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
  • G03C1/00—Photosensitive materials
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
  • G03C1/34—Fog-inhibitors; Stabilisers; Agents inhibiting latent image regression
  • G03C1/346—Organic derivatives of bivalent sulfur, selenium or tellurium
• • 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
• • 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
  • G03C1/00—Photosensitive materials
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
  • G03C1/34—Fog-inhibitors; Stabilisers; Agents inhibiting latent image regression
• • 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
  • G03C2200/00—Details
  • G03C2200/29—Green-sensitive layer
• • 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
  • G03C2200/00—Details
  • G03C2200/53—Red-sensitive layer
• • 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
  • G03C7/302—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials with intensification of the image by oxido-reduction using peroxides
• • 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
  • G03C7/3029—Materials characterised by a specific arrangement of layers, e.g. unit layers, or layers having a specific function

Definitions

• This invention relates to photographic silver halide colour materials and in particular to low silver colour materials suitable for use in redox amplification processing.
• Redox amplification processes have been described, for example in British Specifications 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 treated with a redox amplifying solution (or a combined developer/amplifier) to form a dye image.
• the development and amplification solutions can be separate or combined.
• the combined solution which is more common, is known as developer-amplifier and contains a reducing agent, for example a colour developer, and an oxidizing agent, for example hydrogen peroxide. The latter oxidizes the colour developing agent under the catalytic influence of the developed silver image.
• the oxidized colour developer so formed reacts further with a colour coupler coated in the same or in an adjacent layer to produce an image.
• the emulsion layers of a colour paper photographic material comprise substantially pure silver chloride.
• One feature of a redox system is that since silver acts as a catalyst for amplification it is possible to use only very low levels of coated silver chloride. This has benefits for effluent reduction during processing and also permits the elimination of the bleach solution. Undeveloped silver halide is fixed from the coating, but developed silver is left in the coating after exposure and processing.
• a photographic silver halide colour material suitable for use in redox amplification said material comprising a support bearing one or more emulsion layers, at least one of said layers containing a sulphur-containing antifogging agent, the amount of said agent being effective to reduce fog but not more than 0.5mg/m 2 preferably not more than 0.3mg/m 2 .
• the invention also provides a process for the redox development of an imagewise exposed photographic material which process comprises developing the photographic material in a redox developer/amplifier solution and wherein the photographic material contains in an emulsion layer an effective amount of a sulphur-containing antifogging agent but not more than 0.5mg/m 2 preferably not more than 0.3mg/m 2 .
• a process for the preparation of a photographic silver halide colour material suitable for use in redox amplification comprises forming a plurality of layers on a support and incorporating into the blue or green sensitive layer a sulphur-containing antifogging agent in an amount effective to reduce fogging but less than 0.5mg/m 2 , preferably less than 0.3mg/m 2 .
• the advantage of the present invention is that it enables mercaptotetrazoles and other sulphur-containing antifogging agents to be used in redox development systems without significantly reducing the amplification.
• fog control in all records can be achieved by the placement of a mercaptotetrazole in the yellow and/or magenta layers and specifically in dispersion melts for improved effectiveness.
• the sulphur-containing antifogging agent used in the present invention can be any of those known in the art as antifogging agents and is preferably a heterocyclic organic molecule containing nitrogen in a ring.
• the sulphur is in a mercapto group.
• suitable compounds are mercaptotetrazoles, mercaptotriazoles, mercaptooxadiazoles, mercaptobenzothiazoles and mercaptobenzimidazoles.
• a mercaptotetrazole is preferred and may be substituted in the 1-position by a monovalent organic group for example a hydrocarbyl group which may be aliphatic or aromatic eg phenyl.
• Suitable sulphur-containing antifogging agents are described in United States Patent No 4,088,494.
• the antifogging agent may be used in a blocked form, that is to say, in a form in which it is combined with a blocking group, the latter being removable in the presence of peroxide.
• the blocking and subsequent release of the antifogging agent may be effected as described in European Patent Application No 547,707A.
• the antifogging agent in the photographic material in a blocked form and it may more conveniently be provided in an active form
• an effective amount ie providing a useful antifogging effect, of antifogging agent will be at least 0.05mg/m 2 and will usually be at least 0.10mg/m 2 .
• the amount of antifogging agent is from about one tenth to about one quarter of the amount used in conventional colour papers.
• the redox developer/amplifier solution used in the present invention comprises a colour developing agent, hydrogen peroxide or a compound which provides hydrogen peroxide and hydroxylamine or a salt thereof.
• the colour developing agent may be any of those known in the art,for example, the p-phenylene diamines eg N N N'N'-tetramethyl phenylene diamine. Convenient concentration ranges are:
• the concentration range of the hydrogen peroxide is preferably from 0.5 to 7 ml/l and especially from 0.5 to 2 (as 30% w/w solution).
• the concentration range of the hydroxylamine component is from 0.5 to 4 and especially from 0.5 to 2 g/l (as hydroxylamine sulphate).
• the pH is preferably in the range 11 to 11.7 and especially from 11 to 11.4.
• composition is preferably free of any compound that forms a dye on reaction with oxidised colour developer.
• the photographic material may be first subjected to a development step with a developer solution containing no peroxide or other oxidising agent before the redox amplification.
• the development and amplification may be combined in a single step using a combined developer/amplifier solution.
• the process of redox amplification is conventionally carried out at 32 o C.
• the process of the present invention can however be carried out at temperatures up to 37 o C with acceptable fog control.
• the colour photographic material to be processed may be of any type but will preferably contain low amounts of silver halide.
• Preferred total silver halide coverages are in the range 6 to 300, preferably 10 to 200 mg/m 2 and particularly 10 to 100 mg/m 2 (as silver).
• a particular application of redox amplification is in the processing of silver chloride colour paper, for example, paper comprising at least 85 mole % silver chloride, especially such paper with low silver levels for example levels below 30mg/m 2 preferably below 20mg/m 2 .
• the material may comprise the emulsions, sensitisers, couplers, supports, layers, additives, etc. described in Research Disclosure, December 1978, Item 17643, published by Kenneth Mason Publications Ltd, Dudley Annex, 12a North Street, Emsworth, Hants P010 7DQ, U.K.
• the photographic material to be processed comprises a resin-coated paper support and the emulsion layers comprise more than 80%, preferably more than 90% silver chloride and are more preferably composed of substantially pure silver chloride.
• the photographic materials can be single colour materials or multicolour materials.
• Multicolour materials 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 materials, including the layers of the image-forming units, can be arranged in various orders as known in the art.
• a typical multicolour photographic material comprises a support bearing a yellow dye image-forming unit comprised of at least one blue-sensitive silver halide emulsion layer having associated therewith at least one yellow dye-forming coupler, and magenta and cyan dye image-forming units comprising at least one green- or red-sensitive silver halide emulsion layer having associated therewith at least one magenta or cyan dye-forming coupler respectively.
• the material can contain additional layers, such as filter layers.
• the invention also provides a process for the preparation of a photographic silver halide colour material suitable for use in redox amplification.
• the preparation of photographic papers conventionally involves coating the paper with a number of photographic materials in a plurality of coatings to form separate layers and sometimes up to seven layer may be applied.
• the photosensitive coating material which is to provide one of the layers as two separate components which are mixed together either immediately or shortly before the coating operation.
• One component which is normally referred to as the emulsion comprises a silver halide, usually silver chloride, gelatin and water together with optional ingredients such as chemical sensitizers, spectral sensitizers and antifogging agents. Although this may not be truly an emulsion in the physical-chemical sense, the term has been universally accepted in the photographic art.
• the other component comprises an imaging coupler in a finely divided form in a gelatin medium.
• the emulsion and the dispersion are too concentrated to be used to coat paper and the usual procedure is to dilute them with water and gelatin. After dilution they are usually solid at room temperature ie about 20 o C but melt at about 25 o C. In the melted states they are referred to as the emulsion melt and the dispersion melt respectively.
• the process for the preparation of the photographic materials according to the present invention may comprise forming an emulsion melt and a dispersion melt for coating the base and incorporating the sulphur-containing antifogging agent into either the emulsion melt or the dispersion melt used to form a green or blue sensitive layer of the photographic material.
• the compound 1-phenyl-5-mercaptotetrazole was incorporated into monochrome single-layer or full colour multilayer coatings in the form of a 0.5% by weight solution in ethanol.
• the antifoggant solution was added to either the emulsion melt or to the dispersion melt of the layer of interest.
• the prepared coatings were given an exposure at 0.1 second on the DF1 sensitometer, using neutral and separation step-wedges appropriately colour balanced for colour-negative paper.
• the processing used a redox-amplification procedure, employing the redox-amplifier formulation and process protocol given in Table 1 to 3. Tables 1 and 2 give the formulations for 1.0 litres of redox processing solutions. Table 1 DEVELOPER-AMPLIFIER Component Concentration.
• AC5 is a 60% aqueous solution of 1-hydroxy-ethylidene-1,1-diphosphonic acid.
• AC8 is a 40% aqueous solution of the penta sodium salt of diethylene triamine penta acetic acid.
• CDS is catechol disulphonate
• HAS is hydroxylamine sulphate
• CD3 is N-2-(4 amino-N-ethyl-m-toluidino)ethyl methanesulphonamide sesquisulphate hydrate.
• the separation and/or neutral wedges on the processed material were measured with a densimeter and appropriate sensitometric parameters calculated.
• Yellow monochrome coatings were made by dual melting a blue sensitive emulsion melt together with EKTACOLOR TM yellow dispersion melts which were prepared either with or without the compound of interest.
• the emulsion was similar to that used in EKTACOLORTM paper except for having a reduced cubic grain edge length of 0.45 micrometres.
• the silver laydown was 31mg/m 2 .
• Other component laydowns were as used in EKTACOLORTM paper.
• a common supercoat similar to that employed in EKTACOLORTM was coated over the yellow layer.
• Table 4 gives the details of the quantity of PMT used together with sensitometric data for the coatings when processed in a redox amplifier formulation. Table 4 Coating No.
• Magenta monochrome coatings were made by dual-melting an EKTACOLORTM magenta dispersion melt together with green-sensitive emulsion melts which were prepared either with or without the compound of interest at a series of levels.
• the emulsion was similar to that used in EKTACOLORTM paper, except for having a reduced cubic grain edge length of 0.27micrometres.
• the silver laydown was 16mg/m 2 .
• Other component laydowns were as used in EKTACOLORTM paper.
• a common supercoat similar to that employed in EKTACOLORTM was coated over the magenta layer.
• Table 5 gives details of the quantities of PMT used, together with sensitometric data for the coatings when processed in a redox amplifier solution. Table 5 Magenta Single Colour Records. Coating No.
• Example 3 Full-color multilayer coatings.
• Multilayer coatings were made using the same structure and components as EKTACOLORTM paper, except for the following emulsion changes which were implemented to make the coatings suitable for a redox amplification process.
• Emulsion grain cubic edge lengths and silver laydowns were reduced in all three records to respectively: yellow 0.45 micrometres and 28mg/m 2 ; magenta 0.27 micrometres and 19mg/m 2 ; cyan 0.29 micrometres and 14mg/m 2 .
• Table 6 gives details of the level and placement of PMT which was variously positioned in the yellow emulsion or dispersion then additionally in the magenta or dispersion.
• the sensitometric data for the coatings when processed in a redox amplifier formulation is also given.
• YD stands for yellow dispersion, magenta dispersion etc.
• YD it means that the antifogging agent was added to the yellow dispersion melt.
• Multilayer coatings were made as in Example 3 except that the PMT was confined to the dispersion melts. Its level and distribution between yellow, magenta and cyan records was varied. Table 7 gives details of these changes and the resulting sensitometric effects. Table 7 Coating PMT mg/m 2 Dmin Dmax Contrast Inertial Speed S20366 R 0.0 0.170 2.763 4.395 146.9 G 0.197 2.576 3.900 143.4 B 0.167 2.073 2.441 148.9 S20368 R 0.122 2.777 4.451 146.7 G 0.129 2.594 3.978 142.6 B 0.2 YD 0.111 2.123 2.502 146.0 S20370 R 0.121 2.702 4.084 146.3 G 0.2 MD 0.130 2.567 3.806 141.3 B 0.113 2.138 2.533 144.8 S20372 R 0.116 2.710 4.242 145.4 G 0.1 MD 0.124 2.584 3.927 141.0 B 0.1 YD 0.106 2.081 2.466 144.9 S20375 R 0.05 CD 0.117 2.681 4.000 144.9 G
• coatings S20368,-70,-72,-75 which have a total PMT laydown of 0.2mg/m 2 show that the variation with half of the total in each of the yellow and magenta dispersion melts (coating-72) is marginally preferable to the other coatings for Dmin in all records and substantially superior to coating S20366 which has no PMT.
• Coating -75 with PMT in all dispersions shows some evidence of red Dmax and contrast losses.
• the coating with the even distribution (-73) shows losses in red Dmax and contrast.
• the results suggest that the PMT should be confined to the yellow and magenta dispersion melts with a level at or below 0.3mg/m 2 .
• Example 5 Full colour multilayer coatings, high temperature processing.
• Multilayer coatings were made as in Example 3. The redox development-amplification was conducted at 37 o C instead of the normal 32 o C. Table 8 gives details of the PMT levels and the resulting sensitometric data. Table 8 Full-colour Multilayer Coatings. Higher Temperature Development-Amplification.

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• 1995
  • 1995-11-14 GB GBGB9523218.7A patent/GB9523218D0/en active Pending
• 1996
  • 1996-11-11 EP EP96203141A patent/EP0774685A2/de not_active Withdrawn
  • 1996-11-13 JP JP8301721A patent/JPH09171226A/ja active Pending

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