US3206313A - Chemically sensitized emulsions having low surface sensitivity and high internal sensitivity - Google Patents

Chemically sensitized emulsions having low surface sensitivity and high internal sensitivity Download PDF

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US3206313A
US3206313A US110109A US11010961A US3206313A US 3206313 A US3206313 A US 3206313A US 110109 A US110109 A US 110109A US 11010961 A US11010961 A US 11010961A US 3206313 A US3206313 A US 3206313A
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emulsions
silver halide
sensitivity
emulsion
silver
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Henry D Porter
Wesley G Lowe
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Eastman Kodak Co
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Eastman Kodak Co
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Priority to BE655978A priority patent/BE655978A/xx
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain

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  • This invention relates to photographic elements and photographic emulsions having improved sensitivity, and more particularly, to photographic layers comprising photographic silver halide emulsions which have high internal sensitivity induced by chemical sensitization and low surface sensitivity.
  • Emulsions having high internal sensitivity, but low surface sensitivity have been previously described in the photographic art by Davey and Knott in U .8. Patent 2,592,250, issued April 8, 1952. However, it has not been reviously possible to increase substantially the internal sensitivity of these emulsions by chemical sensitizing. Chemical sensitization as conventionally carried out, for example, by sulfur or gold sensitization, increases the surface sensitivity of the emulsions, but has little or no effect upon the internal sensitivity. In fact, in many cases, the internal sensitivity and gamma decrease during chemical sensitization, while the surface sensitivity and gamma are increased.
  • an object of our invention to provide photographic silver halide emulsions containing silver halide grains which have high internal sensitivity induced by chemical sensitization, but which exhibit low surface sensitivity. Another object of our invention is to protect the high internal sensitivity of the photographic silver halide emulsion prepared according to our invention. Another object is to decrease the reciprocity failure exhibited by photographic silver halide emulsions prepared according to prior art methods which exhibit high internal sensitivity, but low surface sensitivity. Still another object is to reduce the desensitization of many spectral sensitizing dyes in the blue region of the spectrum when these dyes are used to extend the spectral range of silver halide emulsions. Other objects will become apparent from a consideration of the following description and examples.
  • the above objects can be realized 'by blending a very fine grain silver halide emulsion with a chemically sensitized emulsion having considerably larger average grain distribution and holding this mixture for a suflicient time to produce a substantially homogeneous grain size distribution.
  • the composite emulsion shows conventional behavior, high surface speed and fog.
  • the blend is found to alter its characteristics, giving rise to a composite emulsion which exhibits very low surface speed and fog, but very high internal speed.
  • the amount of internal fog obtained can be controlled by the amount of surface fog obtained in the finish of the coarser-grained component of the blend.
  • the coarser-grained component can be termed the core, for it appears that during the aforementioned period of holding, a ripening process 3,206,313 Patented Sept. 14, 1965 occurs during which the finer-grained component partially A dissolves and recrystallizes upon the surface of the coarser-grained silver halide.
  • the original surface sensitivity and fog specks of the coarser-grained silver halide, or the core grains are thus buried, causing them to behave as internal speck-s.
  • the finer-grained silver halide can be termed the shell because it appears that these grains dissolve and recrystallize upon the surface of the core emulsion.
  • the core emulsions used in our invention comprise those which, when examined according to normal photographic testing techniques by coating a test portion of the emulsion on a transparent support, exposing to a light intensity scale for a fixed time between 0.01 and 1 second and development for 6 minutes at 68 F. in De-" veloper A, as hereinafter defined, have a sensitivity greater than the sensitivity of an identical test portion of the same emulsion (measured at a density of 0.1 above fog), which has been exposed in the same way, bleached 5 minutes in an aqueous 0.3 percent potassium ferricyanide. solution at 65 F., and developed for 5 minutes at 65 F.,
  • Developer A is the usual type of surface image developer and Developer B is an internal developer having high silver halide solvent activity.
  • the degree of internal sensitivity of the surface image emulsions is not particularly critical.
  • Suitable surface image silver halide emulsions can be any of the conventional silver halide emulsions, although we have found that silver bromide emul sions containing a relatively high content of bromide are particularly useful. These emulsions can contain up to about 10 percent of another silver halide, uch as silver iodide. Silver bromide and silver bromoiodide emulsions are particularly useful in our invention. Such emulsions have been previously described by Trivelli and Smith in The Photographic Journal, vol. LXXX, July 1940 (pages 2854288).
  • the core emulsions are first chemically sensitized by means which have been previously described in the prior art.
  • chemical sensitization We mean sensitization of the type described by Antoine Hautot and Henri Saubenier in Sci ence et Industries Photographiques, vol. XXVIII, January 1957, pages 123 and January 1957, pages 57-65.
  • Such chemical sensitization includes three major classes, viz., gold or noble metal sensitization, sulfur sensitization, such as by a labile sulfur compound, and reduction sensitization, i.e., treatment of the silver halide with a strong reducing agent which does not fog appreciably the silver halide but introduces small specks of metallic silver into the silver halide crystal or grain.
  • gold or noble metal sensitization sulfur sensitization, such as by a labile sulfur compound
  • reduction sensitization i.e., treatment of the silver halide with a strong reducing agent which does not fog appreciably the silver halide but introduces small specks of metallic silver into the silver halide crystal or grain.
  • the core emulsions can be chemically sensitized by any of the accepted procedures.
  • the core emulsions can' be digested with naturally active gelatin, or sulfur compounds can be added, such as those described in Sheppard- US. Patent 2,448,060, issued August 31, 1948, and as antifoggants in higher amounts, as descirbed in Trivelli and Smith US. Patents 2,566,245, issued August 28, 1951 and 2,566,263, issued August 28, 1951.
  • the core emulsions can also be chemically sensitized with gold salts as described in Waller, et al. U.S. Patent 2,399,083, issued April 23, 1946, and Damschroder et al. U.S. Patent 2,642,361, issued June 16, 1953.
  • Suitable compounds are potassium chloroaurite, potassium aurithiocycanate, potassium chloroaurate, auric trichloride and Z-aurosulfobenzothiazole methochloride.
  • the core emulsions can also be chemically sensitized with reducing agents, such as stannous salts (Carroll U.S. Patent 2,487,85 0, issued November 15, 1949), polyamines, such as diethylene triamine (Lowe and Jones U.S. Patent 2,518,698, issued August 15, 1950), polyamines, such as spermine (Lowe and Allen U.S. Patent 2,521,925, issued September 12, 1950), or bis(B-aminoethyl)sulfide and its water soluble salts (Lowe and Jones U.S. Patent 2,521,926, issued September 12, 1950).
  • reducing agents such as stannous salts (Carroll U.S. Patent 2,487,85 0, issued November 15, 1949), polyamines, such as diethylene triamine (Lowe and Jones U.S. Patent 2,518,698, issued August 15, 1950), polyamines, such as spermine (Lowe and Allen U.S. Patent 2,521,925, issued September 12, 1950), or bis(B-aminoeth
  • the core emulsions can also be optically sensitized with cyanine and merocyanine dyes, such as those described in Brooker U.S. Patents 1,846,301, issued February 23, 1932; 1,846,302, issued February 23, 1932; and 1,942,854, issued January 9, 1934; White U.S. Patent 1,990,507; issued February 12, 1935; Brooker and White U.S. Patents 2,112,140, issued March 22, 1938; 2,165,338, issued July 11, 1939; 2,493,747, issued January 10, 1950 and 2,739,964, issued March 27, 1956; Brooker and Keyes U.S. Patent 2,493,748, issued January 10, 1950; Sprague U.S.
  • the core emulsions can also contain speed increasing compounds of the quaternary ammonium type of Carroll U.S. Patent 2,271,623, issued February 3, 1942; Carroll and Allen U.S. Patent 2,288,226, issued June 30, 1942; and Carroll and Spence U.S. Patent 2,334,864, issued November 23, 1943; or the polyethylene glycol type of Carroll and Beach U.S. Patent 2,708,162, issued May 10, 1955; or the quaternary ammonium salts and polyethylene glycols of Piper U.S. Patent 2,886,437; issued May 12, 1959; as well as the thiopolymers of Graham and Sagal U.S. application Serial No. 779,839, filed December 12, 1958 (now U.S. Patent 3,046,129, issued July 24, 1962) and the Dann and Chechak U.S. application Serial No. 779,874, filed December 12, 1958 (now U.S. Patent 3,046,134, issued July 24, 1962).
  • the shell emulsions useful in our invention can be prepared according to techniques which have been previously described in the prior art. Methods for preparing such emulsions have been previously described by Trivelli and Smith in The Photographic Journal, vol. LXXIX, May 1939, pages 330-338. While any of the usual silver halides, such as silver chlorobromide, and the like, can be used in the shell emulsions, particularly useful results have been obtained with silver bromide emulsions, particularly silver bromide emulsions containing at least 90 mole percent of silver bromide. Other halides, up to about 10 percent, can be used with the silver bromide emulsions.
  • Silver bromide and silver bromoiodide emulsions have been found to be particularly useful in preparing the shell emulsions of our invention.
  • the shell emulsions are chemically unsensitized, although-for special applications it may be desired to sensitize these emulsions according to the technique described above for the core emulsions.
  • the grain size distribution of the shell emulsions be such that the average grain size is not greater than 0.4,u, and preferably about 01,14.
  • the average grain size distribution of the core emulsions should be such that the silver halide grain size has a diameter greater than about 0.8 (e.g., 0.8 to about 1.5
  • the resulting composite emulsion which can be termed a covered grain emulsion, contains a population of silver halide grains which are more or less uniform in grainsize distribution, as contrasted with other emulsion blends which contain at least two types of silver halide grains, which are separate and distinct in their physical and, frequently, photographic properties.
  • EXAMPLE 1 One part of an ordinary photographic gelatino-silver bromoiodide emulsion which had been sulfur-sensitized with a labile sulfur compound, e.g., allylthiourea, con-.
  • a labile sulfur compound e.g., allylthiourea
  • EXAMPLE 3 An ordinary photographic gelatino-silver-bromoiodide emulsion containing about 2 mole percent iodide and having a grain size of about 0.8 to 1.5a diameter was blended with a fine-grain gelatino-silver-bromoiodide emulsion containing 1.2 mole percent of iodide and hav-- ing an average grain size of about 0.1a diameter in the blend-ratios illustrated in the following table. The blends were held together at C. in the presence of Table I 12 In A Surface 10 In An Internal Developer (A) Developer (B) Coating Emulsion Type Number Relative 'y Fog Relatlve 'y Fog Speed Speed (a) Sensitized 100 1.
  • EXAMPLE 2 24 grams per silver mole of potassium bromide until'l the fine-grained emulsion (shell) could no longer be seen upon microscopic examination. The samples were then coated on ordinary cellulose acetate film support, dried, and exposed as described in Example 1 above. Strips of each sample were then developed in Developer B (except that it contained no thiosulfate) for 5 min utes and separate strips were subjected to total development for 5 minutes in Developer D. The following results Were obtained. (In total development the exposed emulsion sample is directly developed Without bleaching off the surface latent image.)
  • Table IV CG emulsion was 0.51 log E faster than the control. Accordingly, the CG emulsion exhibited 0.35 log E less low intensity reciprocity failure if the speeds were equated at second. There was no loss of speed in the normal "Surlace Development Total Development KBr, Coating Mole Ratio, large/small Hold Time g.lsilvcr mole Relative Gamma Fog Relative Gamma Fog Speed Speed EXAMPLE 5 The characteristic results obtained by covering a large emulsion grain (core) with a finer emulsion grain (shell) is also shown in this example.
  • the emulsions used were similar to those described in Example 1 above, except that the ratio of the core emulsion to the shell emulsion was changed.
  • the resulting covered grain (CG) emulsion contained 2 moles of large grain bromoiodide core to 3 moles of fine grain bromoiodide shell emulsion.
  • the covered grain emulsion was coated on cellulose acetate film support, dried, and exposed in an intensity scale sensitometer, followed by development for 5 minutes in Developer B above, except that the developer contained no thiosulfate.
  • Another CG sample was exposed in an identical manner and developed for 5 minutes in Developer D, which caused total development of the silver halide grains.
  • the numbers 150, 99, 191 and 175 appearing in the accompanying drawing are relative speed values for the respective coatings.
  • the size of the covered grain emulsion grains depends Table Vll upon the ratio of large to fine grains in the emulsion blends. As the amount of fine grain emulsion is increased, the volume of the covered grains increases and conse- Gamma quently the surface area. This is reflected in increased g e C s li H speeds as illustrated in the following table. These data um er elm 10 igit... E were obtained exactly as described in Example 5, except exposure that the ratio of large to fine grains was varied as illus- P 2:1 0.95 1.54 tiated 1n the table, and development was total develop 60 g 121m Q61 1.28 ment in Developer D.
  • the CG emulsions of our invention can be spectrally sensitized using amounts of sensitizing dyes comparable to those used to sensitize normal surface sensitive emulsions of the same grain size, with the added advantage that much less blue desensitization is exhibited by the CG emulsions. It was also surprising to find that the CG emulsions exhibited improved incubation characteristics. The following table illustrates this improved incubation characteristic both with surface development for minutes in Developer B minus the thiosulfate and for 5 minutes total development in Developer D. Emulsions similar to those in Example 1 were used, except that the core to shell ratio was varied as illustrated in the table. Data are given both for fresh coatings and coatings incubated for 2 weeks under constant humidity of about 55 percent and a temperature of about 120 F.
  • Patent 3,020,155, issued February 6, 1962 may also be used in color transfer processes which utilize the diffusion transfer of an image-wise distribution of developer, coupler or dye, from a light-sensitive layer to a second layer, while the two layers are in close proximity to one another. Color processes of this type are described in Land US. Patents 2,559,643, issued July 10, 1951, and 2,698,798, issued January 4, 1955; Land and Rogers Belgian Patents 554,933 and 554,934, granted August 12, 1957; International Polaroid Belgian Patents 554,212, granted July 16, 1957 and 554,935, granted August 12, 1957; Yutzy US. Patent 2,756,142, issued July 24, 1956, and Whitrnore and Mader US. patent application Serial No. 734,141, filed May 9, 1958 (now abandoned).
  • the addenda described above for use in conjunction with our emulsions can be employed in emulsions designed for X-ray photography, or in non-optically sensi- Table VIII Surface Development Total Development Coating Description (core/shell) Fresh 2 wk. 120 Inc. Fresh 2 wk. 120 Inc. Number Rel. 'y Fog Rel. 'y Fog Rle. 'y Fog Rel. 'y Fog Speed Speed Speed Core control- 100 2. 40 .16 240 1. 98 .48 102 2.10 .21 214 l. 70 54 It will be noted that the CG emulsions described above were considerably more stable toward fogging and loss of gamma during incubation.
  • the covered grain or CG emulsions of our invention can be further chemically sensitized or treated with sensitizing dyes or antifoggants according to methods well known to those skilled in the photographic art.
  • the CG emulsions of our invention can be chemically sensitized, spectrally sensitized, stabilized, treated with gelatin plasticizers, hardeners and the like, according to the methods described in Luckey and Hoppe US. application Serial No. 786,225, filed January 12, 1959 (now US. Patent 2,996,382, issued August 15, 1961).
  • the dispersing agent for the silver halide in its preparation gelatin or some other colloidal material, such as colloidal albumin, a polyacrylamide having a combined acrylamide content of 3060% and a specific viscosity of 0.25-l.5 or an imidized polyacrylamide of like acrylimide content and viscosity as described in Lowe, Minsk and Kenyon US. Patent 2,541,474, issued February 13, 1951; zein as described in Lowe US.
  • Patent 2,563,791 issued August 7, 1951; or a polymeric material which results from polymerizing a protein or a saturated acylated protein with a monomer having a vinyl group as described in lllingsworth, Dann and Gates US. Patent 2,852,383, issued September 16, 1958.
  • compatible mixtures of two or more of these colloids may be employed for dispersing the silver halide in its preparation.
  • Combinations of antifoggants, sensitizers, hardeners, etc., may be used.
  • the photographic elements or CG emulsions described above may be used in diifusion transfer processes which utilize the undeveloped silver halide in the non-image areas of the negative to form a positive by dissolving the undeveloped silver halide and precipitating it on a receiving layer in close proximity to the silver halide
  • diifusion transfer processes which utilize the undeveloped silver halide in the non-image areas of the negative to form a positive by dissolving the undeveloped silver halide and precipitating it on a receiving layer in close proximity to the silver halide
  • Such processes are described in Rott US Patent 2,352,014, issued June 20, 1944, and Land US. Patents 2,584,029, issued January 29, 1952; 2,698,- 236, issued December 28, 1954, and 2,543,181, issued February 27, 1951; and Yackel et al. US. patent application Serial No. 586,705, filed May 23, 1956 (now US.
  • infra-red sensitized emulsions fore or after sensitizing dyes are added.
  • These addenda can also be used in emulsions designed for color photog raphy, for example, emulsions containing color-forming. compounds or couplers, or emulsions to be developed in solutions containing such couplers, or emulsions of the mixed-packet type, such as described in Godowsky US. Patent 2,698,794, issued January 4, 1955, etc.
  • the covered grain or CG emulsions of our invention can be treated with sufficient chemical sensitizer during the preparation to substantially completely fog the core emulsion component, and the resulting fogged internally sensitive grains used in the invention described in Luckey and Hoppe US. Patent No. 2,996,382, mentioned above.
  • the CG emulsions of our invention are also useful in producing revarsal films, such as those described in Fallesen US. Patent 2,497,875, issued February 21, 1950.
  • a light-sensitive photographic silver halide emulsion containing silver halide grains having high internal sensitivity said grams comprising a central core of chemically sensitized silver halide and covering said central core an outer shell of silver halide having low surface activity, said outer shell of silver halide being substantially free of chemical sensitization.
  • a photographic element comprising a flexible support and at least one light-sensitive photographic silver halide emulsion layer containing silver bromide grains comprising a central core of chemically-sensitized silver bromide and a contiguous, outer shell of silver bromide which is chemically unsensitized.
  • a photographic elements comprising a support and at least one light-sensitive photographic silver halide emulsion layer containing silver halide grains containing not more than 10 mole percent of iodide and at least 90 mole percent bromide, said grains comprising a central core of chemically-sensitized silver bromoio'dide and a contiguous, outer shell iOf unsensitized silver bromoiodide.
  • a photographic element comprising a support and at least one light-sensitive photographic silver halide emulsion layer containing internally, sulfur-sensitized silver halide grains containing at least 90 mole ercent silver bromide, said grains comprising a central core of sulfur-sensitized silver bromide containing at least 90 mole percent silver bromide ad a contiguous, outer shell of unsensitized silver bromide containing at least 90 mole percent silver bromide.
  • a photographic element according to claim 6 wherein said silver halide contains at least 90 mole percent silver bromide and not more than 10 mole percent silver iodide.
  • a photographic element comprising a support and at least one light-sensitive photographic silver halide emulsion layer containing internally, gold-sensitized silver halide grains containing at least 90 mole percent silver bromide, said grain comprising a central core of goldrsensitized silver bromide containing at least 90 mole percent silver bromide and a contiguous, outer shell of unsensitized silver bromide containing at least 90 mole percent silver bromide.
  • a process of preparing photographic silver halide emulsions comprising a central core of chemically-sensitized grains and a shell over said core of chemically-unsensitized silver halide grains com-prising digesting a mixture of chemically-sensitized silver halide grains having an average diameter of at least about 0.8 together with unsensitized silver halide grains having an average diameter less than 0.4; until said mixture has a single population of silver halide grains ⁇ of substantially average uniform diameter sized grains.
  • a photographic element comprising a flexible support and at least one light-sensitive photographic silver halide emulsion layer containing silver bromide grains comprising a central core of sulfur and gold-sensitized silver bromide and a contiguous, outer shell of silver bromide which is chemically unsensitized.
  • a photo-graphic element comprising a support and at least one light-sensitive photographic silver halide emulsion layer containing silver halide grains having high internal sensitivity, said grains comprising a central core of chemically sensitized silver halide and covering said central core an outer shell of silver halide having low surface activity, said outer shell of silver halide being substantially free of chemical sensitization.

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GB18758/62A GB1011062A (en) 1961-05-15 1962-05-15 Photographic silver halide emulsions in which the silver halide grains have a chemically sensitised core
DEF44440A DE1207791B (de) 1961-05-15 1964-11-14 Verfahren zur Herstellung von hochempfindlichen fotografischen Emulsionen fuer latente Halogensilberkorninnenbilder
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Cited By (64)

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US3317322A (en) * 1965-08-27 1967-05-02 Eastman Kodak Co Photographic emulsions having high internal sensitivity
US3367778A (en) * 1965-04-15 1968-02-06 Eastman Kodak Co Silver salt direct positive emulsion
US3404002A (en) * 1963-06-27 1968-10-01 Eastman Kodak Co Interimage characteristics of silver halide dye developer image transfer systems
US3510348A (en) * 1966-03-11 1970-05-05 Eastman Kodak Co Direct positive recording film
US3607278A (en) * 1968-04-18 1971-09-21 Eastman Kodak Co Photographic elements containing fogged and unfogged silver halide grains and a slow silver halide emulsion layer
DE2211728A1 (de) * 1971-03-10 1972-09-21 Eastman Kodak Co , Rochester, N Y (V St A ) Verfahren zur Herstellung positiver photographischer Bilder
DE2203462A1 (de) * 1972-01-26 1973-08-02 Agfa Gevaert Ag Verbesserte photographische silberhalogenidemulsion
US3772030A (en) * 1972-02-29 1973-11-13 Eastman Kodak Co Direct-positive emulsion containing internally fogged, silver halide grains free of surface fog and a desensitizing compound
US3870522A (en) * 1972-05-20 1975-03-11 Agfa Gevaert Ag Fogged, direct-positive emulsion containing heterodisperse and irregular composite silver halide grains
US3888676A (en) * 1973-08-27 1975-06-10 Du Pont Silver halide films with wide exposure latitude and low gradient
US3890154A (en) * 1969-12-24 1975-06-17 Fuji Photo Film Co Ltd Light-sensitive silver halide photographic materials
US3917485A (en) * 1973-01-18 1975-11-04 Eastman Kodak Co Method of making photographic silver halide emulsions and products thereof
US3935014A (en) * 1973-02-20 1976-01-27 Agfa-Gevaert Aktiengesellschaft Direct-positive photographic emulsion containing, unfogged, monodispersed silver halide grains having a layered grain structure of specific silver chloride content
US3957488A (en) * 1973-06-28 1976-05-18 Agfa-Gevaert, A.G. Photographic emulsion containing unfogged, heterodisperse layered silver halide grains having a prodominantly bromide core and total chloride content less than 30 mole percent
US3966476A (en) * 1973-02-09 1976-06-29 Agfa-Gevaert, A.G. Spectrally sensitized silver halide emulsion containing more than 50% of the grains with ripening nuclei in cavities
US3979213A (en) * 1972-06-19 1976-09-07 Gilman Jr Paul B Spectrally sensitized silver halide emulsion containing an internal metal dopant
US3989527A (en) * 1975-01-08 1976-11-02 Eastman Kodak Company Silver halide photographic element containing blended grains
US4040839A (en) * 1975-05-19 1977-08-09 Fuji Photo Film Co., Ltd. Direct-positive process utilizing a supersensitized silver halide emulsion
DE2921077A1 (de) * 1978-05-25 1979-11-29 Ciba Geigy Ag Verfahren zur herstellung von silberhalogenidkristalle vom zwillingstyp enthaltenden photographischen silberhalogenidemulsionen
JPS5512579B1 (en)) * 1970-07-20 1980-04-02
US4229525A (en) * 1970-02-24 1980-10-21 Fuji Photo Film Co., Ltd. Process for improving image-sharpness of photographic silver halide material
US4264724A (en) * 1978-06-28 1981-04-28 Agfa-Gevaert, A.G. Exposure of silver halide emulsions during formation
US4327172A (en) * 1980-12-16 1982-04-27 Western Electric Company, Inc. Photographic image definition improvement
US4335199A (en) * 1980-02-19 1982-06-15 E. I. Du Pont De Nemours And Company High contrast by imagewise iodide infection in a mixed silver halide system
US4339532A (en) * 1981-01-08 1982-07-13 Polaroid Corporation Novel photosensitive silver halide emulsion and method of preparing same
US4368256A (en) * 1980-07-22 1983-01-11 Ciba-Geigy Ag Process for production of masked positive color images by the silver dye bleach process and the silver dye bleach material used in this process
US4379837A (en) * 1980-05-23 1983-04-12 Agfa-Gevaert Aktiengesellschaft Process for the preparation of silver halide emulsions, photographic materials, and a process for the production of photographic images
US4400462A (en) * 1980-06-11 1983-08-23 Konishiroku Photo Industry Co., Ltd. Method for the formation of photographic images
US4433048A (en) * 1981-11-12 1984-02-21 Eastman Kodak Company Radiation-sensitive silver bromoiodide emulsions, photographic elements, and processes for their use
US4444865A (en) * 1981-11-12 1984-04-24 Eastman Kodak Company Blended grain direct-positive emulsions and photographic elements and processes for their use
US4444877A (en) * 1981-02-18 1984-04-24 Konishiroku Photo Ind. Co., Ltd. Light-sensitive silver halide emulsion
US4444874A (en) * 1982-09-15 1984-04-24 Eastman Kodak Company Photographic elements containing direct-positive emulsions and processes for their use
US4451560A (en) * 1982-11-15 1984-05-29 Polaroid Corporation Chemical sensitization of silver halide grains
US4459351A (en) * 1983-06-22 1984-07-10 Eastman Kodak Company Photographic element and process employed combination of surface and internal latent image silver halide
US4504570A (en) * 1982-09-30 1985-03-12 Eastman Kodak Company Direct reversal emulsions and photographic elements useful in image transfer film units
US4507386A (en) * 1982-09-13 1985-03-26 Konishiroku Photo Industry Co., Ltd. Silver halide photographic emulsion
EP0143424A2 (en) 1983-11-25 1985-06-05 Fuji Photo Film Co., Ltd. Heat-developable light-sensitive materials
US4564591A (en) * 1981-12-02 1986-01-14 Konishiroku Photo Industry Co., Ltd. Silver halide color photographic material
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US5306608A (en) * 1991-10-18 1994-04-26 Fuji Photo Film Co., Ltd. Direct positive photographic light-sensitive material
US5326668A (en) * 1990-11-01 1994-07-05 Fuji Photo Film Co., Ltd. Method of image formation by silver salt diffusion transfer
US5340710A (en) * 1987-12-28 1994-08-23 Konica Corporation Photosensitive silver halide photographic material
US5378591A (en) * 1990-07-04 1995-01-03 Eastman Kodak Company Reversal color photographic material
US5427904A (en) * 1992-10-07 1995-06-27 Agfa-Gevaert Ag Process for the preparation of silver halide emulsions
WO1996013755A1 (en) 1994-10-26 1996-05-09 Eastman Kodak Company Photographic emulsions of enhanced sensitivity
US5552265A (en) * 1990-07-04 1996-09-03 Eastman Kodak Company Reversal color photographic material with a fine grain sublayer
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US3890154A (en) * 1969-12-24 1975-06-17 Fuji Photo Film Co Ltd Light-sensitive silver halide photographic materials
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US3979213A (en) * 1972-06-19 1976-09-07 Gilman Jr Paul B Spectrally sensitized silver halide emulsion containing an internal metal dopant
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US4863838A (en) * 1979-03-26 1989-09-05 Konishiroku Photo Industry Co., Ltd. Direct positive type light-sensitive silver halide photographic materials
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US4379837A (en) * 1980-05-23 1983-04-12 Agfa-Gevaert Aktiengesellschaft Process for the preparation of silver halide emulsions, photographic materials, and a process for the production of photographic images
US4400462A (en) * 1980-06-11 1983-08-23 Konishiroku Photo Industry Co., Ltd. Method for the formation of photographic images
US4368256A (en) * 1980-07-22 1983-01-11 Ciba-Geigy Ag Process for production of masked positive color images by the silver dye bleach process and the silver dye bleach material used in this process
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US4339532A (en) * 1981-01-08 1982-07-13 Polaroid Corporation Novel photosensitive silver halide emulsion and method of preparing same
US4444877A (en) * 1981-02-18 1984-04-24 Konishiroku Photo Ind. Co., Ltd. Light-sensitive silver halide emulsion
US4433048A (en) * 1981-11-12 1984-02-21 Eastman Kodak Company Radiation-sensitive silver bromoiodide emulsions, photographic elements, and processes for their use
US4444865A (en) * 1981-11-12 1984-04-24 Eastman Kodak Company Blended grain direct-positive emulsions and photographic elements and processes for their use
USRE32097E (en) * 1981-11-12 1986-03-25 Eastman Kodak Company Blended grain direct-positive emulsions and photographic elements and processes for their use
US4564591A (en) * 1981-12-02 1986-01-14 Konishiroku Photo Industry Co., Ltd. Silver halide color photographic material
US4507386A (en) * 1982-09-13 1985-03-26 Konishiroku Photo Industry Co., Ltd. Silver halide photographic emulsion
US4444874A (en) * 1982-09-15 1984-04-24 Eastman Kodak Company Photographic elements containing direct-positive emulsions and processes for their use
USRE32149E (en) * 1982-09-15 1986-05-20 Eastman Kodak Company Photographic elements containing direct-positive emulsions and processes for their use
US4504570A (en) * 1982-09-30 1985-03-12 Eastman Kodak Company Direct reversal emulsions and photographic elements useful in image transfer film units
US4451560A (en) * 1982-11-15 1984-05-29 Polaroid Corporation Chemical sensitization of silver halide grains
US4623612A (en) * 1983-01-21 1986-11-18 Fuji Photo Film Co., Ltd. Method of developing silver halide photographic light-sensitive materials
US4626498A (en) * 1983-05-20 1986-12-02 Fuji Photo Film Co., Ltd. Color reversal photographic light-sensitive material
EP0127081A3 (en) * 1983-05-20 1986-06-11 Fuji Photo Film Co., Ltd. Color reversal photographic light-sensitive material
US4459351A (en) * 1983-06-22 1984-07-10 Eastman Kodak Company Photographic element and process employed combination of surface and internal latent image silver halide
EP0143424A2 (en) 1983-11-25 1985-06-05 Fuji Photo Film Co., Ltd. Heat-developable light-sensitive materials
US4762778A (en) * 1983-12-08 1988-08-09 Konishiroku Photo Industry Co., Ltd. Silver halide photographic light sensitive material
US4710631A (en) * 1984-08-28 1987-12-01 Fuji Photo Film Co., Ltd. Temperature compensation for a semiconductor light source used for exposure of light sensitive material
EP0200011A1 (en) 1985-03-30 1986-11-05 Fuji Photo Film Co., Ltd. Heat-developable light-sensitive material
EP0198634A2 (en) 1985-04-04 1986-10-22 EASTMAN KODAK COMPANY (a New Jersey corporation) Quaternized tellurium salt fog inhibiting agents for silver halide photography
US4643966A (en) * 1985-09-03 1987-02-17 Eastman Kodak Company Emulsions and photographic elements containing ruffled silver halide grains
EP0215612A2 (en) 1985-09-03 1987-03-25 EASTMAN KODAK COMPANY (a New Jersey corporation) Silver halide photographic emulsions with novel grain faces (5)
US4758505A (en) * 1985-11-09 1988-07-19 Agfa Gevaert Aktiengesellschaft Process and an apparatus for the production of photographic silver halide emulsions
US5340710A (en) * 1987-12-28 1994-08-23 Konica Corporation Photosensitive silver halide photographic material
US4850357A (en) * 1988-01-12 1989-07-25 Cardiac Pacemakers, Inc. Biphasic pulse generator for an implantable defibrillator
US5155017A (en) * 1989-01-09 1992-10-13 Fuji Photo Film Co., Ltd. Silver halide photographic material
US5248588A (en) * 1990-05-23 1993-09-28 Fuji Photo Film Co., Ltd. Silver halide photographic material
US5378591A (en) * 1990-07-04 1995-01-03 Eastman Kodak Company Reversal color photographic material
US5552265A (en) * 1990-07-04 1996-09-03 Eastman Kodak Company Reversal color photographic material with a fine grain sublayer
US5326668A (en) * 1990-11-01 1994-07-05 Fuji Photo Film Co., Ltd. Method of image formation by silver salt diffusion transfer
US5306608A (en) * 1991-10-18 1994-04-26 Fuji Photo Film Co., Ltd. Direct positive photographic light-sensitive material
EP0563985A1 (en) 1992-04-03 1993-10-06 Fuji Photo Film Co., Ltd. Silver halide color photographic material
US5286622A (en) * 1992-04-30 1994-02-15 Fuji Photo Film Co., Ltd. Light-sensitive element for silver salt diffusion transfer method
US5427904A (en) * 1992-10-07 1995-06-27 Agfa-Gevaert Ag Process for the preparation of silver halide emulsions
WO1996013755A1 (en) 1994-10-26 1996-05-09 Eastman Kodak Company Photographic emulsions of enhanced sensitivity
EP0754967A1 (en) 1995-07-14 1997-01-22 Agfa-Gevaert N.V. Photographic direct positive material containing a particular stabilizer
US6656675B2 (en) 2001-07-04 2003-12-02 Eastman Kodak Company Method of preparing a silver halide photographic emulsion

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GB1011062A (en) 1965-11-24
BE655978A (en)) 1965-03-16
DE1207791B (de) 1965-12-23

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