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
  • G03C1/04—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with macromolecular additives; with layer-forming substances
  • G03C1/043—Polyalkylene oxides; Polyalkylene sulfides; Polyalkylene selenides; Polyalkylene tellurides
• • 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
  • 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
  • G03C1/42—Developers or their precursors

Definitions

• This invention relates to photographic compositions, and more particularly to photographic silver halide enulsions containing addenda that improve stability against fogging in the presence of polyalkylene glycol sensitizing compounds.
• Another aspect of this invention is to provide a light sensitive silver halide emulsion which is stable in all of its photographic properties, when manufacturing conditions include high temperatures, or when processed using short development times at elevated temperatures, i.e., in commonly used automatic processing machines.
• a radiographic element comprising a support having thereon at least one silver halide layer wherein the gelatino silver halide layer comprises either at least 90 mole % bromide the remaining halide being iodide or bromide, or at least 50 mole % chloride the remaining halide being made up of either bromide up to 100 mole % and/or iodide to a maximum of 10 mole %.
• the emulsion must be in reactive association with a speed enhancing amount of a polylkylene glycol material and an aryl stabilizing compound.
• the aryl stabilizing compounds of the invention comprise a phenyl ring containing two or more hydroxyl radicals and at least one other radical selected from the group consisting of sulfo radical and a carboxyl radical.
• the water soluble salts of the compounds such as the alkali metal salts (Na or K) and ammonium salts can be used in accordance with usual practice.
• R′ represents a sulfo radical or a hydrogen atom
• R ⁇ represents a sulfo radical and/or a carboxyl radical or a hydrogen atom, which describes such compounds as i.e., 4,5-dihydroxy-1,3-benzene sulfonic acid disodium salt, 2,5-dihydroxy benzene-4-sulfonic acid sodium salt, 2,5-dihydroxy-1,4-benzene disulfonic acid disodium salt or 5-sulfosalicylic acid dihydrate.
• the polyalkylene glycol compounds used as the sensitizer for the silver halide emulsion according to the present invention includes those with a molecular weight between 1000-5000 more particularly between 1500-4000 and most preferably a molecular weight of between 3000 and 3500.
• the sensitizing polyalkylene glycol and aryl stabilizing additions of the invention can be located in any layer of the photographic element which allows the compounds to be in reactive association with the emulsion layer. Reactive association is such a close physical association of the two materials that chemical reaction, physical contact, or electronic contact is effected.
• the polyalkylene glycol sensitizing compound can be located in a overcoat to the silver halide layer, in an undercoat to the silver halide layer, or virtually any layer adjacent to the silver halide layer.
• the aryl stabilizing compounds can be located in any layer of the photographic element, for example the aryl stabilizing compound can be located in an overcoat to the silver halide emulsion layer, as an undercoat to the silver halide emulsion layer, or virtually any layer adjacent to the silver halide emulsion layer, either the same or different layer from the sensitizing compound.
• the polyalkylene glycol, sensitizing, and aryl, stabilizing additions of the invention can be made to the silver halide photographic emulsion utilizing any of the well known techniques in emulsion making.
• the addenda can be added together or separately.
• the photographic material can comprise a support bearing a silver halide emulsion on one or both sides.
• a radiographic material comprising a support bearing on both sides a hydrophilic, preferably a gelatino silver halide emulsion layer wherein the halide comprises at least 90 mole % bromide, the remaining halide being made up of bromide to 100 mole % or a mixture of bromide and iodide to a maximum of 10 mole % iodide.
• the silver halide grains may be present as any crystal habit, including but not limited to, cubic, tetrahedral, tubular, orthorhombic, spherical, etc.
• the compounds used in the present invention may be added together in any effective sensitizing amount (polyalkylene glycol) and any fog stabilizing amount (arylhydroxy compound).
• concentration of the addenda can vary significantly in photographic silver halide emulsions such as from 0.25 to 20.0g/mole of silver halide.
• a generally useful range of the fog stabilizing arylhydroxy compound would be from 0.25 to 20.0g/mole of silver halide.
• a more preferred range would be from 0.25 to 8.0g/mole of silver halide.
• Silver halide emulsions sensitized and stabilized in accordance with this invention can comprise silver chloride, silver bromide, silver bromoiodide, silver chloroiodide, silver chlorobromoiodide or mixtures thereof.
• Such emulsions can be coarse, medium or fine grain (or mixtures thereof) and can be prepared by any of the well-known procedures, e.g., single jet emulsions or double jet emulsions.
• Useful emulsions include Lippmann emulsions, ammoniacal emulsions, thiocyanate or thioether ripened emulsions such as those described in Nietz et al., U.S. Patent No.
• the silver halide emulsions sensitized and stabilized with the compounds of this invention can be unwashed or washed to remove soluble salts.
• the soluble salts can be removed by chill-setting and leeching or the emulsion can be coagulation washed e.g., by the procedures described in Hewitson et al., U.S. Pat. No. 2,618,556; Yutzy et al., U.S. Pat. No. 2,614,928; Yackel, U.S. Pat. No. 2,565,418; Hart et al., U.S. Pat. No. 3,241,969; and Waller et al., U.S. Pat. No. 2,489,341.
• Photographic emulsions containing sensitizing and stabilizing combinations in accordance with this invention can be sensitized with chemical sensitizers, such as with reducing agents; sulfur, selenium or tellurium compounds; gold, platinum or palladium compounds; or combinations of these.
• chemical sensitizers such as with reducing agents; sulfur, selenium or tellurium compounds; gold, platinum or palladium compounds; or combinations of these.
• Suitable chemical sensitization procedures are described in Shepard, U.S. Patent No. 1,623,499; Waller, U.S. Patent No. 2,399,083; McVeigh, U.S. Patent No. 3,297,447; and Dunn, U.S. Patent No. 3,297,446.
• the sensitized silver halide emulsions of this invention can contain speed increasing compounds such as cationic surface active agents and thioethers or combinations of these as described in Piper, U.S. Patent No. 2,886,437; Chechak, U.S. Patent No. 3,046,134; Carroll et al., U.S. Patent No. 2,944,900; and Goffe, U.S. Patent No. 3,294,540.
• speed increasing compounds such as cationic surface active agents and thioethers or combinations of these as described in Piper, U.S. Patent No. 2,886,437; Chechak, U.S. Patent No. 3,046,134; Carroll et al., U.S. Patent No. 2,944,900; and Goffe, U.S. Patent No. 3,294,540.
• Silver halide emulsions containing the sensitizing or stabilising combinations of this invention can be protected against the production of fog and can be stabilized against loss of sensitivity during keeping.
• Suitable antifoggants and stabilizers which can be used alone or in combination, include the thiazolium salts described in Staud, U.S. Patent No. 2,131,038 and Allen, U.S. Patent No. 2,694,716; the azaindenes described in Piper, U.S. Patent No. 2,886,437 and Heimbach, U.S. Patent No. 2,444,605; the mercury salts described in Allen, U.S. Patent No. 2,728,663; the urazoles described in Anderson, U.S. Patent No.
• Photographic elements including emulsions sensitized and stabilized in accordance with this invention can contain incorporated developing agents such as hydroquinones, catechols, aminophenols, 3-pyrazolidones, ascorbic acid and its derivatives, reductones and phenylenediamines, or combinations of developing agents.
• the developing agents can be in the silver halide emulsion and/or in another suitable location in the photographic element.
• the developing agents can be added from suitable solvents or in the form of dispersions as described in Yackel, U.S. Patent No. 2,592,368 and Dunn et al., French Patent No. 1,505,778.
• Silver halide sensitized and stabilzied in accordance with the invention can be dispersed in colloids that can be hardened by various organic or inorganic hardeners, alone or in combination, such as the aldehydes, blocked aldehydes, ketones, carboxylic and carbonic acid derivatives, sulfonate esters, sulfonyl halides and vinyl sulfones, active halogen compounds, epoxy compounds, aziridines, active olefins, isocyanates, carbodiimides, mixed function hardeners and polymeric hardeners such as oxidized polysaccharides, e.g., dialdehyde starch, oxyguargum, etc.
• various organic or inorganic hardeners such as the aldehydes, blocked aldehydes, ketones, carboxylic and carbonic acid derivatives, sulfonate esters, sulfonyl halides and vinyl sulfones, active halogen compounds, epoxy
• Photographic emulsions sensitized and stabilzied with the materials described herein can contain various colloids alone or in combination as vehicles or binding agents.
• Suitable hydrophilic materials include both naturally-occurring substances such as proteins, for example, gelatin, gelatin derivatives (e.g., phthalated gelatin), cellulose derivatives, polysaccharides such as dextran, gum arabic and the like; and synthetic polymeric substances such as water soluble polyvinyl compounds, e.g., poly(vinylpyrrolidone) acrylamide polymers or other synthetic polymeric compounds such as dispersed vinyl compounds in latex form, and particularly those which increase the dimensional stability of the photographic materials.
• Suitable synthetic polymers include those described, for example, in U.S. Patent Nos.
• Emulsions sensitized and stabilized in accordance with this invention can be used in photographic elements which contain antistatic or conducting layers, such as layers that comprise soluble salts, e.g., chlorides, nitrates, etc., evaporated metal layers, ionic polymers such as those described in Minsk, U.S. Patent Nos. 2,861,056 and 3,206,312 or insoluble inorganic salts such as those described in Trevoy, U.S. Patent No. 3,428,451.
• antistatic or conducting layers such as layers that comprise soluble salts, e.g., chlorides, nitrates, etc., evaporated metal layers, ionic polymers such as those described in Minsk, U.S. Patent Nos. 2,861,056 and 3,206,312 or insoluble inorganic salts such as those described in Trevoy, U.S. Patent No. 3,428,451.
• Photographic emulsions containing sensitizing and stabilizing combinations of the invention can be coated on a wide variety of supports.
• Typical supports include polyester film, subbed polyester film, poly(ethylene terephthalate) film, cellulose nitrate film, cellulose ester film, poly(vinyl acetal) film, polycarbonate film and related films or resinous materials, as well as glass, paper, metal and the like.
• a flexible supoprt is employed, especially a paper support, which can be partially acetylated or coated with baryta and/or an alpha-olefin polymer, particularly a polymer of an alpha-olefin containing 2 to 10 carbon atoms such as polyethylene, polypropylene, ethylenebutene copolymers and the like.
• Sensitized and stabilized emulsions of the invention can contain plasticizers and lubricants such as polyalcohols, e.g., glycerin and diols of the type described in Milton, U.S. Patent No. 2,960,404; fatty acids or esters such as those described in Robijns, U.S. Patent No. 2,588,765 and Duane, U.S. Patent No. 3,121,060; and silicone resins such as those described in DuPont British Patent No. 955,061.
• plasticizers and lubricants such as polyalcohols, e.g., glycerin and diols of the type described in Milton, U.S. Patent No. 2,960,404; fatty acids or esters such as those described in Robijns, U.S. Patent No. 2,588,765 and Duane, U.S. Patent No. 3,121,060; and silicone resins such as those described in DuPont British Patent No. 955,061.
• the photographic emulsions sensitized and stabilized as described herein can contain surfactants such as saponin, anionic, compounds, such as the alkylarylsulfonates described in Baldsiefen, U.S. Patent No. 2,600,831 fluorinated surfactants, and amphoteric compounds such as those described in Ben-Ezra, U.S. Patent No. 3,133,816.
• surfactants such as saponin, anionic, compounds, such as the alkylarylsulfonates described in Baldsiefen, U.S. Patent No. 2,600,831 fluorinated surfactants, and amphoteric compounds such as those described in Ben-Ezra, U.S. Patent No. 3,133,816.
• Photographic elements contianing emulsion layers sensitized as described herein can contain matting agents such as starch, titanium dioxide, zinc oxide, silica, poly­meric beads including beads of the type described in Jelley et al., U.S. Patent No. 2,992,101 and Lynn, U.S. Patent No. 2,701,245.
• matting agents such as starch, titanium dioxide, zinc oxide, silica, poly­meric beads including beads of the type described in Jelley et al., U.S. Patent No. 2,992,101 and Lynn, U.S. Patent No. 2,701,245.
• Spectrally sensitized emulsions of the invention can be utilized in photographic elements which contain brightening agents including stilbene, triazine, oxazole and coumarin brightening agents.
• Brightening agents including stilbene, triazine, oxazole and coumarin brightening agents.
• Water soluble brightening agents can be used such as those described in Albers et al., German Patent No. 972,067 and McFall et al., U.S. Patent No. 2,933,390 or dispersions of brighteners can be used such as those described in Jansen, German Pat. No. 1,150,274 and Oetiker et al., U.S. Patent No. 3,406,070.
• Photographic elements containing emulsion layers sensitized and stabilized according to the present invention can be used in photographic elements which contain light absorbing materials and filter dyes such as those described in Sawdey, U.S. Patent No. 3,253,921; Gaspar, U.S. Patent No. 2,274,782; Carroll et al., U.S. Patent No. 2,527,583 and Van Campen, U.S. Patent No. 2,956,879.
• the dyes can be mordanted, for example, as described in Milton and Jones, U.S. Patent No. 3,282,699.
• the sensitizing dyes and/or supersensitizers can be added to the photographic emulsions from water solutions or suitable organic solvent solutions, for example with the procedure described in Collins et al., U.S. Patent No. 2,912,343; Owens et al., U.S. Patent No. 3,342,605; Audran, U.S. Patent No. 2,996,287 or Johnson et al., U.S. Patent No. 3,425,835.
• the dyes can be dissolved separately or together, and the separate or combined solutions can be added to a silver halide emulsion, or a silver halide emulsion layer can be bathed in the solution of supersensitizers and/or dyes.
• Contrast enhancing additives such as hydrazines, rhodium, iridium and combinations thereof are also useful.
• Photographic emulsions of this invention can be coated by various coating procedures including dip coating, air knife coating, curtain coating, or extrusion coating using hoppers of the type described in Beguin, U.S. Patent No. 2,681,294. If desired, two or more layers may be coated simultaneously by the procedures described in Russell, U.S. Patents Nos. 2,761,791 and Wynn, British Patent No. 837,095.
• Silver halide emulsions containing sensitizing and stabilizing combinations of this invention can be used in elements designed for color photography, for example, elements containing color-forming couplers such as those described in Frolich et al., U.S. Patent No. 2,376,679; Vittum et al., U.S. Patent No. 2,322,027; Fierke et al., U.S. Patent No. 2,801,171; Godowsky, U.S. Patent No. 2,698,794; Barr et al., U.S. Patent No. 3,227,554 and Graham, U.S. Patent No.
• Exposed photographic emulsions of this invention can be processed by various methods including processing in alkaline solutions containing conventional developing agents such as hydroquinones, catechols, aminophenols, 3-pyrazolidones, phenylenediamines, ascorbic acid deriva­ tives, hydroxylamines, hydrazines and the like; web proces­sing such as described in Tegillus et al., U.S. Patent No. 3,179,517; stabilization processing as described in Yackel et al. "Stabilization Processing of Films and Papers", PSA Journal, Vol. 16B, Aug. 1950; monobath processing as described in Levy "Combined Development and Fixation of Photographic Images with Monobaths", Phot. Sci.
• conventional developing agents such as hydroquinones, catechols, aminophenols, 3-pyrazolidones, phenylenediamines, ascorbic acid deriva­ tives, hydroxylamines, hydrazines and the like
• web proces­sing
• the photographic emulsions of this invention can be processed in hardening developers such as those described in Allen et al., U.S. Patent No. 3,232,761; in a roller transport processor such as those described in Russell, U.S. Patent No. 3,025,779; or by surface application processing as described in Example 3, of Kitze, U.S. Patent No. 3,418,132.
• a gelatino silver halide emulsion was prepared by precipitation and ripening steps using 98.0 mole percent silver bromide and 2.00 mole percent silver iodide in the presence of 15.0g of gelatin per mole of silver halide.
• the precipitated silver halide was freed of unwanted soluble by-product salts by coagulation and washing using the method disclosed in U.S. Pat. No. 2,489,341 wherein the silver halide and most of the gelatin are coagulated by the addition of sodium lauryl sulfate, using an acid coagulation environment. Following the washing step, the solution was reconstituted in water containing about 67.0g of gelatin per mole of silver halide.
• This emulsion was treated with conventional sulfur and gold sensitizers and was digested at 55°C to increase sensitivity, was cooled to 40°C, and treated with post-sensitization additives and stabilizers, namely tetraazaindines, additional halides, coating aids, and hardening agents, etc. as required and as is known in the art.
• the various emulsions were coated double sided on 7.0 mil (0.18 mm) polyester film base in the usual manner.
• the sensitometric properties of the photographic elements were determined after 7 days storage at 50°C. and 50 % relative humidity, by exposing through a continuous 0-4.0 density photographic wedge with a 1/10 second exposure from 2650°K. The light was filtered with a Corning 5850 blue filter. The exposed films were processed through a 90 second dry-to-dry medical x-ray processor using standard medical x-ray chemistry.
• Table 'A' summarizes the results of the sensitometric tests. The speeds indicated are a function of the exposure necessary to yield a density of 0.10 above the background fog. The initial control speed is taken as 100. Substantial reductions in the general overall fog level, as well as the reduction in fog level attributed to the polyethyleneglycol sensitizer alone are achieved. TABLE A Coating Number PEG3350 g/mole A o X Addenda Conc.

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• Materials Engineering (AREA)
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• 1989
  • 1989-04-20 EP EP89303934A patent/EP0339870A1/fr not_active Withdrawn
  • 1989-04-28 JP JP11195789A patent/JPH0213939A/ja active Pending

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