
  • the method of the invention eliminates the need for a wash step after development. No water needs to be supplied or removed from the processor.
  • the method reduces the number of processing tanks required by avoiding the need for stabiliser and/or wash tanks.
  • a very low volume of liquid can be employed and the method can be used substantially without effluent being produced.
  • Colour developing agent and/or peroxide are destroyed so that the colour developing agent does not couple with any unused couplers in the material.
  • the photographic material e.g. paper is stabilised.
  • the photographic material used in the method of the invention may be any black and white or colour silver halide material.
  • the material is a colour silver halide material e.g. a colour print or film material.
  • dye images can be formed by reaction of oxidised developer with image dye forming couplers.
  • a preferred class of developing agents for chromogenic colour development is the paraphenylene diamine class.
  • a preferred form of photographic processing is redox amplification also known as development amplification. It is an advantage of the development amplification process that a low silver material can be employed. Low silver materials typically contain less than 400mg/m 2 , preferably less than 200mg/m 2 silver.
  • the sulphite compound is a hydrogen sulphite or metabisulphite compound.
  • suitable compounds include soluble alkali metal, alkaline earth metal or ammonium hydrogen sulphites and metabisulphites e.g. sodium hydrogen sulphite and sodium metabisulfite.
  • the solution of the sulphite compound may contain the sulphite compound in an amount from 0.02 to 1 mole/l, preferably from 0.15 to 0.5 mole/l.
  • the oxidant is a salt of a peroxy sulphuric acid such as peroxymonosulphuric acid (H 2 SO 5 ) or peroxydisulphuric acid (H 2 S 2 O 8 ).
  • Salts of peroxydisulphuric acid are often simply referred to as persulphates.
  • suitable compounds include soluble alkali metal, alkaline earth metal or ammonium peroxymonosulphates and persulphates e.g. sodium peroxymonosulphate and sodium persulphate.
  • the solution of the oxidant may contain the oxidant in an amount from 0.02 to 1 mole/l, preferably from 0.15 to 0.5 mole/l.
  • the concentration of the oxidant is less than that of the sulphite compound.
  • the total amount of the solutions of sulphite and oxidant applied to the surface of the developed material does not exceed 100 ml/m 2 .
  • a preferred amount is from 20 to 60 ml/m 2 .
  • the weight ratio of the solutions of sulphite and oxidant applied to the surface of the developed material may vary from 5:1 to 1:5.
  • the solutions are employed in substantially equal amounts.
  • the total amount of the solutions of sulphite and oxidant is such that substantially no effluent is produced.
  • the solutions of sulphite and oxidant are applied to the material by means other than immersion in a tank.
  • suitable means include spraying from a fine nozzle, an air brush, an ink jet head or by application with a roller.
  • the roller may or may not have a surface pattern, or a roller covered with an adsorbent material such as felt or sponge may be used. If two separate applications are required it is preferable that the second solution is applied by a non-contact method such as spraying with a nozzle, an air-brush or an ink-jet head.
  • the solutions of sulphite and oxidant are applied to the material sequentially.
  • the oxidant solution is applied within 20 seconds, more preferably within 10 seconds of application of the sulphite solution.
  • the solutions of sulphite and oxidant are applied to the material simultaneously. If the solutions are mixed together before application, it is preferable to apply the mixture within 10 seconds of mixing.
  • An advantage of the method of the invention is that only very low volumes of sulphite and oxidant solution need be used.
  • the volumes of solution used are such that there is substantially no effluent created.
  • a small volume of solution can be accommodated by the swell of the photographic material being treated. Additional solution can be accommodated on the surface of the material without creating effluent. Subsequent drying of the material removes the unwanted water.
  • the method of the invention is particularly desirable for processing colour photographic materials.
  • the method involves applying in a controlled fashion to the material a colour developer scavenger i.e. the sulphite compound that reacts with oxidised colour developer in preference to the imaging couplers in the material.
  • the oxidant solution is applied in a controlled fashion. If necessary, the pH of these applied solutions is adjusted to ensure that the colour developer will not couple with the image dyes in the film but will react with the colour developer scavenger.
  • the oxidant is colourless and forms colourless harmless products or at least reacts to form colourless and harmless products.
  • a soluble hydrogen sulphite (0.02 - 1.0molar) or metabisulphite solution is applied to a developed colour photographic material by spray, airbrush or ink-jet head in an amount preferably, but not necessarily, less than the swell of the photographic material followed by applying a solution of persulphate of preferably, but not necessarily, lower concentration than the hydrogen sulphite solution and preferably, but not necessarily, in a similar amount to the hydrogen sulphite or metabisulphite solution.
  • the invention may be employed in processing any silver halide photographic material.
  • the photographic elements can be single colour elements or multicolour elements having a paper or a transparent film base.
  • 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 various orders as known in the art.
  • 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 green-sensitive 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 and subbing layers.
  • Suitable materials for use in this invention can have any of the components described in Research Disclosure Item 36544, September 1994, published by Kenneth Mason Publications, Emsworth, Hants P010 7DQ, United Kingdom.
  • Photographic processing steps such as development, bleaching and fixing together with the compositions used in those steps e.g. developing agents are described in, for example, Research Disclosure, September 1994, No.365, Sections XIX & XX and Research Disclosure, September 1997, p. 613, Section XXIII.
  • a preferred form of photographic processing is redox amplification also known as development amplification. Such processes are well known and details may be found in Research Disclosure, September 1997, p. 629-630, Section XVI .
  • Redox amplification processes have been described, for example in British Specification Nos. 1,268,126, 1,399,481, 1,403,418 and 1,560,572.
  • 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 developer-amplifier) 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.
  • Suitable oxidising agents include peroxy compounds including hydrogen peroxide and compounds which provide hydrogen peroxide, e.g. addition compounds of hydrogen peroxide or persulphates; cobalt (III) complexes including cobalt hexammine complexes; and periodates. Mixtures of such compounds can also be used.
  • the invention is further illustrated by way of example as follows.
  • Unexposed Kodak Edge 7TM paper was processed through standard 'Prime'TM processing chemicals in a minilab. The couplers in this coating should remain uncoupled. Similarly, fully exposed Kodak Edge 7TM paper was processed in the same way.
  • the solution was applied as a spot to the dried treated area of paper and left for 1 minute.
  • the whole paper was washed and dried and the density of the spotted area measured and compared to a spot place on untreated paper that had not been dipped in developer, the control C1, and also with paper that was treated by two sprays of demineralised water after being dipped in developer, control C2.
  • Anti-Cal #5 is l-hydroxy-ethylidene-1,1-diphosphonic acid and Anti-Cal #8 is diethylenetriaminepentaacetic acid, pentasodium salt.
  • Devamp Solution Anti-Cal #5 0.5g Anti-Cal #8 0.8g dipotassium hydrogen phosphate 40g hydroxylammonium sulphate (HAS) 1.3g CD3 5.5g potassium chloride 0.5g hydrogen peroxide (30%) 2.7g pH adjusted to 11.5
  • Fix Solution sodium thiosulphate 50g acetic acid 10ml water to 1 litre Bisulphite Solution sodium bisulphite 25g water to 1 litre Persulphate Solution sodium persulphate 5g water to 1 litre
  • Another strip was processed in the devamp solution for 45s at 35°C then passed under an airbrush such that 20ml/m 2 bisulphite solution was laid down. Approximately 10s later the strip was passed under another airbrush and 20ml/m 2 of the persulphate soluion was laid down. The strip was left to dry at room temperature.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
EP01202563A 2001-07-04 2001-07-04 Herstellungsmethode eines photographischen Bildes Withdrawn EP1273968A1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP01202563A EP1273968A1 (de) 2001-07-04 2001-07-04 Herstellungsmethode eines photographischen Bildes

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP01202563A EP1273968A1 (de) 2001-07-04 2001-07-04 Herstellungsmethode eines photographischen Bildes

Publications (1)

Publication Number Publication Date
EP1273968A1 true EP1273968A1 (de) 2003-01-08

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Application Number Title Priority Date Filing Date
EP01202563A Withdrawn EP1273968A1 (de) 2001-07-04 2001-07-04 Herstellungsmethode eines photographischen Bildes

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EP (1) EP1273968A1 (de)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0758762A1 (de) * 1995-08-12 1997-02-19 Kodak Limited Verfahren zur Verarbeitung photographischer Silberhalogenidmaterialien

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0758762A1 (de) * 1995-08-12 1997-02-19 Kodak Limited Verfahren zur Verarbeitung photographischer Silberhalogenidmaterialien

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