US3062654A - Stabilization of photographic silver halide emulsions - Google Patents

Stabilization of photographic silver halide emulsions Download PDF

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US3062654A
US3062654A US827809A US82780959A US3062654A US 3062654 A US3062654 A US 3062654A US 827809 A US827809 A US 827809A US 82780959 A US82780959 A US 82780959A US 3062654 A US3062654 A US 3062654A
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emulsions
silver halide
emulsion
acid
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Frank D Allen
Arthur H Herz
Norman W Kalenda
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Eastman Kodak Co
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Eastman Kodak Co
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Priority to DEE19624A priority patent/DE1188940B/de
Priority to GB24891/60A priority patent/GB957311A/en
Priority to BE601369A priority patent/BE601369A/fr
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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
    • G03C1/34—Fog-inhibitors; Stabilisers; Agents inhibiting latent image regression
    • G03C1/346—Organic derivatives of bivalent sulfur, selenium or tellurium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups

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  • This invention relates to the stabilization of photographic silver halide emulsions, and more particularly, to a method of inhibiting development of spontaneous fog without adversely affecting the sensitivity of the photographic silver halide emulsions.
  • Fog depends both on the emulsion and the conditions of development; for a given emulsion it increases with the degree of development. With constant development conditions, it tends to increase with time, temperature and relative humidity of storage conditions; it is common practice to make accelerated tests of the stability of photographic emulsions by storage at increased temperature or humidity, or both. It is, of course, desirable to have emulsions as stable as possible under the conditions of high temperature and humidity which may occur in tropical climates, for example. Fog usually appears over the whole area of the sensitive coating, but when severe, it frequently is non-uniform. Fog may also be caused by exposure to chemicals, for example, hydrogen sulfide and other reactive sulfur compounds, hydrogen peroxide vapor, and strongly reducing materials. While antifoggants and stabilizers may protect, to some extent, against such effects, it is normally understood that an antifoggant protects against spontaneous growth of fog during prolonged storage or storage at high temperatures and humidities, or during development to maximum contrast and speed, or both.
  • Such disulfides having both sensitizing and some stabilizing activity cannot be employed in unsensitized or undersensitized emulsions.
  • the sensitizing or desensitizing disulfides if they are to act as fog restrainers, must be used at narrow and controlled concentration levels, thus making their introduction into the emulsion, for example, by bathing, impractical.
  • -It is, therefore, an a method of stabilizing object of our invention to provide photographic silver halide emulice sions. Another object is to provide a method of stabilizingphotographic silver halide emulsions without affecting to any material extent the sensitivity of the emulsion. Another object is to provide a method of stabilizing both unsensitized and sensitized emulsions, without introducing any substantial sensitizing or desensitizing effects. Other objects will become apparent from a consideration of the following description and examples.
  • photographic silver halide emulsions can be stabilized against the formation of spontaneous fog by incorporating therein a dicarboxyalkyldisulfide or a Water-soluble salt of said dicarboxya'lkyldisulfide, provided said dicarboxyalkyldisulfide has a molecular weight of at least 238.
  • dicarboxyalkyldisulfides and their water-soluble salts useful in practicing our invention include those compounds represented by the following general formula:
  • R and R each represents a methylene group, which may or may not be substituted by hydrocarbon radicals, such as methyl, ethyl, etc.
  • R R R and R each represents a hydrogen atom, a lower alkyl group (e.g., methyl, ethyl, etc.), or an aralkyl group (e.g., benzyl, fl-phenylethyl, etc.)
  • M and M each represents a cation such as hydrogen, an alkali metal (e.g., sodium, potassium, etc.), ammonium, substituted (e.g., organic) ammonium (e.g., pyridinium, triethanolammonium, etc.), and m and it each represents an integer of from O to about 8, provided that said compounds contain at least 8 carbon atoms.
  • Typical compounds useful in practicing our invention include the following:
  • the disulfides of our invention can be added to the emulsion during the process of manufacture in order to avoid loss of sensitivity and to inhibit the growth of fog with passage of time under non-ideal conditions of storage.
  • An aqueous solution of the disulfides of our invention when added at suitable concentration to unsensitized, chemically sensitized, or optically sensitized photographic emulsions does not appreciably affect the sensitometric values for sensitivity and fog when measurements are made soon after coating.
  • the disulfides of our invention do stabilize speed and maintain fog at a low level.
  • the preparation of silver halide emulsions involves three separate operations: (1) the emulsification and digestion or ripening of the silver halide, (2) the freeing of the emulsion from excess soluble salts, usually by washing, and (3) the second digestion or after-ripening to obtain increased sensitivity. (Mees, The Theory of the Photographic Process (1942)). We prefer to add the fog-inhibiting agents after the final digestion or afterripening, although they can advantageously be added prior to digestion.
  • disulfides of our invention can be incorporated in the emulsions without adverse efiects by bathing techniques known to those skilled in the art.
  • photographic emulsions used in practicing our invention are of the developing-out type.
  • the emulsions can be chemically sensitized by any of the accepted procedures.
  • 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, Sheppard et al. U.S. Patent 1,623,499, issued April 5, 1927 and Sheppard et al., 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.
  • 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 sensitizing in amounts below that which produces any substantial fog inhibition, as described in Smith and Trivelli U.S. Patent 2,448,060, issued August 31, 1948.
  • the emulsions can also be chemically sensitized with gold salts as described in Waller et al. U.S. Patent 2,399,- 083, issued April 23, 1946, or stabilized with gold salts as described 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 Z-aurosulfobenzothiazole methochloride.
  • the emulsions can also be chemically sensitized with reducing agents such as stannous salts (Carroll U.S. Patent 2,487,850, issued November 15, 1949), polyamines, such as diethyl 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, 1949), polyamines, such as diethyl 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
  • 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 U.S.
  • the emulsions may also contain speed-increasing compounds of the quaternary ammonium type of Carroll U.S. Patent 2,271,623, issued February 3, 1942; Carroll and Allen U.S. Patent 2,288,226, issued June 30, 1942; and Carroll and Spence U.S. Patent 2,334,864, issued November 23, 1943; and the polyethylene glycol type of Carroll and Beach U.S. Patent 2,708,162, issued May 10, 1955, and the thioether compounds of Graham and Sagal U.S. application Serial No. 779,839, filed December 12, 1958 (now U.S. Patent 3,046,129, issued July 24, 1962) and the Dann and Gates U.S. application Serial No. 797,577, filed March 6, 1961.
  • the emulsions may contain a suitable gelatin plasticizer such as glycerin; a dihydroxy alkane such as 1,5-pentane diol as described in Milton and Murry U.S. application Serial No. 588,951, filed June 4, 1956 (now 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. application Serial No. 662,564, filed May 31, 1957 (now U.S. Patent 2,904,434, issued September 15, 1959); bis-(ethoxy diethylene glycol) succinate as described in Gray U.S. application Serial No. 604,333, filed August 16, 1956 (now U.S.
  • a suitable gelatin plasticizer such as glycerin
  • a dihydroxy alkane such as 1,5-pentane diol as described in Milton and Murry U.S. application Serial No. 588,951, filed June 4, 1956 (now U.S. Patent 2,960,404
  • the plasticizer may be added to the emulsion before or after the addition of a sensitizing dye, if used.
  • the emulsions may be hardened with any suitable hardener for gelatin such as formaldehyde; a halogensubstituted 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,S-disulfonyl chloride as described in Allen and Carroll US.
  • any suitable hardener for gelatin such as formaldehyde
  • a halogensubstituted aliphatic acid such as mucobromic acid as described in White U.S. Patent 2,080,019, issued May 11, 1937
  • a cyclic 1,2-diketone such as cyclopentane-1,2-dione as described in Allen and Byers U.S. Patent 2,725,305, issued November 29, 1955
  • a bisester or" methane-sulfonic acid such as 1,2-di-(methane-sulfonoxy)-ethane as described in Allen and Laakso U.S
  • Patent 2,732,316 issued January 24, 1956; a dialdehyde or a sodium bisulfite derivative thereof, the aldehyde groups of which are separated by 3 carbon atoms, such as fi-methyl glutaraldehyde bissodium bisulfite as described in Allen and Burness U.S. patent application Serial No. 556,031, filed December 29, 1955 (now abandoned); a bis-aziridine carboxamide such as trimethylene bis(1-aziridine carboxamide) as described in Allen and Webster U.S. patent application Serial No. 599,891, filed July 25, 1956 (now U.S. Patent 2,950,197, issued August 23, 1960); or 2,3-dihydroxy dioxane as described in Jefireys U.S. Patent 2,870,013, issued January 20, 1957.
  • the emulsions may contain a coating aid such as saponin; a lauryl or oleyl 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 oleyl 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 tetra-carboxybutane 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 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 as described in Knox and Wilson U.S. patent application Serial No. 600,679, filed July 30, 1956 (now U.S. Patent 3,038,804, issued June 12, 1962); or a sulfosuccinamate such as tetrasodium N-(1,2-dicarboxyethyl)-N-octadecyl sulfosuccinamate or N-lauryl disodium sulfosuccinamate as described in Knox and Stenberg U.S. patent application Serial No. 691,125, filed October 21, 1957 (now U.S. Patent 2,992,108, issued July 11, 1962).
  • a substituted amino acid such as disodium N-(carbo-p-tert. octylphenoxypentae
  • the addenda which we have described may be used in various kinds of photographic emulsions. In addition to being useful in X-ray and other nonoptically sensitized emulsions they may also be used in orthochromatic, panchromatic, and infrared sensitive emulsions. They may be added to the emulsion before or after any sensitizinzg dyes which are used.
  • Various silver salts may 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 agents may 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 US; 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.
  • These agents 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 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.
  • colloidal albumin colloidal albumin
  • a cellulose derivative a cellulose derivative
  • synthetic resin for instance, a polyvinyl compound.
  • colloids which may 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 cyano-acetyl groups such as the vinyl alcohol-vinyl cyanoacetate copolymer as described in Unruh, Smith and Priest '6 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 U.S. Patent 2,852,382, of 11- lingsworth, Dann and Gates, issued September 16, 1958.
  • cyano-acetyl groups such as the vinyl alcohol-vinyl cyanoacetate copolymer as described in Unruh, Smith and Priest '6 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 U.S. Patent 2,852,382, of 11- lingsworth, Dann and Gates, issued September
  • compatible mixtures of two or more of these colloids may be employed for dispersing the silver halide in its preparation.
  • Combinations of these sensitizers, hardeners, etc., may be used.
  • the disulfides useful in practicing our invention can be added to the photographic emulsions prior to the final digestion, if desired. Generally, these compounds can be added from substantially neutral aqueous solution so that the pH of the emulsion is not disturbed. In the case of compounds containing free carboxylic acid groups, this means that these carboxylic acid groups will be at least partially neutralized.
  • the disulfides of our invention exist in the emulsion in ionic form, inasmuch as they are used in small quantities, and the emulsions useful in practicing our invention ordinarily contain substantial amounts of water.
  • the disulfides useful in practicing our invention can be added to the emulsions in the form of free acids, particularly where the addition is made to an acidic type emulsion.
  • the amount of disulfide compound added to the emulsions of our invention can be varied, depending upon the particular emulsion, the silver halide content of the emulsion, etc. In general, we have found that from about 0.1 to 15.0 grams of disulfi-de per mole of silver halide can advantageously be employed in our invention.
  • One of the outstanding advantages of the disulfides of our invention, as compared with the disulfides which have been previously described in the prior art, is that they can be used in quite substantial quantities without introducing serious desensitizing effects.
  • the disulfides useful in our invention advantageously have little or no sensitizing action on their own, and hence, they can be used to stabilize emulsions which have already been finished to their optimum or near-optimum speeds.
  • addition of our compounds to such finished emulsions does not result in any substantial desensitizing effect, such as might ordinarily be expected.
  • the compound numbers correspond to the numbers used above for the specific disulfides.
  • the compound numbers A and B represent compounds which have been previously used in the prior art to sensitize photographic silver halide emulsions. These data are included to show that such compounds do not provide the useful stabilizing effect provided by the compounds of our invention.
  • the same emulsion batch was used, although dif ferent emulsion batches were used for some of the coating numbers identified in the table. Wherever a different emulsion batch was used, a control series was run for that batch to show the degree of improvement obtained.
  • the silver bromiodide emulsion was a fast panchromatically sensitized bromiodide emulsion.
  • the same general type of emulsion was used in coating series No. 4. The results of these coating series are given in the following table:
  • the curves represent the sensitivity curvs of ordinay photographic silver halide emulsions containing a homologous series of dicarboxyalkyldisulfides. These disulfides (in approximately molar equivalent amounts) were added to aliquot portions of the same batch of coarse-grained silver bromiodide emulsions from substantially neutral aqueous solutions. All of the emulsions were held for about 30 minutes at 60 C. and then coated on ordinary cellulose acetate film.
  • Curve 1 represents the sensitivity of the bromiodide emulsion containing 2.7 grams of dithiodiacetic acid per mole of silver bromiodide.
  • Curve 2 represents the sensitivity of the same emulsion containing 3.15 grams of 3,3- dithiodipropionic acid.
  • Curve 3 represents the sensitivity of the same emulsion containing 3.6 grams of 4,4-dithiodibutyric acid per mole of silver bromiodide.
  • a curve substantially identical to curve 3 was obtained for the untreated emulsion (control) and for the same emulsion containing 4.0 grams of 5,5-dithiodivaleric acid per mole of silver bromiodide.
  • H and D curves shown that the disulfides of the present invention have no substantial sensitizing effect on silver halide emulsions.
  • the data in the accompanying table show that they have a much more useful stabilizing etfe-ct than the lower homologs used in obtaining curves 1 and 2.
  • disulfides useful in stabilizing emulsions according to our invention can be obtained by methods previously described in the prior art.
  • these disulfides can be obtained by the simple oxidation of the corresponding mercaptans, represented by the following general formula:
  • Useful oxidizing agents include aqueous solutions of iodine in potassium iodide, hydro-gen peroxide, etc. The following examples will serve to illustrate the preparation of one of the disulfides useful in practicing our invention,
  • EXAMPLE B 'y,'y-Dithi0dibutyric Acid 'y-Mercaptobutyric acid (123 g., 1.02 moles) was dissolved in dilute sodium hydroxide. This material was oxidized by the slow addition (dropping funnel) of potassium triiodide solution [potassium iodide (200 g.) dissolved in 800 ml. of water. Iodine (100 g.) is then dissolved in the solution]. After the oxidation was complete, enough dilute (3 percent) sodium thiosulfate solution was added to give a colorless solution. The solution was made strongly acidic with dilute sulfuric acid. The material which separated out was recrystallized from water.
  • the yield was g.
  • the M.P. was 107109 C.
  • Compound 3 was synthesized according to the method described by Schoeberl, Berichte 70 (1937), page 1186.
  • R and R each represents a methylene group
  • R R R and R each represents a member selected from the class consisting of a hydrogen atom, a lower alkyl group and an aralkyl group containing from 7 to 8 carbon atoms
  • M and M each represents a cation
  • m and 11 each represents an integer from 0 to 8, provided that said compound contains at least 8 carbon atoms.
  • silver halide emulsion as defined 2.
  • R and R each represents a methylene group
  • R R R and R each represents a member selected from the class consisting of a hydrogen atom, a lower alkyl group and an aralkyl group containing from 7 to 8 carbon atoms
  • M and M each represents a cation

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US827809A 1959-07-17 1959-07-17 Stabilization of photographic silver halide emulsions Expired - Lifetime US3062654A (en)

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BE593048D BE593048A (en)) 1959-07-17
US827809A US3062654A (en) 1959-07-17 1959-07-17 Stabilization of photographic silver halide emulsions
FR832882A FR1269368A (fr) 1959-07-17 1960-07-13 Nouvelle émulsion photographique aux halogénures d'argent
DEE19624A DE1188940B (de) 1959-07-17 1960-07-16 Stabilisierte photographische Halogensilberemulsion
GB24891/60A GB957311A (en) 1959-07-17 1960-07-18 Improvements in photographic silver halide emulsion
BE601369A BE601369A (fr) 1959-07-17 1961-03-15 Procédé de fabrication de purée de pommes de terre cuites déshydratées.

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3226232A (en) * 1963-05-16 1965-12-28 Gen Aniline & Film Corp Fog reduction in silver halide emulsions with a diphenyldisulfide dicarboxylic acid
US3779757A (en) * 1971-01-12 1973-12-18 Agfa Gevaert Nv Silver complex diffusion transfer process utilizing an aromatic disulfide
US3926632A (en) * 1971-09-13 1975-12-16 Agfa Gevaert Nv Photographic silver halide lith material
US4463082A (en) * 1983-04-19 1984-07-31 Polaroid Corporation Silver diffusion transfer film unit with noble metal compound as stabilizer
US4699873A (en) * 1985-01-29 1987-10-13 Fuji Photo Film Co., Ltd. Negative silver halide photographic light-sensitive material
US5035978A (en) * 1989-10-24 1991-07-30 Eastman Kodak Company Image receiving element for use in a silver complex diffusion transfer process
US5217859A (en) * 1992-04-16 1993-06-08 Eastman Kodak Company Aqueous, solid particle dispersions of dichalcogenides for photographic emulsions and coatings
US5219721A (en) * 1992-04-16 1993-06-15 Eastman Kodak Company Silver halide photographic emulsions sensitized in the presence of organic dichalcogenides
US5364754A (en) * 1992-04-16 1994-11-15 Eastman Kodak Company Silver halide photographic emulsions precipitated in the presence of organic dichalcogenides
US5418127A (en) * 1993-05-28 1995-05-23 Eastman Kodak Company Water-soluble disulfides in silver halide emulsions
US6815157B2 (en) * 2003-01-20 2004-11-09 Konica Minolta Holdings, Inc. Silver halide emulsion and silver halide photographic material

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1742042A (en) * 1927-01-07 1929-12-31 Agfa Ansco Corp Sensitized element, silver halid emulsion therefor, and process of manufacturing thesame

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE874702C (de) * 1945-12-15 1953-04-27 Gen Aniline & Film Corp Stabilisatoren fuer photographische Emulsionen
DE957183C (de) * 1953-07-01 1957-01-31 Eastman Kodak Co Stabilisiertes photographisches Material

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1742042A (en) * 1927-01-07 1929-12-31 Agfa Ansco Corp Sensitized element, silver halid emulsion therefor, and process of manufacturing thesame

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3226232A (en) * 1963-05-16 1965-12-28 Gen Aniline & Film Corp Fog reduction in silver halide emulsions with a diphenyldisulfide dicarboxylic acid
US3779757A (en) * 1971-01-12 1973-12-18 Agfa Gevaert Nv Silver complex diffusion transfer process utilizing an aromatic disulfide
US3926632A (en) * 1971-09-13 1975-12-16 Agfa Gevaert Nv Photographic silver halide lith material
US4463082A (en) * 1983-04-19 1984-07-31 Polaroid Corporation Silver diffusion transfer film unit with noble metal compound as stabilizer
US4699873A (en) * 1985-01-29 1987-10-13 Fuji Photo Film Co., Ltd. Negative silver halide photographic light-sensitive material
US5035978A (en) * 1989-10-24 1991-07-30 Eastman Kodak Company Image receiving element for use in a silver complex diffusion transfer process
US5217859A (en) * 1992-04-16 1993-06-08 Eastman Kodak Company Aqueous, solid particle dispersions of dichalcogenides for photographic emulsions and coatings
US5219721A (en) * 1992-04-16 1993-06-15 Eastman Kodak Company Silver halide photographic emulsions sensitized in the presence of organic dichalcogenides
US5364754A (en) * 1992-04-16 1994-11-15 Eastman Kodak Company Silver halide photographic emulsions precipitated in the presence of organic dichalcogenides
EP0566080A3 (en) * 1992-04-16 1995-01-04 Eastman Kodak Co Photographic silver halide emulsions sensitized in the presence of organic dichalcogenides.
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