US3192046A - Photographic silver halide emulsions sensitized with thioether and developer combinations - Google Patents

Photographic silver halide emulsions sensitized with thioether and developer combinations Download PDF

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US3192046A
US3192046A US132011A US13201161A US3192046A US 3192046 A US3192046 A US 3192046A US 132011 A US132011 A US 132011A US 13201161 A US13201161 A US 13201161A US 3192046 A US3192046 A US 3192046A
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silver halide
issued
pyrazolidone
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emulsions
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Kenneth C Kennard
Frederick J Russell
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Eastman Kodak Co
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Eastman Kodak Co
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Priority to FR906800A priority patent/FR1345589A/fr
Priority to GB31253/62A priority patent/GB1016824A/en
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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
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/42—Developers or their precursors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/09—Noble metals or mercury; Salts or compounds thereof; Sulfur, selenium or tellurium, or compounds thereof, e.g. for chemical sensitising

Definitions

  • This invention concerns photographic silver halide emulsions, and more particularly, photographic silver halide emulsions containing novel combinations of sensitizing addenda.
  • silver halide emulsions can be chemically sensitized with a variety of materials in order to increase their speed.
  • Certain chemical sensitizers are believed to react with the silver halide to form on the surface of the silver halide minute amounts of silver sulfide, or of silver, or of other noble metals.
  • other classes of compounds that apparently do not enter into chemical combination with the silver halide can be utilized to increase the sensitivity of photographic silver halide emulsions. Such sensitization reaches a limit beyond which further addition of sensitizer merely increases the fog of the photographic emulsion with constant or decreasing speed.
  • a combination comprising: (1) a thioether silver halide chemical sensitizer, and (2) a photographic silver halide developing agent such as a hydroquinone developing agent with a compound capable of forming a bisulfite ion or a B-pyrazolidone developing agent or combinations of such developing agents.
  • 3-pyrazolidone silver halide developing agents can be utilized in the sensitizer combinations of the invention, a Wide variety of such developing agents being known in the art.
  • Suitable 3-pyrazo1idone developing agents are disclosed in Kendall US. Patent 2,289,- I
  • Typical 3- pyrazolidone developing agents have the formula wherein R can be hydrogen atoms, hydrocarbon radicals such as alkyl heterocyclic or aryl groups including phenyl, naphthyl and substituted hydrocarbon groups; and Wherein R R R and R can be hydrogen atoms, hydrocarbon radicals such as alkyl groups preferably containing 1 to 4 carbon atoms or aryl groups including phenyl, naphthyl and substituted hydrocarbon groups.
  • 2-pyrazolidone silver halide developa means Patented June 29, 1965 ing agent refers to all of such developing agents and substituted derivatives thereof.
  • Typical 3-pyrazolidone silver halide developing agents that can be suitably utilized include:
  • l-phenyl-3-pyrazolidone 1-p-tolyl-3-pyrazolidone, 5-phenyl-3-pyrazolidone, 5-methyl-3-pyrazolidone, 1-p-chlorophenyl-3-pyrazolidone, l-phenyl-S-phenyl-3pyrazolidone, l-m-tolyl-B-pyrazolidone, l-phenyl-5-methyl-3-pyrazolidone, l-p-tolyl-5-pheny1-3-pyrazolidone, 1-p-methoxyphenyl-3-pyrazolidone, 1-acetamidophenyl-3-pyrazolidone, 1-phenyl-2-acetyl-4,4-dimethyl-3-pyrazolidone, l-phenyl-4,4-dimethyl-3-pyrazolidone, 1-m-aminophenyl-4-methyl-4-propyl-3-pyrazolidone, 1-ochlorophenyl-4-methyl-4-ethyl-3-pyrazolidone,
  • hydroquinone silver halide developing agents with compounds capable of releasing or forming bisulfite ions can be utilized in the'present sensitizer combinations.
  • Hydroquinone or substituted hydroquinones including alkyl-substituted hydroquinones, aryl-substitutedhydroquinones and other hydrocarbon-substituted hydroquinones, carboxyl-substituted hydroquinones, acylsubstituted hydroquinone, acyloxy-substituted hydroqinones, 'alkoXy-substituted hydroquinones, such as ptoluhydroquinone, 2,5-dihydroxybenzoic acid, and others can be used.
  • the substituents on the hydroquinone generally have 1 to 20 and more generally 1 to 6 carbon atoms.
  • a particularly useful class of compounds that release bisulfite ions are alkali metal bisulfites such as sodium bisulfite and potassium bisulfite.
  • Other suitable bisulfite ion-producing compounds inclde sodim sulfite and potassium sulfite.
  • Sulfur dioxide also can be utilized as a source of bisulfite ions.
  • Sulfur dioxide and hydroquinones form clathrates, and thesulfur dioxide and hydroquinone are preferably added to the emulsion in this form. Such clathrates weredescribed by Mandelcorn in Chemical Reviews, 59, p. 827-830, October 1959.
  • the bisulfite forming compound usually comprises less than one-half by weight of the combined weight of the hydroquinone and the bisulfite releasing compound, although larger amounts of bisulfite can be utilized. Preferably, at least about 5 molar percent of bisulfite ion based on the hydroquinone is utilized.
  • the hydroquinone and the compound capable of releasing or forming a bisulfite ion are admixed or com.- bined prior to incorporation into photographic emulsions, although these compounds can be individually added to the emulsion.
  • thioether silver halide chemical sensitizers can be utilized in the sensitizer combinations of the invention.
  • a particularly useful group of thioethers are described in Dann and Chechak application U.S. Serial No. 779,874 filed December 12, 1958, now US. Patent No. 3,046,134.
  • the useful Dann and Chechak sensitizers are linear polymers consisting essentially of repetitive units, each of which contains at least one thioether atom, and which have average molecular weights of at least about 250 and generally from 250 to 10,000, although polymers of 500 to 3500 have been found particularly useful.
  • the Dann and Chechak sensitizers can be represented by the formula:
  • R is an aliphatic radical and x represents a positive integer of at least 3.
  • the terminal groups of such polymers are generally hydrogen atoms, halogen atoms, alkenyl groups (e.g., vinyl, allyl, etc.), carboxylic groups (e.g. carboxyl, carboxylic amide, carboxylic ester, such as carbomethoxyl, carbethoxyl, etc.), hydroxyl groups, mercapto groups (or salts thereof, e.g., sodium, potassium, etc.), or combinations of these.
  • linear polymers represented by Formula I above comprise a well-known class of polymeric materials.
  • Typical of the polymers embraced by Formula I are those polymers represented by the following general formula:
  • R R R and R each represents a hydrocarbon alkylene group containing from about 2 to 20 carbon atoms (e.g., ethylene, trimethylene, 1,2-propylene, tetrabutylene, pentamethylene, octamethylene, decamethylene, dodecamethylene, tetradecamethylene, etc.),
  • X and X each represents an oxygen atom, a sulfur atom, an amino group (substituted or not) such as amino, methylamiuo, ethylamino, etc., carbamyl (NHCO), carbonylamido (CONH), carbonyl, oxyca-rbonyloxy, oxycarbonyl (OOC), carbonyloxy (COO), etc., provided that X does not represent an oxycarbonyl group when X represents a carbonyloxy group and X does not represent a carbamyl group when
  • Formula 111 wherein a, b, c and d each represents a positive integer of from 2 to 20, and n, m and p each have the values given above.
  • Z represents a divalent carbonamide linkage, e.g.,
  • Z represents an alkylene group, such as that defined above for R or the group:
  • R R and p each have the values given above, or alternatively, Z can represent an alkylene group such as wherein R represents an alkylene group, such as methylene, ethylene, trimethylene, 1,2-propylene, butylene, pentamethylene, hexamethylene, etc.
  • R represents an alkylene group, such as methylene, ethylene, trimethylene, 1,2-propylene, butylene, pentamethylene, hexamethylene, etc.
  • Another group of polymers embraced by Formula I, which are useful in practicing our invention comprises polymeric linear lactones, such as:
  • R R R R X, X m, n and 2 each have the values given above and R represents a hydrogen atom, a lower alkyl group, such as methyl, ethyl, propyl, etc.
  • the compounds of Formula II above can be prepared according to methods which have been previously described in the prior art.
  • these polymers can be prepared by condensing together at least one dihalogenated compound selected from those represented by the following general formula:
  • condensation can be carried out in the presence of an inert diluent which may be a solvent or non-solvent for the polymeric product obtained.
  • symmetrical polymers embraced by Formula II above can be prepared by condensing together an intermediate represented by Formula Ila with an alkali metal sulfide, such as sodium sulfide.
  • an alkali metal sulfide such as sodium sulfide.
  • The'linear polymers reprsented by Formula V above can advantageously be prepared by self-condensation of at least one hydroxy acid (or alternatively, a lactone of the acid) represented by the following general formula:
  • condensations occur spontaneously on standing, although they can be accelerated by the application of heat, and in some instances, by the use of an inert diluent, such as ethanol, water, etc.
  • linear polymers represented by Formula VII above can advantageously be prepared by condensing together two molecules of at least one amine selected from those represented by the following general formula:-
  • Formula VIIa R NH one molecule of at least one dithiol represented by the following general formula:
  • n is an integer of at least 1 and generally 1 to 10 and R is an alkylene radical generally having 1 to 4 carbon atoms.
  • the present sensitizer addenda are added to the photographic emulsions in sensitizing amounts as determined by methods well known in the art. Generally, however, about .01 to 10 and preferably .1 to 5 grams of the thioether sensitizer, about .01 to 10 and preferably .1 to 5 grams of the 3-pyrazolidone developing agent, and about 1 to grams of the hydroquinone-bisulfite-forming com-' pound are utilized per mole of silver halide present in the emulsion. r
  • the subject sensitizer addenda can be incorporated directly into the photographic silver halide emulsion layer or, -alternatively, they can be utilized in contiguouslayers.
  • the preparation of photographic silver halide emulsions such as are used with the addenda of this invention involves three separate operations: (1) emulsification and digestion of silver halide, (2) the freeing of the emulsion of excess Water-soluble salts, suitably by washing with water, and (3) the second digestion or after-ripening to obtain increased emulsion speed or sensitivity.
  • the addenda of the invention can be added to the emulsion before the final digestion or after-ripening, or they can be added immediately prior to the coating.
  • the addenda of the invention can be added to photographic emulsions using any of the well-known techniques in emulsion making. For example, they can be dissolved in a suitable solvent and added to the silver halide emulsion, or they can be added to the emulsion in the form of a dispersion similar to the technique used toincorporate certain types of color-forming compounds (coupler's) in a photographic emulsion. Techniques of this type are described in Jelley et al. U.S. Patent 2,322,027, issued June 15, 1943, and Fierke et' al. US; Patent 2,801,171, issued July 30, 1957.
  • the solvent should be selected so that it has no harmful effect upon the emulsion in accordance with usual practice, and generally solvents or diluents which are miscible with water are to be preferred.
  • the emulsions can be digested with naturally active gelatln, or sulfur compounds can be added, such as those described in Sheppard U.S. Patent 1,574,944, issued March. 2, 1926, and Sheppard et al. 1,623,499, issued April 5, 1927, and Sheppard and Brigham U.S. Patent 2,410,689, issued November 5, 1946.
  • the emulsions can also be treated with salts of the noble metals such as ruthenium, rhodium, palladium, iridium and platinum.
  • Representative compounds are ammonium chloropalladate, potassium chloroplatinate, and sodium chloropalladite, which are used in amounts below that which produces any substantial fog inhibition, as described in Smith and Trivelli 7 U.S.
  • Patent 2,448,060 issued August 31, 1948, and as antifoggants in higher amounts, as described in Trivelli and Smith U.S. Patents 2,566,245, issued August 28, 1951, and 2,566,263, issued August 28, 1951.
  • the emulsions can also contain small amounts of gold salts as described in Waller et al. U.S. Patent 2,399,083, issued April 23, 1946, or in Damschroder U.S. Patent 2,597,856, issued May 27, 1952, and Yutzy and Leermakers U.S. Patent 2,597,915, issued May 27, 1952.
  • the 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 US.
  • 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.
  • the emulsions can contain a suitable gelatin plasticizer such as glycerin; a dihydroxy alkane such as 1,5-pentanediol as described in Milton and Murray U.S. Patent 2,960,404, issued November 15, 1960; an ester of an ethylene bis-glycolic acid such as ethylene bis(methyl glycolate) as described in Milton U.S. Patent 2,904,434, issued September 15, 1959; bis(ethoxy diethylene glycol) succinate as described in Gray U.S.
  • a suitable gelatin plasticizer such as glycerin
  • a dihydroxy alkane such as 1,5-pentanediol as described in Milton and Murray U.S. Patent 2,960,404, issued November 15, 1960
  • an ester of an ethylene bis-glycolic acid such as ethylene bis(methyl glycolate) as described in Milton U.S. Patent 2,904,434, issued September 15, 1959
  • bis(ethoxy diethylene glycol) succinate as described in Gray U.S.
  • Patent 2,940,854 issued June 14, 1960, or a polymeric hydrosol as results from the emulsion polymerization of a mixture of an amide of an acid of the acrylic acid series, an acrylic acid ester and a styrene-type compound as described in Tong US. Patent 2,852,386, issued September 16, 1958.
  • the plasticizer may be added to the emulsion before or after the addition of a sensitizing dye, if used.
  • the emulsion can be hardened with any suitable hardener for gelatin such as formaldehyde; a halogen-substituted aliphatic acid such as mucobromic acid as described in White U.S. Patent 2,080,019, issued May 11, 1937; a compound having a plurality of acid anhydride groups such as 7,8-diphenylbicyclo(2,2,2)-7-octene- 2,3,5,6-tetracarboxylic dianhydride, or a dicarboxylic or a disulfonic acid chloride such as terephthaloyl chloride or naphthalene-1,5-disulfonyl chloride as described in Allen and Carroll U.S.
  • any suitable hardener for gelatin such as formaldehyde; a halogen-substituted aliphatic acid such as mucobromic acid as described in White U.S. Patent 2,080,019, issued May 11, 1937; a compound having a plurality of
  • Patent 2,732,316 issued January 24, 1956; a dialdehyde or a sodium bisulfite derivative thereof, the aldehyde groups of which are separated by 2-3 carbon atoms, such as B-methylglutaraldehyde bissodium bisulfite; a bisaziridine carboxamide such as trimethylene bis(1-aziridine carboxamide) as described in 8 Allen and Webster U.S. Patent 2,950,197, issued August 23, 1960; or 2,3-dihydroxy dioxane as described in Jeffreys U.S. Patent 2,870,013, issued January 20, 1957.
  • a dialdehyde or a sodium bisulfite derivative thereof the aldehyde groups of which are separated by 2-3 carbon atoms, such as B-methylglutaraldehyde bissodium bisulfite
  • a bisaziridine carboxamide such as trimethylene bis(1-aziridine carboxamide) as described in 8 Allen and Webster U.S. Patent 2,950,197, issued August
  • the emulsions can contain a coating aid such as sa ponin; a lauryl or oleoyl monoether of polyethylene glycol as described in Knox and Davis U.S. Patent 2,831,766, issued April 22, 1958; a salt of a sulfated and alkylated polyethylene glycol ether as described in Knox and Davis U.S. Patent 2,719,087, issued September 27, 1955; an acylated alkyl taurine such as the sodium salt of N-oleoyl- N-methyl taurine as described in Knox, Twardokus and Davis U.S.
  • a coating aid such as sa ponin
  • a lauryl or oleoyl monoether of polyethylene glycol as described in Knox and Davis U.S. Patent 2,831,766, issued April 22, 1958
  • a salt of a sulfated and alkylated polyethylene glycol ether as described in Knox and Davis U.S. Patent 2,719,087, issued September 27, 1955
  • Patent 2,739,891 issued March 27, 1956; the reaction product of a dianhydride of tetracarboxybutane with an alcohol or an aliphatic amine containing from 8 to 18 carbon atoms which is treated with a base, for example, the sodium salt of the monoester of tetracarboxybutane as described in Knox, Stenberg and ⁇ Vilson U.S. Patent 2,843,487, issued July 15, 1958; a water-soluble maleopimarate or a mixture of a water-soluble maleopimarate and a substituted glutamate salt as described in Knox and Fowler U.S.
  • Patent 2,823,123 issued February 11, 1958; an alkali metal salt of a substituted amino acid such as disodium N-(carbo-p-tert. octylphenoxypentaethoxy)glutamate, or a sulfosuccinamate such as tetrasodium N-(1,2-dicarboxyethyl)-N-octadecyl sulfosuccinamate, or N-lauryl disodium sulfosuccinamate.
  • a substituted amino acid such as disodium N-(carbo-p-tert. octylphenoxypentaethoxy)glutamate, or a sulfosuccinamate such as tetrasodium N-(1,2-dicarboxyethyl)-N-octadecyl sulfosuccinamate, or N-lauryl disodium sulfos
  • the emulsions can also be stabilized with the mercury compounds of Allen, Byers and Murray U.S. Patent 2,728,663, issued December 27, 1955; Carroll and Murray U.S. Patent 2,728,664, issued Decmeber 27, 1955; and Leubner and Murray U.S. Patent 2,728,665, issued December 27, 1955; and triazoles of Heimbach and Kelly U.S. Patent 2,444,608, issued July 6, 1948; the azindenes of Heimbach and Kelly U.S. Patents 2,444,605 and 2,444,606, issued July 6, 1948; Heimbach U.S. Patents 2,444,607, issued July 6, 1948 and 2,450,397, issued September 28, 1948; Heimbach and Clark U.S.
  • Patent 2,444,609 issued July 6, 1948; Allen and Reynolds U.S. Patents 2,713,541, issued July 19, 1955 and 2,743,181, issued April 24, 1956; Carroll and Beach U.S. Patent 2,716,062, issued August 23, 1955; Allen and Beilfuss U.S. Patent 2,735,769, issued February 21, 1956; Reynolds and Sagal U.S. Patent 2,756,147, issued July 24, 1956; Allen and Sagura U.S. Patent 2,772,164, issued November 27, 1956, and those disclosed by Birr in Z. wiss. Phot., vol. 47, 1952, pages 2-28; the disulfides of Kodak Belgian Patent 569,317, issued July 31, 1958; the quaternary benzothiazolium compounds of Brooker and Stand U.S.
  • the sensitizing addenda of the invention can be used in various kinds of photographic emulsions. In addition to being useful in orthochromatic, panchromatic, and infrared sensitive emulsions, they are also useful in X-ray and other non-optically sensitized emulsions. They can be added to the emulsion before or after any optical sensitizing dyes which may be used.
  • Various silver salts can be used as the sensitive salt such as silver bromide, silver iodide, silver chloride, or mixed silver halides such as silver chlorobr-omide or silver bromoiodide.
  • the subject addenda can be used in emulsions intended for color photography, for example, emulsions containing color-forming couplers or emulsions to be developed by solutions containing couplers or other color-generating materials, emulsions of the mixed-packet type, such as described in Godowsky U.S. Patent 2,698,794, issued January 4, 1955, or emulsions of the mixed-grain type, such as described in Carroll and Hanson U.S. Patent 2,592,243, issued April 8, 1952.
  • Suitable color couplers usually belong to three widely known types, i.e., pyrazolone couplers, phenol couplers and open-chain ketomethylene couplers which combine with the oxidation products of aromatic primary amine silver halide developing agents to produce magenta, cyan and yellow images respectively.
  • Development accelerators can be utilized in developing such color emulsions including polyethylene glycols, their ester derivatives, their ether derivatives typically having the formula RO(CH CH O),,H wherein R is an alkyl radical having 1 to 5 carbon atoms and wherei in n is 100, and related derivatives.
  • the subject addenda can also be used in emulsions which form latent images predominantly on the surface of the silver halide crystal or in emulsions which form latent images predominantly inside the silve halide crystal, such as those described in Davey and Knott U.S. Patent 2,592,250, issued April 8, 1952.
  • the subject addenda can also be used in emulsions intended for use in dilfusion 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 original silver halide emulsion layer.
  • dilfusion 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 original silver halide emulsion layer.
  • gelatin In the preparation of the silver halide dispersions employed for preparing silver halide emulsions, there can be employed as the dispersing agent for the silver halide in its preparation, gelatin or some other colloidal material such as colloidal albumin, a cellulose derivative, or a synthetic resin, for instance, a polyvinyl compound, although gelatin is preferred.
  • colloids which can be used are polyvinyl alcohol or a hydrolyzed polyvinyl acetate as described in Lowe U.S. Patent 2,286,215, issued June 16, 1942; a far hydrolyzed cellulose ester such as cellulose acetate hydrolyzed to an acetyl content of 1926% as described in U.S.
  • Patent 2,768,154 issued October 23, 1956; or containing cyanoacetyl groups such as the vinyl alcohol-vinyl cyanoacetate copolymer as described in Unruh, Smith and Priest U.S. Patent 2,- 808,331, issued October 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 U.S. Patent 2,852,382, issued September 19, 1958. If desired, compatible mixtures of two or more of these colloids can be employed for dispersing the silver halide in its preparation.
  • Typical supports for photographic elements of the invention include cellulose nitrate film, cellulose acetate film, polyvinyl acetal film, polystyrene Addenda Addenda.
  • EXAMPLE 1 Typical feature addenda of the invention were incorporated into samples of a high speed, negative-type, unoptically sensitized, gelatino-silver bromoiodide emulsion.
  • the silver halide in the emulsion consisted of about 98% by weight of silver bromide and about 2% by weight of silver iodide.
  • About 60 grams of gelatin per mole of silver halide was present in the emulsion.
  • the emulsion was coated at a coverage of about 1100 mg. of silver per square foot, a cellulose acetate film support being utilized.
  • the prepared photo-graphic elements were'then exposed in the form of film strips to kv.
  • EXAMPLE 2 Additional sensit-izer combinations of the invention were incorporated into the gelatino-silver bromoiodide described in Example 1 and coated as described in Example 1. Test samples of the prepared films were then exposed in an Eastman Ib sensitometer, developed for 3 minutes at 68 F. in the developer described in Example 1, and then fixed, washed and dried in the usual manner. The results of the sensitometric tests are summarized by the data set out in Table C below. The relative speeds are a function of the exposure necessary to give a density of 0.3 above background fog.
  • EXAMPLE 3 The invention is further illustrated by incorporating another sensitizer combination of the invention and its components into a high speed, negative-type, unoptically sensitized, gelatino-silver bromoiodide emulsion, and thereafter coating the emulsion on a cellulose acetate film support at a coverage of about 1070 mg. of silver per 7 square foot and 595 mg. of gelatin per square foot.
  • Test samples of the prepared films were exposed, initially and after a one week incubation at 120 F. and 50% relative humidity, in an Eastman Ib sensitometer, developed for 3 minutes at 68 F. in the developer described in Example 1, and then fixed, Washed and dried in the usual manner.
  • the hydroquinone-sulfur dioxide clathrate (Compound III) can be prepared by dissolving 110 g. of hydroquinone in 700 ml. of distilled Water at 50 C. The resulting solution is then saturated with sulfur dioxide and cooled to 5 C. A clathrate forms as yellow crystals which crystallize out of the reaction mixture and which are then filtered off and dried.
  • a photographic silver halide emulsion containing a sensitizing amount of a sensitizer combination compris mg:
  • a photographic silver halide emulsion containing a sensitizing amount of a sensitizer combination comprising:
  • a photographic silver halide emulsion containing a sensitizing amount of a sensitizer combination comprismg:
  • a photographic silver halide emulsion containing a sensitizing amount of a sensitizer combination comprismg:
  • a photographic silver halide emulsion as described in claim 2 wherein the thioether chemical sensitizer has the formula wherein R is an alkylene radical having 1 to 4 carbon atoms and x is an integer of l to 10.
  • a photographic gelatino-silver halide emulsion containing a sensitizer combination comprising:
  • a photographic gelatino-silver halide emulsion containing a sensitizer combination comprising:
  • a photographic gelatino-silver halide emulsion containing a sensitizer combination comprising:
  • a photographic gelatino-silver halide emulsion containing a sensitizer combination comprising:
  • a photographic gelatino-silver halide emulsion containing a sensitizer combination comprising:
  • the thioether silver halide chemical sensitizer is selected from the group consisting of poly (thiodiethylene glutarate), poly(2,2' thiodiethyl succinate), poly(/B-hydroxyethylmercapto acetic acid), 1,10- dithia-4,7,l3,16tetraoxacycloocta decane, and 1,l7-di(

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US132011A 1961-08-17 1961-08-17 Photographic silver halide emulsions sensitized with thioether and developer combinations Expired - Lifetime US3192046A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
BE621460D BE621460A (en, 2012) 1961-08-17
US132011A US3192046A (en) 1961-08-17 1961-08-17 Photographic silver halide emulsions sensitized with thioether and developer combinations
DEE23312A DE1155327B (de) 1961-08-17 1962-08-03 Photographische, sensibilisatorhaltige Silberhalogenidemulsion und damit beschichtetes Traegermaterial
FR906800A FR1345589A (fr) 1961-08-17 1962-08-13 Nouvelle émulsion photographique sensibilisée
GB31253/62A GB1016824A (en) 1961-08-17 1962-08-15 Photographic silver halide emulsions of increased sensitivity

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3243294A (en) * 1963-11-06 1966-03-29 Eastman Kodak Co Photographic direct-positive color process
US3300307A (en) * 1963-01-18 1967-01-24 Eastman Kodak Co Photographic developer composition
US3453109A (en) * 1966-06-24 1969-07-01 Eastman Kodak Co Forming a relief by developing and hardening an exposed unhardened silver halide emulsion in the exposed areas with 3-pyrazolidones having hydroxymethyl substitution in the 4-position
US3531289A (en) * 1966-12-02 1970-09-29 Eastman Kodak Co Silver halide photographic emulsions improved by new precipitation methods
US3632341A (en) * 1970-03-13 1972-01-04 Itek Corp Photographic developer
EP0124795A2 (en) 1983-04-11 1984-11-14 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
US5252449A (en) * 1992-09-25 1993-10-12 E. I. Du Pont De Nemours And Company Photographic silver halide emulsions with improved bright room tolerance

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB845928A (en) * 1957-10-25 1960-08-24 Ilford Ltd Improvements in or relating to photographic emulsions
US3046129A (en) * 1958-12-12 1962-07-24 Eastman Kodak Co Sensitization of photographic silver halide emulsions containing colorforming compounds with polymeric thioethers

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB845928A (en) * 1957-10-25 1960-08-24 Ilford Ltd Improvements in or relating to photographic emulsions
US3046129A (en) * 1958-12-12 1962-07-24 Eastman Kodak Co Sensitization of photographic silver halide emulsions containing colorforming compounds with polymeric thioethers

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3300307A (en) * 1963-01-18 1967-01-24 Eastman Kodak Co Photographic developer composition
US3243294A (en) * 1963-11-06 1966-03-29 Eastman Kodak Co Photographic direct-positive color process
US3453109A (en) * 1966-06-24 1969-07-01 Eastman Kodak Co Forming a relief by developing and hardening an exposed unhardened silver halide emulsion in the exposed areas with 3-pyrazolidones having hydroxymethyl substitution in the 4-position
US3531289A (en) * 1966-12-02 1970-09-29 Eastman Kodak Co Silver halide photographic emulsions improved by new precipitation methods
US3632341A (en) * 1970-03-13 1972-01-04 Itek Corp Photographic developer
EP0124795A2 (en) 1983-04-11 1984-11-14 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
US5252449A (en) * 1992-09-25 1993-10-12 E. I. Du Pont De Nemours And Company Photographic silver halide emulsions with improved bright room tolerance

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GB1016824A (en) 1966-01-12
BE621460A (en, 2012)
DE1155327B (de) 1963-10-03

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