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EP0699944B1 - Emulsionen aus tafelförmigen Körnern mit verbesserter Empfindlichkeit - Google Patents

Emulsionen aus tafelförmigen Körnern mit verbesserter Empfindlichkeit Download PDF

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Publication number
EP0699944B1
EP0699944B1 EP19950420233 EP95420233A EP0699944B1 EP 0699944 B1 EP0699944 B1 EP 0699944B1 EP 19950420233 EP19950420233 EP 19950420233 EP 95420233 A EP95420233 A EP 95420233A EP 0699944 B1 EP0699944 B1 EP 0699944B1
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Prior art keywords
tabular grains
silver
protrusions
iodide
mole percent
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EP19950420233
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English (en)
French (fr)
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EP0699944A1 (de
Inventor
Richard Lee C/O Eastman Kodak Company Daubendiek
Donald Lee C/O Eastman Kodak Company Black
Joseph Charles C/O Eastman Kodak Company Deaton
Timothy Richard c/o Eastman Kodak Company Gersey
Joseph Charles c/o Eastman Kodak Com. Lighthouse
Myra Toffolon C/O Eastman Kodak Company Olm
Xin C/O Eastman Kodak Company Wen
Robert Don C/O Eastman Kodak Company Wilson
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Eastman Kodak Co
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Eastman Kodak Co
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Priority claimed from US08/296,562 external-priority patent/US5503970A/en
Priority claimed from US08/297,430 external-priority patent/US5503971A/en
Priority claimed from US08/297,195 external-priority patent/US5576168A/en
Priority claimed from US08/359,251 external-priority patent/US5494789A/en
Priority claimed from US08/441,491 external-priority patent/US5573902A/en
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Publication of EP0699944A1 publication Critical patent/EP0699944A1/de
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/0051—Tabular grain emulsions

Definitions

  • the invention relates to silver halide photography. More specifically, the invention relates to improved spectrally sensitized silver halide emulsions.
  • Kofron et al U.S. Patent 4,439,520 ushered in the current era of high performance silver halide photography.
  • Kofron et al disclosed and demonstrated striking photographic advantages for chemically and spectrally sensitized tabular grain emulsions in which tabular grains having a diameter of at least 0.6 ⁇ m and a thickness of less than 0.3 ⁇ m exhibit an average aspect ratio of greater than 8 and account for greater than 50 percent of total grain projected area. In the numerous emulsions demonstrated one or more of these numerical parameters often far exceeded the stated requirements.
  • Kofron et al recognized that the chemically and spectrally sensitized emulsions disclosed in one or more of their various forms would be useful in color photography and in black-and-white photography (including indirect radiography). Spectral sensitizations in all portions of the visible spectrum and at longer wavelengths were addressed as well as orthochromatic and panchromatic spectral sensitizations for black-and-white imaging applications. Kofron et al employed combinations of one or more spectral sensitizing dyes along with middle chalcogen (e.g., sulfur) and/or noble metal (e.g., gold) chemical sensitizations, although still other, conventional sensitizations, such as reduction sensitization were also disclosed.
  • middle chalcogen e.g., sulfur
  • noble metal e.g., gold
  • Maskasky I recognized that a site director, such as iodide ion, an aminoazaindene, or a selected spectral sensitizing dye, adsorbed to the surfaces of host tabular grains was capable of directing silver salt epitaxy to selected sites, typically the edges and/or corners, of the host grains. Depending upon the composition and site of the silver salt epitaxy, significant increases in speed were observed.
  • a site director such as iodide ion, an aminoazaindene, or a selected spectral sensitizing dye
  • Maskasky I recognized that even when chloride is the sole halide run into a tabular grain emulsion during epitaxial deposition, a minor portion of the halide contained in the host tabular grains can migrate to the silver chloride epitaxy.
  • Maskasky I offers as an example the inclusion of minor amounts of bromide ion when silver and chloride ions are being run into a tabular grain emulsion during epitaxial deposition. From the iodide levels contained in the tabular grain emulsions of Maskasky I and the investigations of this invention, reported in the Examples below, it is apparent that the epitaxial depositions of Maskasky I contained only a fraction of a mole percent iodide transferred from the host tabular grains.
  • Nonisomorphic silver salts can be selectively deposited on the edges of silver halide host grains without relying on a supplemental site director.
  • the nonisomorphic silver salts include silver thiocyanate, ⁇ phase silver iodide (which exhibits a hexagonal wurtzite type crystal structure), ⁇ phase silver iodide (which exhibits a zinc blende type crystal structure), silver phosphates (including meta- and pyro-phosphates) and silver carbonate.
  • nonisomorphic silver salts exhibit a face centered cubic crystal structure of the type found in photographic silver halides--i.e., an isomorphic face centered cubic crystal structure of the rock salt type.
  • speed enhancements produced by nonisomorphic silver salt epitaxy have been much smaller than those obtained by comparable isomorphic silver salt epitaxial sensitizations.
  • this invention is directed to an improved radiation-sensitive emulsion comprised of (1) a dispersing medium, (2) silver halide grains including tabular grains (a) having ⁇ 111 ⁇ major faces, (b) containing greater than 70 mole percent bromide and at least 0.25 mole percent iodide, based on silver, (c) accounting for greater than 90 percent of total grain projected area, (d) exhibiting an average equivalent circular diameter of at least 0.7 ⁇ m, (e) having an average thickness in the range of from less than 0.3 ⁇ m to at least 0.07 ⁇ m, and (f) having latent image forming chemical sensitization sites on the surfaces of the tabular grains, and (3) a spectral sensitizing dye adsorbed to the surfaces of the tabular grains, characterized in that the tabular grains contain less than 10 mole percent iodide and the surface chemical sensitization sites include epitaxially deposited silver halide protrusions of a face centered cubic crystal lattice structure of the rock salt type forming epi
  • the invention is directed to an improvement in spectrally sensitized photographic emulsions.
  • the emulsions are specifically contemplated for incorporation in camera speed color photographic films.
  • the emulsions of the invention can be realized by chemically and spectrally sensitizing any conventional tabular grain emulsion in which the tabular grains
  • Tabular grain emulsions satisfying criteria (a) through (e) are, apart from their sensitization, which is the subject of this invention, conventional.
  • the following provide illustrative teachings of tabular grain emulsions satisfying these criteria:
  • the halides are named in their order of ascending concentration.
  • the tabular grains contain at least 0.25 (preferably at least 1.0) mole percent iodide, based on silver.
  • the tabular grains in the emulsions of the invention contain in all instances less than 10 mole percent iodide, preferably less than 6 mole percent iodide, and optimally less than 4 mole percent iodide. It is possible to include minor amounts of chloride ion in the tabular grains.
  • Delton U.S. Patent 5,372,927 discloses tabular grain emulsions containing from 0.4 to 20 mole percent chloride and up to 10 mole percent iodide, based on total silver, with the halide balance being bromide.
  • the tabular grains accounting for at least 90 percent of total grain projected area contain at least 70 mole percent bromide and at least 0.25 mole percent iodide, based on silver. These tabular grains include silver iodobromide, silver iodochlorobromide and silver chloroiodobromide grains. All references to the composition of the tabular grains exclude the silver halide epitaxy.
  • the iodide within the tabular grains can be uniformly or non-uniformly distributed in any conventional manner.
  • the emulsions of Wilgus et al U.S. Patent 4,434,226 and Kofron et al U.S. Patent 4,439,520, cited above illustrate conventional uniform iodide silver iodobromide tabular grain emulsions.
  • the emulsions of Solberg et al U.S. Patent 4,433,048 and Chang et al U.S. Patent 5,314,793, cited above, illustrate specifically preferred non-uniform iodide placements in silver iodobromide tabular grains that increase photographic speed without increasing granularity.
  • the tabular grains of the emulsions of the present invention it is specifically preferred that at least the portions of the tabular grains extending between their ⁇ 111 ⁇ major faces that form an epitaxial junction with silver halide deposited as a chemical sensitizer contain a lower iodide concentration than the silver halide epitaxy. Most preferably the tabular grains contain a lower concentration throughout than the silver halide epitaxy, and, optimally, the tabular grains contain less total iodide that the silver halide epitaxy.
  • the tabular grains in the emulsions of the invention all have ⁇ 111 ⁇ major faces. Such tabular grains typically have triangular or hexagonal major faces.
  • the tabular structure of the grains is attributed to the inclusion of parallel twin planes.
  • the tabular grains of the emulsions of the invention account for greater than 90 percent of total grain projected area.
  • Tabular grain emulsions in which the tabular grains account for greater than 97 percent of total grain projected area are preferred. Most preferably greater than 99 percent (substantially all) of total grain projected area is accounted for by tabular grains.
  • Emulsions of this type are illustrated, for example, by Tsaur et al and Delton, cited above.
  • Providing emulsions in which the tabular grains account for a high percentage of total grain projected area is important to achieving the highest attainable image sharpness levels, particularly in multilayer color photographic films. It is also important to utilizing silver efficiently and to achieving the most favorable speed-granularity relationships.
  • the tabular grains accounting for greater than 90 percent of total grain projected area exhibit an average ECD of at least 0.7 ⁇ m.
  • the advantage to be realized by maintaining the average ECD of at least 0.7 ⁇ m is demonstrated in Tables III and IV of Antoniades et al U.S. Patent 5,250,403.
  • ECD's are occasionally prepared for scientific grain studies, for photographic applications ECD's are conventionally limited to less than 10 ⁇ m and in most instances are less than 5 ⁇ m.
  • An optimum ECD range for moderate to high image structure quality is in the range of from 1 to 4 ⁇ m.
  • the tabular grains accounting for greater than 90 percent of total grain projected area exhibit a mean thickness in the range of from less than 0.3 ⁇ m to 0.07 ⁇ m.
  • Emulsions with greater tabular grain thicknesses are taught by Kofron et al, cited above, to be useful for recording blue exposures, but they are definitely inferior for recording in the minus blue (i.e., green and/or red) portion of the spectrum. Efficient levels of imaging with lower silver requirements can be realized when average tabular grain thicknesses are maintained less than 0.3 ⁇ m and spectral sensitizing dyes are employed.
  • the tabular grains have a minimum mean thickness of at least 0.07 ⁇ m a much wider range of emulsion preparation procedures and conditions are available than are required to produce tabular grain emulsions with mean grain thicknesses of less than 0.07 ⁇ m.
  • Preferred tabular grain emulsions are those in which grain to grain variance is held to low levels. It is preferred that greater than 90 percent of the tabular grains have hexagonal major faces. Preferred tabular grain emulsions exhibit a coefficient of variation (COV) based on ECD of less than 25 percent, most preferably less than 20 percent. COV as herein employed is 100 times the quotient of the standard deviation ( ⁇ ) of ECD divided by mean ECD.
  • Maskasky U.S. Patent 4,713,320 (hereinafter referred to as Maskasky III) teaches to reduce methionine levels by oxidation to less than 30 ⁇ moles, preferably less than 12 ⁇ moles, per gram of gelatin by employing a strong oxidizing agent.
  • the oxidizing agent treatments that Maskasky III employ reduce methionine below detectable limits.
  • agents that have been employed for oxidizing the methionine in gelatino-peptizers include NaOCl, chloramine, potassium monopersulfate, hydrogen peroxide and peroxide releasing compounds, and ozone.
  • Gelatino-peptizers include gelatin--e.g., alkali-treated gelatin (cattle, bone or hide gelatin) or acid-treated gelatin (pigskin gelatin) and gelatin derivatives, e.g., acetylated or phthalated gelatin.
  • dopant refers to a material other than a silver or halide ion contained within the face centered cubic crystal lattice structure of the silver halide forming the tabular grains.
  • any conventional dopant known to be useful in a silver halide face centered cubic crystal lattice structure can be employed.
  • Photographically useful dopants selected from a wide range of periods and groups within the Periodic Table of Elements have been reported. As employed herein, references to periods and groups are based on the Periodic Table of Elements as adopted by the American Chemical Society and published in the Chemical and Engineering News , Feb. 4, 1985, p. 26.
  • Conventional dopants include ions from periods 3 to 7 (most commonly 4 to 6) of the Periodic Table of Elements, such as Fe, Co, Ni, Ru, Rh, Pd, Re, Os, Ir, Pt, Mg, Al, Ca, Sc, Ti, V, Cr, Mn, Cu, Zn, Ga, Ge, As, Se, Sr, Y, Mo, Zr, Nb, Cd, In, Sn, Sb, Ba, La, W, Au, Hg, Tl, Pb, Bi, Ce and U.
  • Periodic Table of Elements such as Fe, Co, Ni, Ru, Rh, Pd, Re, Os, Ir, Pt, Mg, Al, Ca, Sc, Ti, V, Cr, Mn, Cu, Zn, Ga, Ge, As, Se, Sr, Y, Mo, Zr, Nb, Cd, In, Sn, Sb, Ba, La, W, Au, Hg, Tl, Pb, Bi, Ce and U.
  • the dopants can be employed (a) to increase the sensitivity, (b) to reduce high or low intensity reciprocity failure, (c) to increase, decrease or reduce the variation of contrast, (d) to reduce pressure sensitivity, (e) to decrease dye desensitization, (f) to increase stability (including reducing thermal instability), (g) to reduce minimum density, and/or (h) to increase maximum density.
  • any polyvalent metal ion is effective.
  • the following are illustrative of conventional dopants capable of producing one or more of the effects noted above when incorporated in the silver halide epitaxy: B. H. Carroll, "Iridium Sensitization: A Literature Review", Photographic Science and Engineering , Vol. 24, No. 6, Nov./Dec. 1980, pp.
  • Patent 5,134,060 Kawai et al U.S. Patent 5,153,110; Johnson et al U.S. Patent 5,164,292; Asami U.S. Patents 5,166,044 and 5,204,234; Wu U.S. Patent 5,166,045; Yoshida et al U.S. Patent 5,229,263; Bell U.S.
  • coordination ligands such as halo, aquo, cyano, cyanate, fulminate, thiocyanate, selenocyanate, tellurocyanate, nitrosyl, thionitrosyl, azide, oxo, carbonyl and ethylenediamine tetraacetic acid (EDTA) ligands have been disclosed and, in some instances, observed to modify emulsion properties, as illustrated by Grzeskowiak U.S.
  • a dopant to reduce reciproc ity failure.
  • Iridium is a preferred dopant for decreasing reciprocity failure.
  • the teachings of Carroll, Iwaosa et al, Habu et al, Grzeskowiak et al, Kim, Maekawa et al, Johnson et al, Asami, Yoshida et al, Bell, Miyoshi et al, Tashiro and Murakami et al EPO 0 509 674, each cited above, can be applied to the emulsions of the invention merely by incorporating the dopant during silver halide precipitation.
  • the dopants are effective in conventional concentrations, where concentrations are based on the total silver, including both the silver in the tabular grains and the silver in the protrusions.
  • concentrations are based on the total silver, including both the silver in the tabular grains and the silver in the protrusions.
  • shallow electron trap forming dopants are contemplated to be incorporated in concentrations of at least 1 X 10 -6 mole per silver mole up to their solubility limit, typically up to about 5 X 10 -4 mole per silver mole.
  • Preferred concentrations are in the range of from about 10 -5 to 10 -4 mole per silver mole. It is, of course, possible to distribute the dopant so that a portion of it is incorporated in the tabular grains and the remainder is incorporated in the silver halide protrusions.
  • the chemical and spectral sensitizations of this invention improve upon the best chemical and spectral sensitizations disclosed by Maskasky I. That is, in the practice of the present invention tabular grains receive during chemical sensitization epitaxially deposited silver halide forming protrusions at selected sites on the tabular grain surfaces.
  • Maskasky I observed that the double jet addition of silver and chloride ions during epitaxial deposition onto selected sites of silver iodobromide tabular grains produced the highest increases in photographic sensitivities.
  • the silver halide protrusions will in all instances be precipitated to contain at least a 10 percent, preferably at least a 15 percent and optimally at least a 20 percent higher chloride concentration than the host tabular grains. It would be more precise to reference the higher chloride concentration in the silver halide protrusions to the chloride ion concentration in the epitaxial junction forming portions of the tabular grains, but this is not necessary, since the chloride ion concentrations of the tabular grains are contemplated to be substantially uniform (i.e., to be at an average level) or to decline slightly due to iodide displacement in the epitaxial junction regions.
  • the silver chloride containing epitaxy contains at least a 1 mole higher iodide concentration than is present in at least those portions of the tabular grains extending between their ⁇ 111 ⁇ major faces and forming epitaxial junctions with the protrusions.
  • the epitaxially deposited protrusions contain a higher (preferably at least 1 mole percent higher) iodide concentration than the average iodide concentration of the tabular grains. Further, it is possible to achieve superior performance with lower total levels of iodide in the emulsions, which in turn results in higher rates of development.
  • iodide ions are much larger than chloride ions, it is recognized in the art that iodide ions can only be incorporated into the face centered cubic crystal lattice structures formed by silver chloride and/or bromide to a limited extent. This is discussed, for example, in Maskasky U.S. Patents 5,238,804 and 5,288,603 (hereinafter referred to as Maskasky IV and V). Precipitation at ambient pressure, which is universally practiced in the art, limits iodide inclusion in a silver chloride crystal lattice to less than 13 mole percent.
  • introducing silver along with an 84:16 chloride:iodide molar ratio during silver halide epitaxial deposition resulted in an iodide concentration in the resulting epitaxial protrusions of less than 2 mole percent, based on silver in the protrusions.
  • By displacing a portion of the chloride with bromide much higher levels of iodide can be introduced into the protrusions.
  • introducing silver along with a 42:42:16 chloride:bromide:iodide molar ratio during silver halide epitaxial deposited resulted in an iodide concentration in the resulting epitaxial protrusions of 7.1 mole percent, based on silver in the protrusions.
  • Preferred iodide ion concentrations in the protrusions are in the range of from 1 to 15 mole percent (most preferably 2 to 10 mole percent), based on silver in the protrusions.
  • One preferred technique relevant to objective (1) is to introduce the different halide ions during precipitation of the protrusions in the order of descending solubilities of the silver halides that they form. For example, if chloride, bromide and iodide ions are all introduced during precipitation of the protrusions, it is preferred to introduce the chloride ions first, the bromide ions second and the iodide ions last. Because silver iodide is less soluble than silver bromide which is in turn less soluble than silver chloride, the sequential order of halide ion addition preferred gives the chloride ion the best possible opportunity for deposition adjacent the junction.
  • a clear stratification of the protrusions into regions exhibiting higher and lower chloride ion concentrations can in some instances be detected, but may not be detectable in every instance in which the preferred sequential halide addition is employed, since both bromide and iodide ions have the capability of displacing chloride to some extent from already precipitated silver chloride.
  • the elevated iodide concentrations in the protrusions are those that can be accommodated in a face centered cubic crystal lattice structure of the rock salt type--that is, the type of isomorphic crystal lattice structure formed by silver and one or both of chloride and bromide. It is, of course, possible to incorporate limited amounts (generally cited as 10 mole percent or less) of bromide and/or chloride ions into nonisomorphic ⁇ or ⁇ phase silver iodide crystal structures; however, nonisomorphic silver halide epitaxy forms no part of this invention.
  • the structures are too divergent to ascribe similar photographic properties, and nonisomorphic epitaxial protrusions have been demonstrated by Maskasky II to produce much lower levels of sensitization than isomorphic crystal structure silver halide epitaxial protrusions.
  • Maskasky I reports improvements in sensitization by epitaxially depositing silver halide at selected sites on the surfaces of the host tabular grains.
  • Maskasky I attributes the speed increases observed to restricting silver halide epitaxy deposition to a small fraction of the host tabular grain surface area.
  • silver halide epitaxy it is contemplated to restrict silver halide epitaxy to those portions nearest peripheral edges of and accounting for less than 50 percent of the ⁇ 111 ⁇ major faces of the tabular grains and, preferably, to a much smaller percent of the ⁇ 111 ⁇ major faces of the tabular grains, preferably less than 25 percent, most preferably less than 10 percent, and optimally less than 5 percent of the ⁇ 111 ⁇ major faces of the host tabular grains. It is preferred to restrict the silver halide epitaxy to those portions of the tabular grains that are formed by the laterally displaced regions, which typically includes the edges and corners of the tabular grains.
  • silver halide epitaxy As low as 0.05 mole percent, based on total silver, where total silver includes that in the host and epitaxy, are effective in the practice of the invention. It is preferred that the silver halide epitaxy be limited to less than 50 percent of total silver. Generally silver halide epitaxy concentrations of from 0.3 to 25 mole percent are preferred, with concentrations of from about 0.5 to 15 mole percent being generally optimum for sensitization.
  • Maskasky I teaches various techniques for restricting the surface area coverage of the host tabular grains by silver halide epitaxy that can be applied in forming the emulsions of this invention.
  • Maskasky I teaches employing spectral sensitizing dyes that are in their aggregated form of adsorption to the tabular grain surfaces capable of direct silver halide epitaxy to the edges or corners of the tabular grains.
  • Cyanine dyes that are adsorbed to host tabular grain surfaces in their J-aggregated form constitute a specifically preferred class of site directors.
  • Maskasky I also teaches to employ non-dye adsorbed site directors, such as aminoazaindenes (e.g., adenine) to direct epitaxy to the edges or corners of the tabular grains.
  • Maskasky I relies on overall iodide levels within the host tabular grains of at least 8 mole percent to direct epitaxy to the edges or corners of the tabular grains. In yet another form Maskasky I adsorbs low levels of iodide to the surfaces of the host tabular grains to direct epitaxy to the edges and/or corners of the grains.
  • the above site directing techniques are mutually compatible and are in specifically preferred forms of the invention employed in combination.
  • iodide in the host grains can nevertheless work with adsorbed surface site director(s) (e.g., spectral sensitizing dye and/or adsorbed iodide) in siting the epitaxy.
  • adsorbed surface site director(s) e.g., spectral sensitizing dye and/or adsorbed iodide
  • the dopants described above in connection with the tabular grains can alternatively be wholly or partly located in the silver halide epitaxy.
  • Silver halide epitaxy can by itself increase photographic speeds to levels comparable to those produced by substantially optimum chemical sensitization with sulfur and/or gold. Additional increases in photographic speed can be realized when the tabular grains with the silver halide epitaxy deposited thereon are additionally chemically sensitized with conventional middle chalcogen (i.e., sulfur, selenium or tellurium) sensitizers or noble metal (e.g., gold) sensitizers.
  • middle chalcogen i.e., sulfur, selenium or tellurium
  • noble metal e.g., gold
  • a specifically preferred approach to silver halide epitaxy sensitization employs a combination of sulfur containing ripening agents in combination with middle chalcogen (typically sulfur) and noble metal (typically gold) chemical sensitizers.
  • Contemplated sulfur containing ripening agents include thioethers, such as the thioethers illustrated by McBride U.S. Patent 3,271,157, Jones U.S. Patent 3,574,628 and Rosencrants et al U.S. Patent 3,737,313.
  • Preferred sulfur containing ripening agents are thiocyanates, illustrated by Nietz et al U.S. Patent 2,222,264, Lowe et al U.S. Patent 2,448,534 and Illingsworth U.S.
  • a preferred class of middle chalcogen sensitizers are tetra-substituted middle chalcogen ureas of the type disclosed by Herz et al U.S. Patents 4,749,646 and 4,810,626.
  • Preferred compounds include those represented by the formula: wherein
  • X is preferably sulfur and A 1 R 1 to A 4 R 4 are preferably methyl or carboxymethyl, where the carboxy group can be in the acid or salt form.
  • a specifically preferred tetra-substituted thiourea sensitizer is 1,3-dicarboxymethyl-1,3-dimethylthiourea.
  • Preferred gold sensitizers are the gold(I) compounds disclosed by Deaton U.S. Patent 5,049,485. These compounds include those represented by the formula: (VI) AuL 2 + X - or AuL(L 1 ) + X - wherein
  • Kofron et al discloses advantages for "dye in the finish" sensitizations, which are those that introduce the spectral sensitizing dye into the emulsion prior to the heating step (finish) that results in chemical sensitization.
  • Dye in the finish sensitizations are particularly advantageous in the practice of the present invention where spectral sensitizing dye is adsorbed to the surfaces of the tabular grains to act as a site director for silver halide epitaxial deposition.
  • Maskasky I teaches the use of J-aggregating spectral sensitizing dyes, particularly green and red absorbing cyanine dyes, as site directors. These dyes are present in the emulsion prior to the chemical sensitizing finishing step.
  • spectral sensitizing dyes When the spectral sensitizing dye present in the finish is not relied upon as a site director for the silver halide epitaxy, a much broader range of spectral sensitizing dyes is available.
  • the selection of J-aggregating blue absorbing spectral sensitizing dyes for use as site directors is specifically contemplated.
  • a general summary of useful spectral sensitizing dyes is provided by Research Disclosure, Item 36544, Section V. Spectral sensitization and desensitization, A. Sensitizing dyes.
  • the spectral sensitizing dye can act also as a site director and/or can be present during the finish, the only required function that a spectral sensitizing dye must perform in the emulsions of the invention is to increase the sensitivity of the emulsion to at least one region of the spectrum.
  • the spectral sensitizing dye can, if desired, be added to an tabular grain according to the invention after chemical sensitization has been completed.
  • the emulsions of this invention and their preparation can take any desired conventional form.
  • a novel emulsion satisfying the requirements of the invention has been prepared, it can be blended with one or more other novel emulsions according to this invention or with any other conventional emulsion.
  • Conventional emulsion blending is illustrated in Research Disclosure, Item 36544, Section I, E. Blends, layers and performance categories.
  • the emulsions once formed can be further prepared for photographic use by any convenient conventional technique. Additional conventional features are illustrated by Research Disclosure Item 36544, cited above, Section II, Vehicles, vehicle extenders, vehicle-like addenda and vehicle related addenda; Section III, Emulsion washing; Section V, Spectral sensitization and desensitization; Section VI, UV dyes/optical brighteners/luminescent dyes; Section VII, Antifoggants and stabilizers; Section VIII, Absorbing and scattering materials; Section IX, Coating physical property modifying addenda; Section X, Dye image formers and modifiers. The features of Sections VI, VIII, IX and X can alternatively be provided in other photographic element layers.
  • novel epitaxial silver halide sensitized tabular grain emulsions of this invention can be employed in any otherwise conventional photographic element.
  • the emulsions can, for example, be included in a photographic element with one or more silver halide emulsion layers.
  • a novel emulsion according to the invention can be present in a single emulsion layer of a photographic element intended to form either silver or dye photographic images for viewing or scanning.
  • the photographic elements can be black-and-white (e.g., silver image forming) photographic elements in which the underlying (first) emulsion layer is orthochromatically or panchromatically sensitized.
  • the photographic elements can be multicolor photographic elements containing blue recording (yellow dye image forming), green recording (magenta dye image forming) and red recording (cyan dye image forming) layer units in any coating sequence.
  • blue recording yellow dye image forming
  • green recording magenta dye image forming
  • red recording cyan dye image forming
  • Photographic speeds are reported as relative log speeds, where a speed difference of 30 log units equals a speed difference of 0.3 log E, where E represents exposure in lux-seconds. Contrast is measured as mid-scale contrast. Halide ion concentrations are reported as mole percent (M%), based on silver.
  • Emulsion A Emulsion A
  • This emulsion was precipitated in a two part process.
  • Part 1 effected the formation of nine moles of a Ag(Br,I) emulsion having mean diameter and thickness values of ca. 1.9 ⁇ m and 0.047 ⁇ m, respectively.
  • a portion of this emulsion was then used as a seed emulsion for further growth in Part 2, during which additionally precipitated silver bromide was deposited mainly on the ⁇ 111 ⁇ major faces of the tabular grains-i.e., thickness rather than lateral growth was fostered in Part 2 of the precipitation.
  • a vessel equipped with a stirrer was charged with 6 L of water containing 3.75 g lime-processed bone gelatin, 4.12 g NaBr, an antifoamant, and sufficient sulfuric acid to adjust pH to 1.8, at 39°C.
  • nucleation which was accomplished by balanced simultaneous, 4 second addition of AgNO 3 and halide (98.5 and 1.5 M% NaBr and KI, respectively) solutions, both at 2.5 M, in sufficient quantity to form 0.01335 mole of silver iodobromide, pBr and pH remained approximately at the values initially set in the reactor solution.
  • the reactor gelatin was quickly oxidized by addition of 128 mg of OxoneTM (2KHSO 5 ⁇ KHSO 4 ⁇ K 2 SO 4 , purchased from Aldrich) in 50 mL of water, and the temperature was raised to 54°C in 9 min. After the reactor and its contents were held at this temperature for 9 min, 100 g of oxidized methionine lime-processed bone gelatin dissolved in 1.5 L H 2 O at 54°C were added to the reactor. Next the pH was raised to 5.90, and 43.75 mL of 2.8 M NaBr were added to the reactor.
  • OxoneTM 2KHSO 5 ⁇ KHSO 4 ⁇ K 2 SO 4
  • Step 1 Six moles of the emulsion formed in Step 1 were removed, and additional growth was carried out on the 3 moles which were retained in the reactor and which served as seed crystals for further thickness growth. Before initiating this additional growth, 34 grams of oxidized, lime-processed bone gelatin, dissolved in 500 mL water at 54°C, were added and the reactor pBr was adjusted to ca. 2.05 by slow addition of AgNO 3 . Next, growth was begun using double jet addition of 3.0 M AgNO 3 and 5.0 M NaBr with relative rates such that the reactor pBr was further adjusted to 3.3 over the next 10 min.
  • the final overall composition of the resulting silver iodobromide tabular grain emulsion was ca. 98.97 M% Br and 1.03 M% I.
  • pBr was lowered to ca. 2
  • the emulsion was coagulation washed.
  • pH and pBr were adjusted to 6.0 and 3.1, respectively, prior to storage.
  • the resulting emulsion was examined by scanning electron microscopy (SEM) and mean grain area was determined from the resulting grain pictures using a Summagraphics SummaSketch Plus sizing tablet that was interfaced to an IBM Personal Computer: More than 98% of total grain projected area were provided by tabular crystals.
  • the mean ECD of the tabular grain emulsion was actually reduced from its value at the end of Part 1.
  • the grain thickness was determined using a dye adsorption technique: The level of 1,1'-diethyl-2,2'-cyanine dye required for saturation coverage was determined, and the equation for surface area was solved assuming the solution extinction coefficient of this dye to be 77,300 L/mole cm and its site area per molecule to be 0.566 nm 2 . This approach gave a mean grain thickness of 0.175 ⁇ m.
  • Samples of the emulsion were next sensitized with silver salt epitaxy being present, with the nominal epitaxy cmposition being silver chloride, silver iodochloride or silver iodobromochloride.
  • Emulsion A A 0.5 mole sample of Emulsion A was melted at 40°C and its pBr was adjusted to ca. 4 with a simultaneous addition of AgNO 3 and KI solutions in a ratio such that the small amount of silver halide precipitated during this adjustment was 12% I.
  • This procedure produced epitaxial growths mainly on the corners and edges of the host tabular grains.
  • the epitaxy amounted to 6 M% of the silver in the starting tabular grain emulsion.
  • the nominal composition of the tabular grain host--that is, the halide added to form the host grains, and the actual composition of the host grains are set out in Table I.
  • the nominal composition of the epitaxy and the actual composition of the epitaxy are set out in Table II.
  • the epitaxial sensitization procedure employed for the Epitaxial Control was repeated, except that CaCl 2 , AgI (Lippmann) and AgNO 3 were added in that order.
  • the total amount of silver added was maintained at 6 M%, based on tabular grain silver.
  • the nominal composition of the tabular grain host and the actual composition of the host grains are set out in Table I.
  • the proportions of the chloride and iodide epitaxy are set out in Table II as nominal (added) and actual (found) AgCl and AgI compositions.
  • Example 2 The epitaxial sensitization procedure of Example 1 was repeated, except that CaCl 2 , NaBr, AgI (Lippmann) and AgNO 3 were added in that order. Thus, chloride, bromide and iodide were added in sequence. The total amount of silver precipitated was maintained at 6 M% of the tabular grain silver.
  • the nominal composition of the tabular grain host and the actual composition of the host grains are set out in Table I.
  • the proportions of the chloride, bromide and iodide in the epitaxy are set out in Table II as nominal and actual AgCl, AgBr and AgI compositions.
  • Analytical electron microscopy (AEM) techniques were employed to determine the actual as opposed to nominal (input) compositions of the silver halide epitaxial protrusions.
  • the general procedure for AEM is described by J. I. Goldstein and D. B. Williams, X-ray Analysis in the TEM/STEM", Scanning Electron Microscopy/1977; Vol. 1, IIT Research Institute, March 1977, p. 651.
  • the composition of an individual epitaxial protrusion was determined by focusing an electron beam to a size small enough to irradiate only the protrusion being examined.
  • the selective location of the epitaxial protrusions at the corners and edges of the host tabular grains facilitated addressing only the epitaxial protrusions.
  • the minimum AEM detection limit was a halide concentration of 0.5 M %.
  • the epitaxially sensitized emulsions were each divided into smaller portions to determine optimal levels of subsequently added sensitizing components and to test effects of level variations. To these portions were added additional portions of Dyes 1 and 2, 60 mg NaSCN/mole Ag, sulfur Sensitizer 1, gold Sensitizer 2, and 11.44 mg 1-(3-acetamidophenyl)-5-mercaptotetrazole (APMT)/mole Ag. After all components were added the mixture was heated to 50°C to complete the sensitization, and after cool-down, 114.4 mg additional APMT was added.
  • Dyes 1 and 2 60 mg NaSCN/mole Ag
  • sulfur Sensitizer 1 sulfur Sensitizer 1
  • gold Sensitizer 2 gold Sensitizer 2
  • APMT 1-(3-acetamidophenyl)-5-mercaptotetrazole
  • Example 1 and Example 2 emulsions Based on photographic element constructions and sensitometric evaluations identical to those reported below using portions of the emulsions, the optimum levels of Dyes 1 and 2 in each of the Control, Example 1 and Example 2 emulsions were determined to be 87.7 and 358.7 mg/mole Ag, respectively. Optimum levels of Sensitizers 1 and 2 in mg/mole Ag were determined to be 3.1 and 0.9 (Control), 1.5 and 0.9 (Example 1) and 2.7 and 0.8 (Example 2), respectively.
  • the resulting optimally sensitized emulsions were coated on a cellulose acetate film support over a gray silver antihalation layer, and the emulsion layer was overcoated with a 4.3 g/m 2 gelatin layer containing surfactant and 1.75 percent by weight, based on total weight of gelatin, of bis(vinylsulfonyl)methane hardener.
  • Emulsion laydown was 0.646 g Ag/m 2 and this layer also contained 0.323 g/m 2 and 0.019 g/m 2 of Couplers 1 and 2, respectively, 10.5 mg/m 2 of 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene (Na + salt), and 14.4 mg/m 2 2-(2-octadecyl)-5-sulfohydroquinone (Na + salt), surfactant and a total of 1.08 g gelatin/m 2 .
  • Couplers 1 and 2 respectively, 10.5 mg/m 2 of 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene (Na + salt), and 14.4 mg/m 2 2-(2-octadecyl)-5-sulfohydroquinone (Na + salt), surfactant and a total of 1.08 g gelatin/m 2 .
  • the emulsions so coated were given 0.01 sec Wratten 23A TM filtered (wavelengths >560 nm transmitted) daylight balanced light exposures through a calibrated neutral step tablet, and then were developed using the color negative Kodak FlexicolorTM C41 process. Speed was measured at a density of 0.15 above minimum density.
  • Granularity measurements were made according to the procedures described in the SPSE Handbook of Photographic Science and Engineering, W. Thomas, Ed., pp. 934-939.
  • the minimum of this gamma-normalized granularity allows a comparison of coatings having differing contrast. Lower values indicate lower granularity.
  • Granularity readings reported were averages of observations from four adjacent exposure steps near the speed point and extending to higher exposure levels. These four readings were typically near the minimum granularity.
  • Example 2 emulsion having the higher iodide level in the epitaxial protrusions, was superior to the Example 1 emulsion.
  • Control 2 and Example 3 Two emulsions, Control 2 and Example 3, were prepared with epitaxial depositions undertaken as described for Control and Example 2, respectively.
  • Optimum levels of Dyes 1 and 2 were 132.4 and 542.8 mg/mole Ag, respectively, for Control 2 and 145.6 and 597 mg/mole Ag, respectively, for Example 3.
  • Optimum levels of Sensitizers 1 and 2 were 2.4 and 0.97, respectively, for Control 2 and 2.7 and 1.08, respectively, for Example 3.

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Claims (10)

  1. Strahlungsempfindliche Emulsion, mit
    (1) einem dispergierenden Medium sowie
    (2) Silberhalogenidkörnern in Form tafelförmiger Körner, die
    (a) {111} größere Flächen umfassen,
    (b) einen Bromidgehalt aufweisen von mehr als 70 Molprozent, bezogen auf Silber,
    (c) mehr als 90 Prozent der projizierten Gesamtfläche der Körner ausmachen,
    (d) einen mittleren äquivalenten Kreisdurchmesser von mindestens 0,7 um haben,
    (e) eine mittlere Dicke im Bereich von weniger als 0,3 um bis mindestens 0,07 um aufweisen, und
    (f) auf den Oberflächen der tafelförmigen Körner ein latentes Bild erzeugende chemische Sensibilisierungsstellen umfassen, und mit
    (3) einem Farbstoff für die spektrale Sensibilisierung, adsorbiert auf der Oberfläche der tafelförmigen Körner,
    dadurch gekennzeichnet, dass die tafelförmigen Körner weniger als 10 Molprozent lodid aufweisen und die an der Oberfläche befindlichen Stellen der chemischen Sensibilisierung epitaxial abgeschiedene Silberhalogenid-Vorsprünge kubisch-flächenzentrierter Kristallstruktur vom Steinsalztyp aufweisen, die mit den tafelförmigen Körnern epitaxial verbunden sind, wobei die Vorsprünge
    (a) auf jene Bereiche der tafelförmigen Körner beschränkt sind, die sich am nächsten zu peripheren Kanten befinden und weniger als 50 Prozent der {111} größeren Flächen der tafelförmigen Körner bilden,
    (b) eine Silberchloridkonzentration aufweisen, die mindestens 10 Molprozent höher ist als die der tafelförmigen Körner, und
    c) mindestens 1 Molprozent lodid, bezogen auf das in den Vorsprüngen enthaltene Silber, umfassen.
  2. Emulsion nach Anspruch 1, dadurch gekennzeichnet, dass die Vorsprünge eine höhere lodidkonzentration aufweisen als die Bereiche der tafelförmigen Körner, die mit den Vorsprüngen epitaxial verbunden sind.
  3. Emulsion nach Anspruch 2, dadurch gekennzeichnet, dass die tafelförmigen Körner weniger als 4 Molprozent lodid aufweisen.
  4. Emulsion nach Anspruch 1 - 3, dadurch gekennzeichnet, dass die Vorsprünge 1 bis 15 Molprozent lodid aufweisen.
  5. Emulsion nach Anspruch 4, dadurch gekennzeichnet, dass die Vorsprünge 2 bis 10 Molprozent lodid aufweisen.
  6. Emulsion nach Anspruch 1 - 5, dadurch gekennzeichnet, dass die Vorsprünge eine um mindestens 15 Molprozent höhere Chloridionen-Konzentration aufweisen als die tafelförmigen Körner.
  7. Emulsion nach Anspruch 1 - 6, dadurch gekennzeichnet, dass die Vorsprünge 0,3 bis 25 % des Gesamtsilbers ausmachen.
  8. Emulsion nach Anspruch 1 - 7, dadurch gekennzeichnet, dass die epitaxial abgeschiedenen Silberhalogenid-Vorsprünge auf weniger als 25 Prozent der Oberflächen der tafelförmigen Körner vorgesehen sind.
  9. Emulsion nach Anspruch 8, dadurch gekennzeichnet, dass die epitaxial abgeschiedenen Silberhalogenidvorsprünge vorwiegend an mindestens eine der Kanten und Ecken der tafelförmigen Körner angrenzen.
  10. Emulsion nach Anspruch 1 bis 9, dadurch gekennzeichnet, dass die tafelförmigen Körner mehr als 97 Prozent der projizierten Gesamtfläche der Körner ausmachen.
EP19950420233 1994-08-26 1995-08-21 Emulsionen aus tafelförmigen Körnern mit verbesserter Empfindlichkeit Expired - Lifetime EP0699944B1 (de)

Applications Claiming Priority (10)

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US297430 1994-08-26
US08/296,562 US5503970A (en) 1994-08-26 1994-08-26 Ultrathin tabular grain emulsions with novel dopant management
US296562 1994-08-26
US297195 1994-08-26
US08/297,430 US5503971A (en) 1994-08-26 1994-08-26 Ultrathin tabular grain emulsions containing speed-granularity enhancements
US08/297,195 US5576168A (en) 1994-08-26 1994-08-26 Ultrathin tabular grain emulsions with sensitization enhancements
US08/359,251 US5494789A (en) 1994-08-26 1994-12-19 Epitaxially sensitized ultrathin tabular grain emulsions
US359251 1994-12-19
US441491 1995-05-15
US08/441,491 US5573902A (en) 1995-05-15 1995-05-15 Tabular grain emulsions with sensitization enhancements

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JPH05281638A (ja) 1992-04-03 1993-10-29 Konica Corp ハロゲン化銀写真用乳剤の製造方法及び、それを用いたハロゲン化銀写真感光材料
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US5300413A (en) 1992-11-27 1994-04-05 Eastman Kodak Company Photoelectric elements for producing spectral image records retrievable by scanning
US5252451A (en) 1993-01-12 1993-10-12 Eastman Kodak Company Photographic emulsions containing internally and externally modified silver halide grains
US5360712A (en) 1993-07-13 1994-11-01 Eastman Kodak Company Internally doped silver halide emulsions and processes for their preparation
US5358840A (en) 1993-07-22 1994-10-25 Eastman Kodak Company Tabular grain silver iodobromide emulsion of improved sensitivity and process for its preparation
US5372927A (en) 1993-10-21 1994-12-13 Eastman Kodak Company Process for the low pag preparation of high aspect ratio tabular grain emulsions with reduced grain thicknesses

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DE69517372T2 (de) 2001-02-15
EP0699944A1 (de) 1996-03-06
JPH08171164A (ja) 1996-07-02
DE69517372D1 (de) 2000-07-13

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