EP0215612B1 - Photographische Silberhalogenidemulsionen mit Kornoberfläche - Google Patents

Photographische Silberhalogenidemulsionen mit Kornoberfläche Download PDF

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EP0215612B1
EP0215612B1 EP19860306797 EP86306797A EP0215612B1 EP 0215612 B1 EP0215612 B1 EP 0215612B1 EP 19860306797 EP19860306797 EP 19860306797 EP 86306797 A EP86306797 A EP 86306797A EP 0215612 B1 EP0215612 B1 EP 0215612B1
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faces
silver halide
grain
grains
silver
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EP0215612A2 (de
EP0215612A3 (en
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Joe Edward Maskasky
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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
    • G03C1/035—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
    • G03C1/0051—Tabular grain emulsions
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/04—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with macromolecular additives; with layer-forming substances
    • G03C1/047—Proteins, e.g. gelatine derivatives; Hydrolysis or extraction products of proteins
    • 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
    • G03C1/0051—Tabular grain emulsions
    • G03C2001/0055—Aspect ratio of tabular grains in general; High aspect ratio; Intermediate aspect ratio; Low aspect ratio
    • 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
    • G03C2001/03511—Bromide content
    • 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
    • G03C2200/00—Details
    • G03C2200/03—111 crystal face

Definitions

  • This invention relates to photography. More specifically, this invention is directed to photographic emulsions containing silver halide grains and to photographic elements containing these emulsions.
  • silver halide grains have been the subject of intense investigation. Although high iodide silver halide grains, those containing at least 90 mole percent iodide, based on silver, are known and have been suggested for photographic applications, in practice photographic emulsions almost always contain silver halide grains comprised of bromide, chloride, or mixtures of chloride and bromide optionally containing minor amounts of iodide. Up to about 40 mole percent iodide, based on silver, can be accommodated in a silver bromide crystal structure without observation of a separate silver iodide phase.
  • silver halide emulsions rarely contain more than about 15 mole percent iodide, with iodide well below 10 mole percent being most common. All silver halide grains, except rarely employed high iodide silver halide grains, hereinafter excluded from consideration except as expressly noted, exhibit cubic crystal lattice structures.
  • the ratio of silver halide grain surface area to grain volume is not constant. Finer silver halide grains exhibit higher grain surface area in relation to grain volume, more commonly referred to indirectly in terms of coating coverages e.g., grams of silver per square meter.
  • An increased ratio of silver halide grain surface area to grain volume hereinafter referred to as the grain surface area ratio, can be advantageous in improving photographic performance dependent on surface effects, such as interaction with processing agents as well as interactions with adsorbed addenda, such as spectral sensitizing dyes.
  • Silver halide favors the formation of crystallographic faces of either the cubic or octahedral form.
  • Silver chloride strongly favors the formation of cubic crystal faces.
  • Silver bromide also favors the formation of cubic crystal faces, but favors the formation of octahedral crystal faces in the presence of an excess of bromide ions.
  • Iodide ions in the crystal structure tend to increase the grain preference for crystal faces of the octahedral form.
  • Regular silver halide grains bounded by cubic crystal faces are cubic in appearance when examined by electron microscopy.
  • a regular cubic grain 1 is shown in Figure 1.
  • the cubic grain is bounded by six identical crystal faces.
  • these crystal faces are usually referred to as ⁇ 100 ⁇ crystal faces, referring to the Miller index employed for designating crystal faces. While the ⁇ 100 ⁇ crystal face designation is most commonly employed in connection with silver halide grains, these same crystal faces are sometimes also referred to as ⁇ 200 ⁇ crystal faces, the difference in designation resulting from a difference in the definition of the basic unit of the crystal structure.
  • the cubic crystal shape is readily visually identified in regular grains, in irregular grains cubic crystal faces are not always square. In grains of more complex shapes the presence of cubic crystal faces can be verified by a combination of visual inspection and the 90° angle of intersection formed by adjacent cubic crystal faces.
  • regular silver halide grains when observed by electron microscopy are octahedral in appearance.
  • a regular octahedral grain 5 is shown in Figure 3.
  • the octahedral grain is bounded by eight identical crystal faces. These crystal faces are referred to as octahedral or ⁇ 111 ⁇ crystal faces.
  • the octahedral crystal shape is readily visually identified in regular grains, in grains of more complex shapes the presence of octahedral crystal faces can be verified by a combination of visual inspection and the 109.5° angle of intersection formed by adjacent octahedral crystal faces.
  • FIG. 4 is a schematic illustration of a ⁇ 111 ⁇ crystal face, analogous to Figure 2, wherein the smaller spheres 2 represent silver ions while the larger spheres 3 designate bromine ions.
  • silver ions are shown at the surface in every available lattice position, it has been suggested that having silver ions in only every other available lattice position in the surface tier of atoms would be more compatible with surface charge neutrality.
  • the surface tier of ions could alternatively be bromide ions.
  • the tier of ions immediately below the surface silver ions consists of bromide ions.
  • both the cubic and octahedral grains have exactly the same cubic crystal lattice structure and thus exactly the same internal relationship of silver and halide ions.
  • the two grains differ only in their surface crystal faces. Note that in the cubic crystal face of Figure 2 each surface silver ion lies immediately adjacent five halide ions, whereas in Figure 4 the silver ions at the octahedral crystal faces each lie immediately adjacent only three halide ions.
  • a regular rhombic dodecahedral grain 7 is shown in Figure 5.
  • the rhombic dodecahedral grain is bounded by twelve identical crystal faces. These crystal faces are referred to as rhombic dodecahedral or ⁇ 110 ⁇ (or, less commonly in reference to silver halide grains, ⁇ 220 ⁇ ) crystal faces.
  • rhombic dodecahedral crystal shape is readily visually identified in regular grains, in grains of more complex shapes the presence of rhombic dodecahedral crystal faces can be verified by a combination of visual inspection and measurement of the angle of intersection of adjacent rhombic dodecahedral crystal faces.
  • Rhombic dodecahedral crystal faces can be theoretically hypothesized to consist of alternate rows of silver ions and halide ions.
  • Figure 6 is a schematic illustration analogous to Figures 2 and 4, wherein it can be seen that the surface tier of ions is formed by repeating pairs of silver and bromide ion parallel rows, indicated by lines 8a and 8b, respectively. In Figure 6 a portion of the next tier of ions lying below the surface tier is shown to illustrate their relationship to the surface tier of ions. Note that each surface silver ion lies immediately adjacent four halide ions.
  • the seven possible crystallographic forms for cubic crystal lattice structure materials are named for the polyhedrons that are produced by a regular crystal structure bounded entirely by faces of a single crystallographic form.
  • regular silver halide grains bounded entirely by crystallographic faces of the cubic form are cubes; bounded entirely by crystallographic faces of the octahedral form are octahedra; etc.
  • Patent 4,478,929 Maskasky U.S. Patent 4,400,463; and Wey et al U.S. Patent 4,414,306.
  • Research Disclosure is published by Kenneth Mason Publications, Ltd., Emsworth, Hampshire P010 7DD, England. While thin and high aspect ratio tabular grain emulsions exhibit high surface area ratios, their major faces are of the same cubic or octahedral crystallographic forms exhibited by silver halide grains of other shapes.
  • Core-shell silver halide emulsions constitute the most common examples of silver halide grains of a composite structure. Core-shell emulsions are illustrated by Porter et al U.S. Patents 3,206,313 and 3,317,322, Berriman U.S. Patent 3,367,778, and Evans U.S. Patent 3,761,276, and, in tabular form, by Evans et al U.S. Patent 4,504,570.
  • Koitabashi et al U.S. Patent 4,349,622 discloses epitaxially depositing on silver halide grains containing from 15 to 40 mole percent iodide silver halide which contains less than 10 mole percent iodide.
  • Hammerstein et al U.S. Patent 3,804,629 discloses that the stability of silver halide emulsion layers against the deleterious effect of dust, particularly metal dust, is improved by adding to physically ripened and washed emulsion before chemical ripening a silver chloride emulsion or by precipitating silver chloride onto the physically ripened and washed silver halide emulsion.
  • Hammerstein et al discloses that silver chloride so deposited will form hillocks on previously formed silver bromide grains.
  • Maskasky U.S. Patent 4,435,501 teaches high aspect ratio tabular grain emulsions having one or more silver salts deposited at selected surface sites.
  • Maskasky U.S. Patent 4,463,087 is essentially cumulative, but additionally discloses deposition at the edges and corners of nontabular silver halide host grains. Each patent teaches the use of adsorbed site directors to locate silver salts at selected sites on the host grains.
  • Halwig U.S. Patent 3,519,426 and Oppenheimer et al disclose additions of 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene to silver chloride and silver bromide emulsions, respectively.
  • a radiation sensitive emulsion comprised of silver halide grains of a cubic crystal lattice structure having faces ruffled by protrusions which are silver halide crystal lattice extensions from a base plane of a first crystallographic form, silver halide adjacent said base plane, both beneath said base plane and in said protrusions, favoring the formation of surfaces of the first crystallographic form, and said protrusions presenting surfaces of a second crystallographic form.
  • the invention makes available to the art silver halide grains presenting surfaces that are increased in area and which are of a crystallographic form differing from that favored by the silver halide forming the grain surfaces. Each of these surface features offers its distinct advantages.
  • a high grain surface area ratio is realized.
  • this invention allows the grain surface area ratio to be increased independently of grain size. Further, the surface area ratio can be increased independently of overall grain shape. Specifically, an increase in grain surface area ratio by ruffled major crystal faces as contemplated by this invention is equally applicable to otherwise regular or irregular cubic or octahedral grains.
  • novel ruffling approach of this invention and other known approaches for increasing grain surface area ratios, specifically reducing grain size or providing irregular grain shapes, are compatible and can be used in combination to produce additive increases in grain surface area ratios.
  • Thin or high aspect ratio tabular grain emulsions can be increased in their grain surface area ratios by providing ruffled major grain faces as contemplated by this invention. This results in emulsions of higher grain surface area ratios than have heretofore been realized for corresponding grain sizes.
  • the invention permits increased grain surface area ratios without resorting to a tabular grain shape.
  • the invention offers particular advantages when applied to regular and other non-tabular grain shapes.
  • the second distinctive silver halide grain surface feature of the invention is that the ruffled grain faces render accessible varied and new choices of crystallographic forms at grain faces for modifying photographic characteristics.
  • this invention permits silver chloride grain faces to be achieved of other crystallographic forms compatible with a cubic crystal lattice structure.
  • thin and high aspect ratio tabular grain emulsions are most easily generated with octahedral crystal faces, this invention allows tabular grain faces to be realized of other crystallographic forms compatible with a cubic crystal lattice structure.
  • the invention offers the advantage of allowing both high grain surface area ratios and grain faces of differing crystallographic forms to be concurrently realized. This combination permits emulsions of unique and diverse photographic properties to be realized.
  • the present invention relates to silver halide photographic emulsions comprised of radiation sensitive silver grains of a cubic crystal lattice structure having ruffled faces and to photographic elements including these emulsions.
  • planar faces By reason of being ruffled these grain faces present a larger surface area than a corresponding planar grain face.
  • planar faces such as the cube 1 in Figure 1 or the octahedron 5 in Figure 3, it is apparent that the planar faces each present the minimum surface area consistent with the size of the polyhedron.
  • the grain surface area ratio of silver halide grains of a cubic crystal lattice structure can be greatly increased without significantly altering the overall shape or size of the grains. This is achieved merely by ruffling the surfaces presented by the grains.
  • the degree to which the grain surface area ratio is increased is a matter of choice that can be varied from slight increases to increases that more than double the grain surface area ratio.
  • the grain faces employed in the practice of this invention are preferably ruffled to an extent sufficient to provide a 50 percent increase in the grains surface area ratio. This is well above the incidental increases in grain surface area heretofore realized by random non-uniformities of crystal faces and unsought increases in grain surface area ratios realized by producing composite silver halide grains.
  • the silver halide emulsions of this invention most preferably exhibit ruffled grain faces which increase grain surface area ratios by at least 100 percent and optimally at least 200 percent as compared to grains of like size and shape, but lacking ruffled faces.
  • the silver halide grains having ruffled faces are formed starting with any conventional emulsion containing silver halide grains of a cubic crystal lattice structure presenting faces of a crystallographic form favored by the silver halide.
  • silver halide grains which are predominantly silver chloride (greater than 50 mole percent chloride, based on silver) and especially grains which are at least 90 mole percent chloride the favored crystallographic form is cubic, and the grain faces to be ruffled are therefore cubic (i.e., ⁇ 100 ⁇ ) crystal faces.
  • the favored crystallographic form and therefore the grain faces can be either cubic or, when formed in the presence of an excess of bromide ions, octahedral (i.e., ⁇ 111 ⁇ ).
  • the grain faces of the favored crystallographic form for the silver halide employed present planar surfaces and serve as deposition sites for additional silver halide forming the ruffles. It is therefore apparent that the planar surfaces of the crystallographic form favored by the silver halide of the host grains form a base plane for the ruffles.
  • the ruffles take the form of protrusions from the base plane which are extensions of the silver halide cubic crystal lattice structure of the underlying host grain.
  • the silver halide within the ruffles adjacent the base plane is of a composition that favors the same crystallographic form as the silver halide of the host grains forming the base plane.
  • the silver halide adjacent the base plane in the host grain and in the protrusions can be identical in composition or different, the choice of silver halide in each location being circumscribed only by the requirement of forming a cubic crystal lattice structure and the requirement that silver halide in each location favor a common crystallographic form corresponding to that of the base plane.
  • the protrusions adjacent the base plane can be formed, for example, of silver halide which is predominantly silver chloride, as defined above, deposited on a predominantly silver chloride base plane; silver bromide deposited on a silver bromide or bromoiodide base plane; silver bromoiodide deposited on a silver bromide or bromoiodide base plane; or silver chlorobromide optionally containing iodide deposited on a silver chlorobromide base plane optionally also containing iodide.
  • silver chloride can be deposited on a ⁇ 100 ⁇ silver bromide or bromoiodide base plane.
  • protrusions which are predominantly silver chloride deposited on a ⁇ 111 ⁇ silver bromide or bromoiodide base plane have no applicability to this invention for reasons presented below.
  • the portion of the protrusions which does not lie adjacent the base plane e.g., the surfaces of the protrusions can be of any known photographically useful silver halide composition independently of the silver halide composition of the host grain adjacent the base plane, since once the protrusions are formed their surface modification in any desired manner is a matter of choice.
  • each protrusion has been observed to take in most instances the form of pyramids and, occasionally, the form of ridges.
  • the discussion which follows is directed specifically to the protrusions in their pyramidal form, but extension to protrusions in the form of ridges is apparent.
  • each protrusion is a pyramid having its base in common with the base plane presented by the underlying host grain.
  • Each pyramid presents a number of surface faces (all faces other than the base) which are of a crystallographic form differing from that of the base plane.
  • the number of surface faces that a pyramid presents is determined by the crystallographic form of the base plane and the crystallographic form of the pyramidal surface faces.
  • the combinations are set forth below in Table I.
  • Table I Pyramidal Surface Faces Pyramidal Faces Favored Host ⁇ 100 ⁇ Grain Faces ⁇ 111 ⁇ ⁇ 100 ⁇ - 3 ⁇ 111 ⁇ 4 - ⁇ 110 ⁇ 4 3 ⁇ hhl ⁇ 8 3 ⁇ hk0 ⁇ 4 6 ⁇ hll ⁇ 4 3 ⁇ hkl ⁇ 8 6
  • FIG. 1 is a plan view of a pyramid 11 having three ⁇ 100 ⁇ crystal faces 11a, 11b, and 11c on a ⁇ 111 ⁇ base plane 12.
  • FIG. 3 is a plan view of a pyramid 13 having four ⁇ 111 ⁇ crystal faces 13a, 13b, 13c, and 13d on a ⁇ 100 ⁇ base plane 14.
  • pyramids with rhombic dodecahedral faces it can been seen in Figure 5 that the regular rhombic dodecahedron 7 has eight corners each formed by the intersection of three crystal faces and six corners formed by the intersection of four crystal faces.
  • a pyramid presenting rhombic dodecahedral or ⁇ 110 ⁇ crystal faces is located on a ⁇ 100 ⁇ base plane, it presents four surface faces, thus appearing in plan similarly as shown in Figure 9; but when a ⁇ 111 ⁇ base plane is presented, a pyramid with ⁇ 110 ⁇ crystal faces presents three surface faces, thus appearing in plan similarly as shown in Figure 8.
  • carbon replicas of silver halide grains are first prepared.
  • the carbon replicas reproduce the grain shape while avoiding shape altering silver print-out that is known to result from employing the silver halide grains without carbon shells.
  • Electrons rather than light are employed for imaging to permit higher ranges of magnification to be realized than when light is employed.
  • a selected grain By tilting the sample being viewed relative to the electron beam a selected grain can be oriented so that the line of sight is substantially parallel to both of two adjacent crystal faces, seen as edges. When the grain faces are parallel to the imaging electron beam, the two corresponding edges of the grain which they define will appear sharper than when the faces are merely close to being parallel.
  • the angle of intersection can be measured from an electron micrograph of the oriented grain. In this way the relative angle presented by any two intersecting crystal faces can be measured.
  • angles of intersection for possible crystal forms can be calculated and compared to measured intersection angle values. In many, if not most, instances visual inspection of host grains by electron microscopy allows positive identification of the base planes so that further investigation can be limited to the pyramidal surface faces.
  • cubic crystal faces are parallel to two of the axes and intersect the third, thus the ⁇ 100 ⁇ Miller index assignment; octahedral crystal faces intersect each of the three axes at an equal interval, thus the ⁇ 111 ⁇ Miller index assignment; and rhombic dodecahedral crystal faces intersect two of the three axes at an equal interval and are parallel to the third axis, thus the ⁇ 110 ⁇ Miller index assignment.
  • Trisoctahedral, tetrahexahedral, icositetrahedral, and hexoctahedral crystal faces can have differing Miller index values and are therefore identified in Table I generically as ⁇ hhl ⁇ , ⁇ hk0 ⁇ , ⁇ hll ⁇ , and ⁇ hkl ⁇ crystal faces, respectively, where h, k, and l are independently in each occurrence unlike integers greater than zero, h is greater than l, and k, when present, is less than h and greater than l. Although there is no theoretical limit on the maximum values of the integer h, crystal faces having a value of h of 5 or less are more easily generated. Subsequent discussion is for convenience directed to faces in which h is 5 or less. Relationships for faces in which h is greater than 5 are entirely analogous.
  • trisoctahedral crystal faces can have any one of the following Miller indices: ⁇ 221 ⁇ , ⁇ 331 ⁇ , ⁇ 441 ⁇ , ⁇ 551 ⁇ , ⁇ 332 ⁇ , ⁇ 552 ⁇ , ⁇ 443 ⁇ , ⁇ 553 ⁇ , or ⁇ 554 ⁇ .
  • Figure 10 is an isometric view of a trisoctahedron 15 bounded by faces of the ⁇ 331 ⁇ crystallographic form.
  • the point or coign 16 is formed by three intersecting crystal faces 16a, 16b, and 16c and is one of eight identical coigns.
  • the point or coign 17 is formed by eight intersecting crystal faces 16a, 16c, 17a, 17b, 17c, 17d, 17e, and 17f and is one of six identical coigns. Referring to Table I, it is apparent that a pyramid having eight surface faces such as those defining coign 17 is present when the surface faces of the pyramid are trisoctahedral or ⁇ hhl ⁇ crystal faces on a cubic or ⁇ 100 ⁇ base plane presented by the host grain. If, on the other hand, the host grain presents an octahedral or ⁇ 111 ⁇ base plane, a pyramid having three surface faces such as those defining coign 16 is present when the surface faces of the pyramid are trisoctahedral. For trisoctahedral crystal faces of differing Miller indices the geometrical relationships are the same, but the angles of surface face intersections, with each other and with the base plane, differ.
  • the ⁇ 331 ⁇ trisoctahedral crystal faces present a unique arrangement of surface silver and halide ions that differs from that presented by all other possible crystal faces for cubic crystal lattice structure silver halides.
  • This unique surface arrangement of ions as theoretically hypothesized is schematically illustrated by Figure 11, wherein a ⁇ 331 ⁇ trisoctahedral crystal face is shown formed by silver ions 2 and bromide ions 3.
  • tetrahexahedral crystal faces can have any one of the following Miller indices: ⁇ 210 ⁇ , ⁇ 310 ⁇ , ⁇ 320 ⁇ , ⁇ 410 ⁇ , ⁇ 430 ⁇ , ⁇ 510 ⁇ , ⁇ 520 ⁇ , ⁇ 530 ⁇ , or ⁇ 540 ⁇ .
  • Figure 12 is an isometric view of a tetrahexahedron 18 bounded by faces of the ⁇ 210 ⁇ crystallographic form.
  • the point or coign 19 is formed by four intersecting crystal faces 19a, 19b, 19c, and 19d and is one of six identical coigns.
  • the coign 20 is formed by six intersecting crystal faces 19a, 19e, 20a, 20b, 20c, and 20d and is one of eight identical coigns.
  • a pyramid having four surface faces such as those defining coign 19 is present when the surface faces of the pyramid are tetrahexahedral or ⁇ hk0 ⁇ crystal faces on a cubic or ⁇ 100 ⁇ base plane presented by the host grain. If, on the other hand, the host grain presents an octahedral or ⁇ 111 ⁇ base plane, a pyramid having six surface faces such as those defining coign 20 is present when the surface faces of the pyramid are tetrahexahedral. For tetrahexahedral crystal faces of differing Miller indices the geometrical relationships are the same, but the angles of surface face intersections, with each other and with the base plane, differ.
  • the ⁇ 210 ⁇ tetrahexahedral crystal faces present a unique arrangement of surface silver and halide ions that differs from that presented by all other possible crystal faces for cubic crystal lattice structure silver halides.
  • This unique surface arrangement of ions as theoretically hypothesized is schematically illustrated by Figure 13, wherein a ⁇ 210 ⁇ tetrahexahedral crystal face is shown formed by silver ions 2 and bromide ions 3. Comparing Figure 13 with Figures 2, 4, 6, and 11, it is apparent that the surface positioning of silver and bromide ions in each figure is distinctive.
  • the ⁇ 210 ⁇ tetrahexahedral crystal face presents an ordered, but more varied arrangement of surface silver and bromide ions than is presented at the cubic, octahedral, or rhombic dodecahedral silver bromide crystal faces. This is a result of the tiering that occurs at the ⁇ 210 ⁇ tetrahexahedral crystal face. Tetrahexahedral crystal faces with differing Miller indices also exhibit tiering. The differing Miller indices result in analogous, but nevertheless unique surface arrangements of silver and halide ions.
  • icositetrahedral crystal faces can have any one of the following Miller indices: ⁇ 211 ⁇ , ⁇ 311 ⁇ , ⁇ 322 ⁇ , ⁇ 411 ⁇ , ⁇ 433 ⁇ , ⁇ 511 ⁇ , ⁇ 522 ⁇ , ⁇ 533 ⁇ , or ⁇ 544 ⁇ .
  • Figure 14 is an isometric view of a icositetrahedron 21 bounded by faces of the ⁇ 211 ⁇ crystallographic form.
  • the point or coign 22 is formed by four intersecting crystal faces 22a, 22b, 22c, and 22d and is one of six identical coigns.
  • the coign 23 is formed by three intersecting crystal faces 22a, 23a, and 23b and is one of eight identical coigns.
  • a pyramid having four surface faces such as those defining coign 22 is present when the surface faces of the pyramid are icositetrahedral or ⁇ hk0 ⁇ crystal faces on a cubic or ⁇ 100 ⁇ base plane presented by the host grain. If, on the other hand, the host grain presents an octahedral or ⁇ 111 ⁇ base plane, a pyramid having three surface faces such as those defining coign 23 is present when the surface faces of the pyramid are icositetrahedral. For icositetrahedral crystal faces of differing Miller indices the geometrical relationships are the same, but the angles of surface face intersections, with each other and with the base plane, differ.
  • the ⁇ 211 ⁇ icositetrahedral crystal faces present a unique arrangement of surface silver and halide ions that differs from that presented by all other possible crystal faces for cubic crystal lattice structure silver halides.
  • This unique surface arrangement of ions as theoretically hypothesized is schematically illustrated by Figure 15, wherein a ⁇ 211 ⁇ icositetrahedral crystal face is shown formed by silver ions 2 and bromide ions 3. Comparing Figure 15 with Figures 2, 4, 6, 11, and 13, it is apparent that the surface positioning of silver and bromide ions in each figure is distinctive.
  • the ⁇ 211 ⁇ icositetrahedral crystal face presents an ordered, but more varied arrangement of surface silver and bromide ions than is presented at the cubic, octahedral, or rhombic dodecahedral silver bromide crystal faces. This is a result of the tiering that occurs at the ⁇ 211 ⁇ icositetrahedral crystal face Icositetrahedral crystal faces with differing Miller indices also exhibit tiering. The differing Miller indices result in analogous, but nevertheless unique surface arrangements of silver and halide ions.
  • hexoctahedral crystal faces can have any one of the following Miller indices: ⁇ 321 ⁇ , ⁇ 421 ⁇ , ⁇ 431 ⁇ , ⁇ 432 ⁇ , ⁇ 521 ⁇ , ⁇ 531 ⁇ , ⁇ 532 ⁇ , ⁇ 541 ⁇ , ⁇ 542 ⁇ , or ⁇ 543 ⁇ .
  • Figure 16 is an isometric view of a hexoctahedron 24 bounded by faces of the ⁇ 321 ⁇ crystallographic form.
  • the coign 25 is formed by eight intersecting crystal faces 25a, 25b, 25c, 25d, 25e, 25f, 25g, and 25h and is one of six identical coigns.
  • the point or coign 26 is formed by six intersecting crystal faces 25g, 25h, 26a, 26b, 26c, and 26d and is one of six identical coigns.
  • the coign 27 is formed by four intersecting crystal faces 25a, 25h, 26a, and 27a. Referring to Table I it is apparent that a pyramid having eight surface faces such as those defining coign 25 is present when the surface faces of the pyramid are hexoctahedral or ⁇ hkl ⁇ crystal faces on a cubic or ⁇ 100 ⁇ base plane presented by the host grain.
  • the host grain presents an octahedral or ⁇ 111 ⁇ base plane
  • a pyramid having six surface faces such as those defining coign 26 is present when the surface faces of the pyramid are hexoctahedral.
  • the base plane were of a rhombic dodecahedral or ⁇ 110 ⁇ crystallographic form, the pyramids thereon would have surface faces corresponding to those forming coign 27.
  • the geometrical relationships are the same, but the angles of surface face intersections, with each other and with the base plane, differ.
  • the ⁇ 321 ⁇ hexoctahedral crystal faces present a unique arrangement of surface silver and halide ions that differs from that presented by all other possible crystal faces for cubic crystal lattice structure silver halides.
  • This unique surface arrangement of ions as theoretically hypothesized is schematically illustrated by Figure 17, wherein a ⁇ 321 ⁇ hexoctahedral crystal face is shown formed by silver ions 2 and bromide ions 3. Comparing Figure 17 with Figures 2, 4, 6, 11, 13, and 15, it is apparent that the surface positioning of silver and bromide ions in each figure is distinctive.
  • the ⁇ 321 ⁇ hexoctahedral crystal face presents an ordered, but more varied arrangement of surface silver and bromide ions than is presented at the cubic, octahedral, or rhombic dodecahedral silver bromide crystal faces. This is a result of the oblique tiering that occurs at the ⁇ 321 ⁇ hexoctahedral crystal face.
  • Icositetrahedral crystal faces with differing Miller indices also exhibit oblique tiering. The differing Miller indices result in analogous, but nevertheless unique surface arrangements of silver and halide ions.
  • the surface area ratio (as opposed to the surface area) presented by ruffled silver halide grains is directly influenced by the size of the pyramids.
  • a hundred pyramids providing the same surface area as a thousand smaller pyramids of the same form nevertheless have a much larger collective volume and therefore require more silver halide to form. This is one reason to favor smaller pyramids over larger pyramids.
  • pyramids When it is desired to maximize the surface area ratio provided by the pyramids, it is, of course, obvious to select pyramids which themselves exhibit a maximum surface area ratio, although the amount of silver halide contained in relatively small pyramids is virtually negligible.
  • a second factor to consider is whether the pyramidal base defines a polygonal figure that can be close packed. All pyramids of the same form on a given base plane are identically oriented. Looking at Figure 9 it can be seen that the base plane 14 can in theory be entirely covered with pyramids of the form of pyramid 13, whether or not the pyramids are of the same or different sizes.
  • the successful formation of crystal faces of a differing crystallographic form from that favored by the silver halide being deposited depends on identifying grain growth conditions that retard the rate of silver and halide ion deposition onto faces of the desired differing crystallographic form.
  • Many examples can be found in the art of growing host grains presenting cubic or octahedral faces to form grains in which some or all of the faces are of the other crystallographic form i.e., octahedral or cubic.
  • rhombic dodecahedral silver halide grains are rare, similar growth conversions in grain shape are equally applicable to this crystallographic form.
  • Berry and Skillman discussed above, grew silver chloride as discrete deposits on the ⁇ 111 ⁇ major surfaces of tabular silver bromide grains.
  • the failure of the silver chloride to simply shell the silver bromide grains can be explained by the fact that silver chloride strongly favors surfaces of a ⁇ 100 ⁇ crystallographic form and was therefore incompatible with continuing ⁇ 111 ⁇ crystal face growth under the conditions of precipitation employed.
  • the present invention employs silver halide to ruffle the host crystal faces that favors a crystallographic form corresponding to that of the crystal faces presented by the host grains.
  • growth modifiers are effective under the conditions of their use in the examples. From empirical screening of a variety of candidate growth modifiers under differing conditions of silver halide precipitation it has been concluded that multiple parameters must be satisfied to achieve ruffled grain faces, including not only the proper choice of a growth modifier, but also proper choice of other precipitation parameters identified in the examples. Failures to achieve ruffled grain faces with compounds shown to be effective as growth modifiers for producing ruffled grain faces have been observed when accompanying conditions for silver halide precipitation have been varied. However, it is appreciated that having demonstrated success in the preparations of silver halide emulsions containing grains with ruffled grain faces, routine empirical studies systematically varying parameters are likely to lead to additional useful preparation techniques.
  • silver halide emulsions containing any identifiable ruffled grain surface are considered within the scope of this invention, in most applications the grains having at least one identifiable ruffled face account for at least 10 percent of the total grain population and usually these grains will account for greater than 50 percent of the total grain population.
  • the host grain emulsions presenting cubic and/or octahedral crystal faces from which the emulsions of this invention are produced and any emulsions lacking ruffled grain faces blended into ruffled grain emulsion according to this invention can be chosen from among a variety of conventional emulsions.
  • the techniques for producing surface latent image forming grains, internal latent image forming grains, internally fogged grains, surface fogged grains, and blends of differing grains described in Research Disclosure , Vol. 176, December 1978, Item 17643, Section I, can be applied to the preparation of emulsions according to this invention.
  • tabular grain emulsions are those comprised of a dispersing medium and silver halide grains, wherein at least 50 percent of the total projected area of the silver halide grains is provided by tabular silver halide grains having a thickness of less than 0.3 ⁇ m, a diameter of at least 0.6 ⁇ m, and an average aspect ratio of greater than 8:1.
  • tabular silver halide grains having a thickness of less than 0.5 ⁇ m, a diameter of at least 0.6 ⁇ m, and an average aspect ratio of greater than 8:1.
  • Preferred high aspect ratio tabular grain emulsions are those in which the average aspect ratio is at least 12:1 and optimally at least 20:1. It is also preferred to increase the projected area referred to above from 50 percent to 70 percent and optimally to 90 percent. Silver bromiodide emulsions are generally preferred for camera speed imaging applications while silver bromide and silver bromoiodide emulsions are preferred for radiographic imaging.
  • thin tabular grain emulsions are those comprised of a dispersing medium and silver halide grains, wherein at least 50 percent of the total projected area of the silver halide grains is provided by tabular silver halide grains having a thickness of less than 0.2 ⁇ m and an average aspect ratio of greater than 5:1.
  • the preferences noted above for high aspect ratio emulsions apply also to thin tabular grain emulsions. Emulsions which satisfy both definitions are preferred for most photographic applications.
  • the radiation sensitive silver halide emulsions and the photographic elements in which they are incorporated of this invention can take any convenient conventional form.
  • the emulsions can be washed as described in Research Disclosure , Item 17643, cited above, Section II.
  • the radiation sensitive silver halide grains of the emulsions can be surface chemically sensitized.
  • Noble metal e.g., gold
  • middle chalcogen e.g., sulfur, selenium, or tellurium
  • reduction sensitizers employed individually or in combination are specifically contemplated.
  • Typical chemical sensitizers are listed in Research Disclosure , Item 17643, cited above, Section III.
  • the silver halide emulsions 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 polynuclear cyanines and merocyanines), oxonols, hemioxonols, styryls, merostyryls, and streptocyanines.
  • Illustrative spectral sensitizing dyes are disclosed in Research Disclosure , Item 17643, cited above, Section IV.
  • the silver halide emulsions as well as other layers of the photographic elements of this invention can contain as vehicles hydrophilic colloids, employed alone or in combination with other polymeric materials (e.g., latices).
  • Suitable hydrophilic materials include both naturally occurring substances such as proteins, protein derivatives, cellulose derivatives e.g., cellulose esters, gelatin 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, collodion, agar-agar, arrowroot, and albumin.
  • the vehicles can be hardened by conventional procedures. Further details of the vehicles and hardeners are provided in Research Disclosure , Item 17643, cited above, Sections IX and X.
  • the silver halide photographic elements of this invention can contain other addenda conventional in the photographic art Useful addenda are described, for example, in Research Disclosure , Item 17643, cited above.
  • Other conventional useful addenda include antifoggants and stabilizers, couplers (such as dye forming couplers, masking couplers and DIR couplers) DIR compounds, anti-stain agents, image dye stabilizers, absorbing materials such as filter dyes and UV absorbers, light scattering materials, antistatic agents, coating aids, and plasticizers and lubricants.
  • the photographic elements of the present invention can be simple black-and-white or monochrome elements comprising a support bearing a layer of the silver halide emulsion, or they can be multilayer and/or multicolor elements.
  • the photographic elements produce images ranging from low contrast to very high contrast, such as those employed for producing half tone images in graphic arts. They can be designed for processing with separate solutions or for in-camera processing. In the latter instance the photographic elements can include conventional image transfer features, such as those illustrated by Research Disclosure , Item 17643, cited above, Section XXIII.
  • Multicolor elements contain dye image forming units sensitive to each of the three primary regions of the spectrum. Each unit can be comprised of a single emulsion layer or of multiple emulsion layers sensitive to a given region of the spectrum.
  • the layers of the element can be arranged in various orders as known in the art.
  • the emulsion or emulsions can be disposed as one or more segmented layers, e.g., as by the use of microvessels or microcells, as described in Whitmore U.S. Patent 4,387,154.
  • a preferred multicolor photographic element according to this invention containing incorporated dye image providing materials comprises a support bearing at least one blue sensitive silver halide emulsion layer having associated therewith a yellow dye forming coupler, at least one green sensitive silver halide emulsion layer having associated therewith a magenta dye forming coupler, and at least one red sensitive silver halide emulsion layer having associated therewith a cyan dye forming coupler, at least one of the silver halide emulsion layers containing grains having ruffled faces as previously described.
  • the elements of the present invention can contain additional layers conventional in photographic elements, such as overcoat layers, spacer layers, filter layers, antihalation layers, and scavenger layers.
  • the support can be any suitable support used with photographic elements. Typical supports include polymeric films, paper (including polymer-coated paper), glass, and metal supports. Details regarding supports and other layers of the photographic elements of this invention are contained in Research Disclosure , Item 17643, cited above, Section XVII.
  • the photographic elements can be imagewise exposed with various forms of energy, which encompass the ultraviolet, visible, and infrared regions of the electromagnetic spectrum as well as electron beam and beta radiation, gamma ray, X ray, alpha particle, neutron radiation, and other forms of corpuscular and wave-like radiant energy in either noncoherent (random phase) forms or coherent (in phase) forms, as produced by lasers.
  • forms of energy which encompass the ultraviolet, visible, and infrared regions of the electromagnetic spectrum as well as electron beam and beta radiation, gamma ray, X ray, alpha particle, neutron radiation, and other forms of corpuscular and wave-like radiant energy in either noncoherent (random phase) forms or coherent (in phase) forms, as produced by lasers.
  • X rays can include features found in conventional radiographic elements, such as those illustrated by Research Disclosure , Vol. 184, August 1979, Item 18431.
  • Processing of the imagewise exposed photographic elements can be accomplished in any convenient conventional manner. Processing procedures, developing agents, and development modifiers are illustrated by Research Disclosure , Item 17643, cited above, Sections XIX, XX, and XXI, respectively.
  • the emulsions of this invention can be substituted for conventional emulsions to satisfy known photographic applications.
  • the emulsions of this invention can lead to further photographic advantages.
  • the further photographic advantages can be attributed one or a combination of (a) the increased surface area ratios which the ruffled grains make possible, (b) the varied crystal faces presented by the ruffled grains, and (c) the high affinity between the ruffled grain faces and adsorbed compounds.
  • the present invention allows increases in photographic speed to be realized.
  • a photographic application in which the emulsions are exposed imagewise to light in the minus blue portion of the spectrum (i.e., the green and/or red portion of the spectrum) and thereby require spectral sensitization
  • decreasing average grain size to increase the surface area ratio of the grains and therefore the amount of sensitizing dye per unit volume of silver halide is ineffective to increase speed. It instead lowers photographic speed.
  • the present invention by increasing the surface area ratio of the grains without reducing average grain size allows an increase in photographic speed to be realized.
  • ruffling of the grain faces does not change the average angle of incidence of exposing radiation with the transition moment dipole of the adsorbed spectral sensitizing dye. In this instance speed increases realizable should be approximate in proportion to the increase in the surface area ratio.
  • the grains are typically oriented with their major faces normal to the direction of unscattered exposing radiation.
  • the transition moment dipole is parallel to the crystal face to which it is absorbed; therefore, a normal orientation of the silver halide crystal faces with respect to the direction of exposing radiation also normally orients the transition moment dipole of the spectral sensitizing dye.
  • the grain faces are already oriented optimally for dye absorption of unscattered light.
  • an optimum location for a spectrally sensitized ruffled thin or high aspect ratio tabular grain emulsion in a photographic element is nearer the support and beneath overlying light scattering layers.
  • such an emulsion is most efficient as the slower green and/or red recording layers normally located nearest the photographic support.
  • the photographic speed of these recording layers can be increased by employing reflective materials, either in the emulsion layer or layers or in underlying layers.
  • the reflective materials in the silver halide emulsion layers can include pigments of high refractive index, as illustrated by marriage U.K. Patent 504,283 and Yutzy et al U.K. Patent 760,775 or reflecting undercoat layers containing silver halide, as illustrated by Russell U.S. Patent 3,140,179.
  • photographic advantages can also be attributed to improved interactions of adsorbed addenda and the ruffled silver halide grains surfaces.
  • a growth modifier is present adsorbed to the ruffled faces of the grains and has a known photographic utility that is enhanced by adsorption to a grain surface, either because of the more intimate association with the grain surface or because of the reduced mobility of the growth modifier, improved photographic performance can be expected.
  • the reason for this is that for the growth modifier to produce a pyramidal crystal face it must exhibit an adsorption preference for that crystallographic form that is greater than that exhibited for any other possible silver halide crystallographic form.
  • Locker U.S. Patent 3,989,527 describes improving the speed of a photographic element by employing an emulsion containing radiation sensitive silver halide grains having a spectral sensitizing dye adsorbed to the grain surfaces in combination with silver halide grains free of spectral sensitizing dye having an average diameter chosen to maximize light scattering, typically in the 0.15 to 0.8 ⁇ m range.
  • Upon imagewise exposure radiation striking the undyed grains is scattered rather than being absorbed. This results in an increased amount of exposing radiation striking the radiation sensitive imaging grains having a spectral sensitizing dye adsorbed to their surfaces
  • spectral sensitizing dyes can migrate in the emulsion, so that to some extent the initially undyed grains adsorb spectral sensitizing dye which has migrated from the initially spectrally sensitized grains.
  • dye migration away from their surfaces reduces sensitization.
  • adsorption of dye on the grains intended to scatter imaging radiation reduces their scattering efficiency.
  • spectral sensitizing dyes have been identified as growth modifiers useful in forming ruffled silver halide grains.
  • radiation sensitive silver halide grains having ruffled faces and a growth modifier spectral sensitizing dye adsorbed to the ruffled faces are substituted for the spectrally sensitized silver halide grains employed by Locker, the disadvantageous migration of dye from the ruffled grain faces to the silver halide grains intended to scatter light is reduced or eliminated. Thus, an improvement in photographic efficiency can be realized.
  • the layer structure of a multicolor photographic element which introduces dye image providing materials, such as couplers, during processing can be simplified.
  • An emulsion intended to record green exposures can be prepared using a growth modifier that is a green spectral sensitizing dye while an emulsion intended to record red exposures can be prepared using a growth modifier that is a red spectral sensitizing dye. Since the growth modifiers are tightly adsorbed to the grains and non-wandering, instead of coating the green and red emulsions in separate color forming layer units, as is conventional practice, the two emulsions can be blended and coated as a single color forming layer unit.
  • the blue recording layer can take any conventional form, and a conventional yellow filter layer can be employed to protect the blended green and red recording emulsions from blue light exposure. Except for blending the green and red recording emulsions in a single layer or group of layers differing in speed in a single color forming layer unit, the structure and processing of the photographic element is unaltered. If silver chloride emulsions are employed, the approach described above can be extended to blending in a single color forming layer unit blue, green, and red recording emulsions, and the yellow filter layer can be eliminated. The advantage in either case is a reduction in the number of emulsion layers required as compared to a corresponding conventional multicolor photographic element.
  • an emulsion according to the invention containing a growth modifier spectral sensitizing dye should produce a more invariant emulsion in terms of spectral properties than a corresponding emulsion containing silver halide grains lacking ruffled faces.
  • the growth modifier is capable of inhibiting fog, such as 2-mercaptoimidazole or any of the tetraazaindenes shown to be effective growth modifiers in the examples, more effective fog inhibition at lower concentrations may be expected
  • Emulsion Example 1 illustrates the preparation of a ruffled tabular grain silver bromoiodide emulsion using as growth modifier Compound I, 5-carbethoxy-4-hydroxy-1,3,3a,7-tetraazaindene, which is known to be useful as an antifoggant and stabilizer.
  • a thin and high aspect ratio tabular grain silver bromoiodide emulsion (6 mole % I) of mean grain size 5.3 ⁇ m, thickness 0.07 ⁇ m, and containing about 40 g/Ag mole gelatin, hereinafter designated Host Grain Emulsion 1.
  • Water was added to make the total weight 50 g.
  • To the emulsion at 40°C was added 6.0 millimole/initial Ag mole of Compound I dissolved in 1mL of methanol, 1mL of water, and 3 drops of triethylamine. The emulsion was then held for 15 min. at 40°C. The pH was adjusted to 6.0 at 40°C.
  • the temperature was raised to 60°C, and the pAg adjusted to 8.5 at 60°C with KBr and maintained at that value during the precipitation.
  • a 2.0M solution of AgNO3 was introduced at a constant rate over a period of 38 min while a solution that was 1.88M in KBr and 0.12M in KI was added as needed to hold the pAg constant.
  • a total of 0.015 mole Ag was added.
  • FIG. 18 A carbon replica electron micrograph of the resulting emulsion grains is shown in Figure 18.
  • the ruffles were small, closely positioned, and uniformly distributed over the faces of the tabular grains.
  • Emulsion Example 2 illustrates the preparation of a ruffled tabular-grain silver bromoiodide emulsion using as a growth modifier, Compound II, which is known to be useful as a blue spectral sensitizing dye.
  • Emulsion Example 2 was prepared as described for Example 1, except that the growth modifier was 6.0 millimole/Ag mole of Compound II, dissolved in 3mL methanol, 2mL water, and 2 drops of triethylamine. The precipitation was carried out for 37.0 min, consuming 0.015 mole Ag.
  • Emulsion Example 3 illustrates the preparation of a ruffled tabular grain pure bromide emulsion using as a growth modifier Compound III, anhydro-5-chloro-9-ethyl-5'-phenyl-3,3'-di-(3-sulfopropyl)oxacarbocyanine hydroxide, triethylamine salt, which is known to be useful as a green spectral sensitizing dye.
  • a thin and high aspect ratio tabular grain AgBr emulsion having major faces of octahedral form, of mean grain size 5.6 ⁇ m and thickness 0.10 ⁇ m containing about 20 g/Ag mole gelatin, hereinafter designated Host Grain Emulsion 2.
  • Water was added to make the total weight 50 g.
  • To the emulsion at 40°C was added 5.0 millimole/initial Ag mole of Compound III dissolved in 2mL methanol. The emulsion was then held for 15 min at 40°C. The pH was adjusted to 6.0 at 40°C.
  • the temperature was lowered to 30°C, and the pAg adjusted to 7.6 at 30°C with KBr and maintained at that level during the precipitation.
  • a 2.0M solution of AgNO3 was introduced at a constant rate over a period of 10 min while a 2.0M solution of KBr was added as needed to hold the pAg constant.
  • a total of 0.020 mole Ag was added.
  • Example 4 show the effects of varying the pAg and temperature of precipitation on the properties of the resulting ruffles.
  • the host was a tabular grain AgBr emulsion, and the growth modifier Compound IV, anhydro-9-ethyl-5,5'-diphenyl-3,3'-di(3-sulfobutyl)oxacarbocyanine hydroxide, monosodium salt, which is known to be useful as a green spectral sensitizing dye.
  • Figures 21A, B, C and D show electron micrographs of the resulting grains.
  • Example 4A produced growths of large flat triangles.
  • Example 4B produced a growth of some flat triangles and some pyramids smaller than in 4A.
  • Example 4C produced fairly uniform pyramids.
  • Example 4D produced uniform closely arranged, small pyramids. Examination indicated the growths to have ⁇ 100 ⁇ (cubic) crystal faces.
  • Compound IV was determined to be a ⁇ 100 ⁇ growth modifier by depositing AgBr onto an regular octahedral grain host emulsion at pAg 7.6, 40°C in the presence of this compound; AgBr cubes resulted.
  • Emulsion Example 5 illustrates the preparation of a ruffled tabular grain silver bromide emulsion using as a growth modifier Compound V, 5-(3-ethyl-2-benzothiazolinylidene)-3- ⁇ -sulfoethylrhodanine, which is known to be useful as a blue spectral sensitizing dye.
  • Example 6 illustrates the preparation of ruffled tabular grain silver bromoiodide emulsions using Compound V (Example 5) as the growth modifier.
  • Example 6A is a control showing that no ruffles are formed if the growth modifier is added following, rather than preceding, the silver halide precipitation on the host emulsion.
  • the host emulsion (0.05 mole for each experiment) and precipitation conditions were as described in Example 1, except that the growth modifier was Compound V and the addition rate of the AgNO3 solution was half that used in Example 1, (precipitation time about 74 min, 0.015 mole Ag added).
  • the details of the three experiments are shown in Table III. TABLE III Example 6 Precipitations Example Figure No Cpd. V mmole/Ag mole Comments 6A 23A 3.0 Control - Cpd. V added after precipitation 6B 23B 3.0 Invention 6C 23C 4.5 Invention
  • Figures 23A, B, and C show electron micrographs of the resulting grains.
  • addition of the growth modifier after the precipitation resulted in no growth of ruffles on the host emulsion grains.
  • Example 6B with the same amount of growth modifier added prior to the precipitation, produced uniform, closely arranged, small ruffles.
  • Example 6C with a higher level of growth modifier, produced a similar result, but with slightly better defined ruffles (pyramids).
  • Example 7 again illustrates the preparation of ruffled tabular grain silver bromoiodide emulsions using Compound V (Example 5) as the growth modifier, but shows the dependence of the result on the level of growth modifier added.
  • Example 7 Precipitations Example Figure No Cpd. V mmole/Ag mole 7A 24A 0 7B 24B 0.75 7C 24C 1.5 7D 24D 3.0
  • Figures 24A, B, C, and D are electron micrographs of the resulting emulsion grains.
  • Example 7D produced uniform, closely arranged, small ruffles.
  • the pyramidal crystal faces were consistent with the ⁇ 211 ⁇ crystal faces expected from using Compound V as a growth modifier in the previous examples.
  • Emulsion Example 8 illustrates the preparation of a ruffled tabular grain silver bromide emulsion using as growth modifier Compound XIII, anhydro-3,9-diethyl-5,5',6'-trimethoxy-3'-(3-sulfopropyl)thiacarbocyanine hydroxide, which is a red spectral sensitizing dye.
  • Figure 25 is an electron micrograph of the resulting emulsion grains. Closely arranged ruffles are uniformly distributed over the faces of the tabular grains.
  • Example 9 illustrate the preparation of ruffled silver bromide tabular grains by physical ripening in the presence of a fine grain silver bromide emulsion and a growth modifier.
  • Figure 26A is an electron micrograph showing the fairly uniform, closely arranged ruffles which resulted.
  • the ruffles were made up of pyramidal crystal faces of the ⁇ 110 ⁇ (rhombic dodecahedral) crystallographic form.
  • Emulsion Example 9B was prepared as described for Example 9A, but with growth modifier Compound VIII, 4-hydroxy-6-methyl-2-methylthio-1,3,3a,7-tetraazaindene, a known antifoggant and stabilizer, dissolved in 2mL water and 2 drops of triethylamine.
  • Figure 26B is an electron micrograph showing the relatively large and closely arranged ruffles which resulted.
  • the ruffles were made up of pyramidal crystal faces of the ⁇ 211 ⁇ icositetrahedral crystallographic form.
  • Emulsion Example 9C was prepared as described for Example 9A, but with Compound V as growth modifier, dissolved in 6mL N,N-dimethylformamide, 2mL water, and 2 drops triethylamine.
  • Figure 26C is an electron micrograph showing the uniform closely arranged ruffles which resulted.
  • the pyramidal crystal faces were consistent with the ⁇ 211 ⁇ crystal faces expected from using Compound V as a growth modifier in the previous examples.
  • Emulsion Example 9D was prepared as described for Example 9A, using Compound IX, 5-imino-3-thiourazole, as a growth modifier, dissolved in 2mL N,N-dimethylformamide.
  • Figure 26D is an electron micrograph showing the resulting uniform, closely arranged ruffles which resulted.
  • the ruffles were made up of pyramidal crystal faces of the ⁇ 110 ⁇ (rhombic dodecahedral) crystallographic form.
  • Figure 26E is an electron micrograph showing the rather large ruffles which resulted.
  • the ruffles were made up of pyramidal crystal faces of the ⁇ 331 ⁇ trisoctahedral crystallographic form.
  • Emulsion Example 10 illustrates the preparation of a ruffled octahedral silver bromide emulsion using Compound I as a growth modifier.
  • Emulsion Example 11 illustrates the preparation of a ruffled octahedral silver bromide emulsion using Compound VII as a growth modifier. New faces formed indicate that in addition to forming ruffles growth of the host grains into rhombic dodecahedral form has commenced.
  • FIG. 28 An electron micrograph of the resulting emulsion grains is shown in Figure 28.
  • the octahedral faces of the host grains appeared to be uniformly ruffled.
  • new faces have begun to form along the edges between the octahedral faces, indicating that the crystals are growing into ⁇ 110 ⁇ rhombic dodecahedra.
  • Emulsion Example 12 illustrates the preparation of a ruffled octahedral silver bromide emulsion using Compound X as growth modifier As the precipitation continued, the formation of trisoctahedra became evident.
  • the host emulsion and procedure was the same as in Example 10.
  • the growth modifier was 6.0 millimole/Ag mole of Compound X dissolved in 3mL of water.
  • the precipitation time was 15 min, using 0.0075 mole Ag.
  • the precipitation time was 30 min, using 0.015 mole Ag.
  • Figures 29A and 29B are electron micrographs showing the resulting emulsion grains of Examples 12A and 12B, respectively.
  • Example 12A uniform ruffles formed over the octahedral faces, while new trisoctahedral faces formed along the edges between the original faces.
  • Example 12B the process of forming ⁇ 331 ⁇ trisoctahedra is almost complete.
  • Emulsion Example 13 illustrates the formation of octahedral silver bromide emulsions which have their surface area increased by ruffles in the form of uniform ridges.
  • the host emulsion and procedure was the same as in Example 10.
  • the growth modifier was 2.0 millimole/initial Ag mole of Compound XI, a known green spectral sensitizing dye, dissolved in 3mL methanol, 2mL water and 3 drops of triethylamine.
  • the precipitation solutions were 2.0M rather than 2.5M AgNO3 and KBr.
  • Example 13A the precipitation time was 200 min, using 0.04 mole Ag.
  • Example 13B the time was 350 min, using 0.07 mole Ag.
  • Figures 30A and 30B are electron micrographs of the resulting emulsion grains produced by Examples 13A and 13B, respectively.
  • the faces are uniformly covered with ridges running in a direction perpendicular to the (110) Ag rows of the lattice. Trisoctahedral faces have begun to form. In Example 13B the ridges remain evident, while the macro habit has become ⁇ 331 ⁇ trisoctahedral.
  • Example 14 illustrates the preparation of ruffled cubic silver bromide grains using Compound XII, 2-mercaptoimidazole as a growth modifier. Continued growth results in icositetrahedral grains.
  • Example 14A A 2.5M solution of AgNO3 was added at a constant rate over a period of 25 min while a 2.5M solution of KBr was added as needed to hold the pAg constant. A total of 0.0125 mole Ag was added to form Example 14A. For Example 14B the precipitation was continued for a total of 175 min, using a total of 0.0875 mole Ag. An additional 3 millimole/initial Ag mole of Compound XII was added after 100 min of precipitation time.
  • Figures 31A and 31B are electron micrographs of the resulting emulsion grains produced by Examples 14A and 14B, respectively.
  • Figure 31A shows a pattern of growths covering the crystal faces.
  • Figure 31B illustrates the formation of ⁇ 533 ⁇ icositetrahedral grains with continued precipitation.
  • Example 15 illustrates the preparation of a ruffled cubic silver bromide emulsion using Compound VIII under ammoniacal precipitation conditions.
  • NH4OH and 0.5 mL of a 0.50M solution of KBr were added.
  • the pAg was found to be 9.1 at 40°C, and was maintained at that value during the precipitation.
  • a 2.5M solution of AgNO3 was introduced at a constant rate over a period of 100 min while a 2.5M solution of KBr was added as needed to hold the pAg constant.
  • a total of 0.05 mole Ag was added.
  • Figure 32 is an electron micrograph of the resulting emulsion grains. The cubes are somewhat rounded with the cubic faces covered with uniform ruffles.
  • This example illustrates an increase in photographic speed which can be realized with ruffled grains according to the present invention.
  • a reaction vessel equipped with a stirrer was charged with 0.05 mole of an octahedral silver bromoiodide emulsion containing 6 mole % silver iodide, of mean grain size 0.3 ⁇ m and containing about 20 g/Ag mole gelatin. Water was added to make the total weight 50 g. The emulsion was heated to 40°C. A solution was prepared 0.625 millimole of growth modifier Compound V, a blue spectral sensitizing dye, in a solvent consisting of 12 mL water and 10 drops of triethylamine made up to 50 mL with N,N-dimethylformamide.
  • Figure 33A is an electron micrograph of the resulting ruffled grain octahedral emulsion.
  • Control Emulsion 16B was prepared as described for Example Emulsion 16A, but without the growth modifier (Compound V) being present during the precipitation. Following precipitation 1.25 millimole of Compound V was added, a typical amount of sensitizing dye for an emulsion of this grain size.
  • Figure 33B is an electron micrograph showing the resulting regular octahedral grains. No ruffling of the grain surfaces is identifiable.
  • Control Emulsion 16B was modified after precipitation and before coating by increasing the total content of Compound V to 3.75 millimole/Ag mole, which equaled its concentration in Example Emulsion 16A.
  • Each of the emulsions was coated on a cellulose acetate support at 1.18 g/m2 silver and 4.20 g/m2 gelatin.
  • Samples of the coatings were exposed for 1/2 second through a graduated tablet to a 365 nm filtered mercury light source to provide a measure of intrinsic speed, and to a Wratten 47 filtered tungsten light source to provide blue speed Eastman 1B Sensitometers were used.
  • the exposed samples were developed for 6 minutes at 20°C in Kodak Rapid X-ray Developer. The difference between blue speed and 365 nm speed was taken as the measure of the relative degree of spectral sensitization for each of the three coatings and is tabulated in in Table V.
  • the data show that Example Emulsion 16A had a significantly greater blue speed relative to its 365 nm speed than did the control unruffled Control Emulsions 16B and 16C with a normal spectral sensitization or with an equal amount of sensitizing dye equal to that of the ruffled grain Example Emulsion 16A, respectively.
  • a reaction vessel equipped with a stirrer was charged with 0.75 g of deionized bone gelatin made up to 50 g with water. 6-Nitrobenzimidazole, 16.2 mg (0.3 weight % based on the Ag used), dissolved in 1mL of methanol, was added, followed by 0.055 mole of KBr. At 70°C 0.05 mole of a 2M solution of AgNO3 was added at a uniform rate over a period of 25 min. The grains formed were relatively thick tablets showing ⁇ 111 ⁇ crystal faces. There was no indication of ruffled crystal faces of the invention.
  • Samples 18c and 18d were prepared similarly as Samples 18a and 18b, respectively, except that 0.8 mmole/l of 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene and 0.6 mmole/l of 1-dodecylquinolinium bromide were used.

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Claims (21)

  1. Strahlungsempfindliche Emulsion mit Silberhalogenidkörnern einer kubischen Kristallgitterstruktur mit

    Flächen, die durch Vorsprünge aufgerauht sind, bei denen es sich um Silberhalogenid-Kristallgitterausdehnungen von einer Basisebene einer ersten kristallographischen Form handelt,

    Silberhalogenid benachbart zu dieser Basisebene, sowohl unterhalb dieser Basisebene wie auch in den Vorsprüngen, das die Bildung von Oberflächen der ersten kristallographischen Form begünstigt und

    bei denen die Vorsprünge Oberflächen einer zweiten kristallographischen Form darstellen.
  2. Strahlungsempfindliche Emulsion nach Anspruch 1, in der die Aufrauhungen einen Gesamtoberflächenbereich darstellen, der um mindestens 50 % größer ist als der Bereich, der durch die Basisebenen, auf denen sie sich befinden, dargestellt wird.
  3. Strahlungsempfindliche Emulsion nach Anspruch 1 oder 2, in der die Basisebene von kubisch-kristallographischer Form ist.
  4. Strahlungsempfindliche Emulsion nach Anspruch 1 oder 2, in der die Basisebene von oktaedrisch-kristallographischer Form ist.
  5. Strahlungsempfindliche Emulsion nach einem der Ansprüche 1 bis 4, in der Silberhalogenid benachbart zu der Basisebene, unterhalb der Basisebene und in den Vorsprüngen im wesentlichen aus Silberbromid besteht, das gegebenenfalls eine untergeordnete Menge an Iodid enthalten kann.
  6. Strahlungsempfindliche Emulsion nach einem der Ansprüche 1 bis 5, in der tafelförmige Silberhalogenidkörner mit mindestens einer rauhen Hauptkristallfläche und einer Dicke von weniger als 0,2 µm ein durchschnittliches Aspektverhältnis von größer als 5:1 haben und mindestens 50 Prozent der gesamten projizierten Fläche sämtlicher Silberhalogenidkörner mit mindestens einer rauhen Hauptkristallfläche ausmachen.
  7. Strahlungsempfindliche Emulsion nach einem der Ansprüche 1 bis 5, in der tafelförmige Silberhalogenidkörner mit mindestens einer rauhen Hauptkristalloberfläche, einer Dicke von weniger als 0,5 µm und einem Durchmesser von mindestens 0,6 µm ein durchschnittliches Aspektverhältnis von größer als 8:1 aufweisen und mindestens 50 Prozent der gesamten projizierten Oberläche sämtlicher Silberhalogenidkörner mit mindestens einer rauhen Hauptkristalloberfläche ausmachen.
  8. Strahlungsempfindliche Emulsion nach einem der Ansprüche 1 bis 7, in dem die Vorsprünge solche einschließen, die in Form von Rippen oder Pyramiden vorliegen.
  9. Strahlungsempfindliche Emulsion nach einem der Ansprüche 1 bis 8, in der die rauhen Oberflächen der Silberhalogenidkörner ein Wachstums-Modifizierungsmittel adsorbiert enthalten.
  10. Strahlungsempfindliche Emulsion nach Anspruch 9, in der das Wachstums-Modifizierungsmittel ausgewählt ist aus: 5-Carbethoxy-4-hydroxy-1,3,3a,7-tetraazainden; 3-Carboxymethyl-5-(2-pyrrolino-1-cyclopenten-1-ylmethylen)rhodanin; Anhydro-5-chloro-9-ethyl-5'-phenyl-3,3'-di-(3-sulfo-propyl)-oxacarbocyaninhydroxid, Triethylaminsalz; Anhydro-9-ethyl-5,5'-diphenyl-3,3'-di-(3-sulfobutyl)-oxacarboxyaninhydroxid, Mononatriumsalz; 5-(3-Ethyl-2-benzothiazolinyliden)-3-β-sulfoethylrhodanin; 4-Hydroxy-6-methyl-1,2,3a,7-tetraazainden; 4-Hydroxy-6-methyl-2-methylthio-1,3,3a,7-tetraazainden; 5-Imino-3-thiourazol; 4-Hydroxy-6-methyl-1,3,3a,7-tetraazainden; 3-Carboxymethyl-5-{[3-(3-sulfopropyl)-2-thiazolidinyliden]ethyliden}rhodanin, Natriumsalz; 2-Mercaptoimidazol; oder Anhydro-3,9-diethyl-5,5', 6'-trimethoxy-3'-(3-sulfopropyl)thiacarbocyaninhydroxid.
  11. Strahlungsempfindliche Emulsion nach einem der Ansprüche 8 bis 10, in der die pyramidalen Vorsprünge einen Oberflächenbereich aufweisen, der um mindestens 100 Prozent größer ist als ihre Basisfläche.
  12. Strahlungsempfindliche Emulsion nach einem der Ansprüche 8 bis 11, in der mindestens ein Teil der Vorsprünge pyramidale Kristallflächen der kristallographischen {hhl}, {hko}, {hll) oder {hkl} Form aufweisen, worin h, k und l in jedem Fall unabhängig voneinander ungleich Zahlen von größer als Null sind, h gleich 5 oder kleiner und größer als l ist und worin k, sofern vorhanden, kleiner als h und größer als l ist.
  13. Strahlungsempfindliche Emulsion nach Anspruch 12, in der mindestens ein Teil der Vorsprünge pyramidale Kristallflächen der icositetraedrischen Form aufweist.
  14. Strahlungsempfindliche Emulsion nach Anspruch 13, in der an den icositetraedrischen pyramidalen Kristallflächen ein Wachstums-Modifizierungsmittel ausgewählt aus 3-Carboxymethyl-5-(2-pyrrolino-1-cyclopenten-1-ylmethylen)-rhodanin; 5-(3-Ethyl-2-benzothiazolinyliden)-3-β-sulfoethylrhodanin; 4-Hydroxy-6-methyl-2-methyl-thio-1,3,3a,7-tetraazainden; oder 2-Mercaptoimidazol adsorbiert vorliegt.
  15. Strahlungsempfindliche Emulsion nach Anspruch 12, in der mindestens ein Teil der Vorsprünge pyramidale Kristallflächen der trisoctaedrischen Form aufweist.
  16. Strahlungsempfindliche Emulsion nach Anspruch 15, in der an den trisoctaedrischen pyramidalen Kristallflächen ein 4-Hydroxy-6-methyl-1,3,3a,7-tetraazainden-Wachstums-Modifizierungsmittel adsorbiert vorliegt.
  17. Strahlungsempfindliche Emulsion nach Anspruch 12, in der mindestens ein Teil der Vorsprünge pyramidale Kristallflächen der rhombischen dodecaedrischen Form aufweist.
  18. Strahlungsempfindliche Emulsion nach Anspruch 17, in der an den rhombischen dodecaedrischen pyramidalen Kristallflächen ein 4-Hydroxy-6-methyl-1,2,3a,7-tetraazainden oder 5-Imino-3-thiourazol adsorbiert vorliegt.
  19. Strahlungsempfindliche Emulsion nach Anspruch 12, in der mindestens ein Teil der Vorsprünge pyramidale Kristallflächen der kubischen Form aufweist.
  20. Strahlungsempfindliche Emulsion nach Anspruch 19, in der ein Wachstums-Modifizierungsmittel an den kubischen pyramidalen Kristallflächen adsorbiert vorliegt, das besteht aus: Anhydro-5-chloro-9-ethyl-5'-phenyl-3,3'-di-(3-sulfopropyl)oxacarbocyaninhydroxid, Triethylaminsalz oder Anhydro-9-ethyl-5,5'-diphenyl-3,3'-di-(3-sulfobutyl)-oxacarbocyaninhydroxid, Mononatriumsalz.
  21. Photographisches Element mit einer Emulsion nach einem der Ansprüche 1 bis 20.
EP19860306797 1985-09-03 1986-09-03 Photographische Silberhalogenidemulsionen mit Kornoberfläche Expired - Lifetime EP0215612B1 (de)

Applications Claiming Priority (6)

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US06/772,271 US4643966A (en) 1985-09-03 1985-09-03 Emulsions and photographic elements containing ruffled silver halide grains
US772271 1985-09-03
US81113285A 1985-12-19 1985-12-19
US81113385A 1985-12-19 1985-12-19
US811132 1985-12-19
US811133 1985-12-19

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IT1189111B (it) * 1986-05-08 1988-01-28 Minnesota Mining & Mfg Elementi radiografici con un ridotto cross-over e ridotta colorazione residua
JP2631720B2 (ja) * 1988-10-31 1997-07-16 コニカ株式会社 ハロゲン化銀結晶粒子及びハロゲン化銀感光材料
JP2767493B2 (ja) * 1990-11-14 1998-06-18 富士写真フイルム株式会社 ハロゲン化銀乳剤

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US4463087A (en) 1982-12-20 1984-07-31 Eastman Kodak Company Controlled site epitaxial sensitization of limited iodide silver halide emulsions

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DE3687808T2 (de) 1993-09-02
EP0215612A2 (de) 1987-03-25
DE3687808D1 (de) 1993-04-01
JPH0812390B2 (ja) 1996-02-07
CA1280312C (en) 1991-02-19
JPS62124552A (ja) 1987-06-05
EP0215612A3 (en) 1988-11-30

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