WO1995002850A1 - Grains photosensibles lamellaires ultraminces ameliorant la sensibilite d'une emulsion photographique - Google Patents

Grains photosensibles lamellaires ultraminces ameliorant la sensibilite d'une emulsion photographique Download PDF

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Publication number
WO1995002850A1
WO1995002850A1 PCT/US1993/012449 US9312449W WO9502850A1 WO 1995002850 A1 WO1995002850 A1 WO 1995002850A1 US 9312449 W US9312449 W US 9312449W WO 9502850 A1 WO9502850 A1 WO 9502850A1
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Prior art keywords
grains
light
sensitive
photosensitive
emulsion
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PCT/US1993/012449
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English (en)
Inventor
George M. Sawyer
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Sawyer George M
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Publication date
Application filed by Sawyer George M filed Critical Sawyer George M
Priority to AU62271/94A priority Critical patent/AU6227194A/en
Publication of WO1995002850A1 publication Critical patent/WO1995002850A1/fr

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    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/005Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/0051Tabular grain emulsions

Definitions

  • the invention is the use of ultra-thin, tabular, light-sensitive grains in a photographic emulsion for the purpose of increasing the sensitivity of films and plates.
  • Silver halide is the preferred light-sensitive material.
  • tabular grains produce an emulsion that is more sensitive than when spherical grains are used, and the emulsion becomes more sensitive as the diameter- o-thickness ratio (aspect ratio) of the tabular grains increases.
  • Fig. 1 shows a pixel in a cross section of an ordinary photograph.
  • Fig. 2 shows a Pixel in a cross section of a Lippmann color photograph.
  • Fig. 3 shows a cross section of a Lippmann color photograph.
  • Fig. 4 shows a cross section of a photosensitive element used in ordinary photography.
  • Fig. 5 shows a cross section of a photosensitive element used in the Lippmann method of color photography.
  • Fig. 6 shows a pixel in a cross section of a photosensitive element used in the Lippmann method of color photography.
  • Fig. 7 shows an oblique view of what happens when one goes from prior art to the invention revealed.
  • Fig. 8 shows a photosensitive grain in a cross section of a photosensitive element used in the prior art Lippmann method of color photography where spherical grains are used.
  • Figs. 9 and 10 show an oblique view of 4 low sensitive grains joined to make a large more sensitive grain.
  • Figs. 11, 12A, and 12B show formulas.
  • Fig. 13 is a diagram showing how relative sensitivities of emulsions depend on the characteristic grain thickness and aspect ratio.
  • Fig. 14 is a diagram showing how relative sensitivities of emulsions depend on the characteristic grain thickness and diameter.
  • Fig. 15 overlays Fig. 13 and shows territories claimed by the instant invention.
  • Fig. 16 also overlays Fig. 13, and on it is shown territory disclosed by U. S. Patent No. 4,434,226.
  • the numeral 0102 refers to Fig. 1, item 02, which is a pixel.
  • the projected (or “projective”) area is the area of the grain when seen through a microscope and the grain rests on a flat surface, as on a microscope slide.
  • the grains are commonly hexagonal, triangular, spherical, or rod shape in outline when viewed through a microscope.
  • the diameter of a grain is the diameter of the circle whose area is equivalent to the area of the grain when the grain rests on a flat surface, as on a microscope slide.
  • a tabular grain, a flat grain, or a pancake shaped grain all mean essentially the same thing, and they have in common (1) two prominent opposite sides, (2) the sides are flat, (3) the sides are parallel, (4) they have diameters that are greater than their thickness.
  • the aspect ratio of a tabular grain is the diameter divided by the thickness.
  • the sensitivity of an emulsion is measured by the area that becomes opaque (black) upon exposure and development.
  • the relative sensitivity (RS) of an emulsion comprised of grains is equal to the diameter squared divided by the thickness of the characteristic grains, where the dimensions are in nanometers.
  • the RS is equal to 50 times 50 divided by 50 equals 50.
  • the characteristic grain has a diameter of 100 and a thickness of 25 nanometers
  • the RS is equal to 100 times 100 divided by 25 equals 400.
  • Gabriel Lippmann invented, in 1891, a process of color photography that produced the first fixed color photographs from nature. His process required the interference of light waves.
  • the Lippmann process of color photography produces color in a photograph for a different reason than color is produced in an ordinary photograph.
  • the Lippmann process produces color by partially reflecting layers within a pixel, whereas, ordinary photography produces color by dye within a pixel.
  • Fig.l is a cross section 0101 of an ordinary photograph.
  • the pixel 0102 is shown with dye 0103 filling the pixel.
  • a pixel of a Lippmann color photograph a plurality of partially reflecting layers is present.
  • a pixel is required to be structured.
  • Fig. 2 is a cross section 0201 of a Lippmann photograph.
  • the pixel 0202 is shown with partially reflecting layers 0203 (3 in this case) .
  • This requirement for structure in a Lippmann photograph pixel is a unique requirement to this process and is a requirement that does not exist in ordinary photography.
  • Fig. 3 also shows a cross section of a Lippmann photograph 0301.
  • the emulsion layer 0302, a base layer 0303, a light absorbing layer as black paint 0304, illumination sources 0305 and 0306, the eyes of an observer 0307 and 0308, partially reflecting layers 0309 within a violet reflecting pixel, and partially reflecting layers 0310 within a red reflecting pixel are shown.
  • the partially reflecting layers are farther apart when the pixel is red 0310 than when the pixel is violet 0309. Thus, color is achieved by controlling the spacing between the partially reflecting layers of the photograph. This exact spacing automatically happens when the unique Lippmann photosensitive element (sensitized plate) is exposed.
  • Fig. 4 shows the photosensitive element 0401 used in ordinary photography wherein an emulsion layer 0402, a base layer 0403, and exposing radiation 0404 on a pixel 0405 are also shown.
  • Fig. 5 shows the photosensitive element 0501 used in the Lippmann method of color photography wherein an emulsion layer 0502, a base layer 0503, a reflecting layer 0504, and exposing radiation 0505 on a pixel 0506 are also shown.
  • the exposing radiation 0404 is partially absorbed by the photosensitive emulsion layer 0402 and what is not absorbed passes through.
  • light travels through the emulsion layer in one direction only, and as a result, light uniformly exists throughout the emulsion pixel 0405 during exposure, except for what is absorbed.
  • the exposing radiation 0505 is partially trapped by the photosensitive emulsion layer 0502 and what is not trapped is purposely reflected by the reflecting layer 0504, and the reflected radiation thus travels in the opposite direction to the incident radiation.
  • the incident and reflected radiation interfere with each other because of their wave nature.
  • light travels through the emulsion layer in opposite directions.
  • an interference pattern occurs in the form of planes of lightness separated by planes of darkness. The orientation of these planes is parallel to the film plane.
  • An enlargement of the pixel 0506, within the emulsion layer 0502 of Fig. 5, is shown as Fig. 6.
  • Fig. 6 shows the emulsion layer 0502, the pixel 0506, and planes of lightness 0601 and planes of darkness 0602.
  • the planes of lightness 0601 result in metallic silver particles after development and for this reason the planes 0601 are shown in the figure as rows of especially dark spots.
  • the purpose of the photosensitive emulsion layer 0502 is to record these planes of lightness and of darkness.
  • the photosensitive emulsion layer 0502 When the photosensitive emulsion layer 0502 is photosensitive because of the presence of photosensitive grains dispersed within it, the grains must be small enough to resolve the planes of lightness and darkness. This resolution requirement is in a direction perpendicular to the film plane. It is to be noted that this direction is in contrast to the ordinary way of measuring film resolution. The ordinary way of measuring resolution for sensitized materials is in a direction parallel to the film plane. Thus, the resolution requirement that is necessary to make a Lippmann photosensitive element 0501 work does not apply to ordinary film 0401; in fact, a single photosensitive grain could conceivably fill the entire pixel 0405 of the ordinary photosensitive element 0401.
  • the distance between the planes of lightness 0601 is ultra small, the largest photosensitive grains that can be used to resolve them are ultra small. (From a resolution standpoint, it is obvious that the grains can be smaller than the largest size.)
  • One of the photosensitive emulsion layers that Lippmann used was of silver halide. One may ask, "What is the diameter of the ultra small photosensitive grains of silver halide required for recording the visible spectrum?" For recording violet (at 400 nm) the grain sized can be about 50 nm or less and for red (at 700 nm) the grain sizes can be 87 nm or less.
  • the rule is, "The diameter of the spherical photosensitive grains used must be about l/8th of the shortest wavelength of radiation to be recorded, or less.” This rule is supported by a theoretical study. Thus, for photographing the visible spectrum of from 400 to 700 nm, the diameters of the spherical grains that can be used are about 50 nm or less.
  • the average diameter of the spherical grains is about 50 nanometers or less.
  • the spacing for the planes of lightness is the wavelength of light (400 nm) divided by two times the refractive index.
  • the refractive index for gelatin and many other dispersing materials is about one and one half.
  • the spacing is thus 133 nm. While the resolution for ordinary photographic film is considered very high when it is 400 lines per millimeter (in a direction parallel to the film plane) , the resolution requirement for the ultra small 133 nm spacing is 7,500 lines per millimeter (in a direction perpendicular to the film plane) .
  • tabular is essentially equivalent to the term “pancakes” in describing the shape of photosensitive grains because they both (1) have two prominent opposite surfaces, (2) said surfaces are flat, (3) said surfaces are parallel, and (4) the diameters of said surfaces are greater than the distance between them.
  • a layered photosensitive element that includes a reflecting layer, of liquid mercury, and an emulsion layer comprising a dispersing medium and photosensitive grains.
  • the photosensitive grains comprise grains characterized as being spherical in shape.
  • the spherical grains comprise grains having diameters (and thickness) of about 50 nanometers and less, when photographing the visible spectrum, and account for essentially 100 percent of the total projection area of all the photosensitive grains.
  • the interference patterns of light waves are required to be present.
  • a layered photosensitive element of improved sensitivity comprising
  • an emulsion layer comprising a dispersing medium and photosensitive grains
  • said photosensitive grains comprise grains characterized as being tabular in shape
  • said grains characterized as being tabular in shape have thicknesses of less than 50 nanometers have average aspect ratios greater than 1 :1 and account for at least 50% of the total projected area of said photosensitive grains, and e. within said emulsion layer the interference patterns of light waves are required to be present during exposure.
  • any added amount of the improved grains that is used is beneficial, the more the better, and that other grains, not of the improved design, may also be present.
  • aspect ratios of greater than 1:1 they could be greater than 2:1, 4:1, 8:1, 10:1, 12:1, 15:1, 20:1, 50:1,100:1, or 300:1 or more, because the greater the aspect ratios, the greater the emulsion sensitivity.
  • thicknesses of less than 50 nanometers claims could be written stating (1) 87 nanometers if the recording light with a wavelength of 700 nanometers is used; here, the territory claimed is shown in Fig.
  • a layered photosensitive element of improved sensitivity comprising b. an emulsion layer comprising a dispersing medium and photosensitive grains, c. wherein said photosensitive grains comprise grains characterized as being tabular in shape, d. wherein said grains characterized as being tabular in shape have thicknesses of less than 50 nanometers have average aspect ratios greater than 1 :1 and account for at least 50% of the total projected area of said photosensitive grains.
  • a layered photosensitive element of improved sensitivity comprising
  • an emulsion layer comprising a dispersing medium and photosensitive grains
  • said photosensitive grains comprise grains characterized as being tabular in shape
  • said grains characterized as being tabular in shape have thicknesses of less than 300 nanometers have average aspect ratios greater than 1 :1 and account for at least 50% of the total projected area of said photosensitive grains.
  • a more limiting case in point is the limitation in the above claim "aspect ratios greater than 1 :1.”
  • a more confining limitation than “1 :1” is “aspect ratios greater than 8:1, and progressively more confining are the aspect ratios of 10:1,12:1, 20:1, 50:1, 100:1 and all fall within the limitation "aspect ratios greater than 1 :1.”
  • a layered photosensitive element of improved sensitivity comprising
  • an emulsion layer comprising a dispersing medium and photosensitive grains
  • said photosensitive grains comprise grains characterized as being tabular in shape
  • said grains characterized as being tabular in shape have thicknesses of less than 300 nanometers have an average aspect ratio greater than 8:1 and account for at least 50% of the total projected area of said photosensitive grains.
  • a high aspect ratio tabular grain photosensitive emulsion comprising a dispersing medium and photosensitive grains, wherein tabular photosensitive grains having a thicknesses of less than 300 nanometers that have an average aspect ratio of greater than 8:1 account for at least 50% of the total projected area of said photosensitive grains.
  • a high aspect ratio tabular grain silver halide emulsion comprising a dispersing medium and silver bromoiodide grains, wherein tabular silver bromoiodide grains having a thicknesses of less than 300 nanometers that have an average aspect ratio of greater than 8:1 account for at least 50% of the total projected area of said silver bromoiodide grains.
  • EMBODIMENT NO.6 does not have the limitation "and a diameter of 600 nanometers.” The effect of this limitation is to reduce some of the territory otherwise covered. It is to be noted that the diameter is not independent from the aspect ratio and thickness; (a) when a diameter and thickness are given, only one possible value of the aspect ratio results; (b) when a diameter and the aspect ratio are given, only one possible value of the thickness results. Hence, when a particular diameter is given, the line representing this diameter may be plotted on a graph where the coordinates are thickness and aspect ratio. A point on the line representing a diameter of 600 nanometers is shown in Fig. 14 at 1805. Dotted curves showing aspect ratios of 8 and 20 are also shown on Fig. 14.
  • a Lippmann light-sensitive element used in the Lippmann method or making colored photographs by the interference of light waves, comprising
  • the light-sensitive layer contains light-sensitive silver halide grains within a transparent material, the improvement for increasing the sensitivity of the Lippmann element, wherein said light-sensitive grains are
  • a layered light-sensitive element including a light-sensitive emulsion layer and a reflecting layer wherein:
  • the light-sensitive emulsion layer contains light-sensitive grains wherein said grains comprise at least one silver salt:
  • the shape of the said light-sensitive grains is characterized as being flat. It is well known that when the Lippmann method of color photography used a light-sensitive layer comprising a silver halide emulsion, that the shape of the grains was characterized as being spherical and that the diameters of said spherical grains were about 50 nanometers or less.
  • a layered light-sensitive element including a light-sensitive emulsion layer and a reflecting layer wherein:
  • the light-sensitive emulsion layer contains light-sensitive grains:
  • Embodiment No. 9 is the same as Embodiment No. 8, except the grain composition limitation has been dropped.
  • a method for increasing the sensitivity of a light-sensitive element by making a light-sensitive element comprised of a multiplicity of very thin emulsion layers, and an emulsion support, wherein said multiplicity of very thin emulsion layers contain light-sensitive grains, wherein said light-sensitive grains are characterized as being flat, comprising the steps of:
  • a process for increasing the sensitivity of a layered light-sensitive element which Includes a light-sensitive layer containing light sensitive grains in a transparent material, and a support layer for the light-sensitive layers, where the improvement includes the steps of
  • Fig. 13 is a plot of the Relative Sensitivities of Emulsions Using Tabular Grains.
  • the information plotted thereon applies to both photosensitive elements that comprise a reflecting layer (interference photography) and those that do not (ordinary photography) .
  • the relative sensitivity curves connect points that are determined from the formula that relates relative sensitivity to grain thickness and aspect ratio.
  • Relative Sensitivity is equal to the aspect ratio squared multiplied by the thickness (in nanometers) .
  • the dimensions of Relative Sensitivity values are in nanometers.
  • Fig. 14 is a plot of the Relative Sensitivities of Emulsions Using Tabular Grains.
  • the information plotted thereon applies to both photosensitive elements that comprise a reflecting layer (interference photography) and those that do not (ordinary photography) .
  • the relative sensitivity curves connect points that are determined from the formula that relates relative sensitivity to grain thickness and grain diameter.
  • Relative Sensitivity is equal to the diameter (in nanometers) squared divided by the thickness (in nanometers)
  • the difference in Figs. 13 and 14 is that the horizontal axis is aspect ratio in Fig. 13 and diameter in Fig. 14.
  • Fig. 15 is an overlay of Fig. 13. On it are shown the territories covered by the preferred embodiments, as follows:
  • Preferred Embodiments 1 and 2 cover territory bounded by the points 1901, 1902, 1903, 1904, and 1901.
  • Preferred Embodiment No. 3 covers territory bounded by the points 1901, 1907, 1908, 1904, and 1901.
  • Preferred Embodiments Nos. 4, 5, and 6 cover territory bounded by the points 1909, 1910, 1908, 1904, and 1909.
  • Fig. 16 is an overlay of Fig. 13 and on it is shown the territory claimed by U. S. Patent No. 4,434,226, Claim #1. This claim is bounded by the points 2001, 2002, 2003, 2004, 2005, and 2001.
  • the line 2001, 2005, and 2004 is the line representing a grain diameter of 600 nanometers.
  • the flat grain has four times the sensitivity of all four of the cubic grains together. This may be explained as follows.
  • the four small grains together have the same area to intercept light as the one large grain. Therefore, if there is just enough light for one developable speck to be initiated on the large grain, there is just enough light for one developable speck to be initiated on the four small grains together, but the speck will be on just one of the four grains.
  • the developable speck spreads over the entire grain. Then, the entire large grain turns black, but only one of the small grains turns black. Therefore, more black (opacity) is produced by the light that was trapped by the single large grain than by the collection of the four separate small grains.
  • Relative Sensitivity equals the diameter squared divided by the thickness.
  • Aspect ratio is defined by the diameter divided by the thickness. See Figs. 11, 12A, and 12B.
  • the dimensional units of Relative Sensitivity are in nanometers, when the dimensions of the grains are in nanometers.
  • Fig. 14 Relative sensitivities of emulsions using tabular grains are shown on Fig. 14, where the grain diameter vs thickness is shown, and on Fig. 13, where the grain aspect ratio vs thickness is given.
  • Fig. 14 When designing a film with for maximum sensitivity, Fig. 14 is most conveniently used. One first determines the maximum grain diameter that can be tolerated from the standpoint of conventional resolution requirements and then makes the thickness of the grains as thin as possible.
  • the maximum diameter of the characteristic grains used depends upon the minimum resolution required of the film. This resolution is measured in lines per millimeter in a direction parallel to the film plane. This maximum diameter is determined by the expression: 370 divided by the required resolution (in lines per millimeter) .
  • a photosensitive element ordinary photographic film is a "photosensitive element" is required to have a minimum resolution of 100 lines per millimeter. Determine the maximum diameter of the characteristic tabular grains of the emulsion. Answer: the maximum diameter is 370 divided by 100 equals 3.7 microns. This is just on the ragged edge. The smaller the diameter of the characteristic grains, the higher the resolution. (But when the grain diameters are reduced, the sensitivity suffers.)
  • Case #1 the reference case.
  • the grains are characterized as being spherical in shape with 1.0 micron diameters.
  • the grains are characterized as being spherical in shape with 0.1 micron diameters. Case #3.
  • the grains are characterized as being tabular in shape with 1.0 micron diameters and 0.1 micron thicknesses.
  • Case 3 the total projective area of all the grains is 10 times that of Case #1, and the relative sensitivity is ten times that of Case #1. It follows that in order for Case #3 to have the same relative sensitivity as Case #1, only one tenth of the amount of light-sensitive material is needed. When the light-sensitive material is a silver halide, one tenth of the amount of silver is needed. As an additional advantage, the image layer can be made correspondingly thinner, and as a consequence, the processing time reduced.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
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Abstract

L'invention porte sur l'utilisation de grains (de préférence en halogénure d'argent) photosensibles lamellaires ultraminces dans une émulsion photographique en vue d'accroître la sensibilité de pellicules ou de plaques photographiques. On est surpris de constater que pour un poids donné de matériel photosensible les grains lamellaires produisent une émulsion plus sensible que les grains sphériques et que l'émulsion est d'autant plus sensible que leur rapport diamètre/épaisseur croît. L'une des conséquence de l'utilisation desdits grains est l'accroissement du pouvoir couvrant, d'où découlent d'importants avantages économiques. Dans un exemple cité, il ne faut plus qu'un dixième de la quantité d'argent. Les enseignements de l'invention s'appliquent aux émulsions pour pellicules ou plaques photographiques pourvues ou non d'une couche réfléchissante.
PCT/US1993/012449 1993-07-12 1993-12-29 Grains photosensibles lamellaires ultraminces ameliorant la sensibilite d'une emulsion photographique WO1995002850A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU62271/94A AU6227194A (en) 1993-07-12 1993-12-29 The use of ultra-thin, tabular, photosensitive grains for the purpose of increasing the sensitivity of a photographic emulsion

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US9048493A 1993-07-12 1993-07-12
US08/090,484 1993-07-12

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WO1995002850A1 true WO1995002850A1 (fr) 1995-01-26

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3107170A (en) * 1960-05-31 1963-10-15 Netke Martin Production of color images in sensitive emulsions
US3503050A (en) * 1965-12-30 1970-03-24 Ibm Wave energy recording in radiation sensitive medium
US4178181A (en) * 1966-04-21 1979-12-11 Sawyer George M Interference film photography
US4414304A (en) * 1981-11-12 1983-11-08 Eastman Kodak Company Forehardened high aspect ratio silver halide photographic elements and processes for their use
US4434226A (en) * 1981-11-12 1984-02-28 Eastman Kodak Company High aspect ratio silver bromoiodide emulsions and processes for their preparation
US4459353A (en) * 1982-12-20 1984-07-10 Eastman Kodak Company Gamma phase silver iodide emulsions, photographic elements containing these emulsions, and processes for their use
US5250403A (en) * 1991-04-03 1993-10-05 Eastman Kodak Company Photographic elements including highly uniform silver bromoiodide tabular grain emulsions

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3107170A (en) * 1960-05-31 1963-10-15 Netke Martin Production of color images in sensitive emulsions
US3503050A (en) * 1965-12-30 1970-03-24 Ibm Wave energy recording in radiation sensitive medium
US4178181A (en) * 1966-04-21 1979-12-11 Sawyer George M Interference film photography
US4414304A (en) * 1981-11-12 1983-11-08 Eastman Kodak Company Forehardened high aspect ratio silver halide photographic elements and processes for their use
US4434226A (en) * 1981-11-12 1984-02-28 Eastman Kodak Company High aspect ratio silver bromoiodide emulsions and processes for their preparation
US4459353A (en) * 1982-12-20 1984-07-10 Eastman Kodak Company Gamma phase silver iodide emulsions, photographic elements containing these emulsions, and processes for their use
US5250403A (en) * 1991-04-03 1993-10-05 Eastman Kodak Company Photographic elements including highly uniform silver bromoiodide tabular grain emulsions

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
JOURNAL OPTICS (PARIS), Vol. 18, No. 4, 1987, CONNES, "Silver Salts and Standing Waves: the History of Interference Colour Photography", pages 147-166. *
PHOTOGRAPHIC EMULSION CHEMISTRY, (DUFFIN), The Focal Press, New York, 1966, pages 66-72. *
SCIENCE ET INDUSTRIES PHOTOGRAPHIQUES, Vol. 33, No. 2, 1962, DE CUGNAC et al., "Evolution of the Morphology of Silver Bromide Crystals During Physical Ripening", pages 121-125. *
THE BRITISH JOURNAL OF PHOTOGRAPHY, Vol. 42, 31 May 1895, BAYLEY, "Lippman's Process of Colour Photography", pages 342-343. *

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