US3367778A - Silver salt direct positive emulsion - Google Patents
Silver salt direct positive emulsion Download PDFInfo
- Publication number
- US3367778A US3367778A US448467A US44846765A US3367778A US 3367778 A US3367778 A US 3367778A US 448467 A US448467 A US 448467A US 44846765 A US44846765 A US 44846765A US 3367778 A US3367778 A US 3367778A
- Authority
- US
- United States
- Prior art keywords
- silver
- core
- emulsion
- shell
- direct positive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- 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
- G03C1/485—Direct positive emulsions
- G03C1/48515—Direct positive emulsions prefogged
- G03C1/48523—Direct positive emulsions prefogged characterised by the desensitiser
Definitions
- Direct positive silver halide emulsions are well known in the photographic art. However, many reversal systems are characterized as being of low speed, producing undesirably high background or D density, requiring special developing compositions, requiring processing steps between exposure and development, being diflicult to control, and the like undesirable features.
- the core emulsion is first chemically or physically treated by methods previously described in the prior art to produce centers which promote the deposition of photolytic silver, i.e., latent image nucleating centers.
- centers can be obtained by various techniques as described herein. Chemical sensitization techniques of the type described by Antoine Hautot and Henri Saubenier in Science et Industries Photographiques, vol. XXVIII, January 1957, pp. 1 to 23 and January 1957, pp. 57 to 65 are particularly useful.
- Such chemical sensitization includes three major classes, namely, 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 introduces small specks of metallic silver into the silver salt crystal or grain.
- the core emulsion When the core emulsion is chemically sensitized, it is preferably sensitized so that 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.
- Developer A has 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 3,367,778 Patented Feb. 6, 1968 5 minutes in an aqueous 0.3 percent potassium ferricyanide solution at F., and developed for 5 minutes at 65 F., in Developer B, as hereinafter defined.
- Developer A is the usual type of surface image developer and Developer B is an internal developer having high silver halide solvent activity.
- 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 U.S. Patent 1,574,944, issued Mar. 2, 1926, Sheppard et al. U.S. Patent 1,623,499 issued Apr. 5, 1927, and Sheppard et a1.
- the core emulsions can also be chemically sensitized with gold salts as described in Waller et al. U.S. Patent 2,399,083 issued Apr. 23, 1946 and Damschroder et al. U.S. Patent 2,642,361 issued June 16, 1953.
- Suitable com pounds are potassium chloroaurite, potassium aurithiocyanate, potassium chloroaurate, auric trichloride and 2- aurosulfobenzothiazole methochloride.
- the core emulsions can also be chemically sensitized with reducing agents, such as stannous salts (Carroll U.S. Patent 2,487,850 issued Nov. 15, 1949), polyamines, such as diethylene triamine (Lowe and Jones U.S. Patent 2,518,698 issued Aug. 15, 1950), polyamines, such as spermine (Lowe and Allen U.S. Patent 2,521,925 issued Sept. 12, 1950), or bis(/i-aminoethyl)sulfide and its watersoluble salts (Lowe and Jones U.S. Patent 2,521,926 issued Sept. 12, 1950).
- reducing agents such as stannous salts (Carroll U.S. Patent 2,487,850 issued Nov. 15, 1949), polyamines, such as diethylene triamine (Lowe and Jones U.S. Patent 2,518,698 issued Aug. 15, 1950), polyamines, such as spermine (Lowe and Allen U.S. Patent 2,521,925 issued Sept. 12, 1950), or bis(/i-a
- the core emulsions can also be treated with salts of the noble metals and/or the metals of Group VIII of the Periodic Table, such as ruthenium, rhodium, palladium, iridium, osmium, and platinum.
- Representative compounds are ammonium ohloropalladate, potassium chloroplatinate, and sodium chloropalladite, which are used for sensitizing in amounts below that which produces any substantial fog inhibition, as described in Smith and Trivelli U.S. Patent 2,448,060, issued Aug. 31, 1948, and as antifoggants in higher amount-s, 'as described in Trivelli and Smith U.S. Patents 2,566,245, issued Aug. 28, 1951 and 2,566,263, issued Aug. 28, 1951.
- the core emulsions can also be subjected to fogging by exposure to light either to low or high intensity light, to produce centers which promote the deposition of photolytic silver prior to forming the shell thereon.
- the core emulsions can also contain speed increasing compounds of the quaternary ammonium type of Carroll U.S. Patent 2,271,623, issued Feb. 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 Nov. 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 US. Patent 2,886,437, issued May 12, 1959; as well as the thiopolymers of Graham and Sagal US. Patent 3,046,129, issued July 24, 1962; and the Dann and Chechak U.S. Patent 3,046,134, issued July 24, 1962.
- the shell of the grains comprising the present emulsions is prepared by precipitating over the core grains a light-sensitive water-insoluble silver salt that can be fogged and which fog is removable by bleaching.
- the shell is of sufficient thickness to prevent access of the developer used in processing the emulsions of the invention to the core.
- the silver salt shell i surface fogged to make it ,developable to metallic silver with conventional surface image developing compositions.
- the silver salt of the shell is sufiiciently fogged to produce a density of at least about 0.5 when developed for 6 minutes at 6 8 F. in Developer A above when the emulsion is coated at a silver coverage of 100 mg. per square foot.
- Such fogging can be effected by chemically sensitizing to fog with the sensitizing agents described for chemically sensitizing the core emulsion, high intensity light and the like fogging means well known to those skilled in the art. While the core need not be sensitized to fog, the shell is fogged. Fogging by means of a reduction sensitizer, a noble metal salt such as gold salt plus a reduction sensitizer, a sulfur sensitizer, high pH and low pAg silver halide precipitating conditions, and
- the shell portion of the subject grains can also be coated prior to fogging.
- the core of the grains of the present emulsions is a coarse grained silver salt and a finer grained silver salt is deposited thereon toform the shell.
- coarse grained silver salts can be used to form a shell over a finer grained core when the shell-forming silver salt is more water-soluble than the core silver salt.
- about 2 to 8 molar equivalents of shell silver salt per molar equivalent of core silver salt are used in the grains comprising the emulsions of the invention.
- the present emulsions which can be termed covered grain emulsions, contain a population of grains which are substantially uniform in grain-size distribution, as contrasted with other emulsion blends which contain at least two types of grains, which are separate and distinct in their physical, and frequently, photographic properties.
- the grain size of the subject emulsions widely varies, typical emulsions having an average grain size of about .1 to 10 microns in diameter.
- Silver halides are preferably utilized to prepare the core as well as the shell of the grains comprising the emulsions of the invention.
- Suitable silver halides include silver chloride, silver bromide, silver chlorobromide, silver bromoiodide and silver chlorobromoiodide.
- Other suitable salts for the core and/ or the shell include silver thiocyanate, silver phosphate, silver cyanide, silver carbonate and the like.
- hydrophilic, water-permeable organic colloids can be suitably utilized in preparing the silver salt emulsions or dispersions of the invention.
- Gelatin is preferably utilized although other colloidal material such as colloidal albumin, cellulose derivatives, synthetic resins or the like can be utilized.
- Suitable colloids that can be used are polyvinyl alcohol or a hydrolyzed polyvinyl acetate as described in Lowe US Patent 2,286,215, issued June 16, 1942; a far hydrolyzed cellulose ester such as cellulose acetate hydrolyzed to an acetyl content of 19 to 26% as described in US. Patent 2,327,808 of Lowe and Clark, issued Aug.
- emulsions of the invention can be coated on a wide variety of supports in accordance with usual practice.
- Typical supports for photographic elements of the invention include glass, metals, paper, polyethylene-coated paper, polypropylene-coated paper, cellulose nitrate film, cellulose acetate film, polyvinyl acetal film, polystyrene film, polyethyleneterephthalate film and related films of resinous materials and others.
- the photographic emulsions of the invention are exposed to an image and thereafter developed in a conventional surface image developer having low silver halide solvent action, a direct positive silver image is formed.
- the unexposed grains develop without substantial reduction of the image-wise exposed grains.
- the image can thereafter be fixed or stabilized by conventional techniques.
- Example 1 A gelatino silver chloride emulsion was prepared by simultaneously adding, over a period of about 20 minutes, 1000 ml. of a 4 molar silver nitrate aqueous solution and 1000 ml. of a 4 molar sodium chloride aqueous solution, to a well-stirred aqueous solution of 1000 ml. of 0.01 molar sodium chloride at 70 C. containing 40 grams of gelatin. Thereafter 5000 ml. of water containing 280 grams of gelatin were added and the emulsion cooled. Oneeighth of the resulting gelatino silver chloride emulsion (containing 0.5 mole percent silver chloride) was melted at 40 C., mg.
- This prepared emulsion constituted the silver chloride core containing physical discontinuities that trap electrons over which was coated a shell of silver chloride.
- the shell of silver chloride was formed by adding to the core emulsion 500 ml. of 4 molar silver nitrate aqueous solution and 500 m1. of 4 molar sodium chloride aqueous solution simultaneously over a period of 20 minutes. Then grams of gelatin, previously soaked in 340 ml. of water were then stirred in, and the emulsion cooled.
- the two solutions were added at approximately constant rates.
- Suflicient silver chloride was formed in the shell to give a ratio of 4 moles of shell silver chloride to 1 mole of core silver chloride.
- the resulting covered grain emulsion was melted, the gelatin content increased to 160 grams per mole of silver chloride, and water added to 4000 grams per mole of silver chloride.
- the covered grain emulsion was then coated on paper at a silver chloride coverage of one mole per 1000 square feet.
- the coated emulsion was surfaced fogged by flashing with a Clive Courtney microflash at a distance of 30 inches (at flash unit with a 50 joule output and an exposure time of about 2 10- seconds).
- a neutral density stepwedge having 0.15 log E increments with a relative low intensity exposure of 30 seconds duration to tungsten light (250- watt bulb at 30 inches) and developed in the developer below, a direct positive image was obtained.
- the development was for three minutes at 20 C.
- the developer had the following composition:
- Example 2 shell over the reduction sensitized silver chloride core. Sufficient silver chloride was formed in this shell to give a ratio of four moles of shell silver chloride to one mole of core silver chloride. The resulting emulsion was coated as described for Emulsion A.
- a gelatino silver bromide emulsion was prepared by Emulsion CC0Te and shell sensl'liled f0 f A gelatthe general method described in Example 1.
- Silver nitrate i110 Silver Chloride emulsion was P p as described and potassium bromide aqueous solutions were run into above for E'mulsion B except that Eiffel the shell silver an aqueous Solution of l i f 20 minutes at 70 C halide was formed, the emulsion was reduction sensitized The emulsion was cooled and 0.2 g.
- Emulsion C was cooled to 40 C- and fogged duction sensitized into fog by adding an excess of silver by adding 3.5 mg. of thiourea dioxide per mo e of S er nitrate as described in more detail for Emulsion A. halide and 4 ml. of 2.5 N Sod u hy r xi pe o of A sample of each of the four coatings was exposed on an silver halide.
- the resulting emu ion was ated to 55 20 intensity scale sensitometer and processed for 10 seconds held for minutes, and cooled.
- the emulsion was at 68 F. in the developer described in Example 2, fixed, acidified and gelatin added to bring the total to 165 g. washed and dried with the following results:
- the resulting emul- Example 4 sion was coated on a paper support at a coverage of about one mole of silver halide per 1000 square feet.
- the coated emulsion was thereafter exposed in an intensity scale sensitometer to tungsten light and developed for 60 seconds at 68 F. in the developer described below, fixed, washed and dried.
- the developer utilized had the following formula:
- the exposed and processed coating exhibited a direct positive image having a D of 0.9.
- Example 3 Four separate gelatino silver chloride emulsions were prepared to illustrate the utility of the present covered grain silver salt emulsions (i.e., a core containing centers which promote formation of photolytic silver and a fogged shell) as direct positive emulsions.
- Emulsion A-Core sensitized to fog A gelatino silver chloride emulsion was prepared by adding aqueous solutions of silver nitrate and potassium chloride simultaneously to a rapidly agitated gelatin solution over a period of 20 minutes at 70 C. This emulsion was then reduction sensitized into fog by adding an excess of silver nitrate and holding for 20 minutes at 70 C. at a pAg of 2.5 and a pH of 7.5. Following this treatment, the pH was adjusted to 5.5 and the pAg to 6.8. The resulting emulsion was coated on a paper support at a coverage of 120 mg. of silver per square foot and 200 mg. of gelatin per square foot.
- Emulsion B-Core sensitized to fog and unjogg d sensitized shell A gelatino silver chloride emulsion was prepared and reduction sensitized into fog as described for Emulsion A above. After the reduction sensitization, aqueous solutions of silver nitrate and potassium chloride were added simultaneously to the core emulsion over a period of 20 minutes at 70 C. to form a silver chloride A gelatino silver chloride core emulsion was prepared by adding aqueous solutions of silver nitrate and sodium chloride simultaneously over a period of 20 minutes to a rapidly agitated aqueous gelatin solution at a temperature of 70 C. To a liquid portion of this emulsion containing 0.5 mole of silver chloride was added 0.1 g.
- the pAg was adjusted to 7.0 by the addition of aqueous potassium chloride solution.
- the resulting emulsion was then coated on a paper support at a coverage of 108 mg. of silver per square foot and 625 mg. of gelatin per square foot.
- a sample of this coating was exposed on an intensity scale sensitometer and processed for three minutes at 20 C. in the developor described in Example 1, fixed, washed and dried.
- a direct-positive image was formed having the following characteristics Contrast 1.20 D 1.10 D 0.20 AD 0.90
- the present invention thus provides a new and useful class of direct positive sliver halide emulsions.
- a light-sensitive photographic direct positive emulsion 'containing'grains comprising a central coreof a water-insoluble silver salt containing centers which promote the deposition of photolytic silver and an outer shell covering said core comprising a fogged water-insoluble silver salt that develops to silver without exposure.
- a light-sensitive photographic direct positive emulsion containing grains comprising a central core of silver halide containing centers which promote the deposition of photolytic silver and an outer shell covering said core comprising a fogged silver halide that develops to silver without exposure.
- a light-sensitive photographic direct positive emulsion containing silver halide grains comprising a central core of chemically sensitized silver halide and an outer shell covering said core comprising fogged silver halide that develops to silver without exposure.
- a light-sensitive photographic direct positive emulsion containing grains comprising a central core of a water-insoluble silver salt containing centers which promote the deposition of photolytic silver, said centers being obtained by treatment of said core with an iridium salt, and an outer shell covering said core comprising a fogged Water-insoluble silver salt that develops to silver Without exposure.
- a light-sensitive photographic direct positive emulsion containing silver halide grains comprising a central core of silver halide containing centers which promote the deposition of photolytic silver, said centers being obtained by treatment of said core with an iridium salt, and an outer-shell covering said core comprising fogged silver halide that develops to silver Without exposure.
- a light-sensitive photographic direct positive emulsion containing silver halide grains comprising a central core of fogged silver halide and an outer shell covering said core comprising fogged silver halide, said outer shell being fogged subsequent to the formation of said outer shell.
- a light-sensitive photographic direct positive gelatino emulsion containing silver chloride grains comprising a central core of silver chloride containing centers which promote the deposition of photolytic silver, said centers being obtained by treatment of said core with an iridium salt, and an outer shell covering said core comprising fogged silver chloride that develops to silver without exposure.
Description
United States Patent 3,367,778 SILVER SALT DIRECT POSITIVE EMULSION Robert W. Berriman, Harrow, England, assignor to Eastman Kodak Company, Rochester, N.Y., a corporation of New Jersey No Drawing. Filed Apr. 15, 1965, Ser. No. 448,467 Claims. (CI. 9664) This invention relates to a novel class of photographic emulsions, and more particularly, to direct positive emulsions (sometimes called reversal emulsion).
Direct positive silver halide emulsions are well known in the photographic art. However, many reversal systems are characterized as being of low speed, producing undesirably high background or D density, requiring special developing compositions, requiring processing steps between exposure and development, being diflicult to control, and the like undesirable features.
It is accordingly an object of this invention to provide a novel class of photographic direct positive emulsions.
It is another object of this invention to provide novel photographic direct positive emulsions having relatively high sensitivity.
It is another object of this invention to provide novel photographic emulsions that are characterized in producing direct positive images having low D It is another object of this invention to provide novel photographic emulsions that can be processed to a direct positive with conventional surface-developing compositions.
It is still another object of this invention to provide novel direct positive silver halide emulsions that have higher sensitivity than conventional direct positive silver halide emulsions utilizing the Herschel effect.
It is likewise an object of this invention to provide new direct positive silver halide emulsions that have rapid processing characteristics.
These and other objects of the invention are accomplished with light-sensitive photographic direct positive emulsions containing grains comprising a central core of a water-insoluble silver salt containing centers which promote the deposition of photolytic silver and an outer shell or covering for such core of a fogged or spontaneously developable water-insoluble silver salt. The fogged shell of such grains develops to silver without exposure.
Before the shell of water-insoluble silver salt is added to the silver salt core, the core emulsion is first chemically or physically treated by methods previously described in the prior art to produce centers which promote the deposition of photolytic silver, i.e., latent image nucleating centers. Such centers can be obtained by various techniques as described herein. Chemical sensitization techniques of the type described by Antoine Hautot and Henri Saubenier in Science et Industries Photographiques, vol. XXVIII, January 1957, pp. 1 to 23 and January 1957, pp. 57 to 65 are particularly useful. Such chemical sensitization includes three major classes, namely, 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 introduces small specks of metallic silver into the silver salt crystal or grain.
When the core emulsion is chemically sensitized, it is preferably sensitized so that 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 Developer A, as hereinafter defined, has 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 3,367,778 Patented Feb. 6, 1968 5 minutes in an aqueous 0.3 percent potassium ferricyanide solution at F., and developed for 5 minutes at 65 F., in Developer B, as hereinafter defined. Developer A is the usual type of surface image developer and Developer B is an internal developer having high silver halide solvent activity.
DEVELOPER A N-methyl-p-aminophenol sulfate grarns 2.5 Ascorbic acid do 10.0 Potassium metaborate do 35.0 Potassium bromide do 1.0 Water to liter 1 pH of 9.6
DEVELOPER B N-methyl-p-aminophenol sulfate grams 2.0 Sodium sulfite, desiccated do 90.0 Hydroquinone do 8.0 Sodium carbonate, monohydrate d0 52.5 Potassium bromide 10---- 5.0 Sodium thiosulfate do 10.0 Water to liter 1 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 U.S. Patent 1,574,944, issued Mar. 2, 1926, Sheppard et al. U.S. Patent 1,623,499 issued Apr. 5, 1927, and Sheppard et a1. U.S. Patent 2,410,689 issued Nov. 5, 1946.
The core emulsions can also be chemically sensitized with gold salts as described in Waller et al. U.S. Patent 2,399,083 issued Apr. 23, 1946 and Damschroder et al. U.S. Patent 2,642,361 issued June 16, 1953. Suitable com pounds are potassium chloroaurite, potassium aurithiocyanate, potassium chloroaurate, auric trichloride and 2- aurosulfobenzothiazole methochloride.
The core emulsions can also be chemically sensitized with reducing agents, such as stannous salts (Carroll U.S. Patent 2,487,850 issued Nov. 15, 1949), polyamines, such as diethylene triamine (Lowe and Jones U.S. Patent 2,518,698 issued Aug. 15, 1950), polyamines, such as spermine (Lowe and Allen U.S. Patent 2,521,925 issued Sept. 12, 1950), or bis(/i-aminoethyl)sulfide and its watersoluble salts (Lowe and Jones U.S. Patent 2,521,926 issued Sept. 12, 1950).
The core emulsions can also be treated with salts of the noble metals and/or the metals of Group VIII of the Periodic Table, such as ruthenium, rhodium, palladium, iridium, osmium, and platinum. Representative compounds are ammonium ohloropalladate, potassium chloroplatinate, and sodium chloropalladite, which are used for sensitizing in amounts below that which produces any substantial fog inhibition, as described in Smith and Trivelli U.S. Patent 2,448,060, issued Aug. 31, 1948, and as antifoggants in higher amount-s, 'as described in Trivelli and Smith U.S. Patents 2,566,245, issued Aug. 28, 1951 and 2,566,263, issued Aug. 28, 1951.
The core emulsions can also be subjected to fogging by exposure to light either to low or high intensity light, to produce centers which promote the deposition of photolytic silver prior to forming the shell thereon.
The core emulsions can also contain speed increasing compounds of the quaternary ammonium type of Carroll U.S. Patent 2,271,623, issued Feb. 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 Nov. 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 US. Patent 2,886,437, issued May 12, 1959; as well as the thiopolymers of Graham and Sagal US. Patent 3,046,129, issued July 24, 1962; and the Dann and Chechak U.S. Patent 3,046,134, issued July 24, 1962.
The shell of the grains comprising the present emulsions is prepared by precipitating over the core grains a light-sensitive water-insoluble silver salt that can be fogged and which fog is removable by bleaching. The shell is of sufficient thickness to prevent access of the developer used in processing the emulsions of the invention to the core. The silver salt shell i surface fogged to make it ,developable to metallic silver with conventional surface image developing compositions. The silver salt of the shell is sufiiciently fogged to produce a density of at least about 0.5 when developed for 6 minutes at 6 8 F. in Developer A above when the emulsion is coated at a silver coverage of 100 mg. per square foot. Such fogging can be effected by chemically sensitizing to fog with the sensitizing agents described for chemically sensitizing the core emulsion, high intensity light and the like fogging means well known to those skilled in the art. While the core need not be sensitized to fog, the shell is fogged. Fogging by means of a reduction sensitizer, a noble metal salt such as gold salt plus a reduction sensitizer, a sulfur sensitizer, high pH and low pAg silver halide precipitating conditions, and
the like can be suitably utilized. The shell portion of the subject grains can also be coated prior to fogging.
In a typical. embodiment of the invention, the core of the grains of the present emulsions is a coarse grained silver salt and a finer grained silver salt is deposited thereon toform the shell. Also, coarse grained silver salts can be used to form a shell over a finer grained core when the shell-forming silver salt is more water-soluble than the core silver salt. Generally, about 2 to 8 molar equivalents of shell silver salt per molar equivalent of core silver salt are used in the grains comprising the emulsions of the invention. The present emulsions, which can be termed covered grain emulsions, contain a population of grains which are substantially uniform in grain-size distribution, as contrasted with other emulsion blends which contain at least two types of grains, which are separate and distinct in their physical, and frequently, photographic properties. The grain size of the subject emulsions widely varies, typical emulsions having an average grain size of about .1 to 10 microns in diameter.
Silver halides are preferably utilized to prepare the core as well as the shell of the grains comprising the emulsions of the invention. Suitable silver halides include silver chloride, silver bromide, silver chlorobromide, silver bromoiodide and silver chlorobromoiodide. Other suitable salts for the core and/ or the shell include silver thiocyanate, silver phosphate, silver cyanide, silver carbonate and the like.
A wide variety of hydrophilic, water-permeable organic colloids can be suitably utilized in preparing the silver salt emulsions or dispersions of the invention. Gelatin is preferably utilized although other colloidal material such as colloidal albumin, cellulose derivatives, synthetic resins or the like can be utilized. Suitable colloids that can be used are polyvinyl alcohol or a hydrolyzed polyvinyl acetate as described in Lowe US Patent 2,286,215, issued June 16, 1942; a far hydrolyzed cellulose ester such as cellulose acetate hydrolyzed to an acetyl content of 19 to 26% as described in US. Patent 2,327,808 of Lowe and Clark, issued Aug. 24, 1943; a water-soluble ethanolamine cellulose acetate as described in Yutzy US. Patent 2,322,- 085, issued June 15, 1943; a polyacrylamide having a combined acrylamide content of 30 to 60% and a specific viscosity of 0.25 to 1.5 of an imidized polyacrylamide of like acrylamide content and viscosity as described in Lowe, Minsk and Kenyon US. Patent 2,541,474, issued Feb. 13, 1951; zein as described in Lowe US. Patent 2,563,791, issued Aug. 7, 1951; a vinyl alcohol polymer containing urethane carboxylic acid groups of the type described in Dumb and Smith US. Patent 2,768,154, issued Oct.
23, 1956; or containing cy ano-acetyl groups such as the vinyl alcohol-vinyl cyanoacet-ate copolymer as described in Unruh, Smith and Priest US. Patent 2,808,331, issued Oct. 1, 1957; 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 Illingsworth, Dann and Gates US Patent 2,852,382, issued Sept. 19, 1958.
The emulsions of the invention can be coated on a wide variety of supports in accordance with usual practice. Typical supports for photographic elements of the invention include glass, metals, paper, polyethylene-coated paper, polypropylene-coated paper, cellulose nitrate film, cellulose acetate film, polyvinyl acetal film, polystyrene film, polyethyleneterephthalate film and related films of resinous materials and others.
When the photographic emulsions of the invention are exposed to an image and thereafter developed in a conventional surface image developer having low silver halide solvent action, a direct positive silver image is formed. The unexposed grains develop without substantial reduction of the image-wise exposed grains. The image can thereafter be fixed or stabilized by conventional techniques.
The invention is further illustrated by the following examples of preferred embodiments thereof.
Example 1 A gelatino silver chloride emulsion was prepared by simultaneously adding, over a period of about 20 minutes, 1000 ml. of a 4 molar silver nitrate aqueous solution and 1000 ml. of a 4 molar sodium chloride aqueous solution, to a well-stirred aqueous solution of 1000 ml. of 0.01 molar sodium chloride at 70 C. containing 40 grams of gelatin. Thereafter 5000 ml. of water containing 280 grams of gelatin were added and the emulsion cooled. Oneeighth of the resulting gelatino silver chloride emulsion (containing 0.5 mole percent silver chloride) was melted at 40 C., mg. of the water-soluble iridium salt, potassium chloroiridite, dissolved in water were added, and the emulsion was heated to 70 C. This prepared emulsion constituted the silver chloride core containing physical discontinuities that trap electrons over which was coated a shell of silver chloride. The shell of silver chloride was formed by adding to the core emulsion 500 ml. of 4 molar silver nitrate aqueous solution and 500 m1. of 4 molar sodium chloride aqueous solution simultaneously over a period of 20 minutes. Then grams of gelatin, previously soaked in 340 ml. of water were then stirred in, and the emulsion cooled. During both additions of the silver nitrate and sodium chloride (i .e., to form both the core and the shell), the two solutions were added at approximately constant rates. Suflicient silver chloride was formed in the shell to give a ratio of 4 moles of shell silver chloride to 1 mole of core silver chloride. The resulting covered grain emulsion was melted, the gelatin content increased to 160 grams per mole of silver chloride, and water added to 4000 grams per mole of silver chloride. The covered grain emulsion was then coated on paper at a silver chloride coverage of one mole per 1000 square feet. The coated emulsion was surfaced fogged by flashing with a Clive Courtney microflash at a distance of 30 inches (at flash unit with a 50 joule output and an exposure time of about 2 10- seconds). When exposed to a neutral density stepwedge having 0.15 log E increments with a relative low intensity exposure of 30 seconds duration to tungsten light (250- watt bulb at 30 inches) and developed in the developer below, a direct positive image was obtained. The development was for three minutes at 20 C. The developer had the following composition:
Grams p-Hydroxyphenyl glycine 24.0 Sodium carbonate (anhydrous) 40.0 Sodium chloride 1.4
Water to make one liter.
Similar results are obtained when the silver salt is silver thiocyanate, sodium thiocyanate being used in lieu of the sodium chloride during the core and/or shell formation.
Example 2 shell over the reduction sensitized silver chloride core. Sufficient silver chloride was formed in this shell to give a ratio of four moles of shell silver chloride to one mole of core silver chloride. The resulting emulsion was coated as described for Emulsion A.
A gelatino silver bromide emulsion was prepared by Emulsion CC0Te and shell sensl'liled f0 f A gelatthe general method described in Example 1. Silver nitrate i110 Silver Chloride emulsion Was P p as described and potassium bromide aqueous solutions were run into above for E'mulsion B except that Eiffel the shell silver an aqueous Solution of l i f 20 minutes at 70 C halide was formed, the emulsion was reduction sensitized The emulsion was cooled and 0.2 g. of potassium chlo- 10 into fog y adding 2 of Thiourea dioxide P mole -m per mole of Silver halide was added, The mof silver halide and holding the resulting emulsion for sion was reheated to 70 C. and more silver nitrate and minutes at The resulting emulsion was then Coated potassium bromide aqueous solution were run in for as described for Emulsion minutes to form a shell of silver bromide. Sufiicient silver Emulsion DUnfogged sensitized core and shell senbromide was formed in the shell to give a ratio of 4 moles 15 sitized t0 fog: An emulsion was prepared as described of shell silver bromide to 1 mole of core silver bromide. above for Emulsion C, except that the core was not re- The resulting emulsion was cooled to 40 C- and fogged duction sensitized into fog by adding an excess of silver by adding 3.5 mg. of thiourea dioxide per mo e of S er nitrate as described in more detail for Emulsion A. halide and 4 ml. of 2.5 N Sod u hy r xi pe o of A sample of each of the four coatings was exposed on an silver halide. The resulting emu ion Was ated to 55 20 intensity scale sensitometer and processed for 10 seconds held for minutes, and cooled. The emulsion was at 68 F. in the developer described in Example 2, fixed, acidified and gelatin added to bring the total to 165 g. washed and dried with the following results:
Emulsion Core Shell Rel. Speed Contrast D max. D min. A D
A sensitized to fog None 1.65 1.65 0 B do Unfogged 0 0 0 1)-. Unfogged sensitized toiog 100 1.6 1.35 0. 04 1.31 C sensitized to fog do 795 5.0 1.30 0.01 1. 29
1A preferred emulsion of the invention.
of gelatin per mole of silver halide. The resulting emul- Example 4 sion was coated on a paper support at a coverage of about one mole of silver halide per 1000 square feet. The coated emulsion was thereafter exposed in an intensity scale sensitometer to tungsten light and developed for 60 seconds at 68 F. in the developer described below, fixed, washed and dried. The developer utilized had the following formula:
Grams N-methyl-p-aminophenol sulfate 3.0 Sodium sulfite (anhydrous) 45.0 Hydroquinone 12.0 Sodium carbonate monohydrate 80.0 Potassium bromide 2.0
Water to make two liters.
The exposed and processed coating exhibited a direct positive image having a D of 0.9.
Example 3 Four separate gelatino silver chloride emulsions were prepared to illustrate the utility of the present covered grain silver salt emulsions (i.e., a core containing centers which promote formation of photolytic silver and a fogged shell) as direct positive emulsions.
Emulsion A-Core sensitized to fog: A gelatino silver chloride emulsion was prepared by adding aqueous solutions of silver nitrate and potassium chloride simultaneously to a rapidly agitated gelatin solution over a period of 20 minutes at 70 C. This emulsion was then reduction sensitized into fog by adding an excess of silver nitrate and holding for 20 minutes at 70 C. at a pAg of 2.5 and a pH of 7.5. Following this treatment, the pH was adjusted to 5.5 and the pAg to 6.8. The resulting emulsion was coated on a paper support at a coverage of 120 mg. of silver per square foot and 200 mg. of gelatin per square foot.
Emulsion B-Core sensitized to fog and unjogg d sensitized shell: A gelatino silver chloride emulsion was prepared and reduction sensitized into fog as described for Emulsion A above. After the reduction sensitization, aqueous solutions of silver nitrate and potassium chloride were added simultaneously to the core emulsion over a period of 20 minutes at 70 C. to form a silver chloride A gelatino silver chloride core emulsion was prepared by adding aqueous solutions of silver nitrate and sodium chloride simultaneously over a period of 20 minutes to a rapidly agitated aqueous gelatin solution at a temperature of 70 C. To a liquid portion of this emulsion containing 0.5 mole of silver chloride was added 0.1 g. of potassium chloroiridite in ml. of water, and the resulting mixture held for 10 minutes at 70 C. to chemically sensitize the core emulsion. Aqueous solutions of silver nitrate and silver chloride were thereafter added simultaneously to the core over a period of 20 minutes at 25 C. to form a silver chloride shell over the chemically sensitized core emulsion. Suificient silver chloride was formed in the shell to give a ratio of four moles of silver chloride shell to one mole of silver chloride core. The resulting emulsion was reduction sensitized into fog by adding an excess of silver nitrate thereto and holding the emulsion for 30 minutes at 55 C. at a pAg of about 2.5 and a pH of 7.4. Following this reduction sensitizing treatment, the pAg was adjusted to 7.0 by the addition of aqueous potassium chloride solution. The resulting emulsion was then coated on a paper support at a coverage of 108 mg. of silver per square foot and 625 mg. of gelatin per square foot. A sample of this coating was exposed on an intensity scale sensitometer and processed for three minutes at 20 C. in the developor described in Example 1, fixed, washed and dried. A direct-positive image was formed having the following characteristics Contrast 1.20 D 1.10 D 0.20 AD 0.90
The present invention thus provides a new and useful class of direct positive sliver halide emulsions.
The invention has been described in considerable detail with particular reference to preferred embodiments thereof, but will be understood that variations and modifications can be effected within the spirit and scope of the invention as described hereinabove and as defined in the appended claims.
7 I claim: 1. A light-sensitive photographic direct positive emulsion 'containing'grains comprising a central coreof a water-insoluble silver salt containing centers which promote the deposition of photolytic silver and an outer shell covering said core comprising a fogged water-insoluble silver salt that develops to silver without exposure.
2. The process which comprises exposing to an image an emulsion as described in claim 1 and thereafter developing the exposed emulsion in a surface image silver halide developing composition of low silver halide solvent action sufiicient to develop unexposed grains of the emulsion without substantial development of the image-wise exposed grains of the emulsion.
3. A light-sensitive photographic direct positive emulsion containing grains comprising a central core of silver halide containing centers which promote the deposition of photolytic silver and an outer shell covering said core comprising a fogged silver halide that develops to silver without exposure.
4. A light-sensitive photographic direct positive emulsion containing silver halide grains comprising a central core of chemically sensitized silver halide and an outer shell covering said core comprising fogged silver halide that develops to silver without exposure.
5. The direct positive emulsion of claim 4 wherein said outer shell is fogged with a reduction sensitizer.
6. The direct positive emulsion of claim 4 wherein said outer shell is fogged with a gold salt and a reduction sensitizer.
7. A light-sensitive photographic direct positive emulsion containing grains comprising a central core of a water-insoluble silver salt containing centers which promote the deposition of photolytic silver, said centers being obtained by treatment of said core with an iridium salt, and an outer shell covering said core comprising a fogged Water-insoluble silver salt that develops to silver Without exposure.
8. A light-sensitive photographic direct positive emulsion containing silver halide grains comprising a central core of silver halide containing centers which promote the deposition of photolytic silver, said centers being obtained by treatment of said core with an iridium salt, and an outer-shell covering said core comprising fogged silver halide that develops to silver Without exposure.
9. A light-sensitive photographic direct positive emulsion containing silver halide grains comprising a central core of fogged silver halide and an outer shell covering said core comprising fogged silver halide, said outer shell being fogged subsequent to the formation of said outer shell.
10. A light-sensitive photographic direct positive gelatino emulsion containing silver chloride grains comprising a central core of silver chloride containing centers which promote the deposition of photolytic silver, said centers being obtained by treatment of said core with an iridium salt, and an outer shell covering said core comprising fogged silver chloride that develops to silver without exposure.
References Cited UNITED STATES PATENTS 4/1965 Luckey et al. 96-64 9/1965 Porter et al. 9 6-l07
Claims (2)
1. A LIGHT-SENSITIVE PHOTOGRAPHIC DIRECT POSITIVE EMULSION CONTAINING GRAINS COMPRISING A CENTRAL CORE OF A WATER-INSOLUBLE SILVER SALT CONTAINING CENTERS WHICH PROMOTE THE DEPOSITION OF PHOTOLYTIC SILVER AND AN OUTER SHELL COVERING SAID CORE COMPRISING A FOGGED WATER-INSOLUBLE SILVER SALT THAT DEVELOPS TO SILVER WITHOUT EXPOSURE.
10. A LIGHT-SENSITIVE PHOTOGRAPHIC DIRECT POSITIVE GELATINO EMULSION CONTAINING SILVER CHLORIDE GRAINS COMPRISING A CENTRAL CORE OF SILVER CHLORIDE CONTAINING CENTERS WHICH PROMOTE THE DEPOSITION OF PHOTOLYTIC SILVER, SAID CENTERS BEING OBTAINED BY TREATMENT OF SAID CORE WITH AN IRIDIUM SALT, AND AN OUTER SHELL COVERING SAID CORE COMPRISING FOGGED SILVER CHLORIDE THAT DEVELOPS TO SILVER WITHOUT EXPOSURE.
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US448467A US3367778A (en) | 1965-04-15 | 1965-04-15 | Silver salt direct positive emulsion |
GB54615/68A GB1151782A (en) | 1965-04-15 | 1966-04-15 | Photographic silver halide emulsions |
GB16507/66A GB1151781A (en) | 1965-04-15 | 1966-04-15 | Photographic direct positive emulsions and Sensitive Materials |
US05/794,489 USRE29974E (en) | 1965-04-15 | 1977-05-06 | Silver salt direct positive emulsion |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US448467A US3367778A (en) | 1965-04-15 | 1965-04-15 | Silver salt direct positive emulsion |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US05/794,489 Reissue USRE29974E (en) | 1965-04-15 | 1977-05-06 | Silver salt direct positive emulsion |
Publications (1)
Publication Number | Publication Date |
---|---|
US3367778A true US3367778A (en) | 1968-02-06 |
Family
ID=23780413
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US448467A Expired - Lifetime US3367778A (en) | 1965-04-15 | 1965-04-15 | Silver salt direct positive emulsion |
US05/794,489 Expired - Lifetime USRE29974E (en) | 1965-04-15 | 1977-05-06 | Silver salt direct positive emulsion |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US05/794,489 Expired - Lifetime USRE29974E (en) | 1965-04-15 | 1977-05-06 | Silver salt direct positive emulsion |
Country Status (2)
Country | Link |
---|---|
US (2) | US3367778A (en) |
GB (2) | GB1151782A (en) |
Cited By (52)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3501309A (en) * | 1966-03-11 | 1970-03-17 | Eastman Kodak Co | Direct positive silver halide emulsions containing halogenated cyanine dyes |
US3531291A (en) * | 1967-04-07 | 1970-09-29 | Eastman Kodak Co | Silver halide emulsions capable of being chemically or photo developed |
US3531288A (en) * | 1966-03-11 | 1970-09-29 | Eastman Kodak Co | Direct positive silver halide emulsions containing excess iodide |
US3632340A (en) * | 1968-09-09 | 1972-01-04 | Eastman Kodak Co | Cored direct positive silver halide emulsion developed with polyhydroxybenzene |
US3709689A (en) * | 1969-04-02 | 1973-01-09 | Agfa Gevaert | Surface development of an imagewise exposed emulsion containing silver halide grains with cores chemically ripened in two stages |
US3717466A (en) * | 1970-04-01 | 1973-02-20 | Agfa Gevaert Nv | Fogged direct positive silver halide element containing a selenium compound sensitizer |
US3719494A (en) * | 1970-10-30 | 1973-03-06 | Eastman Kodak Co | Silver halide emulsion containing a dihydroaromatic quaternary salt nucleating agent and the use thereof |
DE2224837A1 (en) * | 1972-05-20 | 1973-11-29 | Agfa Gevaert Ag | PHOTOGRAPHIC MATERIAL FOR THE PRODUCTION OF DIRECT POSITIVE PHOTOGRAPHIC IMAGES |
US3779777A (en) * | 1971-11-09 | 1973-12-18 | Du Pont | Silver halide emulsion sensitized with a polyhedral haloborane |
US3854949A (en) * | 1971-03-10 | 1974-12-17 | Eastman Kodak Co | Silver halide photographic compositions and processes for obtaining positive images |
US3859093A (en) * | 1972-04-01 | 1975-01-07 | Agfa Gevaert Ag | Fogged, direct positive emulsion containing composite silver halide grains protected with silver halide layer and the use thereof in reversal process |
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 |
US3942986A (en) * | 1973-06-08 | 1976-03-09 | Agfa-Gevaert, N.V. | Photographic element comprising a fogged, direct-positive heterodispersed silver halide emulsion and a fogged, direct-positive monodispersed silver halide |
US3945832A (en) * | 1973-03-27 | 1976-03-23 | Fuji Photo Film Co., Ltd. | Fogged, direct-positive silver halide emulsion containing desensitizers and a dimethine optical sensitizing dye |
US3963493A (en) * | 1972-02-18 | 1976-06-15 | Agfa-Gevaert N.V. | Direct-positive silver halide emulsion fogged to low level and the use thereof in energetic-surface development |
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 |
US3970461A (en) * | 1970-10-01 | 1976-07-20 | Fuji Photo Film Co., Ltd. | Fogged, direct-positive silver halide emulsion containing carbocyanine dye having indolenine nucleus |
US3977880A (en) * | 1973-10-18 | 1976-08-31 | Fuji Photo Film Co., Ltd. | Direct-positive emulsion containing silver halide grains internally doped with metal ions, surface ripened with gold and sulfur compound and fogged by light exposure |
US4009041A (en) * | 1974-10-03 | 1977-02-22 | Polaroid Corporation | Fogged, direct-positive silver halide emulsion containing a gallium sulfide semiconductor |
US4011083A (en) * | 1974-12-10 | 1977-03-08 | Eastman Kodak Company | Surface sensitive silver halide emulsion containing a silver complexing azaindene to reduce desensitization of optical sensitizing dye incorporated therein |
US4023972A (en) * | 1973-06-18 | 1977-05-17 | Agfa-Gevaert N.V. | Method of preparing a blend of fogged, direct-positive silver halide emulsions of different average grain sizes |
US4045228A (en) * | 1972-12-08 | 1977-08-30 | Agfa-Gevaert N.V. | Direct positive emulsions containing fogged, monodispersed silver halide grains having more than 10 mile % iodide |
US4059450A (en) * | 1972-12-08 | 1977-11-22 | Agfa-Gevaert N.V. | Direct positive silver halide elements |
US4246337A (en) * | 1978-05-01 | 1981-01-20 | Corning Glass Works | Photosensitive medium for optical information storage |
US4287296A (en) * | 1972-12-23 | 1981-09-01 | Agfa-Gevaert, N.V. | Direct-positive emulsion containing fogged, silver halide grains of silver iodide content |
US4301242A (en) * | 1977-02-26 | 1981-11-17 | Agfa-Gevaert Aktiengesellschaft | Emulsion mixture for color reversal (reflection viewing) material |
US4327172A (en) * | 1980-12-16 | 1982-04-27 | Western Electric Company, Inc. | Photographic image definition improvement |
JPS58186739A (en) * | 1982-04-26 | 1983-10-31 | Konishiroku Photo Ind Co Ltd | Photosensitive silver halide material for direct positive |
DE3332975A1 (en) * | 1982-09-13 | 1984-03-15 | Konishiroku Photo Industry Co., Ltd., Tokyo | PHOTOGRAPHIC SILVER HALOGEN EMULSION |
DE3419481A1 (en) * | 1983-05-24 | 1984-12-13 | Fuji Photo Film Co., Ltd., Minami-Ashigara, Kanagawa | DIRECT PHOTOGRAPHIC LIGHT-SENSITIVE POSITIVE MATERIAL |
EP0143424A2 (en) | 1983-11-25 | 1985-06-05 | Fuji Photo Film Co., Ltd. | Heat-developable light-sensitive materials |
US4551421A (en) * | 1983-02-14 | 1985-11-05 | Fuji Photo Film Co., Ltd. | Silver halide photographic materials |
US4551419A (en) * | 1983-02-10 | 1985-11-05 | Fuji Photo Film Co., Ltd. | Method of developing silver halide photographic material |
US4552838A (en) * | 1984-05-18 | 1985-11-12 | Eastman Kodak Company | Processes for the preparation of silver halide emulsions of controlled grain size distribution, emulsions produced thereby, and photographic elements |
US4604339A (en) * | 1982-11-30 | 1986-08-05 | Fuji Photo Film Co., Ltd. | Method of developing silver halide photographic light-sensitive material |
EP0200011A1 (en) | 1985-03-30 | 1986-11-05 | Fuji Photo Film Co., Ltd. | Heat-developable light-sensitive material |
US4626498A (en) * | 1983-05-20 | 1986-12-02 | Fuji Photo Film Co., Ltd. | Color reversal photographic light-sensitive material |
EP0204530A2 (en) | 1985-05-31 | 1986-12-10 | Konica Corporation | Method for forming direct positive color image |
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) |
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 |
EP0300631A2 (en) * | 1987-07-21 | 1989-01-25 | Minnesota Mining And Manufacturing Company | Direct-positive silver halide emulsion |
US4863838A (en) * | 1979-03-26 | 1989-09-05 | Konishiroku Photo Industry Co., Ltd. | Direct positive type light-sensitive silver halide photographic materials |
US4902611A (en) * | 1989-01-06 | 1990-02-20 | Leubner Ingo H | Preparation of silver halide emulsions containing iridium |
US5279920A (en) * | 1991-11-01 | 1994-01-18 | Konica Corporation | Silver halide photographic light sensitive material |
US5395746A (en) * | 1994-02-25 | 1995-03-07 | Eastman Kodak Company | Inherently stable high chloride tabular grains with improved blue absorption |
US5424170A (en) * | 1993-08-31 | 1995-06-13 | Konica Corporation | Silver halide photographic light sensitive material |
EP0696757A2 (en) | 1994-08-09 | 1996-02-14 | Eastman Kodak Company | Film for duplicating silver images in radiographic films |
EP0754967A1 (en) | 1995-07-14 | 1997-01-22 | Agfa-Gevaert N.V. | Photographic direct positive material containing a particular stabilizer |
EP1376217A1 (en) * | 2001-02-28 | 2004-01-02 | Dai Nippon Printing Co., Ltd. | Lenticular lens sheet having light-shielding layer and method for manufacture thereof |
WO2011158245A1 (en) * | 2010-06-16 | 2011-12-22 | Department Of Biotechnology | Sealbio: a novel non-obturation regenerative technique of endodontic treatment. |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0711681B2 (en) * | 1986-04-26 | 1995-02-08 | コニカ株式会社 | Silver halide photographic light-sensitive material |
JPH0734103B2 (en) * | 1987-10-19 | 1995-04-12 | 富士写真フイルム株式会社 | Silver halide photographic light-sensitive material |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3178282A (en) * | 1959-01-12 | 1965-04-13 | Eastman Kodak Co | Photographic elements containing surface image and fogged internal image silver halide grains |
US3206313A (en) * | 1961-05-15 | 1965-09-14 | Eastman Kodak Co | Chemically sensitized emulsions having low surface sensitivity and high internal sensitivity |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BE476292A (en) * | 1946-04-01 | |||
GB723019A (en) * | 1952-02-05 | 1955-02-02 | Gevaert Photo Prod Nv | Improvements in or relating to the manufacture of photographic material |
US2717833A (en) * | 1952-05-12 | 1955-09-13 | Sperry Rand Corp | Direct positive emulsions |
FR1367941A (en) * | 1962-09-01 | 1964-07-24 | Agfa Ag | photographic silver halide emulsion containing composite silver halide grains having an extremely narrow particle size distribution |
BE636801A (en) * | 1962-09-01 |
-
1965
- 1965-04-15 US US448467A patent/US3367778A/en not_active Expired - Lifetime
-
1966
- 1966-04-15 GB GB54615/68A patent/GB1151782A/en not_active Expired
- 1966-04-15 GB GB16507/66A patent/GB1151781A/en not_active Expired
-
1977
- 1977-05-06 US US05/794,489 patent/USRE29974E/en not_active Expired - Lifetime
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3178282A (en) * | 1959-01-12 | 1965-04-13 | Eastman Kodak Co | Photographic elements containing surface image and fogged internal image silver halide grains |
US3206313A (en) * | 1961-05-15 | 1965-09-14 | Eastman Kodak Co | Chemically sensitized emulsions having low surface sensitivity and high internal sensitivity |
Cited By (65)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3501309A (en) * | 1966-03-11 | 1970-03-17 | Eastman Kodak Co | Direct positive silver halide emulsions containing halogenated cyanine dyes |
US3510348A (en) * | 1966-03-11 | 1970-05-05 | Eastman Kodak Co | Direct positive recording film |
US3531288A (en) * | 1966-03-11 | 1970-09-29 | Eastman Kodak Co | Direct positive silver halide emulsions containing excess iodide |
US3531290A (en) * | 1966-03-11 | 1970-09-29 | Eastman Kodak Co | Direct positive silver halide emulsions containing excess halide |
US3537858A (en) * | 1966-03-11 | 1970-11-03 | Eastman Kodak Co | Reversal silver halide emulsions |
US3531291A (en) * | 1967-04-07 | 1970-09-29 | Eastman Kodak Co | Silver halide emulsions capable of being chemically or photo developed |
US3632340A (en) * | 1968-09-09 | 1972-01-04 | Eastman Kodak Co | Cored direct positive silver halide emulsion developed with polyhydroxybenzene |
US3709689A (en) * | 1969-04-02 | 1973-01-09 | Agfa Gevaert | Surface development of an imagewise exposed emulsion containing silver halide grains with cores chemically ripened in two stages |
US3717466A (en) * | 1970-04-01 | 1973-02-20 | Agfa Gevaert Nv | Fogged direct positive silver halide element containing a selenium compound sensitizer |
US3970461A (en) * | 1970-10-01 | 1976-07-20 | Fuji Photo Film Co., Ltd. | Fogged, direct-positive silver halide emulsion containing carbocyanine dye having indolenine nucleus |
US3719494A (en) * | 1970-10-30 | 1973-03-06 | Eastman Kodak Co | Silver halide emulsion containing a dihydroaromatic quaternary salt nucleating agent and the use thereof |
US3854949A (en) * | 1971-03-10 | 1974-12-17 | Eastman Kodak Co | Silver halide photographic compositions and processes for obtaining positive images |
US3779777A (en) * | 1971-11-09 | 1973-12-18 | Du Pont | Silver halide emulsion sensitized with a polyhedral haloborane |
US3963493A (en) * | 1972-02-18 | 1976-06-15 | Agfa-Gevaert N.V. | Direct-positive silver halide emulsion fogged to low level and the use thereof in energetic-surface development |
US3859093A (en) * | 1972-04-01 | 1975-01-07 | Agfa Gevaert Ag | Fogged, direct positive emulsion containing composite silver halide grains protected with silver halide layer and the use thereof in reversal process |
DE2224837A1 (en) * | 1972-05-20 | 1973-11-29 | Agfa Gevaert Ag | PHOTOGRAPHIC MATERIAL FOR THE PRODUCTION OF DIRECT POSITIVE PHOTOGRAPHIC IMAGES |
US3870522A (en) * | 1972-05-20 | 1975-03-11 | Agfa Gevaert Ag | Fogged, direct-positive emulsion containing heterodisperse and irregular composite silver halide grains |
US4059450A (en) * | 1972-12-08 | 1977-11-22 | Agfa-Gevaert N.V. | Direct positive silver halide elements |
US4045228A (en) * | 1972-12-08 | 1977-08-30 | Agfa-Gevaert N.V. | Direct positive emulsions containing fogged, monodispersed silver halide grains having more than 10 mile % iodide |
US4287296A (en) * | 1972-12-23 | 1981-09-01 | Agfa-Gevaert, N.V. | Direct-positive emulsion containing fogged, silver halide grains of silver iodide content |
US3917485A (en) * | 1973-01-18 | 1975-11-04 | Eastman Kodak Co | Method of making photographic silver halide emulsions and products thereof |
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 |
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 |
US3945832A (en) * | 1973-03-27 | 1976-03-23 | Fuji Photo Film Co., Ltd. | Fogged, direct-positive silver halide emulsion containing desensitizers and a dimethine optical sensitizing dye |
US3942986A (en) * | 1973-06-08 | 1976-03-09 | Agfa-Gevaert, N.V. | Photographic element comprising a fogged, direct-positive heterodispersed silver halide emulsion and a fogged, direct-positive monodispersed silver halide |
US4023972A (en) * | 1973-06-18 | 1977-05-17 | Agfa-Gevaert N.V. | Method of preparing a blend of fogged, direct-positive silver halide emulsions of different average grain sizes |
US3977880A (en) * | 1973-10-18 | 1976-08-31 | Fuji Photo Film Co., Ltd. | Direct-positive emulsion containing silver halide grains internally doped with metal ions, surface ripened with gold and sulfur compound and fogged by light exposure |
US4009041A (en) * | 1974-10-03 | 1977-02-22 | Polaroid Corporation | Fogged, direct-positive silver halide emulsion containing a gallium sulfide semiconductor |
US4011083A (en) * | 1974-12-10 | 1977-03-08 | Eastman Kodak Company | Surface sensitive silver halide emulsion containing a silver complexing azaindene to reduce desensitization of optical sensitizing dye incorporated therein |
US4301242A (en) * | 1977-02-26 | 1981-11-17 | Agfa-Gevaert Aktiengesellschaft | Emulsion mixture for color reversal (reflection viewing) material |
US4246337A (en) * | 1978-05-01 | 1981-01-20 | Corning Glass Works | Photosensitive medium for optical information storage |
US4863838A (en) * | 1979-03-26 | 1989-09-05 | Konishiroku Photo Industry Co., Ltd. | Direct positive type light-sensitive silver halide photographic materials |
US4327172A (en) * | 1980-12-16 | 1982-04-27 | Western Electric Company, Inc. | Photographic image definition improvement |
JPS58186739A (en) * | 1982-04-26 | 1983-10-31 | Konishiroku Photo Ind Co Ltd | Photosensitive silver halide material for direct positive |
JPS6055822B2 (en) * | 1982-04-26 | 1985-12-06 | コニカ株式会社 | Direct positive silver halide photographic material |
US4507386A (en) * | 1982-09-13 | 1985-03-26 | Konishiroku Photo Industry Co., Ltd. | Silver halide photographic emulsion |
DE3332975A1 (en) * | 1982-09-13 | 1984-03-15 | Konishiroku Photo Industry Co., Ltd., Tokyo | PHOTOGRAPHIC SILVER HALOGEN EMULSION |
US4604339A (en) * | 1982-11-30 | 1986-08-05 | Fuji Photo Film Co., Ltd. | Method of developing silver halide photographic light-sensitive material |
US4551419A (en) * | 1983-02-10 | 1985-11-05 | Fuji Photo Film Co., Ltd. | Method of developing silver halide photographic material |
US4551421A (en) * | 1983-02-14 | 1985-11-05 | Fuji Photo Film Co., Ltd. | Silver halide photographic materials |
US4626498A (en) * | 1983-05-20 | 1986-12-02 | Fuji Photo Film Co., Ltd. | Color reversal photographic light-sensitive material |
DE3419481A1 (en) * | 1983-05-24 | 1984-12-13 | Fuji Photo Film Co., Ltd., Minami-Ashigara, Kanagawa | DIRECT PHOTOGRAPHIC LIGHT-SENSITIVE POSITIVE MATERIAL |
EP0143424A2 (en) | 1983-11-25 | 1985-06-05 | Fuji Photo Film Co., Ltd. | Heat-developable light-sensitive materials |
EP0161682A3 (en) * | 1984-05-18 | 1987-08-26 | Eastman Kodak Company | Processes for the preparation of silver halide emulsions of controlled grain size distribution and emulsions produced thereby |
EP0161682A2 (en) * | 1984-05-18 | 1985-11-21 | EASTMAN KODAK COMPANY (a New Jersey corporation) | Processes for the preparation of silver halide emulsions of controlled grain size distribution |
US4552838A (en) * | 1984-05-18 | 1985-11-12 | Eastman Kodak Company | Processes for the preparation of silver halide emulsions of controlled grain size distribution, emulsions produced thereby, and photographic elements |
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 |
EP0204530A2 (en) | 1985-05-31 | 1986-12-10 | Konica Corporation | Method for forming direct positive color image |
EP0215612A2 (en) | 1985-09-03 | 1987-03-25 | EASTMAN KODAK COMPANY (a New Jersey corporation) | Silver halide photographic emulsions with novel grain faces (5) |
US4643966A (en) * | 1985-09-03 | 1987-02-17 | Eastman Kodak Company | Emulsions and photographic elements containing ruffled silver halide grains |
EP0300631A2 (en) * | 1987-07-21 | 1989-01-25 | Minnesota Mining And Manufacturing Company | Direct-positive silver halide emulsion |
JPS6440942A (en) * | 1987-07-21 | 1989-02-13 | Minnesota Mining & Mfg | Directly positive silver halide emulsion |
US4814263A (en) * | 1987-07-21 | 1989-03-21 | Minnesota Mining And Manufacturing Company | Direct-positive silver halide emulsion |
EP0300631A3 (en) * | 1987-07-21 | 1989-06-28 | Minnesota Mining And Manufacturing Company | Direct-positive silver halide emulsion |
US4902611A (en) * | 1989-01-06 | 1990-02-20 | Leubner Ingo H | Preparation of silver halide emulsions containing iridium |
US5279920A (en) * | 1991-11-01 | 1994-01-18 | Konica Corporation | Silver halide photographic light sensitive material |
US5424170A (en) * | 1993-08-31 | 1995-06-13 | Konica Corporation | Silver halide photographic light sensitive material |
US5395746A (en) * | 1994-02-25 | 1995-03-07 | Eastman Kodak Company | Inherently stable high chloride tabular grains with improved blue absorption |
EP0696757A2 (en) | 1994-08-09 | 1996-02-14 | Eastman Kodak Company | Film for duplicating silver images in radiographic films |
EP0754967A1 (en) | 1995-07-14 | 1997-01-22 | Agfa-Gevaert N.V. | Photographic direct positive material containing a particular stabilizer |
EP1376217A1 (en) * | 2001-02-28 | 2004-01-02 | Dai Nippon Printing Co., Ltd. | Lenticular lens sheet having light-shielding layer and method for manufacture thereof |
EP1376217A4 (en) * | 2001-02-28 | 2006-06-07 | Dainippon Printing Co Ltd | Lenticular lens sheet having light-shielding layer and method for manufacture thereof |
WO2011158245A1 (en) * | 2010-06-16 | 2011-12-22 | Department Of Biotechnology | Sealbio: a novel non-obturation regenerative technique of endodontic treatment. |
US9180072B2 (en) | 2010-06-16 | 2015-11-10 | Department Of Biotechnology | Sealbio: a novel non-obturation regenerative technique of endodontic treatment |
Also Published As
Publication number | Publication date |
---|---|
USRE29974E (en) | 1979-04-24 |
GB1151782A (en) | 1969-05-14 |
GB1151781A (en) | 1969-05-14 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US3367778A (en) | Silver salt direct positive emulsion | |
US3317322A (en) | Photographic emulsions having high internal sensitivity | |
US3206313A (en) | Chemically sensitized emulsions having low surface sensitivity and high internal sensitivity | |
US3178282A (en) | Photographic elements containing surface image and fogged internal image silver halide grains | |
US3761266A (en) | Silver halide emulsions predominantly chloride containing silver halide grains with surfaces chemically sensitized and interiors free fromchemical sensitization and the use thereof in reversal processes | |
US3761276A (en) | Photographic element containing monodispersed unfogged silver halide grains chemically sensitized internally and externally | |
US3260598A (en) | Photographic element-developer system | |
US4035185A (en) | Blended internal latent image emulsions, elements including such emulsions and processes for their preparation and use | |
US4177071A (en) | Rapidly processable radiographic materials | |
US3672900A (en) | Fogged direct-positive emulsion production by increased flow of silver halide-forming precipitants in grain-ripenerfree acidic medium | |
US3103437A (en) | Hardening | |
US3057723A (en) | Hardening of gelatin with oxystarch | |
US3761267A (en) | Photographic element containing monodispersed unfogged dye sensitizedsilver halide grains metal ions sensitized internally and the use theeof in reversal process | |
US3519426A (en) | Preparation of silver halide emulsions having high covering power | |
US3477852A (en) | Direct-positive silver halide emulsion resistant to kink-marking desensitization | |
US3458317A (en) | Print-out silver halide emulsions containing acceptors in combination with development restrainers | |
US3942986A (en) | Photographic element comprising a fogged, direct-positive heterodispersed silver halide emulsion and a fogged, direct-positive monodispersed silver halide | |
US3690891A (en) | Infrared-sensitized silver halide systems | |
US3128180A (en) | Hardened high-contrast photographic silver chloride emulsions and method of processing | |
US4078937A (en) | Process for sensitizing a fine grain silver halide photographic emulsion | |
US3632340A (en) | Cored direct positive silver halide emulsion developed with polyhydroxybenzene | |
US3782959A (en) | Polyhedral borane fogged direct-positive silver halide emulsion containing an organic sulfoxide | |
US3586505A (en) | Sensitizing silver halide emulsion layers | |
JPH0525107B2 (en) | ||
US3249440A (en) | Radiation-sensitive elements and their preparation |