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
  • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
• • 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
  • G03C1/07—Substances influencing grain growth during silver salt formation
• • 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

Definitions

• This invention relates to silver halide photography and specifically to silver halide emulsions with high silver chloride content, and methods of forming silver halide with suitable photographic properties.
• dopant refers to a material other than a silver or halide ion contained within a silver halide grain.
• Grain sizes are edge length of a cube, where the crystals have a cubic morphology. It is well known that the sensitometric properties of silver halide photographic emulsions may be varied widely depending upon such factors as crystal structure, crystal size, crystal size distribution, chemical and spectral sensitization. This is described in, for example, "The Theory of the Photographic
• Ammoniacal emulsions are prepared by adding ammonium hydroxide during precipitation and/or ripening. Although excess halide and ammonia are the most common ripening agents, others mentioned in literature include thiocyanates such as described in U.S. Patents 2,222,264 and 3,320,069 and thioethers as described in U.S. Patent 3,271,157. It is known that incorporating any of the above ripening agents during formation of the silver halide crystals or shortly thereafter provides an emulsion with increased grain size and usually increased photographic sensitivity.
• modifying compounds which can be present during emulsion precipitation.
• Such compounds can be initially in the reaction vessel or can be added along with one or more of the reactants according to conventional procedures.
• Modifying compounds such as compounds of copper, thallium, lead, bismuth, cadmium, zinc, middle chalcogens (i.e., sulfur, selenium, and tellurium) , gold, and group B to 10 noble metals having an atomic weight greater than 100, can be present during silver halide precipitation, as illustrated by Arnold et al U.S. Patent 1,195,432, Hochstetter U.S. 1,951,933,
• the art has recognized a distinct difference in the photographic effect of metal compounds in silver halide emulsions, depending upon whether the compound is introduced into the emulsion during precipitation of silver halide grains or subsequently in the emulsion preparation process.
• the metal can enter the silver halide grain as a dopant and, therefore, be effective to modify photographic properties, though present in very small concentrations.
• metal compounds When metal compounds are introduced into an emulsion after silver halide grain precipitation is complete, they can be adsorbed to the grain surfaces, but are sometimes largely precluded from grain contact by peptizer interactions.
• Section IA dealing with metals introduced during grain precipitation
• Section IIIA dealing with metal sensitizers introduced during chemical sensitization
• the metals most commonly incorporated into silver halide grains are the group 8 to 10 elements having an atomic weight greater than 100.
• the most common dopant of these is irrdiu , which is known to give a variety of useful photographic effects.
• Rhodium introduced in the form of a rhodium hexachloride or hexabromide has also been extensively investigated.
• Grzeskowiak in published European Patent Application No. 0 242 190/A2 discloses reductions in high intensity reciprocity failure in silver halide emulsions formed in the presence of one or more complex compounds of rhodium (III) having 3, 4, 5, or 6 cyanide ligands attached to each rhodium ion.
• Zinc, cadmium, mercury, and lead dopants have been used to obtain various photographic effects, as illustrated by McBride U.S. Patent 3,287,136; Iwaosa et al U.S. Patent 3,901,711; Shiba et al U.S. Patent 3,790,390; Ohkubo et al U.S. Patent 3,890,154; and Habu et al U.S. Patent 4,147,542 disclose silver halide grains doped with iron, cobalt, and nickel.
• the silver halides of practical importance include silver iodide, bromide, chloride, and their mixed salts. It is well known that a silver chlorobromide emulsions do not consist of some crystals containing one halide and some containing the other, but rather that all the crystals are mixed crystals containing both halides. Inclusion of one halide into the lattice of the other results in some deformation in the lattice structure of mixed crystals. Because this deformation causes stresses within a silver halide grain, one can -change the total sensitivity and/or sensitivity distribution among grain sizes depending upon the way the bromide salt is introduced. In some applications, one halide can be epitaxially deposited on another as described by Maskasky U.S. Patent 4,435,501.
• a high silver chloride emulsions containing substantially no silver iodide are known as a preferable material for reducing the time of development, bleaching, and fixing steps.
• cubic grains having a (100) crystal plane are usually formed.
• Such emulsions are prone to fog, especially when sensitized with the use of soluble gold.
• the problem is aggravated in color developer having high activity for rapid development, for example, Kodak RA-4 process. Reciprocity failure and storage fog generated when light sensitive high chloride photographic material is stored also poses problems.
• German Offenlegugsschrift DE 38 28 312 suggests that the use of oxidized gelatin that has a gold number of not greater tha 10 ⁇ mole per gram of gelatin and a cystein content not in excess of 6 ppm may be utilized in formation of silver chlorobromide emulsions that have lower fog.
• European Patent Application 0 315 833 alleges that the pure chloride emulsions prepared in a way as to minimize the iron content of the emulsion, exhibits sensitivity equal to check but at lower fog level.
• An object of the invention is to overcome disadvantages of prior methods of emulsion formation and prior emulsions.
• Another object is to reduce fog in photographic products.
• Another additional object is to improve sensitivity to fog ratio in photographic products.
• a further object of this invention is to produce improved color paper.
• Another object of this invention is to produce rapidly developing color papers that are environmentally desirable.
• a monovalent or trivalent gold compound in an amount of up to 3 X 10 ⁇ 5 mole per mole of silver as a dopant during emulsion formation.
• the silver halide is predominantly silver chloride and is utilized as a silver halide emulsion for color paper formation.
• the silver halide emulsions can be comprised of silver bromide, silver chloride, silver chlorobromide, silver chloroiodide, silver bromoiodide, silver chlorobromoiodide, and mixtures thereof.
• the emulsion of this invention does not contain substantial amounts of silver iodide, which means that the molar content of silver iodide is 2% or less and more preferable 0.01 mole % or less.
• At least 60% of the emulsion of this invention is silver chloride. More preferable, silver chloride content is 75% or more. Even more preferable, 90% or more and most preferable, 95% because of undesirable effects of bromide during RA-4 processing.
• the emulsion grains of this invention may have a uniform composition or structured structure. Silver bromide or iodide in the quantities defined above may be introduced at any phase of emulsion production including that of epitaxial deposition of one or the other.
• the emulsion grain may be of any morphology with the cubic morphology characteristic for high chloride emulsions.
• the individual reactants can be added to the reaction vessel through surface or sub-surface delivery tubes by gravity feed or by delivery apparatus for maintaining of the rate of delivery and the pH and/or vAg of the reaction vessel constant, as illustrated by Culhane et al U.S. Patent 3,821,002, Oliver U.S.
• specially constructed mixed devices can be employed, as illustrated by Audran U.S. Patent 2,996,287, McCrossen et al U.S. Patent 3,342,605, Frame et al U.S. Patent 3,415,650, Porter et al U.S. Patent 3,785,777, Saito et al German OLS 2,556,885, and Sato et al German OLS 2,555,364.
• an average grain size of this invention is not limited, it is preferably 0.1 ⁇ m to 5 ⁇ m, and more preferably 0.2 ⁇ m to 3 ⁇ m for use in color paper with good image quality.
• a grain size distribution of this emulsion may be either polydisperse or monodisperse, with monodisperse being preferable.
• a solvent for silver halide may be used.
• This may include thiocyanate ripened emulsions, as illustrated by Illingsworth U.S. Patent 3,320,069, thioether ripened emulsions, as illustrated by McBride U.S. Patent 3,271,157, Jones U.S. Patent 3,574,628, and Rosecrants et al U.S. Patent 3,737,313, or emulsions containing weak silver halide solvents, such as ammonium salts, as illustrated by Perumble U.S. Patent 3,784,381, and Research Disclosure, Vol. 134, June 1975, Item 13452.
• cadmium salt zinc salt, lead salt, thallium salt, mercuric salt, iridium salt or its complex salt, osmium salt, rhodium salt or its complex salt, or iron salt or its complex salt
• iridium salt or rhodium salt is preferable because of improvements in reciprocity failure and other photographic properties. It is significant finding of this invention that Gold(I) and Gold(III) compounds, when added to the emulsion described above, significantly reduce its level of fog during subsequent sensitization without deleterious effect on the properties of the emulsions formed by the methods mentioned above.
• the amount of monovalent or trivalent gold utilized to produce the antifoggant properties of the silver halide of the invention may be any effective amount. It has been found that preferable concentration is up to about 3 X 10" 5 moles of monovalent or trivalent gold compound per mole of silver. More preferred concentration is between about 3 X 10" ⁇ and about 3 X 10-8. A most preferred concentration is between 3 X 10" " 6 and 3 X 10 ⁇ 7 moles of gold compound per mole of silver because optimum performance.
• Typical of the gold compounds are potassium chloroaurate, KAUCI4; auric trichloride, AUCI3; gold sulfide, AU2S; myochrisine (gold sodium-thiomalate) ; KAu(CNS)4; solganol-B olesoum (aurothioglucose in sesame oil); pyridino-trichlorogold, (C5H5N)AuCl3.HCl; trichlorogold-dimethyl sulfide, AUCI3. (CH3)2S; diethyl- monobrom-gold, Au(C2H5)2Br; monochlorogold-dimethyl sulfide, AuCl. (CH3)2S; potassium aurothiocyanate, KAu(CNS)2; and bis(methylhydaintonato)gold(I) sodium salt (hereinafter referred to as Gold(I) compound).
• the gold compounds can be added to the emulsion in the form of solutions in suitable solvents, e.g., water, methyl alcohol, ethyl alcohol, acetone, etc., or as dispersions in colloids, such as gelatin, polyvinyl alcohol, partially hydrolyzed cellulose acetate, casein, etc., or without any solvent or colloid.
• suitable solvents e.g., water, methyl alcohol, ethyl alcohol, acetone, etc.
• colloids such as gelatin, polyvinyl alcohol, partially hydrolyzed cellulose acetate, casein, etc., or without any solvent or colloid.
• the gold co pound should, of course, be thoroughly dispersed throughout the emulsions, e.g., by stirring.
• the gold compound may be added at any time during the emulsion formation that results in improved antifogging characteristics. It is preferred that the gold is added during substantially all of the precipitation, and most preferably as a component of silver feed solution (silver nitrate) , as this will give continuous antifogging protection during grain formation when it is believed the fogging takes place.
• silver feed solution silver nitrate
• the soluble salts of the emulsion of this invention can be removed by coagulation washing, as illustrated by Hewitson et al U.S. Patent 2,618,556, Yutzy et al U.S. Patent 2.614,928, Yackel U.S. Patent 2,656,418, Hart et al U.S. Patent 3,241,969, Weller et al U.S. Patent 2,489,341, Klinger U.K. Patent 1,305,409, and Dersh et al U.K. Patent 1,167,159; by diafiltration with semipermeable membrane, as illustrated by Research Disclosure, Vol. 102, October 1972, Item 10208, Hagemaier et al Research Disclosure, Vol.
• the silver halide emulsion of this invention can be chemically sensitized with sulfur, selenium, tellurium, gold, platinium, palladium, iridium, osmium, rhenium or phosphorous sensitizers or combinations of these sensitizers, such as pAg levels from 5 to 10, pH levels from 4 to 8, and temperatures of from 30 to 80°C, as illustrated by Research Disclosure, Vol. 120, April 1974, Item 12008, Research Disclosure, Vol. 134, June
• the silver halide emulsions of this invention can be spectrally sensitized with dyes from a variety of classes, including the polymethine dye class, which includes the cyanines, merocyanines, complex cyanines and merocyanines (i.e., tri-, tetra-, and poly-nuclear cyanines and merocyanines) , oxonols, hemioxonols, styryls, merostyryls, and streptocyanines.
• the polymethine dye class which includes the cyanines, merocyanines, complex cyanines and merocyanines (i.e., tri-, tetra-, and poly-nuclear cyanines and merocyanines) , oxonols, hemioxonols, styryls, merostyryls, and streptocyanines.
• the cyanine spectral sensitizing dyes include, joined by a methine linkage, two basic heterocyclic nuclei, such as those derived from quinolinium, pyridinium, isoquinolinium, 3H-indolium, benz(e)indolium, oxazolium, thiazolium, selenazolium, imidazolinium, benzoxazolinium, benzothiazolium, benzoselenazolium, benzimidazolium, naphtooxazolium, naphtothiazolium, naphtoselenazolium, thiazolinium dihydronaphtothiazolium, pyrylium, and imidazopyrazinium quaternary sats.
• two basic heterocyclic nuclei such as those derived from quinolinium, pyridinium, isoquinolinium, 3H-indolium, benz(e)indolium, oxazol
• the merocyanine spectral sensitizing dyes include, joined by a methine linkage, a basic heterocyclic nucleus of the cyanine dye type and an acidic nucleus, such as can be derived from barbituric acid, 2-thiobarbituric acid, rhodanine, hydantoin, 2- thiohydantoin, 4-thiohydantoin, 2-pyrazolin-5-one, 2- isoxazoli-5-oneindan-l,3-dione, cyclohexan-1,3-dione, l,3-dioxan-4,6-dione, pyrazolin-3,5-dione, pentan-2,4- dione, alkylsulfonyl acetonitrile, melononitrile, isoquinolin-4-one; and chroman-2,4-dione.
• One or more spectral sensitizing dyes may be used. Dyes with sensitizing maxima at wavelengths throughout the visible spectrum and with a great variety of spectral sensitivity curve shapes are known.
• Combinations of spectral sensitizing dyes can be used which result in supersensitization; that is, spectral sensitization that is greater in some spectral region than that from any concentration of one of these dyes alone or that which would result from the additive effect of the dyes.
• Any processing can be applied to the light- sensitive material of the present invention, including black-and-white and color processes. Processing for color paper, color reversal paper, a color positive film, a color negative film, and color reversal film is known.
• Silver halide emulsion, type (1) was prepared as follows:
• Solution 1 is heated up to 55°C, and Solution 2 and Solution 3 added to it simultaneously with agitation over 13 minutes at starting flow rate of 22 l/min. and final flow rate of 97 ml/min. Concentration of Solution 2 and Solution 3 is 4 mole/liter. Following a ramp flow, both solutions are fed into the reactor at 97 ml/min. over the time of 27 minutes. The ramp flow is linear. After that emulsion is cooled down to 43°C and desalted, and Solution 4 is added. The effective edge length of the resultant silver chloride cubic Emulsion #101, as shown in Table II, is 0.33 ⁇ m.
• Emulsion #102 dilute solution of HgCl2 in the amount corresponding to 3 X 10 "7 mole Hg per mole Ag replaced some of the water in Solution 3.
• dilute solution of KAUCI4 in the amounts correspond- ing to 3 X 10 ⁇ 7 mole Au per mole Ag and 3 X 10-6 mole Au per mole Ag, respectively, replaces some of the water in Solution 3.
• All the samples are chemically sensitized in the following manner: sodium thiosulfate, potassium chloroaurate, and potassium bromide are added to the emulsions and chemical ripening is performed for 60 minutes at 70°C.
• the gold compound added during precipitation exhibits a strong antifogging effect, comparable to that of less environmentally desirable mercuric chloride.
• the sensitivity to fog ratio which can be used as a measure of emulsion photographic potential, is the highest for the Emulsion #104 treated with gold compound.
• Solution 1 was heated up to 68.3°C, and Solution 2 and Solution 3 are added to it simultaneously, with agitation over 5 minutes at the flow rate of 49 ml/min. Concentration of Solution 1 and Solution 2 was 3.8 mole/liter. After one minute the thioether ripener 1,8-dithiaoctanediol, as described previously in the previous section, is added to the reactor. Then the flow rate is linearly ramped from 49 ml/min. up to 85 ml/min. over 6 minutes. The flow of the reactants is continued at 85 ml/min. for another 23 minutes. After that the emulsion is cooled down to 43°C and desalted, and Solution 4 is added.
• the effective edgelength of the resultant silver chloride cubic Emulsion #201 is 0.73 ⁇ m.
• dilute solution of HgCl2 in the amount corresponding to 3 X 10 "7 mole Hg per mole Ag replaced some of the water in Solution 3.
• dilute solution of KACI4 in the amount corresponding to 3 X 10 "7 mole Au per mole Ag replaced some of the water in the Solution 3.
• All these emulsions are coated at 26 mg of silver, 100 mg of coupler, and 77 mg of gelatin per square foot on resin coated paper support and were subjected to sensitometric gradation exposure through the set of Kodak filters and heat absorbing filter using a sensitometer IB (available from Eastman Kodak Company; color temperature of light source: 3,000° K) . Exposure times are 1/10 of a second.
• the coatings were developed in Kodak RA-4 chemistry (Research Disclosure, Vol. 308, 1989, p. 933), and the results are summarized below:
• Silver halide emulsion, type (3) was prepared as follows:
• Solution 1 is heated up to 68.3°C, and Solution 2 and Solution 3 are added to it simultaneously over 5 minutes at the flow rate of 49 ml/min.
• Concentration of Solution 1 and Solution 2 is 3.0 mole/liter. Both solutions are fed into the reactor at the constant rate of 20 ml/min. over one minute. Then the flow rate is linearly ramped from 20 ml/min. up to 80 ml/min. over 39 minutes. The flow of the reactants is continued at 80 ml/min. for another 9 minutes. After that the emulsion is cooled down to 43°C and desalted, and Solution 4 is added.
• the effective edge length of the resultant silver chloride cubic Emulsion #301, as shown in Table VI is 0.61 ⁇ m.
• This example shows a strong antifogging action of both gold compounds, i.e., Gold(I) compound and KAUCI4, when added during emulsion precipitation and sulfur plus gold sensitized emulsions.
• This type of emulsion cannot be sulfur plus gold sensitized to the comparable photographic sensitivity without the use of the above compounds.
• the invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifica ⁇ tions can be effected within the spirit and scope of the invention.

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• 1992
  • 1992-07-21 EP EP19920916612 patent/EP0548354A1/en not_active Withdrawn
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