EP0362699A2 - Emulsionen mit tafelförmigen Körnern eines hohen Aspektverhältnisses, die eine engere Korngrössenverteilung aufweisen - Google Patents

Emulsionen mit tafelförmigen Körnern eines hohen Aspektverhältnisses, die eine engere Korngrössenverteilung aufweisen Download PDF

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Publication number
EP0362699A2
EP0362699A2 EP89117978A EP89117978A EP0362699A2 EP 0362699 A2 EP0362699 A2 EP 0362699A2 EP 89117978 A EP89117978 A EP 89117978A EP 89117978 A EP89117978 A EP 89117978A EP 0362699 A2 EP0362699 A2 EP 0362699A2
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Prior art keywords
aspect ratio
grain
emulsion
tabular
silver
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French (fr)
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EP0362699A3 (de
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Philip Joseph C/O Eastman Kodak Company Zola
Roger Anthony C/O Eastman Kodak Company Bryant
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Eastman Kodak Co
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Eastman Kodak Co
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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
    • G03C1/0051—Tabular grain emulsions

Definitions

  • This invention relates to the field of photography. More particularly, the invention is directed to improvements in radiation sensitive silver-­halide emulsions.
  • both the halide and silver salts are concurrently introduced into the reaction vessel.
  • Silver halide emulsions having a low variance of grain sizes are referred to as monodisperse emulsions.
  • Monodisperse emulsions are recognized to offer a variety of photographic advantages. For example, a larger percentage of the grains in a monodisperse emulsion can be optimally sensitized as a result of their similar surface areas. Fine grain populations, which disproportionately contribute to light scattering and therefore image sharpness reduction, are restricted. Larger grain populations, which contribute disproportionately to image granularity, are restricted. The reproducibility of the emulsions and their photographic performance rises as dispersity is reduced. Contrast of a single monodisperse emulsion is higher than that of polydisperse emulsion of the same mean grain size.
  • Monodisperse emulsions are employed not only for photographic applications requiring higher contrast, but are also blended to achieve aim contrasts in photographic applications requiring relatively lower contrast, since a blended monodisperse emulsion retains photographic advantages over a polydisperse emulsion of the same mean grain size and contrast.
  • Maternaghan U.S. Patents 4,150,994 and 4,184,878 are representative of early reported attempts to prepare tabular grain silver bromoiodide emulsions. Covering power advantages were postulated. Low coefficients of variation were reported for the emulsions. However, in retrospect this is not surprising, since from remakes and grain characterizations the average aspect ratios (most simply measured as mean grain diameter divided by mean grain thickness) of these emulsions are approximately 4:1.
  • Patent 4,435,501 are representative of the earliest published teachings relating to high aspect ratio silver bromoiodide emulsions. More recently Daubendiek et al U.S. Patent 4,693,964 and 4,672,027 have reported the preparation of high aspect ratio silver bromoiodide emulsions of much smaller mean grain diameters, referred to as small, thin tabular grain silver bromoiodide emulsions. Maskasky U.S. Patent 4,713,320 illustrates the effect of gelatin methionine reduction on silver bromoiodide high aspect ratio tabular grain emulsion preparation.
  • the advantages of silver bromoiodide high aspect ratio tabular grain emulsions include an improved relationship between speed and granularity, sharper images ⁇ both in single and multilayer photographic elements, accelerated development, higher insensitivity to temperature variations during development, higher fixing rates, more favorable toning, higher covering power, an increased separation between minus blue (green or red) and blue speeds when spectrally sensitized to the minus blue portion of the spectrum, increased blue speed when spectrally sensitized to blue light, and a variety of other advantages observed in the context of specific photographic applications.
  • tabular grain emulsions are prepared by double jet precipitation techniques, difficulties were experienced from the outset in reducing the dispersity of the emulsions.
  • regular grain emulsions produced by double jet precipitation e.g., regular cubic or octahedral grain emulsions
  • tabular grain emulsions are rarely prepared with only tabular grains present.
  • having mixed populations of tabular and nontabular grains is one source of dispersity in tabular grain emulsions.
  • the second source of dispersity is the dispersity variances within the tabular grain population itself, which is a function of the twinning followed by edge deposition growth pattern that distinguishes tabular grain emulsions from regular grain emulsions, wherein twinning is absent or rare and deposition favors no particular set of crystal faces.
  • dispersity in tabular grain emulsions increases as the average aspect ratios of the tabular grains increases. Therefore, dispersity levels which are easily attained in lower aspect ratio tabular grain emulsions have not been attainable at higher aspect ratios.
  • Saitou et al West German OLS 3,707,135 A1 employs double and single jet precipitation techniques to produce silver bromide emulsions which exhibit higher coefficients of variation at aspect ratios comparable to those of Mignot, even though Saitou et al reports coefficients of variations based solely on the tabular grain population.
  • the emulsion is characterized in that the quotient of the average silver bromoiodide tabular grain aspect ratio divided by the coefficient of variation of the total silver bromoiodide grain population is greater than 0.7.
  • the present invention is an improvement on the teachings of Wilgus et al U.S. Patent 4,434,226, Kofron et al U.S. Patent 4,439,520, Solberg et al U.S. Patent 4,433,048, Daubendiek et al U.S. Patent 4,414,310, 4,693,964 and 4,672,027, Evans et al U.S. Patent 4,504,570, and Maskasky U.S. Patents 4,435,501 and 4,713,320. All features of the emulsions of this invention, their preparation, and their photographic applications, except as otherwise indicated, are to be understood as being as described by these incorporated teachings.
  • the present invention is directed to silver bromoiodide tabular grain emulsions which exhibit an improved relationship of grain tabularity to dispersity. A detailed discussion requires more definitive terms.
  • high aspect ratio tabular grain emulsion refers to an emulsion in which the tabular grains having a thickness of less than 0.3 ⁇ m have an average aspect ratio of greater than 12 and account for greater than 50% of the total grain projected area.
  • the average aspect ratio of the tabular grains can be determined by determining the aspect ratio of each grain and averaging the aspect ratios of all tabular grains or by dividing the average diameter of all of the tabular grains by the average thickness of all the tabular grains.
  • coefficient of variation is employed in its art recognized sense as 100 times the standard deviation of all silver bromoiodide grain diameters divided by the average silver bromoiodide grain diameter. All grains, including both tabular and nontabular grains, are counted in arriving at averages. Defined in this way, the coefficients of variation reported have higher numerical values than those based solely on the tabular grain population.
  • the reason for defining the invention in terms of the quotient of the average aspect ratio divided by the coefficient of variation rather than simply in terms of a minimum coefficient of variation is that coefficients of variation increase linearly with increases in the average aspect ratios of tabular grains using comparable processes of emulsion preparation.
  • monodispersities acceptable for present photographic performance requirements are readily achieved.
  • at average aspect ratios greater than 12:1 and beyond the art has an unsatisfied need for higher levels of monodispersity.
  • the present invention makes possible an improved balance of tabular grain average aspect ratios and monodispersity in the aspect ratio ranges where satisfaction of desired monodispersity have not been heretofore realized.
  • the preferred emulsions of the invention are those in which the tabular silver bromoiodide grains having a thickness of less than 0.3 ⁇ m (optimally less than 0.2 ⁇ m) have an average aspect ratio of greater than 12 (optimally at least 20). Very high average aspect ratios ranging up to 100 or more are contemplated.
  • the tabular silver bromoiodide grains satisfying the thickness criteria above account for greater than 70 percent (optimally greater than 90 percent) of the total silver bromoiodide grain projected area.
  • the emulsions of the invention consist essentially of tabular silver bromoiodide grains satisfying the thickness criteria above.
  • the mean grain size (diameter) of the emulsions of this invention is less than 10 ⁇ m. While the invention can be employed to produce very small diameter (0.2 to 0.6 ⁇ m mean diameter) tabular grain emulsions, such as those disclosed by Daubendiek et al U.S. Patents 4,672,027 and 4,693,964, as well as those having mean tabular grain diameters above 0.6 ⁇ m, the present invention has particular preferred applicability to emulsions having mean grain diameters in the range of from 1.5 to 3.5 ⁇ m, particularly 1.5 to 2.5 ⁇ m.
  • the unique silver bromoiodide grain population required by the tabular grain emulsions of this invention has resulted from replacing the empirical methods of emulsion preparation disclosed in the art by a strategy for grain nucleation and growth specifically devised to preserve monodispersity in the context of silver bromoiodide tabular grain precipitation.
  • the strategy begins with dividing the emulsion precipitation process into three distinct stages:
  • the most important single process variation for achieving emulsions satisfying the requirements of this invention is to implement a technique for as nearly concurrent formation of all of the grain nuclei as possible.
  • an aqueous solution supersaturated with silver and bromide ions precipitation occurs to produce a grain nucleus. This nucleus immediately begins to grow. Unless all nuclei are concurrently formed, the earlier formed nuclei will be larger than the initially formed nuclei.
  • concentrations of the aqueous silver and bromide salts added to the reaction vessel are increased and the duration of their addition is condensed into a period of less than 10 seconds.
  • both silver and bromide salt additions are completed in less than 5 seconds and ideally in less than 1 second.
  • concentra­tions above 1 molar are preferred. This decreases the bulk of the materials to be introduced.
  • temperature can be controlled to limit solubility. Whereas precipitation temperatures are known to range up to 90°C, it is preferred to limit temperatures at nucleation to 60°C or less.
  • reducing the elapsed time of initial silver and bromide salt additions is the most important single process modification.
  • iodide ion is preferably omitted from the nucleation stage to avoid unnecessarily complicating nucleation.
  • the next stage of the precipitation strategy is to reverse immediately the initial direction of net ion transfer from solution to nuclei, but in a controlled manner so that the majority of the nuclei remain. This is achieved by abruptly moving from a supersaturated solution to a solution which is below its silver and bromide ion saturation limit.
  • the second stage is then a ripening stage in which the smaller silver halide nuclei disappear while the remaining nuclei remain. This can be achieved by employing any one or combination of known ripening procedures. The simplest of these is to adjust upwardly the temperature of the nuclei emulsion, thereby raising the solubility level of the silver and bromide ions.
  • the ripening can be conducted by raising the temperature up to 90°C, producing a temperature differential between nucleation and ripening of 70°C.
  • the temperature differential between nucleation and ripening is in the range from about 10 to 40°C, optimally about 15 to 30°C.
  • the duration of ripening in the second stage is preferably from 5 to 30 minutes in the absence of a ripening agent other than the dissolved bromide ion.
  • a ripening agent other than the dissolved bromide ion.
  • known ripening agents such as thioethers, thiocyanate, ammonia, and the like, accelerate ripening. If ammonia is employed as a ripening agent, it is preferably deactivated at the end of the ripening interval by an appropriate pH adjustment.
  • the nuclei ripening procedure of Nottorf U.S. Patent 4,722,886 is specifically contemplated.
  • Iodide ion is introduced in the growth stage.
  • the teachings of Solberg et al U.S. Patent 4,433,048 disclose preferred considerations for iodide addition.
  • the pBr of the reaction vessel during both the ripening and growth stage be well above the pBr of the reaction vessel during nucleation. It is generally preferred to adjust the pBr of the reaction vessel at the outset of the ripening stage above 1.6 up to the growth stage pBr limits of the teachings cited above. Further increase of the pBr will result in deposition onto the major faces of the tabular grains and reduce the average aspect ratio of the emulsion.
  • Modifying compounds can be present during silver bromoiodide precipitation. Such compounds can be initially in the reaction vessel or can be added along with one or more of the salts 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 VIII noble metals, can be present during precipitation, as illustrated by Arnold et al U.S. Patent 1,195,432, Hochstetter U.S. Patent 1,951,933, Trivelli et al U.S. Patent 2,448,060, Overman U.S. Patent 2,628,167, Mueller et al U.S.
  • Patent 2,950,972 Sidebotham U.S. Patent 3,488,709, Rosecrants et al U.S. Patent 3,737,313, Berry et al U.S. Patent 3,772,031, Atwell U.S. Patent 4,269,927, and Research Disclosure , Vol. 134, June 1975, Item 13452.
  • the tabular grain emulsions can be internally reduction sensitized during precipitation, as illustrated by Moisar et al, Journal of Photographic Science , Vol. 25, 1977, pp. 19-27.
  • the silver bromoiodide high aspect ratio tabular grain emulsions can be shelled to produce a core-shell emulsion by procedures well known to those skilled in the art.
  • Any photograph­ically useful silver salt can be employed in forming shells on the high aspect ratio tabular grain emulsions prepared by the present process. Techniques for forming silver salt shells are illustrated by Evams et al U.S. Patent 4,504,570.
  • peptizer concentrations of from 0.2 to about 10 percent by weight, based on the total weight of emulsion components in the reaction vessel, can be employed. It is common practice to maintain the concentration of the peptizer in the reaction vessel in the range of below about 6 percent, based on the total weight, prior to and during grain formation and to adjust the emulsion vehicle concentration upwardly for optimum coating characteristics by delayed, supplemental vehicle additions. It is contemplated that the emulsion as initially formed will contain from about 5 to 50 grams of peptizer per mole of silver halide, preferably about 10 to 30 grams of peptizer per mole of silver halide.
  • vehicle can be added later to bring the concentration up to as high as 1000 grams per mole of silver halide.
  • concentration of vehicle in the finished emulsion is above 50 grams per mole of silver halide.
  • the vehicle When coated and dried in forming a photographic element the vehicle preferably forms about 30 to 70 percent by weight of the emulsion layer.
  • Vehicles which include both binders and peptizers
  • Preferred peptizers are hydrophilic colloids, which can be employed alone or in combination with hydrophobic materials.
  • Suitable hydrophilic materials include substances such as proteins, protein derivatives, cellulose derivatives ⁇ e.g., cellulose esters, gelatine ⁇ e.g., alkali-treated gelatin (cattle bone or hide gelatin) or acid-treated gelatin (pigskin gelatin), gelatin derivatives ⁇ e.g., acetylated gelatin, phthalated gelatin and the like, polysacch­arides such as dextran, gum arabic, zein, casein, pectin, collagen derivatives, agar-agar, arrowroot, albumin and the like as described in Yutzy et al U.S. Patents 2,614,928 and '929, Lowe et al U.S.
  • Patent 2,343,650 Yutzy U.S. Patent 2,323,085, Lowe U.S. Patent 2,563,791, Talbot et al U.S. Patent 2,725,293, Hilborn U.S. Patent 2,748,022, DePauw et al U.S. Patent 2,956,883, Ritchie U.K. Patent 2,095, DeStubner U.S. Patent 1,752,069, Sheppard et al U.S. Patent 2,127,573, Lierg U.S. Patent 2,256,720, Gaspar U.S. Patent 2,361,936, Farmer U.K. Patent 15,727, Stevens U.K. Patent 1,062,116 and Yamamoto et al U.S. Patent 3,923,517.
  • hydrophilic colloid peptizers include synthetic polymeric peptizers, carriers and/or binders such as poly(vinyl lactams), acrylamide polymers, polyvinyl alcohol and its derivatives, polyvinyl acetals, polymers of alkyl and sulfoalkyl acrylates and methacrylates; hydrolyzed polyvinyl acetates, polyamides, polyvinyl pyridine, acrylic acid polymers, maleic anhydride copolymers, polyalkylene oxides methacrylamide copolymers, polyvinyl oxazolidinones, maleic acid copolymers, vinylamine copolymers, methacrylic acid copolymers, acryloyloxyalkylsulfonic acid copolymers, sulfoalkyl­acrylamide copolymers, polyalkyleneimine copoly
  • Patent 3,284,207 Lohmer et al U.S. Patent 3,167,430, Williams U.S. Patent 2,957,767, Dawson et al U.S. Patent 2,893,867, Smith et al U.S. Patents 2,860,986 and 2,904,539, Ponticello et al U.S. Patents 3,929,482 and 3,860,428, Ponticello U.S. Patent 3,939,130, Dykstra U.S. Patent 3,411,911 and Dykstra et al Canadian Patent 774,054, Ream et al U.S. Patent 3,287,289, Smith U.K. Patent 1,466,600, Stevens U.K. Patent 1,062,116, Fordyce U.S.
  • Patent 3,748,143 Dickinson et al U.K. Patents 808,227 and '228, Wood U.K. Patent 822,192 and Iguchi et al U.K. Patent 1,398,055.
  • vehicle materials including particularly the hydrophilic colloids, as well as the hydrophobic materials useful in combination therewith can be employed not only in the emulsion layers of photographic elements, but also in other layers, such as overcoat layers, interlayers and layers positioned beneath the emulsion layers.
  • ripening can occur during the hold stage of emulsion preparation. However, ripening need not and commonly is not confined to just this one stage of emulsion preparation.
  • Known silver halide solvents are useful in promoting ripening. For example, an excess of bromide ions, when present in the reaction vessel, is known to promote ripening. It is therefore apparent that the bromide salt solution run into the reaction vessel can itself promote ripening.
  • Other ripening agents can also be employed and can be entirely contained within the dispersing medium in the reaction vessel before silver and halide salt addition, or they can be introduced into the reaction vessel along with one or more of the halide salt, silver salt, or peptizer. In still another variant the ripening agent can be introduced independently during halide and silver salt additions.
  • ripening agents are those containing sulfur.
  • Thiocyanate salts can be used, such as alkali metal, most commonly sodium and potassium, and ammonium thiocyanate salts. While any conventional quantity of the thiocyanate salts can be introduced, preferred concentrations are generally from about 0.1 to 20 grams of thiocyanate salt per mole of silver halide.
  • Illustrative prior teachings of employing thiocyanate ripening agents are found in Nietz et al, U.S. Patent 2,222,264, cited above; Lowe et al U.S. Patent 2,448,534 and Illingsworth U.S. Patent 3,320,069.
  • conventional thioether ripening agents such as those disclosed in McBride U.S. Patent 3,271,157, Jones U.S. Patent 3,574,628, and Rosecrants et al U.S. Patent 3,737,313.
  • the silver bromoiodide high aspect ratio tabular grain emulsions of the present invention are preferably washed to remove soluble salts. Conventional washing procedures, such as those disclosed in Research Disclosure , Vol. 176, Dec. 1978, Paragraph II are contemplated.
  • the high aspect ratio tabular grain emulsions prepared by the process of the present invention with each other or with conventional emulsions to satisfy specific emulsion requirements.
  • emulsions can be blended with conventional silver halide emulsions, such as those described in Research Disclosure , Item 17643, cited above, Paragraph 1.
  • conventional silver halide emulsions such as those described in Research Disclosure , Item 17643, cited above, Paragraph 1.
  • silver bromoiodide high aspect ratio tabular grain emulsions have been prepared by the process of the present invention, they can be further modified, coated, exposed, and processed following procedures well known to those skilled in the art.
  • the emulsions prepared by the present process can be chemically sensitized, as described in Research Dis­closure , Item 17643, cited above, Paragraph III.
  • the emulsions can be spectrally sensitized and/or desensitized, as described in Paragraph IV. It is specifically prefer- red to substantially optimally chemically and spec- trally sensitize the emulsions prepared by the present process by the techniques disclosed in Kofron et al, and Maskasky U.S. Patent 4,435,501, cited above.
  • the photographic emulsions can contain brighteners, antifoggants, stabilizers, scattering or absorbing materials, hardeners, coating aids, plasticizers, lubricants, and matting agents, as described in Item 17643, Paragraphs V, VI, VIII, X, XI, XII, and XVI. Methods of addition and coating and drying procedures can be employed, as described in Paragraphs XIV and XV. Conventional photographic supports can be employed, as described in Paragraph XVII.
  • the photographic elements produced can be black-and-white or, preferably, color photographic elements which form silver images and/or dye images through the selective destruction, formation, or physical removal of dyes, as described in Paragraph VII.
  • Specifically preferred color photographic elements are those which form dye images through the use of color developing agents and dye-forming couplers. To put the photographic elements to use, they can be conventionally exposed, as described in Paragraph XVIII, and they can be conventionally processed, as described in Paragraph XIX.
  • a halide solution containing sodium bromide (1.89M) plus potassium iodide (0.06M) and a 1.50M silver nitrate solution were added by double jet addition utilizing accelerated flow (7 X increase in flow rates from start to finish) for 40 minutes at pBr 1.13 at 70°C, consuming 99.45 percent of the total silver used. Approximately 2.2 moles of silver were used to prepare this emulsion.
  • the resultant silver bromoiodide high aspect ratio tabular grain emulsion had an average grain diameter of 2.17 ⁇ m, an average tabular grain thickness of 0.08 ⁇ m, an average aspect ratio of 27, and a coefficient of variation, based on the total grain population, of 69. Tabular grains accounted for 85% of the total grain projected area.
  • Emulsion 2 (Invention)
  • a halide solution containing sodium bromide (1.89M) plus potassium iodide (0.06M) and a 1.5M silver nitrate solution were added by double jet addition utilizing accelerated flow (14 X increase in flow rates from start to finish) for 42 minutes at pBr 1.78 at 70°C, consuming 99.45 percent of the total silver used. Approximately 2.2 moles of silver were used to prepare this emulsion.
  • the resultant silver bromoiodide high aspect ratio tabular grain emulsion had an average grain diameter of 1.78 ⁇ m, an average tabular grain thickness of 0.08 ⁇ m, an average aspect ratio of 22, and a coefficient of variation, based on the total grain population, of 29. Tabular grains accounted for 85% of the total grain projected area.
  • Emulsion 3 (Invention)
  • a halide solution containing sodium bromide (1.89M) plus potassium iodide (0.06M) and a 1.5M silver nitrate solution were added by double jet addition utilizing accelerated flow (14 X increase in flow rates from start to finish) for 42 minutes at pBr 1.78 at 70°C, consuming 99.45 percent of the total silver used. Approximately 2.2 moles of silver were used to prepare this emulsion.
  • the resultant silver bromoiodide high aspect ratio tabular grain emulsion had an average grain diameter of 2.35 ⁇ m, an average tabular grain thickness of 0.12 ⁇ m, an average aspect ratio of 20, and a coefficient of variation, based on the total grain population, of 23. Tabular grains accounted for 88% of the total grain projected area.
  • This emulsion is neither a conventional emulsion or an example of the invention. It is an in-between emulsion offered to shed light on the question suggested by a comparison of Emulsions 2 and 3 as to whether reliance on the thioether ripening agent without concurrent reliance on accelerated nucleation would produce an emulsion satisfying the tabularity to dispersity requirement of this invention.
  • a halide solution containing sodium bromide (1.89M) plus potassium iodide (0.06M) and a 1.5M silver nitrate solution were added by double jet addition utilizing accelerated flow (7 X increase in flow rates from start to finish) for 40 minutes at pBr 1.78 at 70°C, consuming 99.45 percent of the total silver used. Approximately 2.2 moles of silver were used to prepare this emulsion.
  • the resultant silver bromoiodide high aspect ratio tabular grain emulsion had an average grain diameter of 1.77 ⁇ m, an average tabular grain thickness of 0.09 ⁇ m, an average aspect ratio of 20, and a coefficient of variation of 31. Tabular grains accounted for 88% of the total grain projected area.
  • Emulsion 5 (Invention)
  • This emulsion is offered to illustrate the formation of a silver bromoiodide high aspect ratio tabular grain emulsion according to the invention having a mean grain thickness of less than 0.05 ⁇ m, facilitated by the use of gelatin peptizer treated with an oxidizing agent to eliminate methionine.
  • the resultant silver bromoiodide high aspect ratio tabular grain emulsion had an average grain diameter of 2.9 ⁇ m, an average tabular grain thickness of 0.04 ⁇ m, an average aspect ratio of 72, and a coefficient of variation, based on the total grain population, of 56.
  • Emulsion 6 (Invention)
  • Emulsion 5 Because of the very favorable relationship of tabularity and dispersity achieved by the Emulsion 5, it was possible to substitute a single jet nucleation for the double jet nucleation employed in the preparation of Emulsion 5 while still obtaining a silver bromoiodide high aspect ratio tabular grain emulsion having a quotient of average aspect ratio divided by coefficient of variation well in excess of 0.7.
  • the initial solution before nucleation was prepared as described for Emulsion 5.
  • the balanced double jet nucleation employed for Emulsion 5 was replaced by a single jet nucleation consisting of 8.0 mL of 1.67M silver nitrate solution delivered at approximately 5000 mL per minute. This was immediately followed by a temperature rise, hold time, gelatin addition, pH and pBr adjustments, and an initial constant flow rate triple jet addition that were identical to that of Emulsion 5.
  • the pBr adjustment to 1.55 of Emulsion 5 was replaced with a pBr adjustment to 1.85 using the 1.6M silver nitrate solution.
  • the final ramped flow rate triple jet addition was identical to that of Emulsion 5, except that the pBr was controlled at 1.85.
  • the resultant silver bromoiodide high aspect ratio tabular grain emulsion had bin average grain diameter of 2.3 ⁇ m, an average tabular grain thickness of 0.045 ⁇ m, an average aspect ratio of 51, and a coefficient of variation, based on the total grain population, of 43.
  • Emulsion 7 (Invention)
  • This emulsion is offered to illustrate the formation of a silver bromoiodide high aspect ratio tabular grain emulsion according to the invention wherein silver iodide was abruptly added as a Lippmann emulsion during grain growth.
  • the invention has been described in terms of coefficients of variation of grain diameters. Since nontabular grain populations exhibit diameters based on their projected areas that are essentially the same as their thickness, the art has not yet addressed the coefficients of variation for tabular grain emulsions based on variations in tabular grain thicknesses as opposed to variations in tabular grain diameter (the diameter of a circle having the same projected area as the tabular grain). Measurements of tabular grain thickness variation are of necessity somewhat more difficult to generate, since tabular grain thicknesses are much smaller than tabular grain diameters and mist be determined indirectly by shadow length measurements of carbon grain replicas.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
EP19890117978 1988-10-03 1989-09-28 Emulsionen mit tafelförmigen Körnern eines hohen Aspektverhältnisses, die eine engere Korngrössenverteilung aufweisen Withdrawn EP0362699A3 (de)

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US252723 1988-10-03
US35899989A 1989-05-30 1989-05-30
US358999 1989-05-30

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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5104786A (en) * 1990-10-29 1992-04-14 Eastman Kodak Company Plug-flow process for the nucleation of silver halide crystals
WO1992007295A1 (en) * 1990-10-23 1992-04-30 Eastman Kodak Company Low temperature growth emulsion making process
US5210013A (en) * 1991-05-14 1993-05-11 Eastman Kodak Company Very low coefficient of variation tabular grain emulsion
US5250403A (en) * 1991-04-03 1993-10-05 Eastman Kodak Company Photographic elements including highly uniform silver bromoiodide tabular grain emulsions
EP0566083A1 (de) * 1992-04-16 1993-10-20 Eastman Kodak Company Photographische Mehrfarbelemente mit erhöhtem Empfindlichkeits-Körnigkeits-Verhältnis
US5411851A (en) * 1994-02-14 1995-05-02 Eastman Kodak Company Grain growth process for the preparation of high bromide ultrathin tabular grain emulsions
US5411853A (en) * 1994-09-08 1995-05-02 Eastman Kodak Company Grain growth process for the preparation of high bromide ultrathin tabular grain emulsions
US5418125A (en) * 1994-09-08 1995-05-23 Eastman Kodak Company Grain growth process for the preparation of high bromide ultrathin tabular grain emulsions
US5460934A (en) * 1993-10-21 1995-10-24 Eastman Kodak Company Chloride containing high bromide ultrathin tabular grain emulsions
EP0699950A1 (de) 1994-08-26 1996-03-06 Eastman Kodak Company Emulsionen mit ultradünnen tafelförmigen Körnern und neuer Behandlung von Dotiermitteln
EP0699949A1 (de) 1994-08-26 1996-03-06 Eastman Kodak Company Emulsionen mit ultradünnen tafelförmigen Körnern und Dotierungsmitteln auf ausgewählten Stellen
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EP0758758A1 (de) 1995-08-10 1997-02-19 Eastman Kodak Company Emulsionen enthaltend ultradünne tafelförmige Körner mit hohem Bromidgehalt verbessert durch modifizierten Peptisierer
US6228573B1 (en) 1999-12-15 2001-05-08 Eastman Kodak Company Process for the preparation of high bromide ultrathin tabular grain emulsions

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DE68914303T2 (de) * 1988-01-18 1994-11-10 Fuji Photo Film Co Ltd Photographische Silberhalogenidemulsionen und Verfahren zu deren Herstellung.

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WO1992007295A1 (en) * 1990-10-23 1992-04-30 Eastman Kodak Company Low temperature growth emulsion making process
US5248587A (en) * 1990-10-23 1993-09-28 Eastman Kodak Company Low temperature growth emulsion making process
US5104786A (en) * 1990-10-29 1992-04-14 Eastman Kodak Company Plug-flow process for the nucleation of silver halide crystals
US5250403A (en) * 1991-04-03 1993-10-05 Eastman Kodak Company Photographic elements including highly uniform silver bromoiodide tabular grain emulsions
US5210013A (en) * 1991-05-14 1993-05-11 Eastman Kodak Company Very low coefficient of variation tabular grain emulsion
EP0514742B1 (de) * 1991-05-14 1995-12-13 Eastman Kodak Company Verfahren zur Herstellung einer Emulsion mit tafelförmigen Körnern eines sehr niedrigen Variationskoeffizienten.
EP0566083A1 (de) * 1992-04-16 1993-10-20 Eastman Kodak Company Photographische Mehrfarbelemente mit erhöhtem Empfindlichkeits-Körnigkeits-Verhältnis
US5460934A (en) * 1993-10-21 1995-10-24 Eastman Kodak Company Chloride containing high bromide ultrathin tabular grain emulsions
US5411851A (en) * 1994-02-14 1995-05-02 Eastman Kodak Company Grain growth process for the preparation of high bromide ultrathin tabular grain emulsions
EP0699949A1 (de) 1994-08-26 1996-03-06 Eastman Kodak Company Emulsionen mit ultradünnen tafelförmigen Körnern und Dotierungsmitteln auf ausgewählten Stellen
EP0699950A1 (de) 1994-08-26 1996-03-06 Eastman Kodak Company Emulsionen mit ultradünnen tafelförmigen Körnern und neuer Behandlung von Dotiermitteln
EP0699946A1 (de) 1994-08-26 1996-03-06 Eastman Kodak Company Emulsionen mit ultradünnen tafelförmigen Körnern mit verbesserter Empfindlichkeit (II)
US5418125A (en) * 1994-09-08 1995-05-23 Eastman Kodak Company Grain growth process for the preparation of high bromide ultrathin tabular grain emulsions
US5411853A (en) * 1994-09-08 1995-05-02 Eastman Kodak Company Grain growth process for the preparation of high bromide ultrathin tabular grain emulsions
EP0758758A1 (de) 1995-08-10 1997-02-19 Eastman Kodak Company Emulsionen enthaltend ultradünne tafelförmige Körner mit hohem Bromidgehalt verbessert durch modifizierten Peptisierer
US6228573B1 (en) 1999-12-15 2001-05-08 Eastman Kodak Company Process for the preparation of high bromide ultrathin tabular grain emulsions

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EP0362699A3 (de) 1991-03-13

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