Photographic emulsions containing tabular grains with a band structure and a central grain portion of high bromide concentration

Abstract: Radiation-sensitive emulsions are disclosed in which tabular grains of a face centered cubic crystal lattice structure having parallel {111} major faces and an average aspect ratio of at least 5 are comprised of a central region containing greater than 50 mole percent bromide and a tabular band containing at least 60 mole percent chloride and extending laterally outwardly from the central region to form at least 2 percent of the {111} major faces.

Description: The invention relates to radiation-sensitive emulsions useful in photography. Brief Description of the Drawings Figure 1 is a plan view of a tabular grain with dashed lines added to demonstrate two alternate growth patterns. Figure 2 is a sectional view of the tabular grain of Figure 1. Figure 3 is a sectional view of the tabular grain of Figures 1 and 2 with conventional shelling. Figure 4 is a sectional view of the tabular grain of Figures 1 and 2 with a shell according to the invention. During the 1980's a marked advance took place in silver halide photography based on the discovery that a wide range of photographic advantages, such as improved speed-granularity relationships, increased covering power both on an absolute basis and as a function of binder hardening, more rapid developability, increased thermal stability, increased separation of native and spectral sensitization imparted imaging speeds, and improved image sharpness in both mono- and multi-emulsion layer formats, can be realized by increasing the proportions of selected high (>50 mole %) bromide tabular grain populations in photographic emulsions. The advantages of tabular grain emulsions stem from the high proportion of tabular grains--that is, grains with parallel {111} major faces, having a relatively large equivalent circular diameter (ECD) as compared to their thickness (t) . By increasing the percentage of total grain projected area accounted for tabular grains, increasing the aspect ratio of the tabular grains (ECD + t) , and decreasing grain thickness, the advantages imparted by tabular grain geometries can be enhanced. From the very outset it was recognized that tabular grains with {111} major faces could be prepared by introducing parallel twin planes in the face centered cubic crystal lattice structure of silver bromide grains. It was subsequently discovered that the desired tabular grain characteristics could, with proper precautions, be maintained when minor amounts of iodide were incorporated. Kofron et al U.S. Patent 4,439,520 was the first to report silver bromide and iodobromide high aspect ratio ( ECD/t > 8) tabular grain emulsions chemically and spectrally sensitized to yield high levels of photographic performance. Kofron et al suggested creating high bromide tabular grains with core-shell structures, but suggested no specific advantage for tabular grain core-shell structures. In fact there are fundamental problems in shelling high bromide tabular grain emulsions. The problem is illustrated by reference to Figures 1 to 3 . In Figures 1 and 2 a high bromide tabular grain 100 is shown. The upper major face 102 of the tabular grain is large compared to its thickness t . It is the large upper major face available to capture exposing radiation and the limited thickness of the tabular grain that provide the advantages of this grain shape. If a conventional shelling procedure is followed, the grain structure shown in Figure 3 results. Although the shell S produces a layer of uniform thickness on all external surfaces of the grain 100 , the additional silver halide precipitated to form the shell is located primarily on the major faces of the original tabular grains. Only a very small fraction of the additionally deposited silver halide is located on the edges of the tabular grain 100, since the edge surface area of the tabular grain 100 is small compared the surface area of the major faces. The shell increases the projected area of the tabular grain available to capture exposing radiation only slightly. This is shown by comparing the location of the peripheral edge 204 of the shelled grain to that of tabular grain 100 in Figure 1. However, the thickness t 1 of the shelled tabular grain shows a high percentage increase when compared to the thickness t of tabular 100 . Ihama et al U.S. Patent 4,977,075 illustrates an emulsion in which silver iodobromide tabular grains have silver chloride deposited on their major faces. Stated another way, conventional shelling procedures degrade desirable tabular grain properties. Tabular grain projected area is increased little, while tabular grain aspect ratio is reduced significantly and tabular grain thickness is increased significantly. Wey U.S. Patent 4,399,215 produced the first silver chloride high aspect ratio tabular grain emulsion. An ammoniacal double-jet precipitation technique was employed. The average aspect ratio of the emulsions was not high compared to contemporaneous silver bromide and bromoiodide tabular grain emulsions because the ammonia thickened the tabular grains. A further disadvantage was that significant reductions in tabularity occurred when bromide and/or iodide ions were included in the tabular grains. Wey et al U.S. Patent 4,414,306 developed a process for preparing high bromide tabular grains having a significant chloride concentration of up to 40 mole % in an annular band. This was achieved by first forming a high bromide tabular grain emulsion by conventional techniques and then continuing grain precipitation with an excess of chloride ion in the dispersing medium surrounding the grains to cause minor amounts of chloride to be incorporated into the annular region of the tabular grain formed by further grain growth. Wey et al never realized that potential advantages of creating a high bromide tabular grain with a high chloride region, since the process of Wey et al is limited to incorporating minor amounts of chloride in the tabular grains. Maskasky U.S. Patent 4,435,501 (hereinafter Maskasky I) discovered large sensitivity enhancements when silver chloride is epitaxially deposited at selected sites on high bromide tabular grains. The silver chloride epitaxy precipitated by Maskasky is in all instances clearly nontabular in form, typically taking the form of nontabular edge or corner protrusions. Thus, the tabular grain geometries of the emulsions of Maskasky are not enhanced by epitaxy. Maskasky U.S. Patent 4,400,463 (hereinafter designated Maskasky II) developed a strategy for preparing a high chloride, high aspect ratio tabular grain emulsion capable of tolerating minor inclusions of the other halides. The strategy was to use a particularly selected synthetic polymeric peptizer in combination with a grain growth modifier having as its function to promote the formation of {111} crystal faces. Adsorbed aminoazaindenes, preferably adenine, and iodide ions were disclosed to be useful grain growth modifiers. The principal disadvantage of this approach has been the necessity of employing a synthetic peptizer as opposed to the gelatino-peptizers almost universally employed in photographic emulsions. This work has stimulated further investigations of grain growth modifiers for preparing tabular grain high chloride emulsions, as illustrated by Takada et al U.S. Patent 4,783,398, which employs heterocycles containing a divalent sulfur ring atom; Nishikawa et al U.S. Patent 4,952,491, which employs spectral sensitizing dyes and divalent sulfur atom containing heterocycles and acyclic compounds; Ishiguro et al U.S. Patent 4,983,508, which employs organic bis-quaternary amine salts; Tufano et al U.S. Patent 4,804,621, which employs selected 4,6-diaminopyrimidines capable of promoting the formation of tabular grains, but excludes the possibility of having an amino substituent present in the 5-position on the pyrimidine ring; Maskasky U.S. Patent 5,061,617 (hereinafter designated Maskasky III), which employs thiocyanate as a grain growth modifier; Maskasky U.S. Patent 5,178,997 (hereinafter designated Maskasky IV), which employs 7-azaindole and related compounds; Maskasky and Chang U.S. Patent 5,178,998, which employs xanthine and related compounds; Maskasky U.S. Patent 5,183,732 (hereinafter designated Maskasky V), which employs adenine; and Maskasky U.S. Patent 5,185,239 (hereinafter designated Maskasky VI), which employs specified 4,5,6-triaminopyrimidine and related compounds. The present invention provides an emulsion with tabular grains that combine the performance advantages of high bromide tabular grains with those of providing an interface with a high chloride region while at the same time enhancing performance characteristics attributable to tabular grain geometry by increasing tabular grain projected area without a concomitant increase in tabular grain thickness. In fact, significant increases in tabular grain projected area have been achieved without any measurable increase in tabular grain thickness. In one aspect this invention is directed to a radiation-sensitive emulsion comprised of a dispersing medium and silver halide grains, at least 50 percent of total grain projected area being accounted for by tabular grains of a face centered cubic crystal lattice structure having parallel {111} major faces, an average thickness of less that 0.2 micrometer, and an average aspect ratio of at least 5, the tabular grains each being comprised of a central region and a shell differing in halide content, characterized in that the central region contains greater than 50 mole percent bromide, the shell contains at least 60 mole percent chloride, the shell is comprised of a band extending laterally outward from the central region and forming at least 2 percent of the {111} major faces, the band accounting for at least half the volume of shell, and the emulsion containing a 4,5,6-triaminopyrimidine, a polyiodophenol or an iodo-8-hydroxyquinoline grain growth modifier. The Figure 4 a tabular grain 400 is shown that illustrates the unique features of the emulsions of this invention. A central region 401 of the grain can be and is, as shown, identical to a conventional high bromide tabular grain 100 . Surrounding the central region is a shell 403 . The shell forms the major {111} crystal faces 405 and 407 of the tabular grain. The shell 403 differs from conventional shell S in that at least half of the volume of the shell is located in a band B extending laterally outwardly from the central region and forming at least 2 percent of the major {111} crystal faces of the tabular grain. The remainder of the shell consists of surface regions SR1 and SR2 that are interposed between the surface region and the major {111} crystal faces 405 and 407, respectively. Although the surface regions SR1 and SR2 are shown thinner than the corresponding surface regions of the conventional shell S , which contains the same total amount of silver halide, the thickness of the surface regions SR1 and SR2 has been exaggerated for ease of visualization. There are two significant effects of disproportionately locating the silver halide forming the shell 403 in the band B , both beneficial. First, the amount of silver halide contained in the surface regions SR1 and SR2 of the shell is minimized, thereby minimizing increase in the thickness of the tabular grain. Note that the thickness t 1 of the shelled tabular grain in Figure 3 is significantly greater than the thickness of the thickness t 2 of tabular grain 400 . Second, by directing at least half of the silver halide to the band B , the projected area of the tabular grain 400 is significantly increased as compared to the conventional shell tabular grain shown in Figure 3 . This is illustrated by comparing in Figure 1 the location of peripheral edge 409 of tabular grain 400 with the peripheral edge 204 of the conventionally shelled grain. The increase of the projected area of the tabular grain increases its ability of intercept and absorb exposing radiation. An important feature of the invention is that the portion of the shell forming the band B is itself tabular in character, unlike conventional shells that are nontabular overgrowths on tabular grains. The formation of tabular bands has been achieved by the discovery of heretofore unrealized conditions for tabular grain preparation, described in detail and demonstrated below. The radiation-sensitive emulsions of the invention are comprised of tabular grains accounting for at least 50 percent of total grain projected area having structural features of the type described for grain 400 . Preferably these tabular grains account for at least 70 percent of total grain projected area and optimally at least 90 percent of total grain projected area. These tabular grains have an average aspect ratio of at least 5, preferably >8. Since the tabular grains are actually increased in aspect ratio by shelling according to the teachings of the invention, the tabular grain emulsions of the invention can have average aspect ratios equaling or exceeding the highest average aspect ratios reported for high bromide tabular grain emulsions. The central regions of the tabular grains of this invention can correspond to conventional high bromide tabular grains, which provide convenient starting materials for the formation of the tabular grain emulsions of the invention. Conventional high bromide tabular grain emulsions that can be employed to provide the central regions of the grains of this invention are illustrated by the following: Wilgus et al U.S. Patent 4,434,226; Kofron et al U.S. Patent 4,439,520; Daubendiek et al U.S. Patent 4,414,310; Black et al U.S. Patent 5,334,495; Solberg et al U.S. Patent 4,433,048; Yamada et al U.S. Patent 4,647,528; Sugimoto et al U.S. Patent 4,665,012; Daubendiek et al U.S. Patent 4,672,027; Yamada et al U.S. Patent 4,679,745; Daubendiek et al U.S. Patent 4,693,964; Maskasky U.S. Patent 4,713,320; Nottorf U.S. Patent 4,722,886; Sugimoto U.S. Patent 4,755,456; Goda U.S. Patent 4,775,617; Ellis U.S. Patent 4,801,522; Ikeda et al U.S. Patent 4,806,461; Ohashi et al U.S. Patent 4,835,095; Makino et al U.S. Patent 4,835,322; Daubendiek et al U.S. Patent 4,914,014; Aida et al U.S. Patent 4,962,015; Ikeda et al U.S. Patent 4,985,350; Piggin et al U.S. Patent 5,061,609; Piggin et al U.S. Patent 5,061,616; Tsaur et al U.S. Patent 5,147,771; Tsaur et al U.S. Patent 5,147,772; Tsaur et al U.S. Patent 5,147,773; Tsaur et al U.S. Patent 5,171,659; Chaffee et al U.S. Patent 5,358,840; and Delton U.S. Patent 5,372,927. The high bromide tabular grain emulsions employed to prepare the central regions of the tabular grains of the invention contain greater than 50 mole percent, preferably at least 70 mole percent and optimally at least 90 mole percent bromide, based on total silver. It is specifically contemplated to employ emulsions as starting materials that consist essentially of silver bromide. Minor amounts of other halides can be present. Silver bromide and silver chloride are compatible in all ratios in the face centered cubic crystal lattice structure that forms the grains. Thus, silver chloride can be present in the high bromide tabular grains and in the central regions of the tabular grains of the invention in concentrations of up to 50 mole percent, based on silver. Silver iodide does not alone form a face centered cubic crystal lattice structure under conditions relevant to photographic emulsion preparation. Silver iodide can under ordinary precipitation conditions be tolerated in the face centered cubic crystal lattice structure of silver bromide in concentrations of up to approximately 40 mole percent. Silver iodide can be tolerated in the face centered cubic crystal lattice structure of silver chloride under ordinary precipitation conditions in concentrations of up to approximately 13 mole percent. Maskasky U.S. Patents 5,238,804 and 5,288,603 disclose elevated temperature precipitation techniques for increasing maximum iodide incorporation levels. It is contemplated that silver iodide can be present in the high bromide tabular grains forming the central regions up to its saturation level in the face centered cubic crystal lattice structure. However, for ease of emulsion preparation, it is generally preferred to limit iodide concentrations in the high bromide tabular grains forming the central regions to 20 mole percent or less, most preferably 15 mole percent or less. The presence of even small amounts of iodide can significantly enhance photographic sensitivity. Hence it is preferred that the high bromide tabular grains contain at least 0.1 mole percent iodide, preferably at least 0.5 mole percent iodide, based on total silver forming the grain structure. The high bromide tabular grain emulsions used to provide the central regions of the tabular grain emulsions of the invention can have any average aspect ratio compatible with achieving an average aspect ratio of at least 5 in the final emulsion. Since the band structure added disproportionately increases tabular grain ECD as compared to tabular grain thickness, the starting emulsion can have an average aspect ratio somewhat less than 5, but the aspect ratio is preferably at least 5. The starting emulsion can have any convenient conventional higher average aspect ratio, such as any average aspect ratio reported in the patents cited above. The average thickness of the high bromide tabular grains employed to form the central regions is less than 0.2 µm. It is specifically contemplated to employ as starting materials ultrathin tabular grain emulsions--i.e., those having an average tabular grain thickness of <0.07 µm. High bromide ultrathin tabular grain emulsions are included among the emulsion disclosures of the patents cited above to show conventional high bromide tabular grain emulsions and are additionally illustrated by the following: Zola and Bryant EPO 0 362 699; Antoniades et al U.S. Patent 5,250,403; and Sutton et al U.S. Patent 5,334,469. It is additionally preferred to select host high bromide tabular grain emulsions to exhibit limited grain dispersity. That is, the high bromide tabular grain emulsions are preferably selected so that both the starting emulsions and the completed emulsions satisfying the requirements of the invention are monodisperse. That is, the emulsions exhibit a coefficient of variation ( COV ) of grain ECD of less than 30 percent, where COV is defined as 100 times the standard deviation of grain ECD divided by average grain ECD. Generally the advantages of monodispersity are enhanced as COV is decreased below 30 percent. High bromide tabular grain emulsions useful in forming the central regions of the shelled grains of the emulsions of this invention are known to the art exhibiting COV values of less than 15 percent and, in emulsions where particular care has been exercised to limit dispersity, less in 10 percent. Low COV high bromide tabular grain emulsions are included among the emulsion disclosures of the patents cited above to show conventional high bromide tabular grain emulsions and are additionally illustrated by the following: Saito et al U.S. Patent 4,797,354; Tsaur et al U.S. Patent 5,210,013; Kim et al U.S. Patent 5,272,048; and Sutton et al U.S. Patent 5,334,469. Low COV host tabular grains can be shelled according to the invention without increasing their dispersity. The high bromide tabular grain emulsions employed as starting materials have tabular grain projected areas sufficient to allow the tabular grains in the final emulsion to account for at least 50 percent of total grain projected area. The preferred starting materials are those that contain tabular grain projected areas of at least 70 percent and optimally at least 90 percent. Generally, the exclusion of nontabular grains to the extent conveniently attainable is preferred. When silver chloride is precipitated in the presence of high bromide tabular grains, the silver chloride shows a strong affinity for the high bromide tabular grain surfaces to form a substantially uniform shell as shown in Figure 3. This occurs whether the silver chloride is precipitated in situ from soluble silver and chloride salts or introduced as preformed Lippmann silver chloride grains. If a site director is employed, as taught by Maskasky U.S. Patent 4,435,501, the additional silver halide is deposited non-uniformly, but in the form of nontabular epitaxial deposits concentrated at the corners and/or edges of the grains. It has been discovered quite unexpectedly that a few of the many known grain growth modifiers that produce high chloride tabular grains can be used to produce a shell structure on a pre-existing high bromide tabular grain population, where the shell structure itself retains tabular grain precipitation characteristics. That is, as the shell is formed silver halide is deposited preferentially onto the peripheral edges of the host high bromide tabular grains and precipitation onto the major faces of the high chloride tabular grains is disproportionately limited. The following conventional grain growth modifiers have not been found to be useful in achieving shell band formation satisfying the requirements of the invention: adenine, xanthine and 4-aminopyrazolo[3,4-d]pyrimidine. Grain growth modifiers of these types are disclosed in Maskasky U.S. Patents 4,400,463, 4,713,323 and 5,183,732, Maskasky and Chang U.S. Patent 5,178,998, Tufano et al U.S. Patent 4,804,621 and Houle et al U.S. Patent 5,035,992. Grain growth modifiers of the 4,5,6-triaminopyrimidine type have been observed to be useful in growing tabular bands on high chloride tabular grain emulsions. These grain growth modifiers satisfy the following formula: where R 1 is independently in each occurrence hydrogen or a monovalent hydrocarbon group of from 1 to 7 carbon atoms of the type indicated above, preferably alkyl of from 1 to 6 carbon atoms. The following are illustrations of varied 4,6-di(hydroamino)-5-aminopyrimidine compounds within the purview of the invention: The techniques for shelling the high bromide host tabular grains can be identical to the conditions for precipitating high chloride tabular grains in the presence of a 4,5,6-triaminopyrimidine grain growth modifier. Such techniques are taught, for example, in Maskasky U.S. Patent 5,185,239. The sole difference is that the high bromide host grain emulsion is formed or placed in the reaction vessel prior to commencing shell precipitation. Instead of forming the high bromide tabular grain emulsion by conventional techniques it is specifically contemplated to form the high bromide tabular grain emulsion in the presence of the 2,4,6-triaminopyrimidine grain growth modifier. In this process an aqueous dispersion is prepared containing at least 0.1 percent by weight silver, based on total weight, in the form of seed grains containing at least 50 mole percent bromide and having an average grain thickness ( ECD for nontabular grains) less than that of the thickness of the tabular grains to be formed. The weight of silver in the dispersing medium can range up to 20 percent by weight, based on total weight, but is preferably in the range of from 0.5 to 10 percent by weight, based on the total weight of the dispersion. The aqueous dispersion also receives the water and peptizer that are present with the high bromide tabular grains in the starting emulsion. The peptizer typically constitutes from about 1 to 6 percent by weight, based on the total weight of the aqueous dispersion. In the simplest mode of practicing the invention, the tabular band growth process of the invention is undertaken promptly upon completing precipitation of the high bromide tabular grain emulsion, and only minimum required adjustments of the dispersing medium of the starting emulsion are undertaken to satisfy the aqueous dispersion requirements of the tabular band growth process. Intermediate steps, such as washing, prior to commencing the tabular band growth process are not precluded. The pH of the aqueous dispersion employed in the tabular band growth process is in the range of from 4.6 to 9.0, preferably 5.0 to 8.0. Adjustment of pH, if required, can be undertaken using a strong mineral base, such as an alkali hydroxide, or a strong mineral acid, such as nitric acid or sulfuric acid. If the pH is adjusted to the basic side of neutrality, the use of ammonium hydroxide should be avoided, since under alkaline conditions the ammonium ion acts as a ripening agent and will increase grain thickness. To minimize the risk of elevated minimum densities in the emulsions prepared, it is common practice to prepare photographic emulsions with a slight stoichiometric excess of bromide ion is present. At equilibrium the following relationship exists: (I) -log K sp = pBr + pAg where K sp is the solubility product constant of silver bromide; pBr is the negative logarithm of bromide ion activity; and pAg is the negative logarithm of silver ion activity. The solubility product constant of silver bromide emulsions in the temperature range of from 0 to 100°C has been published by Mees and James The Theory of the Photographic Process, 3th Ed., Macmillan, New York, 1966, page 6. The equivalence point, pBr = pAg = -log K sp ÷ 2, which is the point at which no stoichiometric excess of bromide ion is present in the aqueous dispersion, is known from the solubility product constant. By employing a reference electrode and a sensing electrode, such as a silver ion or bromide ion sensing electrode or both, it is possible to determine from the potential measurement of the aqueous dispersion its bromide ion content (pBr). Lin et al U.S. Patent 5,317,521 shows electrode selections and techniques for monitoring pBr. To avoid unnecessarily high bromide ion concentrations in the aqueous dispersion (and hence unnecessary waste of materials) the pBr of the aqueous dispersion is adjusted to at least 1.5, preferably at least 2.0 and optimally greater than 2.6. Soluble bromide salt (e.g. alkali bromide) addition can be used to decrease pBr while soluble silver salt (e.g. silver nitrate) additions can be used to increase pBr. The triaminopyrimidine grain growth modifier is added to the aqueous dispersion, either before, during or following the pBr and pH adjustments indicated. One of the surprising discoveries has been that grain growth modifiers that function similarly as the triaminopyrimidines of the invention when employed in the preparation of high chloride {111} tabular grain emulsions are not effective when substituted for the grain growth modifiers of the invention in the tabular band growth process. It is believed that the effectiveness of the grain growth modifier to produce tabular bands is attributable to its preferential absorption to {111} crystal faces and its ability to preclude additional silver halide deposition on these surfaces. This explanation does not, however, explain the failure of other grain growth modifiers that are also believed to perform the same function. Actual observations indicate that the interactions between the various grain surfaces present in the aqueous dispersion and the grain growth modifier are, in fact, complex. Why one type of grain growth modifier is useful to prepare tabular bands while another has not been explained. Contemplated concentrations of the grain growth modifier for use in the tabular growth process are from 0.1 to 500 millimoles per silver mole. A preferred grain growth modifier concentration is from 0.4 to 200 millimoles per silver mole, and an optimum grain growth modifier concentration is from 4 to 100 millimoles per silver mole. With the grain growth modifier present in the aqueous dispersion, tabular bands are grown on the high bromide tabular grains by providing the silver and chloride ions required to form the shell and holding the aqueous dispersion at any convenient temperature known to be compatible with grain ripening. This can range from about room temperature (e.g., 15°C) up to the highest temperatures conveniently employed in silver halide emulsion preparation, typically up to about 90°C. A preferred holding temperature is in the range of from about 20 to 80°C, optimally from 35 to 70°C. The holding period will vary widely, depending upon the starting grain population, the temperature of holding and the objective sought to be obtained. For example, starting with a high bromide tabular grain emulsion to provide the starting grain population with the objective of increasing mean ECD by a minimum 0.1 µm, a holding period of no more than a few minutes may be necessary in the 30 to 60°C temperature range, with even shorter holding times being feasible at increased holding temperatures. On the other hand, if the starting grains are intended to form a minimal proportion of the final grain structure, holding periods can range from few minutes at the highest contemplated holding temperatures to overnight (16 to 24 hours) at ambient temperatures. The holding period is generally comparable to run times employed in preparing high bromide tabular grain emulsions by double jet precipitation techniques when the temperatures employed are similar. The holding period can be shortened by the introduction into the aqueous dispersion of a ripening agent of a type known to be compatible with obtaining thin (less than 0.2 µm mean grain thickness) tabular grain emulsions, such as thioether ripening agents. Grain growth modifiers of the iodo-8-hydroxyquinoline type can be substituted for the 4,5,6-triaminopyrimidine grain growth modifiers described above. The required iodo substituent can occupy any synthetically convenient ring position of the 8-hydroxyquinolines. When the 8-hydroxyquinoline ring is not otherwise substituted, the most active sites for introduction of a single iodo substituent are the 5 and 7 ring positions, with the 7 ring position being the preferred substitution site. Thus, when the 8-hydroxyquinoline contains two iodo substituents, they are typically located at the 5 and 7 ring positions. When the 5 and 7 ring positions have been previously substituted, iodo substitution can take place at other ring positions. Further ring substitutions are not required, but can occur at any of the remaining ring positions. Strongly electron withdrawing substituents, such as other halides, pseudohalides (e.g., cyano, thiocyanato, isocyanato, etc.), carboxy (including the free acid, its salt or an ester), sulfo (including the free acid, its salt or an ester), α-haloalkyl, and the like, and mildly electron withdrawing or electron donating substituents, such as alkyl, alkoxy, aryl and the like, are common at a variety of ring positions on both of the fused rings of the 8-hydroxyquinolines. Polar substituents, such as the carboxy and sulfo groups, can perform the advantageous function of increasing the solubility of the iodo-substituted 8-hydroxyquinoline in the aqueous dispersing media employed for emulsion precipitation. In one specifically preferred form the iodo-8-hydroxyquinolines satisfy the following formula: where R 1 and R 2 are chosen from among hydrogen, polar substituents, particularly carboxy and sulfo substituents, and strongly electron withdrawing substituents, particularly halo and pseudohalo substituents, with the proviso that at least one of R 1 and R 2 is iodo. The following constitute specific illustrations of iodo-substituted 8-hydroxyquinoline grain growth modifiers contemplated for use in the practice of the invention: IHQ-1 5-Chloro-8-hydroxy-7-iodoquinoline IHQ-2 8-Hydroxy-7-iodo-2-methylquinoline IHQ-3 4-Ethyl-8-hydroxy-7-iodoquinoline IHQ-4 5-Bromo-8-hydroxy-7-iodoquinoline IHQ-5 5,7-Diiodo-8-hydroxyquinoline IHQ-6 8-Hydroxy-7-iodo-5-quinolinesulfonic acid IHQ-7 8-Hydroxy-7-iodo-5-quinolinecarboxylic acid IHQ-8 8-Hydroxy-7-iodo-5-iodomethylquinoline IHQ-9 8-Hydroxy-7-iodo-5-trichloromethylquinoline IHQ-10 α-(8-Hydroxy-7-iodoquinoline)acetic acid IHQ-11 7-Cyano-8-hydroxy-5-iodoquinoline IHQ-12 8-Hydroxy-7-iodo-5-isocyanatoquinoline Grain growth modifiers of the polyiodophenol type can alternatively be substituted for 4,5,6-triaminopyrimidine grain growth modifiers. Polyiodophenols are arylhydroxides containing two or more iodo substituents. In one simple form the phenol can be a hydroxy benzene containing at least two iodo substituents. It is synthetically most convenient to place the iodide substituents in at least two of the 2, 4 and 6 ring positions. When the benzene ring is substituted with only the one hydroxy group and iodo moieties, all of the possible combinations are useful as grain growth modifiers in the practice of the invention. The hydroxy benzene with two or more iodo substituents remains a useful grain growth modifier when additional substituents are added, provided none of the additional substituents convert the compound to a reducing agent. Specifically, to be useful in the practice of the invention the phenol with two or more iodo substituents must be incapable of reducing silver chloride under the conditions of precipitation. Silver chloride is the most easily reduced of the photographic silver halides; thus, if a compound will not reduce silver chloride, it will not reduce any photographic silver halide. The reason for excluding compounds that are silver chloride reducing agents is that reduction of silver chloride as it is being precipitated creates Ag° that produces photographic fog on processing. Fortunately, phenols that are capable of reducing silver chloride are well known to the art, having been extensively studied for use as developing agents. For example, hydroquinones and catechols are well known developing agents as well as p-aminophenols. Thus, those skilled in the art through years of extensive investigation of developing agents have already determined which phenols are and are not capable of reducing silver chloride. According to James The Theory or the Photographic Process, 4th Ed., Macmillan, New York, 1977, Chapter 11, D. Classical Organic Developing Agents, 1. RELATION BETWEEN DEVELOPING ACTION AND CHEMICAL STRUCTURE, compounds that satisfy the following structure are developing agents: where, in the case of a phenol, a is hydroxy, a ' is hydroxy or amino (including primary, secondary or tertiary amino), and n = 1, 2 or 4. From the foregoing it is apparent that the overwhelming majority of phenol substituents in addition to the required hydroxy and iodo substituents are incapable of rendering the phenols reducing agents for silver chloride. Such additional substituents, hereinafter referred to as photographically inactive substituents, include, but are not limited to, the following common classes of substituents for phenols: alkyl, cycloalkyl, alkenyl (e.g., allyl), alkoxy, aminoalkyl, aryl, aryloxy, acyl, halo (i.e., F, Cl or Br), nitro (NO 2 ), and carboxy or sulfo (including the free acid, salt or ester). All aliphatic moieties of the above substituents preferably contain from 1 to 6 carbon atoms while all aryl moieties preferably contain from 6 to 10 carbon atoms. When the phenol contains two iodo substituents and an additional, photographically inactive substituent, the latter is preferably located para to the hydroxy group on the benzene ring. It has been demonstrated that phenols contain two or three iodo substituents are highly effective as grain growth modifiers, but that phenols with a single iodo substituent are ineffective. This was not predicted and is, in fact, quite unexpected. There are, of course, many varied phenols known to the art that are available for selection as grain growth modifiers in the practice of the invention. The following are specific illustrations of polyiodophenol grain growth modifiers contemplated for use in the practice of the invention: The procedures for using the iodo-8-hydroxyquinoline and polyiodophenol grain growth modifiers are similar to those described in detail for using the 4,5,6-triaminopyrimidine grain growth modifiers, except for the following differences: When an iodo-8-hydroxyquinoline grain growth modifier is employed, the pH of the dispersing medium can range from 2 to 8, preferably from 3 to 7. When a polyiodophenol grain growth modifier is employed, the pH of the dispersing medium can range from 1.5 to 10, preferably from 2 to 7. When an iodo-8-hydroxyquinoline or polyiodophenol grain growth modifier is employed, the ripening temperature is preferably at least 40°C. The tabular band can be formed of any silver halide composition that forms a face centered cubic crystal lattice structure, but is limited to halide compositions that contain at least 60 mole percent chloride for the purpose of creating a difference in halide compositions between the central region and the shell. The shell preferably contains at least 70 mole percent chloride, most preferably at least 80 mole percent chloride. Minor amounts of iodide, up to the solubility limit of iodide, can be incorporated during shell formation. Even when no bromide is added to the dispersing medium during shell growth minor amounts of bromide can still be present, since some degree of halide migration between the central region and the shell can be expected to occur during tabular band growth. The division of total silver between the central region and the shell can vary widely. As little as 5 percent of the total silver in a completed emulsion can be located in the central grain regions, while the balance of the silver is located in the grain shells. It is generally preferred that the central regions on average account for at least 50 percent, most preferably at least 75 percent of the total silver forming the shelled tabular grains. A distinctive and highly advantageous feature of the emulsions of the invention is that a disproportionately large fraction of the total silver forming the shell is contained in a tabular band laterally surrounding the central region and forming a large fraction of the {111} major faces of the tabular grains. Maximizing the growth of the tabular band while minimizing thickness growth of the tabular grains during shelling improves the aspect ratios of the tabular grains. The tabular band accounts for at least half of the silver forming the shell. Preferably the tabular band accounts for at least 70 percent of the total silver forming the shell, most preferably at least 80 percent. The proportion of total grain projected area increases as the percentage of total silver accounted for by the shell increases and as the percentage of shell silver accounted for by the tabular bands increases. It is specifically contemplated to form tabular grains according to the invention in which the tabular bands account for at least 2 percent, preferably at least 5 percent and optimally at least 10 percent of total grain projected area. Generally the advantages of a high chloride band can be largely realized without having the high chloride band account for a high proportion of the total silver. Different choices of halide compositions in the shell and central region as well as different photographic applications can dictate different ratios. It is specifically contemplated to form the high chloride bands to account for at least 25 percent of the {111} major faces, with the balance of the major faces overlying the central regions of the grains, as described above. Apart from the features that have been specifically disclosed, the emulsions of the invention, their preparation and photographic elements containing these emulsions can take any convenient conventional form. Conventional features are illustrated by Research Disclosure, Vol. 365, September 1994, Item 36544. Examples The invention can be better appreciated by reference to the following specific examples. Emulsion A AgIBr (0.1% mole I) Tabular Grain Emulsion To Be used as Core Grains. To a vigorously stirred reaction vessel containing 2L of a solution at pH 2.0 (adjusted with HNO 3 ) and at 35°C that was 0.38% in oxidized gelatin, 6.75 mM in NaBr, were added 2 M AgNO 3 solution at 50 mL/min and 2 M NaBr solution to maintain a pBr of 2.21. The additions were stopped after 10 mL of the AgNO 3 solution was added and the temperature of the reaction vessel was increased to 60°C at a rate of 5 °C per 3 min. Then 150 mL of a solution of 33% oxidized gelatin at 60 °C was added and the pH was increased to 6.0 with NaOH solution. Then 14 mL of a 2 M NaBr solution was added and the addition of the AgNO 3 solutions was resumed at 60°C and 20 mL/min until 500 mL of the AgNO 3 solution was added. A solution consisting of 2 M NaBr and 0.002 M KI was concurrently added to maintain a pBr of 1.74. The resulting emulsion was not washed. It consisted of AgIBr (0.1 mole % iodide) tabular grains having an average diameter of 2.1 µm, and average thickness of 0.05 µm, and average aspect ratio of 44 and 97% of the projected area of the grains were tabular grains. Emulsion B AgIBr (0.1 mole % I) Monodisperse Tabular Emulsion To Be Used as Core Grains. To a vigorously stirred reaction vessel containing 6 L of a solution at pH 1.85 (adjusted with HNO 3 ) and at 45°C that contained 7.5 g of oxidized gelatin, 14.6 g NaBr, and 0.53 g of a polyalkylene oxide surfactant (described in Tsaur and Kam-Ng U.S. Patent 5,210,013 Structure II x=25, y=7) diluted with 0.25 mL methanol, were added 0.5 M AgNO 3 and 0.5 M NaBr at 80 mL/min each. After 1 min the additions were stopped, after 1 min the temperature was raised to 60 °C at a rate of 5 °C per 3 min. Then 100 mL of a 0.765 M ammonium sulfate solution was added and the pH was adjusted to 9.5 with NaOH solution. The emulsion was held at this pH for 9 min before adding 600 mL of a 17 % oxidized gelatin solution, and the pH was adjusted to 6.5 ± 0.05 with HNO 3 . Then a 1.6 M AgNO 3 solution was added at 12 mL/min for 40 min, the flow rate was linearly accelerated to 90 mL/min during 35 min and finally held at 90 mL/min until a total of 3 L were added. A solution that was 1.68 M in NaBr and 0.0016 M in KI was concurrently added to maintain a pBr of 1.74. The emulsion was cooled to 40 °C and was not washed. The emulsion was comprised of a tabular grain population having an average ECD of 1.04 µm, an average thickness of 0.088 µm, and average aspect ratio of 11.8. Tabular grains accounted for 95% of the total projected area of the grains. The total of all of the emulsion grain populations had a coefficient of variation of 11 %. Emulsion C Fine Grain AgBr Emulsion To a stirred reaction vessel containing 2L of 5 wt % gelatin at 35°C were added 2M AgNO 3 solution and 2M NaBr solution. The AgNO 3 solution was added at 300 mL/min and the NaBr solution was added as needed to maintain a pBr of 3.63. A total of 0.6 moles of AgNO 3 was added. Emulsion D. AgBr Core Tabular Grain Emulsion To a stirred reaction vessel containing 7.5 g of oxidized gelatin, 1.39 g NaBr, and distilled water to 2L at 35°C and pH 2.0, 10 mL of 2M AgNO 3 solution were added at 50 mL/min. Concurrently, 2M NaBr solution was added to maintain a pBr of 2.21. The temperature was increased to 60°C at a rate of 5°C/ 3 min then 150 mL of a 33% oxidized gelatin solution at 60°C was added, the pH was adjusted to 6.0, and 14 mL of a 2M NaBr solution was added. At 60°C and pH 6.0, 500 mL of a 2M AgNO 3 solution were added at 20 mL/min. Concurrently, 2M NaBr solution was added to maintain a pBr of 1.76. The resulting tabular grains were 1.3 µm in ECD and 0.04 µm in thickness. Example 1 Ultrathin Tabular Grain AgIBr (0.1 mole %) Core with a High Chloride Annular Band Containing 39 mole % of Total Ag To a vigorously stirred reaction vessel at 40°C and pH 6.0 containing 400g of a mixture of 1% oxidized gelatin, 0.1 mole of Emulsion A, 0.8 mmoles of a solution of 4,5,6-triaminopyrimidine, 80 mmoles of sodium acetate and 15.9 mmoles of NaCl was added 4 M AgNO 3 solution at 0.2 mL/min until the pBr reached 1.40 (12 mmole AgNO 3 solution required) then a 4.04 M NaCl solution was concurrently added to maintain this pBr, and the AgNO 3 solution addition rate was then linearly accelerated to 0.94 mL/min in 15 min adding a total of 0.052 mmole of AgNO 3 . The pH was maintained at 6.0. The silver nitrate added for the high chloride phase precipitation and for the pBr adjustment was 39 mole % of the total silver of the resulting emulsion. The emulsion was comprised of a tabular grain population having an average diameter of 2.6 µm, an average thickness of 0.06 µm, and average aspect ratio of 43. The tabular grain population accounted for approximately 95% of the total projected area of the grains. The results are given in Table I. X-ray powder diffraction data showed that 3 phases were present. One phase (the core) was 100 mole % AgBr; a minor phase was 79 mole % AgCl and the third phase was 52 mole % AgCl. Energy Dispersive Spectroscopy composition analysis showed that sampled points extending through the thickness of the central regions of the grains consisted of 88-94 mole % AgBr and 12-6 mole % AgCl and sampled points extending through the annular regions of the grains consisted of 78-81 mole % AgCl, 22-19 mole % AgBr. Example 2 Ultrathin Tabular Grain AgIBr (0.1 mole %) Core with a High Chloride Annular Band Containing 61 mole % of Total Ag This example was prepared similarly to that of Example 1, except that the AgNO 3 solution flow rate was linearly accelerated to 1.9 mL/min in 27 min adding a total of 0.124 mmole of Ag. The amount of silver added for the pBr adjustment and to precipitate the high chloride phase was 61 mole % of the total silver of the resulting emulsion. The emulsion was comprised of a tabular grain population having an average ECD of 3.0 µm, an average thickness of 0.065 µm, and average aspect ratio of 46. Tabular grains accounted for 95% of the total grain projected area. The results are given in Table I. A low temperature (77°K) luminescence microscopy through a UV to 515 nm blocking filter revealed bright green regions (AgIBr) concentrated areas in the central regions of the grains, except for an outermost band which resulted from light piping of the core luminescence. The low temperature luminescence microscope is described in Maskasky, J. Imaging Sci . Vol. 32 (1988) pg. 15. X-ray powder diffraction data showed that 3 phases were present. One phase (the central region) was 100 mole % AgBr; another phase was 61 mole % AgCl and the third phase was 82 mole % AgCl. The iodide concentration was too low to be observed. Example 3 Monodisperse AgIBr (0.1 mole %) Tabular Grains with High Chloride Annular Band Comprising 55 mole % of Total Silver To a vigorously stirred reaction vessel at 40°C and pH 6.0 containing 400 g of a mixture of 1% nonoxidized gelatin (~50 µmole methionine per g gelatin), 0.1 mole of Emulsion B, 0.8 mmoles of a solution of 4,5,6-triaminopyrimidine, 80 mmoles of sodium acetate, and 15.9 mmoles of NaCl was added 2 M AgNO 3 solution at 0.2 mL/min until the pBr reached 1.40 (3.0 mmole AgNO 3 solution required) then a solution 2.08 M NaCl and 8.1 mM in 4,5,6-triaminopyrimidine (adjusted to pH 6.0) was concurrently added to maintain this pBr, and the AgNO 3 solution addition rate was then linearly accelerated to 2.3 mL/min in 40 min then held at this rate until a total of 0.123 mole AgNO 3 solution had been added. The pH was maintained at 6.0 ± 0.1. The high chloride phase precipitation was 55 mole % of the total silver of the resulting emulsion. The emulsion was comprised of a tabular grain population having an average ECD of 1.43 µm, an average thickness of 0.10 µm, and average aspect ratio of 14. Tabular grains accounted for 95% of the total projected area of the grains. The total of all of the emulsion grain populations had a coefficient of variation of 13%; not much increase from that of the core emulsion. The results are given in Table I. X-ray powder diffraction data showed that 3 phases were present. One phase (the core) was 100 mole % AgBr; a minor phase was 66 mole % AgCl and the third phase was 90 mole % AgCl. Energy Dispersive Spectroscopy composition analysis showed that at sampled points through the central regions the grains consisted of 75-94 mole % AgBr and 25-6 mole % AgCl and at sampled points through the annular regions consisted of 93-96 mole % AgCl, 7-4 mole % AgBr. Example 4 Monodisperse AgIBr (0.1 mole %) Tabular Grains with High Chloride Annular Band Comprising 67 mole % of Total Silver This emulsion was prepared similarly to that of Example 3, except that the AgNO 3 solution addition rate was held at 2.3 mL min until a total of 0.203 moles of AgNO 3 solution had been added. The high chloride phase precipitation was 67 mole % of the total silver of the resulting emulsion. The emulsion was comprised of a tabular grain population having an average diameter of 1.55 µm, an average thickness of 0.12 µm, and average aspect ratio of 13. Tabular grains accounted for 95% of the projected area of the grains. The total of all of the emulsion grain populations had a coefficient of variation of 14 %; not much increase from that of the core emulsion. The results are given in Table I. Low temperature (77°K) luminescence microscopy through a uv-515 nm blocking filter showed bright green regions, indicative of AgIBr, concentrated in the central regions of the tabular grains, except for outermost bands attributable to light piping of the core luminescence. Emulsion Average Diameter Average Thickness Volume of Band Volume of Shell Over Major {111} Core Faces Band % of Total Shell Core Emulsion A 2.1 0.05 None N.A. N.A. Example 1 2.6 0.06 0.111 0.0346 76 Example 2 3.0 0.065 0.2344 0.0520 82 Core Emulsion B 1.04 0.088 None N.A. N.A. Example 3 1.43 0.10 0.0761 0.0102 88 Example 4 1.55 0.12 0.124 0.0272 82 Control Example 5 Testing Compounds as AgBr Tabular Grain Growth Modifiers At 40°C to 0.021 mole Emulsion C was added with stirring, 0.0032 mole Emulsion D. The pBr was adjusted to 3.55. A solution of the potential tabular grain growth modifier was added in the amount of 7.0 mmole/mole Ag. The mixture was adjusted to a pH of 6.0 then heated to 70°C, the pH was again adjusted to 6.0. After heating for 17 hr at 70°C, the resulting emulsions were examined by optical and electron microscopy to determine mean diameter and thickness. The compounds tested for utility as AgBr grain growth modifiers and the results are given in Table II. Emulsion Potential AgBr Tabular Grain Growth Modifier Average {111} Tabular Grain Dimensions (µm) % Projected Area of Nontabular Grains % Projected Area as {111} Tabular Grains Core Emulsion D N.A. 1.3 x 0.04 5% 95% Control 5A none 1.7 x 0.18 40% 60% Control 5B adenine None 100% 0% Control 5C xanthine 1.3 x 0.20 60% 40% Control 5D 4-aminopyrazolo[3,4-d]pyrimidine 2.0 x 0.20 10% 90% Control 5E 4,5,6-triaminopyrimidine 4.3 x 0.042 <5% >95% Control 5F 2,4,6-triiodophenol 4.0 x 0.055 18% 82% As the above results show, only Control Emulsion 5E (4,5,6-triaminopyrimidine) and Control Emulsion 5F (2,4,6-triiodophenol) yielded tabular grains having reduced thickness relative to Control Emulsion 5A. Control Emulsion 5A, with no added tabular grain growth modifier, resulted in significant thickness growth compared to the core emulsion. Control Emulsion 5B (adenine) yielded nontabular grains, including large grains lacking {111} major faces.

Claims: A radiation-sensitive emulsion comprised of a dispersing medium and silver halide grains, at least 50 percent of total grain projected area being accounted for by tabular grains of a face centered cubic crystal lattice structure having parallel {111} major faces, an average thickness of less than 0.2 micrometer, and an average aspect ration of at least 5, the tabular grains each being comprised of a central region and a shell differing in halide content, characterized in that the central region contains greater than 50 mole percent bromide, the shell contains at least 60 mole percent chloride, the shell is comprised of a band extending laterally outwardly from the central region and forming at least 2 percent of the {111} major faces the band accounting for at least half the volume of the shell, and the emulsion containing a 4,5,6-triaminopyrimidine, a polyiodophenol or an iodo-8-hydroxyquinoline grain growth modifier. A radiation-sensitive emulsion according to claim 1 further characterized in that the tabular grains accounting for at least 50 percent of total grain projected area have an average thickness of less than 0.2 µm. A radiation-sensitive emulsion according to claim 2 further characterized in that the tabular grains accounting for at least 50 percent of total grain projected area have an average thickness of less than 0.07 µm. A radiation-sensitive emulsion according to any one of claims 1 to 3 inclusive further characterized in that the band accounts for at least 70 percent of the silver contained in the shell. A radiation-sensitive emulsion according to claim 4 further characterized in that the band accounts for at least 80 percent of the silver contained in the shell. A radiation-sensitive emulsion according to any one of claims 1 to 5 inclusive further characterized in that the shell is comprised of detectable surface regions interposed between the central region and the {111} major faces. A radiation-sensitive emulsion according to any one of claims 1 to 6 inclusive further characterized in that the central region contains at least 70 mole percent bromide. A radiation-sensitive emulsion according to any one of claims 1 to 7 inclusive further characterized in that the shell contains at least 70 mole percent chloride in the band. A radiation-sensitive emulsion according to any one of claims 1 to 8 inclusive further characterized in that the coefficient of variation of equivalent circular diameters of the tabular grain is less than 30 percent. A radiation-sensitive emulsion according to claim 9 further characterized in that the coefficient of variation of equivalent circular diameters of the tabular grains is less than 15 percent.

Inventors: MASKASKY JOE E, MASKASKY, JOE E., Maskasky, Joe E., Eastman Kodak Company
Applicants: EASTMAN KODAK CO, EASTMAN KODAK COMPANY
Application year: 1996
Main classification: G03C1
IPC codes: G03C1