EP0486629B1 - Fotografische filme enthaltend silberhalogenidkörner mit geringen zwillingsebenenabständen - Google Patents

Fotografische filme enthaltend silberhalogenidkörner mit geringen zwillingsebenenabständen Download PDF

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EP0486629B1
EP0486629B1 EP91909166A EP91909166A EP0486629B1 EP 0486629 B1 EP0486629 B1 EP 0486629B1 EP 91909166 A EP91909166 A EP 91909166A EP 91909166 A EP91909166 A EP 91909166A EP 0486629 B1 EP0486629 B1 EP 0486629B1
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micrometer
tabular
emulsion
grains
grain
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EP0486629A1 (de
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Donald Lee C/O Eastman Kodak Company Black
Robert Don C/O Eastman Kodak Company Wilson
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Eastman Kodak Co
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/0051—Tabular grain emulsions
    • 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
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/10—Organic substances
    • G03C1/12—Methine and polymethine dyes
    • G03C1/14—Methine and polymethine dyes with an odd number of CH groups
    • G03C1/18—Methine and polymethine dyes with an odd number of CH groups with three CH groups

Definitions

  • This invention relates to silver halide grains having small spacing between twin-plane separations.
  • it relates to silver halide emulsions containing such grains and methods of their formation.
  • U.S. Patent 4,439,520 - Kofron et al, and U.S. Patent 4,433,048 - Solberg et al disclose that high aspect ratio silver halide emulsions provide improvements in photographic materials over those having low aspect ratios. These materials when chemically sensitized have been shown to provide improved products with improved sharpness and grain.
  • U.S. Patent 4,672,027 - Daubendiek et al and U.S. Patent 4,693,964 - Daubendiek et al disclose that silver halide grains of a high aspect ratio but very small mean diameter may be formed with enhancement of speed granularity relationships. The materials of Daubendiek et al are very thin.
  • European Patent Application 0,273,411-Makino et al discloses silver halide emulsions in which the grains have a mean aspect ratio of not more than 8.0 and a diameter of at least 0.15 ⁇ m.
  • the emulsion materials of Makino et al further form tabular grains in which the ratio of the thickness (b) of the tabular grain to the longest spacing (a) between two or more parallel twinning planes of the tabular grain is at least 5.
  • An object of the invention is to provide improved photographic elements.
  • Another object of the invention is to provide silver halide grains having an improved sensitivity/granularity relationship.
  • a tabular-grain silver halide emulsion in which at least 50 percent of the total grain projected area is accounted for by tabular grains having a mean diameter of at least 0.6 micrometer and a spacing between at least two parallel twin planes of less than 0.012 micrometer.
  • at least 90 percent of the total grain projected area is accounted for by the tabular grains of the invention having a mean diameter of at least 0.6 micrometer and a mean spacing between at least two parallel twin planes of less than 0.012 micrometer.
  • the grains used in the invention provide an increase in speed without an increase in granularity as the grains of the invention are of higher speed than previous silver halide grains of the same size.
  • the invention in particular concerns a photographic element as defined in Claims 1-10.
  • the invention moreover, concerns a process for the preparation of silver halide grains to be utilized in the photographic element according to the invention this process being defined in Claims 11 and 12.
  • the invention has advantages over prior practices in that, while it was known that the growth in tabular grains involved a parallel twin-plane mechanism, it was not known that, by control of the twin-plane separation, the photographic performance of the emulsion containing the grain could be controlled and improved.
  • the grains of the invention having the same equivalent diameter and thickness as prior-art grains, exhibit higher sensitivity and lower granularity as a result of decreasing the separation between the parallel twin planes to less than that of the prior art grains.
  • the grains used in the invention surprisingly provide an increase in speed of films formed of a particular grain projected size without also causing an increase in granularity.
  • the tabular grains used in the invention and forming greater than at least 50 percent of the total grain projected area of the emulsions of the invention have a diameter of at least 0.6 micrometer. Suitable grain size has been found to be up to about 10 microns. A preferred grain size has been found to be a diameter of between 0.6 and 5 micrometer because of speed granularity advantage. The suitable thickness of the grains of at least 0.6 micrometer diameter has been found to be between 0.05 and 0.5 micrometer.
  • the parallel twin plane necessary for the growth of tabular grains can be directly observed using cross-sectioning techniques at cryogenic temperatures to provide samples with the correct crystallographic orientation and thickness for study by electron microscopy. These temperatures are necessary to change the physical properties of the gelatin and silver halide grains to obtain the thin sections necessary for accurate measurements.
  • cross sections are prepared by mounting a sample of a silver halide emulsion coated in a gelatin matrix on a film support in a cryo-ultramicrotome.
  • the sample, knife, and chamber are cooled to approximately -100°C.
  • a cross section less than 0.05 microns thick is cut from the sample by a diamond knife. It is observed in a transmission electron microscope and recorded on an electron micrograph from which the twin plane separation is measured directly. For these studies the twin plane separations from at least 100 grains were measured to obtain the average values.
  • An average parallel twin plane spacing in the tabular grain of up to less than 0.012 micrometer has been found to be suitable for the invention.
  • a parallel twin-plane separation of less than 0.011 micrometer is preferred.
  • a preferred range of spacing between the twin planes has been found to be between less than 0.011 and 0.005 micrometers for highest sensitivity and lowest granularity.
  • the narrow twin-plane grains may be present in any amount comprising at least 50 percent of the total grain projected area.
  • a projected area of at least 70 percent of the total grain projected area has been found to be particularly suitable.
  • a preferred amount has been found to be at least 90 percent of the total projected area of the grains of the emulsion accounted for by tabular grains having a mean diameter of at least 0.6 micrometer and a spacing between at least two parallel twin planes of less than 0.012 micrometer.
  • at least 50 percent of the total grain projected area is accounted for by tabular grains satisfying the relationship ECD/t 2 greater than 25 where ECD is the mean effective circular diameter in micrometers of the tabular grains and t is the mean thickness in micrometers of the tabular grains.
  • any method of forming the grains may be employed .
  • the method of formation is by a twin-jet process.
  • the method of the invention requires a shift in pBr during growth of an emulsion which is nucleated under conditions yielding small twinned nuclei which therefore contain closely spaced twin planes.
  • the formation of tabular silver halide grains is generally carried out in three stages; nucleation, ripening, and growth.
  • the invention requires a shift in the growth environment from a pBr at the beginning of growth of between 1.4 and about 1.9 pBr to between about 3.0 and 3.6 pBr. The change takes place after between 25 and about 80 percent of the total silver is added.
  • Vehicles for the emulsions can be selected from those conventionally employed in photographic silver halide emulsions.
  • Preferred peptizers are hydrophilic colloids which can be used alone or in combination with hydrophobic materials.
  • Useful hydrophilic materials include both naturally occurring substances such as proteins, protein derivatives, cellulose derivatives such as cellulose esters, gelatin such as alkali-treated gelatin or acid-treated gelatin, gelatin derivatives such as acetylated gelatin and phthalated gelatin, polysaccharides such as dextran, gum arabic, zein, casein, pectin, collagen derivatives, agar-agar, arrowroot and albumin and other vehicles and binders known in the photographic art. Gelatin is highly preferred.
  • the silver halide emulsions are preferably washed to remove soluble salts. Any of the processes and compositions known in the photographic art for this purpose are useful for washing the silver halide emulsions of the invention.
  • the soluble salts can be removed by decantation, filtration, and/or chill setting and leaching and coagulation washing, by centrifugation, and by other methods and means known in the photographic art.
  • the photographic silver halide can be chemically sensitized by procedures and with compounds known in the photographic art.
  • the silver halide can be chemically sensitized with active gelatin or with sulfur, selenium, tellurium, gold, platinum, iridium, indium, palladium, osmium, rhodium, rhenium or phosphorous sensitizers or combinations of these sensitizers, such as at pAg levels within the range of 5 to 10 and at pH levels within the range of 5 to 8 at temperatures within the range of 30° to 80°C.
  • the silver halide can be chemically sensitized in the presence of antifoggants, also known as chemical finish modifiers, such as compounds known to suppress fog and increase speed during chemical sensitization, such as azaindenes, azapyridazines, azapyrimidines, benzothiazolium salts, and sensitizers having one or more heterocyclic nuclei.
  • antifoggants also known as chemical finish modifiers, such as compounds known to suppress fog and increase speed during chemical sensitization, such as azaindenes, azapyridazines, azapyrimidines, benzothiazolium salts, and sensitizers having one or more heterocyclic nuclei.
  • antifoggants also known as chemical finish modifiers, such as compounds known to suppress fog and increase speed during chemical sensitization, such as azaindenes, azapyridazines, azapyrimidines, benzothiazolium salts, and sensitizers having one or more heterocyclic
  • the photographic silver halide emulsion can be spectrally sensitized by, for example, dyes of a variety of classes, including the polymethine-dye class, including cyanines, merocyanines, complex cyanines and merocyanines, oxonols, hemioxonols, styryls, merostyryls, and streptocyanines. Combinations of spectral sensitizers are also useful.
  • the photographic silver halide elements can be either single-color (monochrome) or multicolor elements.
  • a cyan dye-forming coupler is typically associated with a red-sensitive emulsion
  • a magenta dye-forming coupler is typically associated with a green-sensitive emulsion
  • a yellow dye-forming coupler is associated with a blue-sensitive emulsion.
  • Multicolor elements typically contain dye-forming units sensitive to each of the three primary regions of the spectrum. Each unit can comprise a single emulsion layer or multiple emulsion layers. The layers of the element and the image-forming units can be arranged in various orders as known in the photographic art. Color photographic reversal materials are preferred for use of the emulsions of this invention.
  • the photographic element can contain added layers such as filter layers, interlayers, overcoat layers, subbing layers, and other layers known in the art.
  • any coupler or combination of couplers known in the photographic art can be used with the silver halide emulsions as described to form color-producing photographic elements.
  • Examples of useful couplers are described in, for example, Research Disclosure Section VII, paragraphs D, E, F, and G and in U.S. Patent 4,433,048 and the publications cited therein.
  • the couplers can be incorporated as described in Research Disclosure Section VII and the publications cited therein.
  • the photographic emulsions and elements can contain addenda known to be useful in the photographic art.
  • the photographic emulsions and elements can contain brighteners (Research Disclosure Section V), antifoggants and stabilizers (Research Disclosure Section VI), antistain agents and image-dye stabilizers (Research Disclosure Section VII, paragraphs I and J), light-absorbing and -scattering materials (Research Disclosure Section VIII) hardeners (Research Disclosure Section XI), plasticizers and lubricants (Research Disclosure Section XII), antistatic agents (Research Disclosure Section XIII), matting agents (Research Disclosure Section XVI), and development modifiers (Research Disclosure Section XXI).
  • the photographic elements can be coated on a variety of supports such as film and paper base, as described in Research Disclosure Section XVII and the references described therein.
  • the photographic elements can be exposed to actinic radiation, typically in the visible region of the spectrum, to form a latent image as described in Research Disclosure Section XVIII and then processed to form a visible image using processes and compositions known in the art, such as described in Research Disclosure Section XIX and U.S. Patent 4,433,048 and the references described therein.
  • Processing of a color photographic element as described to form a visible dye image includes the step of contacting the element with a color photographic silver halide developing agent to reduce developable silver halide and oxidize the color-developing agent.
  • the oxidized color-developing agent in turn reacts with at least one coupler to yield a dye.
  • Preferred color-developing agents are p -phenylenediamines.
  • 4-amino-3-methyl-N,N-diethylaniline hydrochloride 4-amino-3-methyl-N-ethyl-N- ⁇ -(methanesulfonamido)-ethylaniline sulfate hydrate, 4-amino-3-methyl-N-ethyl-N- ⁇ -hydroxyethylaniline sulfate, 4-amino-3- ⁇ -(methanesulfonamido)ethyl-N,N-diethylaniline hydrochloride, and 4-amino-N-ethyl-N-(2-methoxyethyl)- m -toluidine di- p -toluene sulfonic acid.
  • this processing step leads to a negative image.
  • this step can be preceded by development with a nonchromogenic developing agent to develop exposed silver halide but not form dye, and then uniform fogging of the element to render unexposed silver halide developable.
  • the silver halide emulsions of this invention are preferably employed in photographic elements designed to be processed to form a color negative image.
  • the doping of the invention may take place during the growth stage of the silver halide grains.
  • cadmium salts, zinc salts, selenium salts, lead salts, thallium salts, rhodium salts or its complex salts, ion or its complex salts, or the like may be present for various purposes such as, for example, to achieve hard toning, sensitization, desensitization and internal latent-image formation.
  • This example illustrates the preparation of a tabular emulsion with a small twin-plane separation (0.011 microns) according to the present invention. It yields a tabular silver halide grain emulsion of equivalent circular diameter 0.74 micrometers (as measured by sizing scanning electron microscope photos on a SUMMA graphics tablet) and a thickness of 0.116 micrometers. The percent of grains with an aspect ratio greater than 8 was > 95% (number weighted). The halide composition is 96.7% BR- and 3.3% I- (as found by neutron activation analysis) and this is nominally distributed uniformly throughout the grain.
  • the basic precipitation sequence is one of (i) nucleation at a high molar addition rate, low pH, high pBr (2.18), low temperature, and using an oxidized gelatin at a low level. This is followed by (ii) a transition to a higher temperature, higher pH, higher Br- concentration, and higher oxidized gelatin level (without additional AgNO 3 flow). Next follows the (iii) growth stage in which a AgI source of I- is added (at 0.03 molar ratio of the AgNO 3 stream) in a triple jet addition with an aqueous solution of NaBr and a solution of AgNO 3 , and in such a way that the pBr of the reaction vessel is controlled. This procedure is similar to one described in U.S.
  • Aqueous solutions of 8 mL of 1.25 M AgNO 3 and 8 mL of 1.25 M NaBr.99I.01 are added together at 80 mL/min into a vessel containing 3 liters of solution at 35°C which consists of 7.5 g H 2 O 2 -oxidized gelatin, approximately 45 mL of 2 N H 2 SO 4 to adjust the solution pH to 1.8, 0.02 moles NaBr, and 0.7 mL of antifoamant (Nalco 2341), plus distilled water to bring the total volume to 3000 mL.
  • no additional AgNO 3 is added to the vessel, but temperature, gel concentration, pH, and pBr are all adjusted.
  • growth is carried out by double-jet addition of a total of 2.96 liters of 1.2 M AgNO 3 and 1.2 M NaBr, but with a 3rd jet (coupled to the AgNO 3 delivery rate) running in a dilute (0.36 M) emulsion of AgI (ca 0.1 ⁇ m esd grains) for an overall 3m% I- final grain composition.
  • This growth stage is performed at 60°C and with the pBr maintained at 1.9 into; 30% of the total molar amount of Ag (from all sources) has been added. At that point the pBr is shifted up to 3.3 (by temporarily terminating the halide solution delivery) and the remainder of the growth occurs under those conditions.
  • the reactant addition rates are not constant but are linearly increased from 16.5 mL/min to 19.5 mL/min over the first 60 minutes and then are kept at that 19.5 mL/min for the remainder of the precipitation.
  • the final emulsion is washed by ultra-filtration.
  • Sensitization results of this emulsion will follow the description of the comparison tabular grain emulsion.
  • This example illustrates the preparation of a conventional emulsion of the same outward dimensions and iodide composition as that formed in Example 1, but one which will have a larger average twin-plane separation (0.015 microns).
  • the procedure below yields comparably sized grains to Example 1.
  • the number weighted equivalent circular diameter is 0.77 micrometers (via SEM/SUMMA sizing), and the thickness as estimated by an interference reflectance technique is 0.106 micrometers.
  • the measured I-composition is matched (97,1% Br- and 2.9% I- as determined by NAA).
  • This precipitation is an iso-thermal one which employs non-oxidized gelatin and an additional gelatin solution dump (in which the dilution effect also results in a small upward pBr shift).
  • the growth is via double-jet addition of AgNO 3 and mixed halide (97 mol % NaBr and 3 mol % KI) aqueous solutions with pBr controlled at 1.7 during most of the precipitation and then a shift to high pBr (3.3 pBr) at a specified point in the final portion of the growth stage.
  • the specific precipitation parameters follow.
  • Aqueous solutions of 70 mL of 2.5 M AgNO 3 and 70 mL of 2.5 M NaBr are added together at 35 mL/min into a vessel containing 4 liters of solution at 65°C which consists of 12.0 g of non-oxidized non-deionized lime-processed bone gelatin, 0.272 moles NaBr, and 0.7 mL of antifoamant (Nalco 2341), plus D.W. to bring the total volume to 4000 mL.
  • the pH is 5.84 and the 1.4 pBr (at 65°C) during this nucleation.
  • the pBr is shifted up to 3.3 (by temporarily terminating the halide solution delivery) and the remainder of the growth occurs under these conditions using a constant reactant flow rate of 40 mL/minute.
  • the emulsion is washed using ultra-filtration then finally adjusted to 3.4 pBr at 40°C.
  • Equivalent finish positions were chosen based on the fact that the emulsions were of matched average diameter and thickness and hence are nominally equal in molar surface area. Specifically, the following sensitizer reagent levels were used (on a Ag mole basis):
  • the sensitized emulsions were coated in a color format at 25 mg/ft 2 silver, with 60 mg/ft 2 of a magenta dye forming coupler A, 2.0 g/Ag mol of 5-methyl-s-triazole-[2-3-a]-pyrimidine-7-ol-(Na salt), and 200 mg/ft 2 , on a acetate film support having antihalation protection.
  • the coatings also contained an overlying 150 mg/ft 2 gelatin layer.
  • the sensitometric responses of a coating containing the green sensitized emulsion of Example 1 and the equivalent coating of the sensitized emulsion of Example 2, are shown in Figs. 1 and 2 respectively.
  • a 1/50 sec exposure through a Wratten-9 spectral filter was used along with development of 3.5 minutes in the C-41 color process.
  • step 6 The measurements at step 6 (midscale) were then normalized by dividing by the incremental gamma ( ⁇ ) and multiplying by 1000 to obtain gamma normalized granularity ( ⁇ / ⁇ ).
  • ⁇ gamma normalized granularity
  • the ⁇ normalized granularity is obtained by dividing the RMS Granularity by the slope of the H and D curve.
  • One of the rationales for this improved sensitometry may be a lower competition for internal latent image formation (relative to surface image formation) for the emulsion in which the twin plane separation is narrower and hence further removed from the surface.
  • a test of the potential difference in relative amounts of surface image (detectable in a non-solvent developer) to internal image (as revealed by the solvent developer KRX & KI does indeed show a lower internal response for the Example 1 material.
  • This example is a further illustration of the invention and similar to the Example 1. However, changes were made to further enhance the narrowness of the twin-plane separation.
  • the measured mean separation value found by the cryo-ultramicrotomy technique is 0.007 micrometers for the grains generated from the procedure described below.
  • the grains produced in this example are 0.61 micrometers in number-weighted equivalent circular diameter and 0.096 micrometers in overall thickness, both as found by sizing scanning electron micrographs (SEM) on a SUMMA sizing tablet.
  • SEM scanning electron micrographs
  • the iodide composition is nominally 3 mole %-I (except for the small, ca. 1%, nucleation portion which is 6 mole%-I) and it is uniformly distributed.
  • Example 1 The principal points of difference relative to Example 1 are (i) the employment of a constant 60°C temperature instead of the low temperature nucleation of Example 1, (ii) a larger volume solution present at nucleation, and (iii) unmatched molar amounts of AgNO 3 and halide introduced at nucleation. A further change was the requirement of the removal of a certain fraction of the vessel contents during growth simply due to vessel capacity constraints. The specific details are provided in the paragraph below.
  • This growth stage is performed at 60°C and with the pBr maintained at 1.7 until 468 mL of the AgNO 3 solution has been added, after which the halide delivery is interrupted in such a way that the pBr is shifted up to 3.3, and the remainder of the growth is carried out with pBr maintained at this value until the 2.61 liters of 2.3 M AgNO 3 solution initially present is consumed.
  • the remainder of the growth is carried out with pBr maintained at this value until the 2.61 liters of 2.3 M AgNO 2 solution initially present is consumed.
  • This example describes the preparation of a tabular silver halide emulsion that displays the same external thickness and diameter values as those of Example 3 but with a more conventional larger parallel twin-plane separation (measured at a mean value of 0.012 micrometers).
  • the grain size of the ca 3 mole%-I silver bromoiodide emulsion generated in the precipitation detailed below averages 0.68 micrometers in number-weighted equivalent circular diameter and 0.099 micrometers in overall thickness based on measurements of the electron micrographs.
  • a secondary thickness estimate by an interference reflectance technique agrees well at 0.095 micrometers.
  • This emulsion preparation retains generally the same nucleation scheme as used in Example 2. Like Example 2, this precipitation is isothermal, involves a shift to high pBr at a specified point in the final portion of the growth stage, and utilizes non-oxidized gelatin. The details of the precipitation follows.
  • Aqueous solutions of 70 mL of 2.5 M AgNO 3 and 70 mL of 2.5 M NaBr are introduced at the same time at a rate of 35 mL/min into a vessel charged with 4 liters of a solution at 65°C consisting of 12.0 g of non-oxidized non-deionized lime-processed bone gelatin, 0.272 moles NaBr, and 0.7 mL of an antifoamant (Nalco 2341), plus enough distilled water to bring the total volume to 4000 mL.
  • the silver nitrate and halide deliveries are interrupted for 2 minutes during which time a 65°C pre-heated 5 liter aqueous solution containing 140 g additional gelatin is added.
  • sensitized emulsions were coated in the same format as employed previously for Examples 1 & 2 involving 60 mg/ft 2 of a magenta dye forming coupler and 25 mg/ft 2 of silver.
  • This example describes a procedure which gives a final grain dimension of 0.42 micrometers (number-weighted equivalent circular diameter) by 0.06 micrometers in thickness. Both values were measured by sizing SEM micrographs on a graphics pad. The double parallel twin-plane separation was 0.007 micrometers as measured by the sectioning technique described.
  • the halide composition of these tabular grains was the same as in Example 3 - nominally 3 mole percent iodide and 97 mole percent bromide, uniformly distributed in the grain except for a very small (ca. 1% of total silver) portion of 6 mole % I- & 94 mole % Br- reactant addition during nucleation.
  • Example 3 differs from Example 1 mainly in employing (i) a constant 60°C temperature, (ii) a larger volume initial solution at nucleation, and (iii) unmatched halide and AgNO 3 nucleation reactants. This further varies from Example 3 in having a larger volume of nucleation reagents and not requiring removal of a certain fraction of the vessel contents during growth simply due to vessel capacity constraints. More specific details of the precipitation conditions are given in the following paragraph.
  • This growth stage is performed at 60°C and with the pBr maintained at 1.7 until 53% of the total molar amount of Ag (from all sources) has been added.
  • the pBr is then shifted up to 3.3 (by interrupting the halide solution delivery) and the remainder of the growth occurs under these conditions.
  • the reactant addition rates for this growth stage are linearly increased from 33 mL/min to 73 mL/min.
  • the emulsion is washed by ultra-filtration and finally adjusted to 3.4 pBr at 40°C.
  • This example represents the conventional "control" emulsion which shares common external dimensions and iodide content as that formed in Example 5, but the emulsion resulting from the procedure described below will have a larger mean value of twin-plane separation (.012u) than that of Example 5.
  • twin-plane separation (.012u)
  • Example 5 the photographic performance of a narrow twin-plane separation case (Example 5) is not improved over this wide twin-plane separation version as judged by the sensitization and sensitometric responses given in the section following the preparation paragraph.
  • Example 2 The procedure given here will yield a nominally uniformly distributed 3 mole%-I silver bromoiodide grain (neglecting a small pure AgBr nucleation portion) with final dimensions of 0.40 micrometers (number-weighted equivalent circular diameter) by 0.060 micrometers in thickness as determined by sizing SEM micrographics using a SUMMA graphics tablet.
  • This precipitation is patterned after Example 2 being (i) high-temperature in nucleation, involving a gelatin solution dump but not using oxidized gelatin and undergoing a late-stage shift to high pBr for final growth.
  • the specific conditions are supplied below.
  • the reaction vessel is charged with 4 liters of solution which contains 12.0 g of non-oxidized non-deionized lime-processed bone gelatin, 0.272 moles NaBr, 0.7 mL of antifoamant (Nalco 2341), and D.W. to bring the total volume to 4000 mL.
  • This solution is heated to 65°C and by double-jet addition, aqueous solutions of 70 mL of 2.5 M AgNO 3 and 70 mL of NaBr are added together at 35 mL/minute.
  • the pH is 5.80 and the pBr equals 1.3 (at 65°C) at the start of this nucleation.
  • the pBr is shifted up to 2.3 (by temporarily stopping the halide solution delivery) and the rest of the growth occurs under these conditions and using a constant reactant flow rate of 30 mL/minute.
  • the emulsion is washed by ultrafiltration and then adjusted to 3.4 at 40°C.
  • sensitized emulsions were coated in the same color negative film format as described previously for Examples 1 & 2 involving 25 mg/ft 2 silver and 60 mg/ft 2 of magenta coupler A.
  • the sensitometric responses of a ctg containing the green sensitized emulsion of Example 5 and the equivalent ctg of the sensitized emulsion of Example 6 are shown in Fig. 6.
  • a 1/50 sec exposure through a Wratten-9 spectral filter was used along with development of 3.5 minutes in the C-41 color process.
  • Table 1 below is a comparison of the Examples and clearly shows that for the invention the small twin plane separation (up to .012 microns) and large size (ECD greater than .6) produces improved results.
  • Table 1 Example ECD (Micron) Thickness (Microns) (Microns) TP Separation Photography Response 1 0.76 0.11 0.011 Ex. 1 better speed/Grain 2 0.76 (control) 0.11 0.015 Response than Example 2 3 0.67 0.12 0.007
  • Example 3 has better speed at same grain as Example 4 4 0.68 (control) 0.10 0.012 5 0.42 (control) 0.06 0.007 Shows small grain size & small TP Separation not an advantage 6 0.40 (control) 0.06 0.012 Shows small grain size & wide TP no advantage

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Claims (12)

  1. Photographisches Element mit einem Filmträger und einer auf den Träger aufgetragenen Silberbromoiodidemulsion mit tafelförmigen Körnern, in der mindestens 50 % der gesamten projizierten Kornfläche auf tafelförmige Silberbromoiodidkörner entfallen, die weniger als 10 Mol-% Iodid, bezogen auf das Gesamthalogenid enthalten, mit einem mittleren Durchmesser von mindestens 0,5 Mikrometern und einem Abstand zwischen mindestens zwei parallelen Zwillingsebenen von weniger als 0,012 Mikrometern.
  2. Photographisches Element nach Anspruch 1, in dem in der Emulsion mit den tafelförmigen Körnern mindestens 70 % der gesamten projizierten Kornfläche auf tafelförmige Körner entfallen, die einen mittleren Durchmesser von mindestens 0,6 Mikrometern und einen Abstand zwischen mindestens zwei parallelen Zwillingsebenen von weniger als 0,012 Mikrometern haben.
  3. Photographisches Element nach Anspruch 1, in dem in der Emulsion mit den tafelförmigen Körnern mindestens 90 % der gesamten projizierten Kornfläche auf tafelförmige Körner entfallen, die einen mittleren Durchmesser von mindestens 0,6 Mikrometern und einen Abstand zwischen mindestens zwei parallelen Zwillingsebenen von weniger als 0,012 Mikrometern haben.
  4. Photographisches Element nach Anspruch 1, in dem in der Emulsion mit den tafelförmigen Körnern der Abstand zwischen Zwillingsebenen kleiner als 0,011 Mikrometer ist.
  5. Photographisches Element nach Anspruch 1, in dem in der Emulsion mit den tafelförmigen Körnern mindestens 50 % der gesamten projizierten Kornfläche auf tafelförmige Körner entfallen, die einen mittleren Durchmesser im Bereich von 1,0 bis 10,0 Mikrometern haben.
  6. Photographisches Element nach Anspruch 1, in dem in der Emulsion mit den tafelförmigen Körnern mehr als 50 % der gesamten projizierten Kornfläche auf tafelförmige Körner entfallen, die der Beziehung genügen: ECD/t 2 > 25
    Figure imgb0006
     worin
    ECD der mittlere effektive kreisförmige Durchmesser in Mikrometern der tafelförmigen Körner ist und
    t die mittlere Dicke in Mikrometern der tafelförmigen Körner darstellt.
  7. Photographisches Element nach Anspruch 1, in dem in der Emulsion mit den tafelförmigen Körnern mehr als 50 % der gesamten projizierten Kornfläche auf tafelförmige Körner entfallen, die der Beziehung genügen: ECD/t 2 > 40
    Figure imgb0007
     worin
    ECD der mittlere effektive kreisförmige Durchmesser in Mikrometern der tafelförmigen Körner ist und
    t die mittlere Dicke in Mikrometern der tafelförmigen Körner darstellt.
  8. Photographisches Element nach Anspruch 1, in dem Iodid 0,1 bis weniger als 10 Mol-Prozent des gesamten Halogenides, das die tafelförmigen Körner bildet, ausmacht.
  9. Photograpisches Element nach Anspruch 8, in dem Iodid 1 bis weniger als 10 Mole-% des gesamten Halogenides ausmacht, das die tafelförmigen Körner bildet.
  10. Photographisches Element nach Anspruch 1, in dem in der Emulsion mit den tafelförmigen Körnern mindestens 90 % der gesamten projizierten Kornfläche auf tafelförmige Körner entfallen, die einen mittleren Durchmesser von mindestens 0,6 Mikrometern und einen Abstand zwischen mindestens zwei parallelen Zwillingsebenen im Bereich von 0,005 bis 0,011 Mikrometern haben.
  11. Verfahren zur Herstellung von Silberhalogenidkörnern nach einem der vorstehenden Ansprüche, bei dem während des Wachstums der Emulsion und nachdem zwischen 25 und 80 % des gesamten Silbers zugegeben wurden, der pBr-Wert von zwischen 1,4 und 1,9 nach zwischen 3,0 und 3,6 verschoben wird.
  12. Verfahren nach Anspruch 11, bei dem die Verschiebung bei etwa 3,3 liegt.
EP91909166A 1990-05-14 1991-05-08 Fotografische filme enthaltend silberhalogenidkörner mit geringen zwillingsebenenabständen Expired - Lifetime EP0486629B1 (de)

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US52271890A 1990-05-14 1990-05-14
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PCT/US1991/003180 WO1991018320A1 (en) 1990-05-14 1991-05-08 Silver halide grains having small twin-plane separations

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JPH05165133A (ja) * 1991-12-18 1993-06-29 Konica Corp ハロゲン化銀写真乳剤及びハロゲン化銀カラー写真感光材料
DE69227016T2 (de) * 1991-12-30 1999-02-18 Eastman Kodak Co., Rochester, N.Y. Kratz-resistentes dickes T-Korn
EP0569075B1 (de) * 1992-05-05 1998-03-25 Agfa-Gevaert N.V. Verfahren zur Herstellung von tafelförmigen Silberhalogenid-Körnern
DE69317593T2 (de) * 1992-05-05 1998-11-05 Agfa Gevaert Nv Verfahren zur Herstellung von tafelförmigen Silberhalogenid-Körnern
JPH06235987A (ja) * 1993-02-10 1994-08-23 Konica Corp ハロゲン化銀写真感光材料
DE69420605T2 (de) * 1993-03-18 2000-04-06 Eastman Kodak Co. Farbphotographisches Element mit niedrigem Silbergehalt und Verfahren zur Farbbildherstellung
KR100619651B1 (ko) 1998-03-17 2006-09-05 콘린코 인크. 공액 리놀레산 조성물
US6965160B2 (en) 2002-08-15 2005-11-15 Micron Technology, Inc. Semiconductor dice packages employing at least one redistribution layer

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