EP0903621A1 - Verfahren zur Herstellung eines photographischen Silberhalogenidelements - Google Patents

Verfahren zur Herstellung eines photographischen Silberhalogenidelements Download PDF

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Publication number
EP0903621A1
EP0903621A1 EP97116342A EP97116342A EP0903621A1 EP 0903621 A1 EP0903621 A1 EP 0903621A1 EP 97116342 A EP97116342 A EP 97116342A EP 97116342 A EP97116342 A EP 97116342A EP 0903621 A1 EP0903621 A1 EP 0903621A1
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EP
European Patent Office
Prior art keywords
silver halide
group
silver
halide emulsion
compound
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.)
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Application number
EP97116342A
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English (en)
French (fr)
Inventor
Elio Cavallo
Giuseppe Loviglio
Alain Dominique Sismondi
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Eastman Kodak Co
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Eastman Kodak Co
Imation Corp
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Priority to EP97116342A priority Critical patent/EP0903621A1/de
Priority to JP25995098A priority patent/JPH11143013A/ja
Publication of EP0903621A1 publication Critical patent/EP0903621A1/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Withdrawn legal-status Critical Current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
    • 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
    • G03C1/33—Spot-preventing agents
    • 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
    • G03C1/0051—Tabular grain emulsions
    • 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
    • G03C5/16—X-ray, infrared, or ultraviolet ray processes
    • G03C5/17—X-ray, infrared, or ultraviolet ray processes using screens to intensify X-ray images

Definitions

  • the present invention relates to a process for preparing a silver halide photographic element.
  • the present invention relates to the use of an aryl derivative in a process for the preparation of a silver halide photographic element to reduce or eliminate spot defects in the photographic element due to metallic contamination.
  • Silver halide emulsions are usually prepared by precipitating silver halide (silver bromide, silver iodide, silver chloride or mixture thereof) in the presence of a hydrophilic colloid (normally gelatin).
  • the silver halide emulsions are subjected to a sensitization process for increasing their sensitivity to light.
  • sensitization process There are two primary methods for sensitization: spectral sensitization and chemical sensitization.
  • Spectral sensitization comprises the addition of spectral sensitizing dyes which can be adsorbed on the silver halide grain surface to make the emulsion sensitive to the imaging or phosphor emitted radiation, typically visible or infrared radiation.
  • Chemical sensitization involves the addition of various chemical substances to obtain a prescribed value of sensitivity and contrast.
  • Typical methods for chemical sensitizing a silver halide photographic emulsion include sulfur sensitization, noble metal sensitization, and reduction sensitization. It is also common in the art to have combination methods, such as sulfur-noble metal sensitization, reduction-noble metal sensitization, and the like.
  • the silver halide emulsion is coated onto a support together with coating additives.
  • coating additives A wide description of useful coating aids can be found in Research Disclosure No. 38597, September 1996, "Photographic Silver Halide Emulsions, Preparations, Addenda, Systems and Processing", Item IX.
  • the elements are free from any metal contamination.
  • fine metal particles may be produced by the equipment during the manufacturing process. Metal contamination can occur during any step from the base preparation to final coating. Even though different metals like copper or nickel can be present in the final material, the main metal contaminant is fine iron particles.
  • the presence of iron ions like Fe (III) can desensitize the silver halide and produce a lower density halo on the developed film appearing as a white spot.
  • the presence of fine metallic iron particles or iron ions like Fe (II) can generate, by oxidation, the release of one or two electrons, which produce a sensitized halo on the developed film appearing as black spots.
  • white or black spot are relative terms merely meaning that the spot either appears whiter or blacker than the surrounding non contaminated area of the film.
  • White and/or black spots in a developed image give rise to poor image quality and are unacceptable in many photographic films, especially, in an X-ray application where spots interfere with medical diagnosis.
  • One approach used in the art to control or eliminate these defects is to add a sequestering or chelating agent.
  • the chemical compound generally forms a strong complex with the metal so that the metal can be removed from the photosensitive element thus preventing spot formation.
  • complexing agents have been described in the art.
  • US Patent 3,443,951 discloses the use of phosphoric acid esters in photographic element to prevent spot formation caused by metal particles.
  • US Patent 4,340,665 discloses the use of phosphate and amine complexing agents in synergistic combination to reduce spot formation caused by iron contamination of photographic element.
  • US Patent 3,925,086 discloses the use of azotriazoles and azotetrazoles as antispot agent in photographic silver halide emulsion or in processing baths.
  • US Patent 3,300,312 discloses the use of sulfosalicylic acid in photographic elements to reduce spotting from metallic particles.
  • EP 733,940 discloses the use of both phosphate and sulfosalicylic acid in photographic elements to reduce spotting from spurious metal particle contamination.
  • GB Patent 1,350,303 discloses the use of thienyl or furyl compound to reduced tendency to spot formation due to metal or metal oxide contamination.
  • GB Patent 1,350,302 discloses the use of aldoxime compound to reduced tendency to spot formation due to metal or metal oxide contamination.
  • US Patent 4,340,665 discloses the use of phosphate and hydroxyethylene diamine triacetate in photographic silver halide materials to reduce metal particle contamination.
  • US 5,028,520 discloses the use of hydroquinone sulfonic acid potassium salt on tabular silver halide emulsion in an amount of from 0.03 to 0.5 moles per mole of silver to decrease the surface glossiness. It is also disclosed that no effect is obtained with amount lower than 0.03 mole per mole of silver.
  • JP 54-040729, JP 56-001936 and JP 62-021143 disclose the use of polyhydroxybenzene derivatives on cubic silver halide emulsions to decrease pressure sensitivity in graphic art films.
  • EP 452772, EP 476521, EP 482599 and EP 488029 disclose the use of polyhydroxybenzene derivatives with functional groups that allow better silver halide grain adsorption to decrease pressure sensitivity of final film.
  • EP 339870 discloses a silver halide photographic emulsion having in reactive association a sensitizing amount of polyalkylene glycol compound and a fog reducing amount of an arylhydroxy compound.
  • the present invention provides a process for manufacturing a silver halide photographic element comprising the step of adding an aryl compound having at least two hydroxyl groups and at least one additional substituent represented by a sulfonic group, an hydroxyl group, a carboxy group or a hydroxymethyl group in an amount less than 0.03 moles per mole of silver to a silver halide emulsion before coating onto a support base.
  • the addition of the aryl compound reduces or eliminates spot defects due to metallic contamination of a silver halide photographic emulsion comprising silver halide tabular grains.
  • the aryl compound is represented by the following formula: wherein R 1 to R 4 are selected from the group consisting of a hydrogen atom, a sulfonic group, an hydroxyl group, a carboxy group and an hydroxymethylene group, provided that at least one of R 1 to R 4 is different from hydrogen atom.
  • a silver halide photographic material comprising a support based having coated thereon at least one silver halide emulsion layer, wherein said silver halide emulsion layer comprises an aryl compound having at least two hydroxyl groups and at least one additional substituent represented by a sulfonic group, an hydroxyl group, a carboxy group or an hydroxymethyl group in an amount less than 0.03 moles per mole of silver.
  • the process for manufacturing silver halide elements typically involves an emulsion-making step, a chemical and optical sensitization step, and a coating step.
  • the silver halide emulsion-making step generally comprises (i) a nucleation step, where silver halide grain seeds are formed, (ii) one or more growing steps, where the grain seeds achieve their final dimension, and (iii) a washing step, where all soluble salts are removed from the final emulsion.
  • a ripening step is usually performed between the nucleation and growing step and/or between the growing and the washing steps.
  • Silver halide emulsions can be prepared using a single-jet method, a double-jet method, or a combination of these methods and can be ripened using, for example, an ammonia method, a neutralization method, or an acid method. Parameters which may be adjusted to control grain growth include pH, pAg, temperature, shape and size of reaction vessel, and the reaction method (e.g., accelerated or constant flow rate precipitation, interrupted precipitation, ultrafiltration during precipitation, reverse mixing processes and combinations thereof).
  • a silver halide solvent such as ammonia, thioethers, thioureas, etc., may be used, if desired, for controlling grain size, grain structure, particle size distribution of the grains, and the grain-growth rate.
  • halogen compositions of the silver halide grains can be used.
  • Typical silver halides include silver chloride, silver bromide, silver iodide, silver chloroiodide, silver bromoiodide, silver chlorobromoiodide and the like.
  • silver bromide and silver bromoiodide are preferred silver halide compositions with silver bromoiodide compositions containing from 0 to 10 mol% silver iodide, preferably, from 0.2 to 5 mol% silver iodide, and more preferably, from 0.5 to 1.5mol% silver iodide.
  • the halogen composition of individual grains may be homogeneous or heterogeneous.
  • gelatin As a binder for silver halide emulsions, gelatin is preferred, but other hydrophilic colloids can be used, alone or in combination, such as, dextran, cellulose derivatives (e.g., hydroxyethylcellulose, carboxymethyl cellulose), collagen derivatives, colloidal albumin or casein, polysaccharides, synthetic hydrophilic polymers (e.g., polyvinylpyrrolidone, polyacrylamide, polyvinylalcohol, polyvinylpyrazole) and the like.
  • Gelatin derivatives such as, highly deionized gelatin, acetylated gelatin and phthalated gelatin can also be used.
  • hydrophilic colloids in combination with synthetic polymeric binders and peptizers such as acrylamide and methacrylamide polymers, polymers of alkyl and sulfoalkyl acrylates and methacrylates, polyvinyl alcohol and its derivatives, polyvinyl lactams, polyamides, polyamines, polyvinyl acetates, and the like.
  • synthetic polymeric binders and peptizers such as acrylamide and methacrylamide polymers, polymers of alkyl and sulfoalkyl acrylates and methacrylates, polyvinyl alcohol and its derivatives, polyvinyl lactams, polyamides, polyamines, polyvinyl acetates, and the like.
  • the grains of these silver halide emulsions may be coarse or fine, and the grain size distribution of them may be narrow or broad.
  • the silver halide grains may be regular grains having a regular crystal structure such as cube, octahedron, and tetradecahedron, or the spherical or irregular crystal structure, or those having crystal defects such as twin planes, or those having a tabular form, or combination thereof.
  • the grain structure of the silver halides may be uniform from the interior to exterior thereof, or be multilayer.
  • the grains may comprise a core and a shell, which may have different halide compositions and/or may have undergone different modifications such as the addition of doping agents.
  • the silver halide grains may also comprise different phases in-between.
  • the silver halides may be of such a type as allows a latent image to be formed mainly on the surface thereof or of such type as allows it to be formed inside the grains thereof.
  • tabular silver halide emulsions are used having an aspect ratio of at least 2:1, preferably, 2:1 to 20:1, more preferably, 2:1 to 14:1, and most preferably, 2:1 to 8:1.
  • aspect ratio refers to the average diameter:thickness ratio of the silver halide grains.
  • Average diameters of the tabular silver halide grains range from about 0.3 to about 5 ⁇ m, preferably, from about 0.5 to about 3 ⁇ m, more preferably, from about 0.8 to about 1.5 ⁇ m.
  • the tabular silver halide grains have a thickness of less than 0.4 ⁇ m, preferably, less than 0.3 ⁇ m, and more preferably, within 0.1 to 0.3 ⁇ m.
  • the projected area of the tabular silver halide grains accounts for at least 50%, preferably, at least 80%, and more preferably, at least 90% of the projected area of all the silver halide grains of the emulsion.
  • the tabular silver halide grain dimensions and characteristics described above can be readily ascertained by procedures well known to those skilled in the art.
  • the term "diameter” is defined as the diameter of a circle having an area equal to the projected area of the grain.
  • the term “thickness” refers to the distance between two substantially parallel main planes constituting the tabular silver halide grains. From the measure of diameter and thickness of each grain the diameter:thickness ratio of each grain can be calculated, and the diameter:thickness ratios of all tabular grains can be averaged to obtain their average diameter:thickness ratio.
  • the average diameter:thickness ratio is the average of individual tabular grain diameter:thickness ratios. In practice, it is simpler to obtain an average diameter and an average thickness of the tabular grains and to calculate the average diameter:thickness ratio as the ratio of these two averages. Whatever the method used, the average diameter:thickness ratios obtained do not greatly differ.
  • Silver halide emulsions containing tabular silver halide grains can be prepared by various processes known to those of ordinary skill in the art for the preparation of photographic elements.
  • water soluble salts are removed from the emulsion by procedures generally known by those skilled in the art. Suitable washing processes are those wherein the dispersing medium and soluble salts dissolved therein can be removed from the silver halide emulsion on a continuous basis, such as, for example, a combination of dialysis or electrodialysis for the removal of soluble salts or a combination of osmosis or reverse osmosis for the removal of the dispersing medium.
  • ultrafiltration is a particularly advantageous washing processes for the practice of this process.
  • an ultrafiltration unit comprising membranes of inert, non-ionic polymers is used as a washing process. Since silver halide grains are large in comparison with the dispersing medium and the soluble salts or ions, silver halide grains are retained by the membranes while the dispersing medium and the soluble salts dissolved therein are removed.
  • silver halide grain emulsions Prior to use, silver halide grain emulsions are generally fully dispersed and bulked up with gelatin or other dispersion of peptizer and subjected to any of the known methods for achieving optimum sensitivity.
  • a wide description of methods and compounds useful in chemical and optical sensitization may be found in Research Disclosure No. 38597, September 1996, "Photographic Silver Halide Emulsions, Preparations, Addenda, Systems and Processing", Items IV and 5.
  • Chemical sensitization is performed by adding chemical sensitizers and other additional compounds to the silver halide emulsion, followed by the so-called chemical ripening at high temperature for a predetermined period of time.
  • Chemical sensitization can be performed by a variety of chemical sensitizers such as gold, sulfur, reducing agents, platinum, selenium, sulfur plus gold, and the like.
  • Tabular silver halide grains, after grain formation and desalting, are preferably chemically sensitized by at least one gold sensitizer and at least one sulfur sensitizer.
  • other compounds can be added to improve the photographic performances of the resulting silver halide emulsion, such as, for example, antifoggants, stabilizers, optical sensitizers, supersensitizers, and the like.
  • Gold sensitization is performed by adding a gold sensitizer to the emulsion and stirring the emulsion at high temperature of preferably 40°C or more for a predetermined period of time.
  • a gold sensitizer any gold compound which has an oxidation number of +1 or +3 and is normally used as gold sensitizer can be used.
  • Preferred examples of gold sensitizers are chloroauric acid, the salts thereof and gold complexes, such as those described in US 2,399,083.
  • gold sensitizers include chloroauric acid, potassium chloroaurate, auric trichloride, sodium aurithiosulfate, potassium aurithiocyanate, potassium iodoaurate, tetracyanoauric acid, 2-aurosulfobenzothiazole methochloride and ammonium aurothiocyanate.
  • Sulfur sensitization is performed by adding a sulfur sensitizer to the silver halide emulsion and stirring the emulsion at a high temperature of 40°C or more for a predetermined period of time.
  • sulfur sensitizer include thiosulfonates, thiocyanates, sulfinates, thioethers, and elemental sulfur.
  • the amounts of the gold sensitizer and the sulfur sensitizer change in accordance with the various conditions, such as activity of the gold and sulfur sensitizer, type and size of silver halide grains, temperature, pH and time of chemical ripening. These amounts, however, are preferably from 1 to 20 mg of gold sensitizer per mole of silver, and from 1 to 100 mg of sulfur sensitizer per mole of silver.
  • the temperature of chemical ripening is preferably 45°C or more, and more preferably 50°C to 80°C.
  • the pAg and pH may take arbitrary values.
  • times and order of addition of the gold sensitizer and sulfur sensitizer are not particularly limited.
  • gold and sulfur sensitizers can be added at the initial stage of chemical sensitization or at a later stage either simultaneously or at different times.
  • gold and sulfur sensitizers are added to the silver halide emulsion as aqueous solutions, in a water-miscible organic solvent, such as methanol, ethanol and acetone, or mixtures thereof.
  • a stabilizer is preferably added at any time before the addition of the sulfur sensitizer. Even if the action of the stabilizer is not yet fully understood, it is believed that it acts as a digest stabilizer and a site director for the sulfur sensitizer.
  • the stabilizer is added before the addition of sulfur chemical sensitizer in an amount of from 1 to 500 milligrams per mole of silver, preferably, from 10 to 300 milligrams per mole of silver.
  • useful stabilizers include thiazole derivatives; benzothiazole derivatives; mercapto-substituted heterocyclic compounds, such as, for example, mercaptotetrazoles, mercaptotriazoles, mercaptodiazoles, mercaptopyrimidines, mercaptoazoles; azaindenes, such as triazaindenes and tetrazaindenes; triazoles; tetrazoles; and sulfonic and sulfinic benzene derivatives.
  • Azaindenes are preferably used, more preferably, tetraazaindenes.
  • the silver halide grain emulsion may be optically sensitized to a desired region of the visible spectrum.
  • the method for spectral sensitization is not particularly limited.
  • optical sensitization may be achieved by using an optical sensitizer, including a cyanine dye, a merocyanine dye, complex cyanine and merocyanine dyes, oxonol dyes, hemioxonol dyes, styryl dyes and streptocyanine dyes, either alone or in combination.
  • Useful optical sensitizers include cyanines derived from quinoline, pyridine, isoquinoline, benzindole, oxazole, thiazole, selenazole, imidazole.
  • optical sensitizers are the dyes of the benzoxazole-, benzimidazole- and benzothiazole-carbocyanine type.
  • the addition of the spectral sensitizer is performed after the completion of chemical sensitization.
  • spectral sensitization may be performed concurrently with chemical sensitization, entirely precede chemical sensitization, or even commence prior to the completion of silver halide precipitation.
  • the preferential absorption of spectral sensitizing dyes on the crystallographic faces of the tabular grains allows chemical sensitization to occur selectively at unlike crystallographic surfaces of the tabular grains.
  • the spectral sensitizers produce J aggregates, if adsorbed on the surface of the silver halide grains, and a sharp absorption band (J-band) with a bathochromic shift with respect to the absorption maximum of the free dye in aqueous solution.
  • J-band sharp absorption band
  • spectral sensitizing dye absorbed on the surface of the light-sensitive silver halide grains will vary with the quantity of the specific dye chosen as well as the size and chemical composition of the grains.
  • the maximum intensity of J-band has been obtained with silver halide grains having the above described sizes and the chemical compositions absorbed with J-band spectral sensitizing dyes in a concentration of from 25 to 100 percent or more of monolayer coverage of the total available surface area of the silver halide grains.
  • Optimum dye concentration levels can be chosen in the range of 0.5 to 20 millimoles per mole of silver halide, preferably, in the range of 2 to 10 millimoles.
  • Spectral sensitizing dyes producing J aggregates are well known in the art, as illustrated by F. M. Hamer, Cyanine Dyes and Related Compounds , John Wiley and Sons, 1964, Chapter XVII and by T. H. James, The Theory of the Photographic Process , 4th Edition, MacMillan, 1977, Chapter 8.
  • J-band exhibiting dyes are cyanine dyes having two basic heterocyclic nuclei joined by a linkage of methine groups.
  • the heterocyclic nuclei preferably include fused benzene rings to enhance J aggregation.
  • Preferred heterocyclic nuclei include quinolinium, benzoxazolium, benzothiazolium, benzoselenazolium, benzimidazolium, naphthoxazolium, naphthothiazolium and naphthoselenazolium quaternary salts.
  • the cyanine dyes which are joined by a methine linkage, include two basic heterocyclic nuclei, such as pyrrolidine, oxazoline, thiazoline, pyrrole, oxazole, thiazole, selenazole, tetrazole and pyridine and nuclei obtained by fusing an alicyclic hydrocarbon ring or an aromatic hydrocarbon ring to each of the above nuclei, such as indolenine, benzindolenine, indole, benzoxazole, naphthoxazole, benzothiazole, naphthothiazole, benzoselenazole, benzimidazole and quinoline.
  • nuclei can have substituents groups.
  • the merocyanine dyes which are joined by a methine linkage, include a basic heterocyclic nucleus of the type described above and an acid nucleus, such as a 5- or 6-membered heterocyclic nucleus derived from barbituric acid, 2-thiobarbituric acid, rhodanine, hydantoin, 2-thiohydantoin, 4-thiohydantoin, 2-pyrazolin-5-one, 2-isoxazolin-5-one, indan-1,3-dione, cyclohexane-1-3-dione, and isoquinolin-4-one.
  • an acid nucleus such as a 5- or 6-membered heterocyclic nucleus derived from barbituric acid, 2-thiobarbituric acid, rhodanine, hydantoin, 2-thiohydantoin, 4-thiohydantoin, 2-pyrazolin-5-one, 2-isoxazolin-5-one
  • the methine spectral sensitizing dyes are generally known in the art. Particular reference can be made to US Pat. Nos. 2,503,776; 2,912,329; 3,148,187; 3,397,060; 3,573,916; and 3,822,136 and FR Pat. No. 1,118,778. Also their use in photographic emulsions is very well known wherein they are used in optimum concentrations corresponding to desired values of sensitivity to fog ratios. Optimum or near optimum concentrations of spectral sensitizing dyes generally go from 10 to 500 mg per mole of silver, preferably, from 50 to 200, and more preferably, from 50 to 100.
  • Spectral sensitizing dyes can be used in combinations which result in supersensitization, i.e., spectral sensitization which is greater in a spectral region than that from any concentration of one dye alone or which would result from an additive effect of the dyes.
  • Supersensitization can be obtained with selected combinations of spectral sensitizing dyes and other addenda, such as stabilizers and antifoggants, development accelerators and inhibitors, optical brighteners, surfactants and antistatic agents, as described by Gilman, Photographic Science and Engineering , 18, pp. 418-430, 1974 and in US Pat. Nos. 2,933,390; 3,635,721; 3,743,510; 3,615,613; 3,615,641; 3,617,295; and 3,635,721.
  • an aryl compound having at least two hydroxyl groups and at least one additional substituent represented by a sulfonic group, an hydroxyl group, a carboxy group or an hydroxymethyl group is added to the silver halide emulsion in an amount of less than 0.03 moles per mole of silver before coating the silver halide emulsion onto the support base.
  • the aryl compound is represented by the following formula: wherein R 1 to R 4 are selected from the group consisting of a hydrogen atom, a sulfonic group, an hydroxyl group, a carboxy group and an hydroxymethylene group, provided that at least one of R 1 to R 4 is different from hydrogen atom.
  • Suitable aryl compounds represented by the above-referenced general formula include the following:
  • the amount of the above described aryl compound is preferably in the range of from 0.0001 to 0.03 moles per mole of silver, more preferably from 0.001 to 0.03 moles per mole of silver, and most preferably from 0.005 to 0.03 moles per mole of silver.
  • the use of the above described aryl compounds alllows to reduce or eliminate spot defects due to metallic contamination of a silver halide photographic emulsion.
  • Metallic contamination is due to the presence of metals, in particular heavy metals, such as iron, copper, chromium, tin, nickel, and also aluminium.
  • metals contaminate the emulsion during the various steps of preparation, coating and/or storage and cause sensitization or desensitization of the silver halide grains, thus causing the appearance of black or white spot in the developed photographic material.
  • the aryl compounds used in the present invention are able to chelate the metal ions so reducing the concentration of free metal ions to a harmless level.
  • the resulting metal-contaminate free silver halide emulsion comprises less than 1 micromoles of free metal ions per gram of emulsion.
  • additives can be added to the silver halide emulsion before or during coating, such as, for example, stabilizers or antifoggants such as azaindenes, triazoles, tetrazoles, imidazolium salts, polyhydroxy compounds and others; developing promoters such as benzyl alcohol, polyoxyethylene type compounds, etc.; image stabilizers such as compounds of the chromane, cumaran, bisphenol type, etc.; and lubricants such as wax, higher fatty acids glycerides, higher alcohol esters of higher fatty acids, etc. may be added.
  • coating aids, modifiers of the permeability in the processing liquids, defoaming agents, antistatic agents and matting agents may be used.
  • Other useful additives are disclosed in Research Disclosure , Item 17643, December 1978; Research Disclosure , Item 18431, August 1979; Research Disclosure , Item 308119, Section IV, December 1989; and Research Disclosure Item 36544, September 1994.
  • Suitable support materials include glass, paper, polyethylene-coated paper, metals, polymeric film such as cellulose nitrate, cellulose acetate, polystyrene, polyethylene terephthalate, polyethylene, polypropylene and the like.
  • Preferred light-sensitive silver halide photographic elements are radiographic light-sensitive elements employed in X-ray imaging comprising a silver halide emulsion layer(s) coated on both surfaces of a support, preferably, a polyethylene terephthalate support.
  • the silver halide emulsions are coated on the support at a silver coverage in the range of 1.5 to 3 g/m 2 per side.
  • the radiographic light-sensitive elements are associated with intensifying screens so as to be exposed to radiation emitted by the screens.
  • the screens are made of relatively thick phosphor layers which transform the X-rays into more imaging-effective radiation such as light (e.g., visible light).
  • the screens absorb a larger portion of X-rays than the light-sensitive elements do and are used to reduce the X-ray dose necessary to obtain a useful image.
  • Intensifying screens absorbing more than 25% of the total X-radiation are preferably used.
  • the phosphors can emit radiation in the ultraviolet, blue, green or red region of the visible spectrum and the silver halide emulsions are sensitized to the wavelength region of the radiation emitted by the screens. Sensitization is performed by using spectral sensitizing dyes absorbed on the surface of the silver halide grains as described above.
  • Dye underlayers are particularly useful to reduce the cross-over of the double coated silver halide radiographic element. Reference to well-known dye underlayer may be found in US Pat. Nos.
  • a dye underlayer is coated on at least one side of the support, more preferably, on both sides of the support, before the coating of at least two silver halide emulsion.
  • the silver halide radiographic elements are preferably fore-hardened.
  • organic or inorganic hardeners include chrome salts (e.g., chrome alum, chromium acetate), aldehydes (e.g., formaldehyde and glutaraldehyde), isocyanate compounds (hexamethylene diisocyanate), active halogen compounds (e.g., 2,4-dichloro-6-hydroxy-s-triazine), epoxy compounds (e.g., tetramethylene glycol diglycidylether), N-methylol derivatives (e.g., dimethylolurea, methyloldimethyl hydantoin), aziridines, mucohalogeno acids (e.g., mucochloric acid), active vinyl derivatives (e.g., vinylsulfonyl and hydroxy-substituted vinylsulfonyl derivatives) and the like.
  • chrome salts e.g., chrome alum,
  • the silver halide photographic element can be exposed and processed by any conventional processing technique.
  • Any known developing agent can be added into the developer, such as, for example, dihydroxybenzenes (e.g., hydroquinone), pyrazolidones (1-phenyl-3-pyrazolidone or 4,4-dimethyl-1-phenyl-3-pyrazolidone), and arninophenols (e.g., N-methyl-p-aminophenol), alone or in combinations thereof.
  • the silver halide photographic elements are developed in a developer comprising dihydroxybenzenes as the main developing agent, and pyrazolidones and p-aminophenols as auxiliary developing agents.
  • additives can be present in the developer, such as, for example, antifoggants (e.g., benzotriazoles, indazoles, tetrazoles), silver halide solvents (e.g., thiosulfates, thiocyanates), sequestering agents (e.g., aminopolycarboxylic acids, aminopolyphosphonic acids), sulfite antioxidants, buffers, restrainers, hardeners, contrast promoting agents, surfactants, and the like.
  • Inorganic alkaline agents such as KOH, NaOH, and LiOH are added to the developer composition to obtain the desired pH which is usually higher than 10.
  • the silver halide photographic element can be processed with a fixer of a typical composition for the application required.
  • the fixing agents include thiosulfates, thiocyanates, sulfites, ammonium salts, and the like.
  • the fixer composition can comprise other well known additives, such as, for example, acid compounds (e.g., metabisulfates), buffers (e.g., carbonic acid, acetic acid), hardeners (e.g., aluminum salts), tone improving agents, and the like.
  • the exposed radiographic elements can be processed by any of the conventional processing techniques. Such processing techniques are illustrated for example in Research Disclosure , Item 17643, cited above, and Research Disclosure 36544 September 1994. Roller transport processing is particularly useful, such as those illustrated in US Pat. Nos. 3,025,779; 3,515,556; 3,545,971; and 3,647,459 and in UK Patent 1,269,268. Hardening development can be achieved, as illustrated in US Patent 3,232,761.
  • a silver bromoiodide emulsion with an average grain equivalent diameter of 1.25 micron, an average grain thickness of 0.18 micron, a COV of 37 % and 0.9 percent iodide in mole respect to the total halide ions was prepared by double jet method.
  • the emulsion was chemically and spectrally sensitized using sulfur, gold, mercury and palladium sensitizers plus a triethyl ammonium salt of 5,5'-dichloro-9-ethyl-3,3'-di-(3-sulfopropyl) oxacarbocyanine as spectral sensitization dye.
  • the digest was performed about 120 to 130 minutes at 60° and stabilized successively with 200 mg of potassium iodide and 1366 mg of 5-methyl-7-hydroxy-2-3-4-triazoindolizine (4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene) before chilling.
  • the sensitized silver halide emulsion was melted at 45°C and subjected to coating finals in laboratory.
  • coating auxiliaries were added 1293 mg of calcium nitrate, 80 mg of azodicarboxylic dimorpholide, 18338 mg of polyethylacrylate (in dispersion at 20% in water plus 367 mg of lauryl sulfate), 66738 mg of dextran (manufactured by Pharmacosmos) as gel extender, 267 mg of Colanyl blueTM (manufactered by Hoechst Chemical Co.) as chromatic corrector.
  • the pH was corrected to 6.3 before adding 3774 mg of SSMA copolymer (copolymer of Styrene sulfonic acid and maleic anhydride, manufactured by Aquaness Corp., Texas, USA).
  • the resulting silver halide emulsion was immediately coated on the two faces of blue 7 mil polyester base code with a conventional antistatic top-coat containing hardening agents.
  • the coating speed was 8.3 meters per minute and the covering weight was around 2.25 g of silver per m 2 per side.
  • the fresh film sample was kept 3 days at 38°C before being subjected to iron (III) contamination. This was done by applying on one side and at the rate of 11.4 ml per square meter a solution containing 0.1% by weight ferric sulfate Fe 2 (SO 4 ) 3 as iron source, 1% standard gelatin (manufactured by Deutche Gelatin Fabrik AG, Germany) as coating auxiliary and 0.12% TritonTM X 100 as surfactant. This solution is coated on half surface of a 10 by 28 cm sheet with a Mayer bar number five. This method allows to ensure that a determined level of contaminant is present and to make discernible the compounds that are capable of removing defects caused by the contaminant.
  • TritonTM is a non-ionic surfactant of the alkylphenoxyethylene type having the following formula:
  • the contaminated film was dried and exposed to white light with a standard bromograph for 3/10 of second with filter number 8.
  • the exposed films were processed through a 90 seconds dry to dry medical X-ray automatic processor type XP 515 (manufactured by IMATION Corp., MN, USA) with standard chemistry (XAD 3 developer and XAF 3 fixer, both manufactured by IMATION Corp., MN, USA).
  • sample 1 The procedure of sample 1 is repeated, except that during addition of coating finals, 5 g of compound 1 (2,5-dihydroxybenzenesulfonic acid potassium salt) is added per one mole of silver, corresponding to 0.0219 moles of compound per mole of silver and 209 mg of compound per square meter of coated film.
  • the iron contamination process is carried out in the same manner on the half sheet to determine the protection effect of compound 1. The results are reported in the following Table 1.
  • sample 1 The procedure of sample 1 is repeated, except that during addition of coating finals, 7.55 g of compound 2 (2,5-dihydroxy-1,4-benzenedisulfonic acid dipotassium salt) is added per one mole of silver, corresponding to 0.0218 moles of compound per mole of silver and 315 mg of compound per square meter of coated film.
  • the iron contamination process is carried out in the same manner on the half sheet to determine the protection effect of compound 2.
  • the results are reported in the following Table 1.
  • control sample 1 shows the desensitizing effect of 0.06 millimole per square meter of iron (III).
  • invention samples 2 and 3 clearly show that the aryl compounds described in the present invention are able to reduce the negative effect of iron (III).
  • sample 1 The procedure of sample 1 is repeated, except that the fresh film sample was kept 3 days at 38°C before being subjected to copper (II) contamination using 11.4 ml per m 2 of a solution containing 0.5% by weight cupric nitrate Cu(NO 3 ) 2 as copper source, 1% standard gelatin (manufactured by Deutsche Gelatin Fabrik AG, Germany) as coating auxiliary, 0.12% of TritonTM X 100 as surfactant coated on half the surface of a 10 by 28 cm sheet with a Mayer bar number five.
  • the results are reported in the following Table 2.
  • sample 4 The procedure of sample 4 is repeated, except that during addition of coating finals, 7.55 g of compound 2 (2,5-dihydroxy-1,4-benzenedisulfonic acid dipotassium salt) is added per one mole of silver, corresponding to 0.0218 moles of compound per mole of silver and 315 mg of compound per square meter of coated film.
  • the copper contamination process is carried out in the same manner on the half sheet to determine the protection effect of compound 2.
  • the results are reported in the following Table 2.
  • control sample 7 shows the desensitization effect of 0.06 millimole per square meter of iron (III) on our system.
  • the data of invention samples 8 to 13 clearly show that the aryl compounds described in the present invention are able to reduce the negative effect of iron (III).
  • sample 1 The procedure of sample 1 is repeated, except that the film sample is subjected to iron (III) contamination using 23 ml per square meter of a solution containing 0.1% by weight ferric sulfate Fe 2 (SO 4 ) 3 as iron source, 1% of standard gelatin (manufactured by Deutsche Gelatin Fabrik AG, Germany) as coating auxiliary and 0.12% of TritonTM X 100 as surfactant.
  • This solution is coated on half the surface of a 10 by 28 cm sheet with a Mayer bar number ten.
  • Table 4 The results are reported in the following Table 4.
  • the control sample 14 shows the desensitization effect of 0.12 millimole per square meter of iron (III).
  • the data of invention samples 15 to 20 show the positive effects of the aryl compounds described in the present invention even when the contaminant is present in high proportion with respect to the aryl compounds.
  • sample 1 The procedure of sample 1 is repeated, except that the fresh film sample was kept 3 days at 38°C before being subjected to copper (II) contamination using 11.4 ml per m 2 of a solution containing 0.125% by weight cupric nitrate Cu(NO 3 ) 2 as copper source, 1% standard gelatin (manufactured by Deutsche Gelatin Fabrik AG, Germany) as coating auxiliary, 0.12% of TritonTM X100 as surfactant coated on half the surface of a 10 by 28 cm sheet with a Mayer bar number five.
  • the results are reported in the following Table 5.
  • sample 21 The procedure of sample 21 is repeated, except that during addition of coating finals, 8.85 g of compound 2 (2,5-dihydroxy-1,4-benzenedisulfonic acid dipotassium salt) is added per one mole of silver, corresponding to 0.0256 moles of compound per mole of silver and 368 mg of compound per square meter of coated film.
  • Table 5 Sample Compound Contaminant Amount (mmol/m2/side) ⁇ D% 21 (C) - 0.48 - 10.0 22 (I) 3 0.48 - 3.9 23 (I) 3 0.48 0 24 (I) 3 0.48 - 1.7 25 (I) 2 0.48 - 3.5 26 (I) 2 0.48 - 4.3 27 (I) 2 0.48 - 4.2
  • control sample 21 shows the desensitization effect of 0.48 millimole per square meter of copper (II).
  • the results of samples 22 to 27 clearly show that the aryl compounds described in the present invention are able to reduce the negative effect of copper (II).
  • sample 1 The procedure of sample 1 was repeated, except that the emulsion was coated on the two faces of a contaminated 7 mil blue polyester base.
  • the contamination was produced during the base manufacturing process by fine metallic iron and copper particles
  • the fresh film sample was kept 3 days at 38°C before having been exposed to white light with a standard bromograph for 3/10 of second with filter number 5.
  • sample 28 was repeated, except that during addition of coating finals, 7.543 g of compound 2 (2,5-dihydroxy-1,4-benzenedisulfonic acid dipotassium salt) is added per one mole of silver, corresponding to 0.0218 moles of compound per mole of silver and 314 mg of compound per square meter of coated film.
  • Table 6 Sample Compound Contaminant Spot Number 28 (C) - Fe + Cu 224 29 (I) 2 Fe + Cu 16 30 (I) 2 Fe + Cu 8 31 (I) 2 Fe + Cu 18
  • the control sample 28 shows a high number of spot defects due to iron and copper contamination during base preparation.
  • the invention samples 29 to 31 clearly show that the aryl compounds described in the present invention are able to drastically reduce the number of defects. So, these compounds are able to efficiently prevent the formation of spot defects on a film prepared with a very highly contaminated base.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
EP97116342A 1997-09-19 1997-09-19 Verfahren zur Herstellung eines photographischen Silberhalogenidelements Withdrawn EP0903621A1 (de)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP97116342A EP0903621A1 (de) 1997-09-19 1997-09-19 Verfahren zur Herstellung eines photographischen Silberhalogenidelements
JP25995098A JPH11143013A (ja) 1997-09-19 1998-09-14 ハロゲン化銀写真材料の作製方法

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JP5128256B2 (ja) * 2007-12-07 2013-01-23 富士フイルム株式会社 イムノクロマトグラフ方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3236652A (en) * 1963-01-10 1966-02-22 Eastman Kodak Co Stabilized silver halide emulsions
EP0339870A1 (de) * 1988-04-29 1989-11-02 Minnesota Mining And Manufacturing Company Antischleiermittel für Polyalkylenglykolsensibilisatoren
US5631126A (en) * 1994-12-23 1997-05-20 Eastman Kodak Company Epitaxially sensitized tabular grain emulsions containing speed/fog sulfodihydroxy aryl enhancing addenda

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3236652A (en) * 1963-01-10 1966-02-22 Eastman Kodak Co Stabilized silver halide emulsions
EP0339870A1 (de) * 1988-04-29 1989-11-02 Minnesota Mining And Manufacturing Company Antischleiermittel für Polyalkylenglykolsensibilisatoren
US5631126A (en) * 1994-12-23 1997-05-20 Eastman Kodak Company Epitaxially sensitized tabular grain emulsions containing speed/fog sulfodihydroxy aryl enhancing addenda

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