US3043696A - Substituted disulfides as antifoggants for silver halide emulsions - Google Patents

Substituted disulfides as antifoggants for silver halide emulsions Download PDF

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US3043696A
US3043696A US838224A US83822459A US3043696A US 3043696 A US3043696 A US 3043696A US 838224 A US838224 A US 838224A US 83822459 A US83822459 A US 83822459A US 3043696 A US3043696 A US 3043696A
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silver halide
emulsions
disulfides
emulsion
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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 FR836724A priority patent/FR1266141A/fr
Priority to GB30247/60A priority patent/GB963987A/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
    • G03C1/34—Fog-inhibitors; Stabilisers; Agents inhibiting latent image regression
    • G03C1/346—Organic derivatives of bivalent sulfur, selenium or tellurium

Definitions

  • This invention relates to the stabilization of photo graphic silver halide emulsions, and. more particularly,
  • 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 con ditions, 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 3,043,696 Patented July 10, 1962 duction into the emulsion, for example, by bathing, im-' practical.
  • an object of our invention to provide. a method of stabilizing photographic silver halide emulsions. Another object is to provide a method of stabilizing photographic silver halide emulsions without afiecting to any material extent the sensitivity of the emulsions. Another object is to provide a method of stabilizing both unsensitized and sensitized emulsions, without introducing any substantial sensitizing or desensitizing elfect. Still another object is to provide new organic disulfides and a method of preparation. Other objects will become apparent from a consideration of the following description and examples.
  • photographic silver halide emulsions can be stabilized and the development 0t spontaneous fog substantially inhibited by incorporating therein certain organic disulfides.
  • substituted organic disulfides useful in practicing our invention can be represented by the following general formula:
  • COORi fonyl, toluenesulfonyl, etc. i.e., an acyl group of an ali-' other reactive sulfur compounds, hydrogen peroxide vapor, and strongly reducing materials. While antifog-j gants and stabilizers may protect, to some extent, against such efiects, it is normally understood that antifoggants protect against spontaneous growthof fog during prolonged storage or storage at high temperatures and humidities, or during development to maximum contrast and. speed, or both.
  • cystine is known to exhibit both sensitizing and example:
  • R ' represents a hydrogen atom, an alkali metal atom (e.g., sodium,-potassium, etc.), an ammonium group (i.e., ammonium or organic ammonium, including pyridinium, triethylammonium, triethanolammonium, etc.), or a lower alkyl group, such as methyl, ethyl, etc, and n represents a posi-f tive integer of from about 1 to 4.
  • Typical organic disulfides embraced by Formula 1 above which can be used in practicing our invention include the following, for
  • 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 'undernon-ideal conditions of storage.
  • An aqueous or organic; 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 0r 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.
  • the disulfides of our invention can be incorporated in the emulsions without adverse effects by bath i'ng techniques known to those skilled in the art.
  • the photographic emulsions used in practicing our invention areof 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 2,448,060, issued August 31, 194 8, 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 be chemically sensitized with gold salts as described in Waller et la].
  • Suitable compounds are potassium chloroaurite, potassium'aurithiocyanate, potas- 4 sium chloroaurate, auric trichloride and 2-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), polyarnines, 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 (Loweand 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), polyarnines, 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
  • 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 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
  • 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, as well as the thiopol-ymers of Graham and Sagal U.S. application Serial No. 779,839, filed December 12, 1958, and Dann and Chechak U.S. application Serial No. 779,874, filed December 12, 1958.
  • 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 Murray U.S. application 0 Serial No. 588,951, filed June 4, 1956; an ester of an ethylene bis-glycolic acid such as ethylene bis(met1hyl glycolate) 'as described in Milton U.S. application Serial No. 662,564, filed May 31, 1957; bis-( ethoxy diethylene glycol) succinate as described in Gray U.S. application Serial No.
  • 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-diphenyl-bicyclo (2,2,2)-7-octene- 2,3,5,6-tetra-carboxylic 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 halogensubstituted aliphatic acid such as mucobromic 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 bisulfite derivative thereof, the aldehyde groups of which are separated by 2-3 carbon atoms, such as fl-meth-yl glutaraldehyde bissodium bisulfite as described in Allen and Burness U.S. patent application Serial No. 556,031, filed December 29, 1955; a bis-aziridine carb'oxamide such as trimethylene bis(1-aziridine carboxamide) as described in Allen and Webster U.S. patent application Serial No.
  • 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 sensitizing dyes which are used.
  • Various silver salts may be 1186i 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, forexample, 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.
  • 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. I
  • the dispersing agent for the silver halide in its preparation gelatin or some othercolloidal material such as colloidal albumin, a cellulose derivative, or a synthetic resin, for instance, a polyvinyl compound.
  • colloids which may be used are polyvinyl alcohol or a hydrolyzed polyvinyl acetate as described in Lowe US. Patent 2,286,215, issued June 16, 1942; a far hydrolyzed celulose ester such as cellulose acetate hydrolyzed to an acetyl content of 19-26% as described in US.
  • Patent 2,768,154 issued October 23, 1956; or containing cyano-acetyl groups such as the vinyl alcohol-vinyl cyanoacetate copolyrner 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 U.S. Patent 2,852,382, of Illingsworth, Dann and Gates, issued September 16, 8.
  • cyano-acetyl groups such as the vinyl alcohol-vinyl cyanoacetate copolyrner 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 U.S. Patent 2,852,382, of Illingsworth, Dann and Gates, issued September 16, 8.
  • compatible mixtures of two or more of these colloids may be employed for dispersing the silver halide in its preparation.
  • Combinations of these anti fogg-ants, sensitizers, hardeners, etc., may be used.
  • the organic 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 a substantially neutral solution so that the pH of the emulsion is not disturbed. In the case of compounds containing free carboxylic acid groups, this means that one or more of these carboxylic acid groups may be neutralized. However, where it is desired to stabilize an acidic emulsion, it is obviously not necessary that the antifoggant be added from substantially neutral solutions. Since the disulfides of our invention can be added to the emulsions in such small quantities, it is apparent that they will generally have no adverse effect upon the pH of the emulsions.
  • organic disulfides useful in practicing our invention can be added to the emulsions in the form of substantially neutral aqueous solutions. If a particular disulfide does not have sufii'cient solubility in water, addition to the emulsion can be made in the form of a water-miscible organic solvent, such as methanol, ethanol, dioxane, pyridine, etc.
  • a water-miscible organic solvent such as methanol, ethanol, dioxane, pyridine, etc.
  • 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 1.0 to 10.0 grams of disulfide 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 of their own, and hence, they can be used to stabilize emulsions which have already been finished to their optimum or nearoptimum speeds.
  • addition of our compounds to such finished emulsions does not result in any substantial desensitizing effect, such as might ordinarily be expected.
  • Fresh tests and incubation tests (one week at 120 F, constant relative humidity of about or for two weeks under the same conditions) were also run for the same emulsion series with development under the same conditions.
  • the relative speed and fog for each of the series coatings werethen measured, the speed being determined at a point about 0.3 density above fog.
  • the disulfides of our invention can be used in gram quantities in order to increase the stability of the emulsions, without having any substantial effect upon the sensitivity or speed of the emulsions. While the compound of our inventions can be employed in relatively large amounts, it has been found that such well-known disulfides as cystine and certain of its derivatives cannot be employed in amounts even approaching those used in the present invention. This adverse eifect accompanying the use of cystine, or a derivative thereof, without the use of other addenda to control the adverse effect of these compounds, is illustrated in Table II below.
  • disulfides of Formula I can be obtained by simple acylation of the corresponding aminodisulfides represented by the following general formula:
  • R and n each have the values given above.
  • Acylation of the depicted amines can be accomplished by simply reacting these amines with an acylhalide, such as acetylchloride, methanesulfonylchloride, benzenesulfonylchloride, etc.
  • the amines of Formula II above can be prepared by simple oxidation of the corresponding mercapto-substituted amines, represented by the following general formula:
  • Oxidation can conveniently be accomplished by simply contacting the mercapto-amine of Formula III with an oxidizing agent, such as hydrogen peroxide, sodium perchlorate, etc.
  • an oxidizing agent such as hydrogen peroxide, sodium perchlorate, etc.
  • R-NHOH(CH2)-S-S-(OH:)nONHHR C0OR 000R1 wherein R represents an acyl group of an organic acid selected from the class consisting of an aliphatic carboxylic acid, an aromatic carboxylic acid, an aliphatic sulfonic acid and an aromatic sulfonic acid, R representsa member selected from the class consisting of a hydrogen atom, an alkali metal atom, an ammonium group, and an alkyl group, and n represents a positive 2.
  • n represents a positive integer of from about 1 to 4.
  • R represents an acyl group of a sulfonic acid
  • R represents an alkyl group
  • n represents a positive integer of from 1 to 4.
  • a photographic silver halide emulsion sensitized with a labile sulfur compound and a gold compound said silver halide emulsion being stabilized With from 1.0 to 10.0 g./mol. of silver halide of a compound selected from those represented by the following general formula:
  • R represents an acyl group of an organic acid selected from the class consisting of an aliphatic carboxylic acid, an aromatic carboxylic acid, an aliphatic sulfonic acid and an aromatic sulfonic acid
  • R represents a member selected from the class consisting of a hydrogen atom, an alkali metal atom, an ammonium group and an alkyl group
  • n represents a positive integer of from about 1 to 4.

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US838224A 1959-09-04 1959-09-04 Substituted disulfides as antifoggants for silver halide emulsions Expired - Lifetime US3043696A (en)

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BE594454D BE594454A (en, 2012) 1959-09-04
US838224A US3043696A (en) 1959-09-04 1959-09-04 Substituted disulfides as antifoggants for silver halide emulsions
DEE19800A DE1188942B (de) 1959-09-04 1960-08-19 Stabilisierte photographische Halogensilberemulsion
FR836724A FR1266141A (fr) 1959-09-04 1960-08-25 Nouvelle émulsion photographique stabilisée
GB30247/60A GB963987A (en) 1959-09-04 1960-09-01 Improvements in photographic silver halide emulsions

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Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3114637A (en) * 1961-05-01 1963-12-17 Eastman Kodak Co Photographic emulsions stabilized with 1, 2-dithiacyclopent-3-enes
US3547638A (en) * 1967-06-20 1970-12-15 Eastman Kodak Co N,n-disubstituted amino-methylthiocarboxylic acids and use thereof as antifoggants in photographic emulsions
FR2179136A1 (en, 2012) * 1972-04-05 1973-11-16 Ilford Ltd
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
US4120726A (en) * 1975-04-15 1978-10-17 Veb Filmfabrik Wolfen Silver-halide emulsion sensitized with an asymmetrical disulfide
US4314024A (en) * 1979-08-04 1982-02-02 Agfa-Gevaert Aktiengesellschaft Stabilized photographic emulsion, a process for its preparation and stabilized photographic materials
US4316953A (en) * 1979-08-04 1982-02-23 Agfa-Gevaert Aktiengesellschaft Photographic emulsion containing a stabilizer, a process for its production and photographic materials
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
US5356770A (en) * 1992-05-29 1994-10-18 Eastman Kodak Compamn Color photographic materials and methods with stabilized silver chloride emulsions
US5364754A (en) * 1992-04-16 1994-11-15 Eastman Kodak Company Silver halide photographic emulsions precipitated in the presence of organic dichalcogenides
US5415992A (en) * 1993-11-30 1995-05-16 Eastman Kodak Company Heat stabilized silver chloride photographic emulsions containing phosphine compounds
US5418127A (en) * 1993-05-28 1995-05-23 Eastman Kodak Company Water-soluble disulfides in silver halide emulsions
US5443947A (en) * 1993-11-30 1995-08-22 Eastman Kodak Company Heat stabilized silver chloride photographic emulsions containing thiosulfonate/sulfinate compounds
US5601970A (en) * 1995-01-03 1997-02-11 Eastman Kodak Company Photographic elements exhibiting improved stability
US5652090A (en) * 1996-03-15 1997-07-29 Eastman Kodak Company Silver halide photographic elements containing dithiolone compounds

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE788687A (nl) * 1971-09-17 1973-03-12 Agfa Gevaert Nv Ontwikkeling van zilverhalogenide-materiaal bij verhoogde temperatuur
JPS5986039A (ja) * 1982-11-08 1984-05-18 Fuji Photo Film Co Ltd ハロゲン化銀写真感光材料

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2438716A (en) * 1944-10-06 1948-03-30 Gen Aniline & Film Corp Stabilized silver halide emulsions
US2597915A (en) * 1949-09-24 1952-05-27 Eastman Kodak Co Stabilization of photographic emulsions sensitized with gold compounds

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 (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2438716A (en) * 1944-10-06 1948-03-30 Gen Aniline & Film Corp Stabilized silver halide emulsions
US2597915A (en) * 1949-09-24 1952-05-27 Eastman Kodak Co Stabilization of photographic emulsions sensitized with gold compounds

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3114637A (en) * 1961-05-01 1963-12-17 Eastman Kodak Co Photographic emulsions stabilized with 1, 2-dithiacyclopent-3-enes
US3547638A (en) * 1967-06-20 1970-12-15 Eastman Kodak Co N,n-disubstituted amino-methylthiocarboxylic acids and use thereof as antifoggants in photographic emulsions
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
FR2179136A1 (en, 2012) * 1972-04-05 1973-11-16 Ilford Ltd
US4120726A (en) * 1975-04-15 1978-10-17 Veb Filmfabrik Wolfen Silver-halide emulsion sensitized with an asymmetrical disulfide
US4314024A (en) * 1979-08-04 1982-02-02 Agfa-Gevaert Aktiengesellschaft Stabilized photographic emulsion, a process for its preparation and stabilized photographic materials
US4316953A (en) * 1979-08-04 1982-02-23 Agfa-Gevaert Aktiengesellschaft Photographic emulsion containing a stabilizer, a process for its production and photographic materials
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
US5356770A (en) * 1992-05-29 1994-10-18 Eastman Kodak Compamn Color photographic materials and methods with stabilized silver chloride emulsions
US5418127A (en) * 1993-05-28 1995-05-23 Eastman Kodak Company Water-soluble disulfides in silver halide emulsions
US5415992A (en) * 1993-11-30 1995-05-16 Eastman Kodak Company Heat stabilized silver chloride photographic emulsions containing phosphine compounds
US5443947A (en) * 1993-11-30 1995-08-22 Eastman Kodak Company Heat stabilized silver chloride photographic emulsions containing thiosulfonate/sulfinate compounds
US5601970A (en) * 1995-01-03 1997-02-11 Eastman Kodak Company Photographic elements exhibiting improved stability
US5652090A (en) * 1996-03-15 1997-07-29 Eastman Kodak Company Silver halide photographic elements containing dithiolone compounds

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