US3212899A - Photographic silver halide emulsions sensitized with quaternary ammonium salt and developer combinations - Google Patents

Photographic silver halide emulsions sensitized with quaternary ammonium salt and developer combinations Download PDF

Info

Publication number
US3212899A
US3212899A US132012A US13201261A US3212899A US 3212899 A US3212899 A US 3212899A US 132012 A US132012 A US 132012A US 13201261 A US13201261 A US 13201261A US 3212899 A US3212899 A US 3212899A
Authority
US
United States
Prior art keywords
silver halide
issued
compound
plus
pyrazolidone
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
Application number
US132012A
Other languages
English (en)
Inventor
Kenneth C Kennard
Frederick J Russell
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eastman Kodak Co
Original Assignee
Eastman Kodak Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority to BE621461D priority Critical patent/BE621461A/xx
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Priority to US132012A priority patent/US3212899A/en
Priority to DEE23283A priority patent/DE1163672B/de
Priority to FR906801A priority patent/FR1345590A/fr
Priority to GB31254/62A priority patent/GB1009475A/en
Application granted granted Critical
Publication of US3212899A publication Critical patent/US3212899A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/10—Organic substances
    • 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

Definitions

  • This invention concerns photographic silver halide emulsions, and more particularly, photographic silver ha- R N NH I ca lide 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 emulsion. Such sensitization reaches a limit beyond which further addition of sensitizer merely increases the fog of the photographic emulsion with constant or decreasing speed.
  • photographic silver halide emulsions sensitizing amounts of a combination comprising: (1) a quaternary ammonium salt silver halide chemical sensitizer, and (2) a photographic silver halide de veloping agent such as a hydroquinone developing agent, with a compound capable of forming a bisulfite ion, or a 3-pyrazolidone developing agent, or combinations of such developing agents.
  • a combination comprising: (1) a quaternary ammonium salt silver halide chemical sensitizer, and (2) a photographic silver halide de veloping agent such as a hydroquinone developing agent, with a compound capable of forming a bisulfite ion, or a 3-pyrazolidone developing agent, or combinations of such developing agents.
  • quaternary ammonium salts can be utilized in the sensitizer combinations of the invention, a wide variety of such sensitizers being known in the art.
  • Bis-quaternary ammonium salt silver halide chemical sensitizing agents are more generally utilized, with the his pyridinium salts wherein the pyridine nucleus is linked together by a divalent radical having at least 7 carbon atoms being particularly useful.
  • Suitable quaternary ammonium salts are disclosed in Carroll U.S. Patent 2,271,623, issued February 3, 1942; Carroll et al. U.S. Patent 2,288,- 226, issued June 30, 1942; Trivelli et al. U.S. Patent 2,419,975, issued May 6, 1947; Piper U.S. Patent 2,886,-
  • R is an alkyl radical generally having 2 to 20 carbon atoms
  • R is an alkylene radical generally having 2 to 20 carbon atoms
  • X is an anion such as are derived from such acids as p-toluene sulfonic acid, perchloric acid, hydrochloric acid, hydrobromic acid etc.
  • Typical quaternary ammonium salts of the sensitizer combinations of the invention include:
  • 3-pyrazolidone silver halide developing agents can be utilized in the sensitizer combinations of the invention, a wide variety of such developers being known in the art.
  • Suitable 3-pyrazolidone developing agents are disclosed in Kendall US. Patent 2,289,367 issued July 14, 1942; Wilson US. Patent 2,685,516, issued August 3, 1954; Allen et al. US Patent 2,772,282, issued November 27, 1956; and others.
  • 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.
  • R can be hydrogen atoms, hydrocarbon radicals such as alkyl heterocyclic or aryl groups including phenyl, naphthyl and substituted hydrocarbon groups
  • 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.
  • 3-pyrazolidone silver halide developing agents refers to all of such developing agents and substituted derivatives thereof.
  • 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 such groups as alkyl, aryl and other hydrocarbons, carboxyl, acyl, acyloxy, alkoxy etc.
  • the substituents on the hydroquinone suitably have 1 to 20 and more generally 1 to 6 carbon atoms.
  • Typical hydroquinones include: hydroquinone, p-toluhydroquinone, 2,5-dihydroxybenzoic acid and the like.
  • a particularly useful class of compounds that release bisulfite ions are alkali metal bisulfites such as sodium bisulfite and potassium bisulfite.
  • bisulfite ion-producing compounds include sodium sulfite and potassium sulfite.
  • Sulphur dioxide also can be utilized as a source of bisulfite ions.
  • Sulfur dioxide and hydroquinones form clathrates, and the sulfur dioxide and hydroquinone are preferably added to the emulsion in this form. Such clathrates were described by Mandelcorn in Chemical Reviews, 59, pp. 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.
  • At least about 5 molar percent of bilsulfite ion based on the hydroquinone is utilized.
  • the hydroquinone and the compound capable of releasing or forming a bisulfite ion are admixed or combined prior to incorporation into photographic emulsions, although these compounds can be individually added to the emulsion.
  • 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 quaternary ammonium salt, about .01 to 10 and preferably .l to 5 grams of the 3-pyrazolidone developing agent, and about 1 to grams of the hydroquinone-bisulfite forming compound are utilized per mole of silver halide present in the emulsion.
  • the subject sensitizer addenda can be incorporated directly into the photographic silver halide emulsion layer or, alternatively, they can be utilized in contiguous layers.
  • 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 to incorporate certain types of color-forming compounds (couplers) in a photographic emulsion. Techniques of this type are described in Jelley et al. US. 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 gelatin, 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 for amounts below that which produce any substantial fog inhibition, as described in Smith and Trivelli 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 2 8, 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.
  • Suitable compounds are potassium chloroaurite, potassium aurithiocyanate, potassium chloroaurate, auric trichloride and 2-aur-osulfobenzothiazole methochloride.
  • the emulsions can also contain small amounts of reducing agents such as stannous salts (Carroll U.S. Patent 2,487,850, issued November 15, 1959), p-olyamines, such as diethylene triamine (Lowe and Jones U.S. Patent 2,518,698, issued August 15, 1950), polyamines, such as spermine (Lowe and Allen U.S. Patent 2,521,925, issued September 12, 1950), or bis(B-aminoethyl)sulfide and its water-soluble salts (Lowe and Jones U.S. Patent 2,521,926, issued September 12, 1950).
  • reducing agents such as stannous salts (Carroll U.S. Patent 2,487,850, issued November 15, 1958), p-olyamines, such as diethylene triamine (Lowe
  • the emulsions can also be optically sensitized with cyanine and merocyanine dyes, such as those described in Brooker US. Patents 1,846,301, issued February 23, 1932; 1,846,302, issued February 23, 1932; and 1,942,854, issued January 9, 1934; White U.S. Patent 1,990,507, issued February 12, 1935; Brooker and White U.S. Patents 2,112,140, issued March 22, 1938; 2,165,338, issued July 11, 1939; 2,493,747, issued January 10, 1950; and 2,739,964, issued March 27, 1956; Brooker and Keyes U.S. Patent 2,493,748, issued January 10, 1950; Sprague U.S.
  • the 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 ethylenebis(rnethyl 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 ethylenebis(rnethyl 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
  • 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 U.S. 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 mucobr-omic 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 mucobr-omic acid as described in White U.S. Patent 2,080,019, issued May 11, 1937
  • Patent 2,732,316 issued January 24, 1956; a dialdehyde or a sodium bis-ulfite derivative thereof, the aldehyde groups of which are separated by 2-3 carbon atoms, such as fl-methylglutaraldehyde bis-sodium bisul fite; a bisaziridine carboxamide such as trimethylenebis (l-aziridine carboxamide) as described in Allen and Webster U.S. Patent 2,950,197, issued August 23, 1960; or 2,3-dihydroxy dioxane as described in JeflFreys U.S. Patent' 2,870,013, issued January 20, 1957.
  • the emulsions can contain a coating aid such as saponin; 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 saponin
  • 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 Wilson U.S. Patent 2,843,487, issued July 15, 1958; a water-soluble maleopimarate or a mixture of a water-soluble maleopirnarate 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 sulfosuccinamate
  • 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 December 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 azaindenes 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 US. 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 addena 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 chlorobromide or silver bromoiodide.
  • the subject addenda can be used in emulsions intended for color photography, for example, emulsions containing colorforming 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 Jannary 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 arcmatic 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 wherein n is 15-100, 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 silver 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 diffusion 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.
  • diffusion 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.
  • Such processes are described in Rott U.S. Patent 2,352,014, issued June 20, 1944, and Land U.S. Patents 2,584,029, issued January 29, 1952; 2,608,236, issued December 28, 1954, and 2,543,181, issued February 27, 1951.
  • 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 material such as colloidal albumin, a cellulose derivative, or a synthetic resin, for instance, a polyvinyl com-pound, 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 film, polyethylene terephthalate film and related films of resinous materials, as well as glass, paper, wood, metals and others.
  • the present invention is illustrated by photographic emulsions containing at least two of the following listed addenda, the addenda numbers below being used in specific examples and tables below to identify the addenda for purposes of convenience.
  • Hydroquinone-sulfur dioxide clathrate (10.6% by weight sulfur dioxide).
  • EXAMPLE 1 Typical feature addenda of the invention were incorporated into samples of a high speed negative-type gelatino-silver bromoiodide emulsion that was sulfur and gold sensitized and panchromatically sensitized with cyanine dye.
  • the silver halide in the emulsion consisted of about 96% by weight of silver bromide and about 4% by weight of silver iodide.
  • About 200 grams of gelatin per mole of silver halide was present in the emulsion.
  • the emulsion was coated at a coverage of about 700 mg. of silver per square foot, a cellulose acetate film support being utilized.
  • the hydroquinone-sulfur dioxide clathrate (compound III) can be prepared by dissolving 110 g. of hydroquinone in 700 ml. of distilled water at 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 wide variety tertiary ammonium salt silver halide chemical sensitizers in combination with a wide variety of hydroquinone silver halide developing agents in combination with a compound capable of forming a bisulfite ion or 3-pyrazolidone silver halide developing agents, or mixtures of such developing agents cooperate to substantially increase the speed of photographic silver halide emulsions. If substantial or extreme below. 30 amounts of quarternary ammonium salt silver halide Table B Original test 1 week incubation 2 week incubation Feature addenda, g. [mole AgX Rel. 'y Fog Rel. 'y Fog Rel.
  • sensitizing amount of sensitizer combination comprising: (a) a quarternary ammonium salt silver halide chemical sensitizer; and
  • a photographic silver halide emulsion containing sensitizing amount of a combination comprising:
  • a photographic silver halide emulsion containing a sensitizing amount of a combination comprising:
  • a photographic silver halide emulsion containing a sensitizing amount of a combination comprising:
  • a photographic silver halide emulsion containing a sensitizing amount of a combination comprising:
  • a photographic silver halide emulsion containing a sensitizing amount of a combination comprising:
  • a photographic silver halide emulsion containing a sensitizing amount of a combination comprising:
  • a hydrazinium salt selected from the group consisting of (1) an a,w-alkylenebis(l,l dimethylhydrazinium salt) silver halide chemical sensitizer, and
  • (d) a hydroquinone silver halide developing agent and a compound capable of forming a bisulfite ion.
  • a photographic gelatino-silver halide emulsion containing a sensitizer combination comprising:
  • a photographic gelatin-o-silver halide emulsion containing a sensi-tizer combination comprising:
  • a photographic gelatino-silver halide emulsion containing a sensitizer combination comprising:

Landscapes

  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
US132012A 1961-08-17 1961-08-17 Photographic silver halide emulsions sensitized with quaternary ammonium salt and developer combinations Expired - Lifetime US3212899A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
BE621461D BE621461A (en(2012)) 1961-08-17
US132012A US3212899A (en) 1961-08-17 1961-08-17 Photographic silver halide emulsions sensitized with quaternary ammonium salt and developer combinations
DEE23283A DE1163672B (de) 1961-08-17 1962-07-28 Photographisches, eine stabilisatorhaltige sensibilisierte Silberhalogenidemulsionsschicht enthaltendes Material
FR906801A FR1345590A (fr) 1961-08-17 1962-08-13 Nouvelle émulsion photographique contenant une association de sensibilisateurs
GB31254/62A GB1009475A (en) 1961-08-17 1962-08-15 Photographic silver halide emulsions of increased sensitivity

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US132012A US3212899A (en) 1961-08-17 1961-08-17 Photographic silver halide emulsions sensitized with quaternary ammonium salt and developer combinations

Publications (1)

Publication Number Publication Date
US3212899A true US3212899A (en) 1965-10-19

Family

ID=22452028

Family Applications (1)

Application Number Title Priority Date Filing Date
US132012A Expired - Lifetime US3212899A (en) 1961-08-17 1961-08-17 Photographic silver halide emulsions sensitized with quaternary ammonium salt and developer combinations

Country Status (4)

Country Link
US (1) US3212899A (en(2012))
BE (1) BE621461A (en(2012))
DE (1) DE1163672B (en(2012))
GB (1) GB1009475A (en(2012))

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2312798A1 (fr) * 1975-05-29 1976-12-24 Eastman Kodak Co Produit photographique donnant des epreuves a ton chaud
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
US5384232A (en) * 1991-12-02 1995-01-24 E. I. Du Pont De Nemours And Company Process for rapid access development of silver halide films using pyridinium as development accelerators
EP0802452A1 (en) * 1996-04-19 1997-10-22 Eastman Kodak Company Method for developing a photographic product with incorporated developer

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2419975A (en) * 1943-08-26 1947-05-06 Eastman Kodak Co Increasing speed and contrast of photographic emulsions
US2940851A (en) * 1957-11-27 1960-06-14 Eastman Kodak Co Sensitization of photographic emulsions
GB845928A (en) * 1957-10-25 1960-08-24 Ilford Ltd Improvements in or relating to photographic emulsions
US3017270A (en) * 1958-03-31 1962-01-16 Eastman Kodak Co Photographic silver halide diffusion transfer process

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2419975A (en) * 1943-08-26 1947-05-06 Eastman Kodak Co Increasing speed and contrast of photographic emulsions
GB845928A (en) * 1957-10-25 1960-08-24 Ilford Ltd Improvements in or relating to photographic emulsions
US2940851A (en) * 1957-11-27 1960-06-14 Eastman Kodak Co Sensitization of photographic emulsions
US3017270A (en) * 1958-03-31 1962-01-16 Eastman Kodak Co Photographic silver halide diffusion transfer process

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2312798A1 (fr) * 1975-05-29 1976-12-24 Eastman Kodak Co Produit photographique donnant des epreuves a ton chaud
US5384232A (en) * 1991-12-02 1995-01-24 E. I. Du Pont De Nemours And Company Process for rapid access development of silver halide films using pyridinium as development accelerators
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
EP0802452A1 (en) * 1996-04-19 1997-10-22 Eastman Kodak Company Method for developing a photographic product with incorporated developer
FR2747806A1 (fr) * 1996-04-19 1997-10-24 Kodak Pathe Nouveau procede de developpement d'un produit photographique a developpateur incorpore
US5789144A (en) * 1996-04-19 1998-08-04 Eastman Kodak Company Method for developing a photographic product with incorporated developer

Also Published As

Publication number Publication date
GB1009475A (en) 1965-11-10
BE621461A (en(2012))
DE1163672B (de) 1964-02-20

Similar Documents

Publication Publication Date Title
US3178282A (en) Photographic elements containing surface image and fogged internal image silver halide grains
US3021215A (en) Polythialkylenediols as sensitizers for photographic silver halide emulsions
US3047393A (en) Esters of thiosulfonic acids as antifoggants
US2716062A (en) 4-hydroxy-6-alkyl-1, 3, 3a, 7-tetrazaindene stabilizers for emulsions sensitized with alkylene oxide polymers
US3017280A (en) Hardening of coatings of polymers containing carboxyl groups
US2839405A (en) Inorganic salt antifoggants for photographic emulsions
US3128183A (en) Photographic halide emulsions sensitized with alkylene oxide polymers and aliphatic amines
US3062646A (en) Sensitization of silver halide emulsions with macrocyclic compounds
US3312550A (en) Processing photographic elements containing developing agent
US3260598A (en) Photographic element-developer system
US2960404A (en) Gelatin coating compositions
US3201242A (en) Accelerators for reversal color development
US3547638A (en) N,n-disubstituted amino-methylthiocarboxylic acids and use thereof as antifoggants in photographic emulsions
US3041170A (en) New class of development promoter precursors for dry processing self-developing silver halide coatings
US3103437A (en) Hardening
US2708162A (en) Urazole stabilizer for emulsions sensitized with alkylene oxide polymers
US2983609A (en) Chemical sensitization of photographic emulsions
US3057724A (en) Internal amide, nonpolymeric thioether sensitizers for photographic emulsions
US3189458A (en) Sensitizing photographic silver halide emulsions with elemental sulfur and an organic thiol
US2772164A (en) Photographic silver halide emulsions containing 1-thia-3, 5, 7-triazaindenes
US3046133A (en) Sensitization of photographic silver halide emulsions with polyester compounds containing thioether-sulfur atoms in the side chain
US3212899A (en) Photographic silver halide emulsions sensitized with quaternary ammonium salt and developer combinations
US3030209A (en) High-contrast photographic silver chloride emulsions and method of processing
US3192046A (en) Photographic silver halide emulsions sensitized with thioether and developer combinations
US2835581A (en) Tetrazaindenes and photographic emulsions containing them