US3811896A - Silver halide emulsion stabilized with isoselenoureas or ketoselenozolidines - Google Patents

Silver halide emulsion stabilized with isoselenoureas or ketoselenozolidines Download PDF

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US3811896A
US3811896A US00139942A US13994271A US3811896A US 3811896 A US3811896 A US 3811896A US 00139942 A US00139942 A US 00139942A US 13994271 A US13994271 A US 13994271A US 3811896 A US3811896 A US 3811896A
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silver halide
pat
compounds
issued
emulsion
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A Herz
E Westcott
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Eastman Kodak Co
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Eastman Kodak Co
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Priority to US00139942A priority Critical patent/US3811896A/en
Priority to CA138,915A priority patent/CA976410A/en
Priority to FR7214463A priority patent/FR2135176B1/fr
Priority to BE782639A priority patent/BE782639A/xx
Priority to GB2065172A priority patent/GB1390661A/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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D293/00—Heterocyclic compounds containing rings having nitrogen and selenium or nitrogen and tellurium, with or without oxygen or sulfur atoms, as the ring hetero atoms
    • C07D293/10—Heterocyclic compounds containing rings having nitrogen and selenium or nitrogen and tellurium, with or without oxygen or sulfur atoms, as the ring hetero atoms condensed with carbocyclic rings or ring systems
    • C07D293/12—Selenazoles; Hydrogenated selenazoles

Definitions

  • m is an integer of from about 0 to about 4 and n is an integer of from about 0 to about 4 such that their combined total is a positive integer of not more than about 8; and -Y is a divalent 'group; or
  • This invention relates to the stabilization of photographic elements and compositions. More particularly it relates in one aspect to the stabilization of silver halide containing compositions against spontaneous fog. In another aspect, the invention relates to certain new and known organic selenium derivatives which are useful in stabilizing light sensitive silver halide emulsions and layers of photographic elements.
  • fog While the degree of fog depends in part on the particular emulsion and conditions of development, fog usually increases with increases in time, temperature and relative humidity of storage conditions.
  • addenda have been employed in the past to increase the stability of the photosensitive silver halidecontaining elements and compositions. Some such addenda reduce the tendency to fog but likewise exhibit the disadvantage of decreasing the sensitivity and/or the contrast of the silver halide-containing element and composition. This is especially true in those photographic preparations which are optically sensitized to the. various spectral regions, such as those preparations adapted for use in color photography.
  • N-allgyl substituted azoles containing an oxygen, sulfur or selenium atom as a component of the azole ring are disclosed as photographic antifogging agents which,
  • This invention relates to new photographic compositions and elements comprising light sensitive silver halide which is fog stabilized by an effective concentration of a selenium containing organic compound.
  • These compounds are generically described as, 'isoselenoureas and ketoselenozolidines.
  • n and n are each about to 4fand together represent a positive integer generally less than about 8. Since these pseudoselenourea compounds are bases, their l-lX salts can be used where X is an organic anion, like p-toluene sulfonate or an inorganic anion like bro mide and the like.
  • Y is a divalent organic moiety such as ether (-O), thiother (-S--), keto and the like and each R to R group is hydrogen or a hydrocarbon like phenyl or lower alkyl, i.e., having one to six carbon atoms, or is an acid residue like carboxylic,'sulfuric, sulfonic and the like or their corresponding anionicderivatives like sulfonates, or a selenourea group like v i in order to complete a bisisoselenourea compound, L,
  • L and L having the same meaning as below or its salts such as bromides and the like, and L, L and L" are each hydrogen or organic residue which can be linked together to complete a heterocyclic ring or as a free base or its salts in which the R, R, R and R groups are each hydrogen or organic residues such as hydrocarbon residues like alkyl groups and preferably lower alkyl such as having from one to six carbon atoms like methyl, ethyl, propyl, butyl and the like; and, since these selenazolidine-4-ones are bases, their HX salts can be used where X is an organic anion like para-toluenesulfonate and the like or an inorganic anion such as a chloride, bromide and the like.
  • Organic residues can be hydrocarbon and functionally substituted hydrocarbon groups like alkyl or substimula (I) include for example: 3(amidoseleno)-1-propanesulfonic acid; 4-(amidoseleno)butyric acid; 2-(2- hydroxyethyl-2selenopseudourea hydrochloride; 2-(1- methyl-3-sulfopropyl-2-selenopsuedourea; 2- (amidoseleno)butyric acid hydrobromide; 2,2- ethylene bis (2-selenopseudourea)dihydrobromide; 6- (amidoseleno)butyric' acid hydrobromide; 6- (amidoseleno)hexanoic acid hydrobromide; 4-(N,N- dimethylamidoseleno)- 1 -butanesulfonic acid; 4-(N,N- dimethylamidoseleno)-l-butanesulfonic acid; 4- (amidoseleno
  • the stabilizing compounds defined by these structural formulae can be utilized in a variety of ways such as being incorporated directly into silver halide containing elements, such asin the silver halide layer, silver halide. emulsions orin various layers contiguous thereto such as overcoat, intermediate and the like layers. In this manner it can be said that these selenium containing antifoggant compounds are incorporated into photographic elements and compositions in a concentration and manner sufficient to insure a fog inhibiting effect. This relationship is likewise insured by use of said compounds in various solutions or sprays in which the finished or processed photographic material is so stabilized or in using various wrapping or storage materials or environments juxtaposed to the layers,
  • the compounds within the scope defined by the above formulae are effective antifoggants and emulsion stabilizers when employed either in or contiguous to a photographic silver halide gelatin-containing emulsion layer.
  • a preferred concentration of said compounds of Formula 1 is from about 0.005 to about 1.0 gram per mole of silver halide and that of Formula 11 is from about 0.01 to about 1.0 gram per mole of silver halide while for purposes of incorporating an alkali and/or heat releasable silver halide solvent for transfer or clearing use, the desired molar concentration of compounds of Formula 1 and ll can be similar to that of the silver halide.
  • the developing solution is not sufficiently alkaline to activate the selenium containing derivatives iii of this invention, the photographic element having the developed emulsion coated thereon can subsequently be immersed in a stronger alkaline bath for fixing.
  • a photographic element comprising a support bearing a fog stabilized light sensitive silver halide-containing layer and comprising a silver halide solvent concentration of a selenium-containing organic compound having the structural formula:
  • RJElYlZlM ⁇ t- ⁇ l'a Nu where m and n are each about 0 to about 4 and together are a positive integer generally less than about 8; since these pseudoselenourea compounds are bases, their HX salts can be used where X is an organic anion like p-toluene sulfonate or an inorganic anion like bromide and the like.
  • Y is a divalent organic moiety such as ether (-O-), thioether (-.-S--), ketoand the like and each R to R group is hydrogen or a hydrocarbon like phenyl or lower alkyl, i.e., having one to six carbon atoms, or is an acid residue like carboxylic, sulfuric,
  • L, L and L having the same meaning as below or its salts such as bromides and the like
  • L, L and L are each hydrogen or organic residue which can be linked together to complete a heterocyclic ring or 1 R NR5 as a free base or its salts in which the RR, R. and R groups are each hydrogen or organic residues such as alkyl' groups, preferably lower alkyl such as having from one to six carbon atoms like methyl, ethyl, propyl,
  • HX salts can be used where X is an organic anion like p-toluene sulfonate or an inorganic anion such as a halide like chloride, bromide and the like; or in which the phenyl group can be part of a con densed polycyclic or hetero aromatic nucleus, for example, naphthalene, quinoline; and the like or it can be substituted with other functional groups, for example, amine, amide, acylamino, carboxylate groups and the like.
  • Compounds of formula (I) can be generally prepared I as described in Knott et al US. Pat. No. 2,514,650 issued July ll, 1950, by using the corresponding selenourea derivatives. These compounds, especially those compounds containing a ureido group, are preferably employed as their salts, e.g., hydrohalide which are usually more stable than the bases and are watersoluble.
  • 3-(amidinoseleno)-l-propanesulfonic acid is prepared from 39 g (0.25 mole) of l-bromo-3-chloropropane and 25 g (0.20 mole) of sodium sulfite which are stirred and refluxed for 2 hours in 300 ml of a 1:1 mixture of ethyl alcohol and water. This mixture is concentrated to about ml and 20 g (0.17 mole) of selenourea is added. This mixture is stirred and refluxed for one-half hour, concentrated to 75 ml., then chilled. From a mushy, off-white cream, the final product is recrystallized from about 50 ml of water in a 16 g yield which has a melting point of 225 to 227C.
  • the process for preparing the 6- (amidose1eno)hexanoic acid hydrobromide is also novel.
  • g (0.1 mole) of 6- bromohexanoic acid and 12 g (0.1 mole) of selenourea are dissolved in 125 ml of isopropyl alcohol, placed on a heating mantle and stirred and refluxed for about 4 hours, then filtered hot.
  • the solvent is removed in vacuo and the remaining solid of 27 g crude weight is then recrystallized from 150 ml of acetic acid.
  • the resulting white crystals are washed with acetone and dried to yield 19.8 g having a'melting point of 170 to 171C.
  • the silver halide emulsions used in the practice of this invention can be additionally protected against the production of fog and can be stabilized against loss of sensitivity during keeping.
  • Suitable other antifoggants and stabilizers each used alone or in combination in-' clude thiazolium salts described in Brooker et a1 U.S. Pat. No. 2,131,038 issued Sept. 27, 1938, and Allen et a1 U.S. Pat. No. 2,694,716 issued Nov. 16, 1954; the azaindenes described in Piper U.S. Pat. No. 2,886,437 issued May 12, 1959; and Heimbach et al. U.S. Pat. No.
  • the isoselenourea derivatives are alkali or heat releasable agents able to convert silver halides to the various alkyl, aryl or heteroaromatic residues (such as phenyl, benzothiazolyl and the like) of silver se1enide.
  • selenium-containing compounds are unexpectedly effectiveas emulsion stabilizers and antifoggants.
  • R is ethyl, phenyl, naphthyl; R is hydrogen, alkali metal or a substituted alkyl group ending in an acid radical.
  • Typical compounds are:
  • various polyazaindenes can be used with good results.
  • triand tetraazaindenes such as 1,3,4 and 1,3,5-tri and 1,2,3,4- and 1,2,3,5-tetraazaindenes are effective antifoggants when incorporated inthe silver halide layer, a layer adjacent thereto and in'various solutions, such as processing solutions and the like, used to contact the silver halide and other layers.
  • polyazaindenes are conveniently prepared from their corresponding diaminopyridines by conventional methods-An effective concentration range is from about 0.95 g to about 4.0 g/mole of silver and preferably from about 0.75 g/mole to about 3.0g/mole.
  • these polyazaindenes are effective in concentrations of from about 0.15 to about 0.75 grams/liter and preferably 0.25 to about 0.50 grams/liter of solution.
  • the silver halide emulsions used with this invention can comprise silver chloride, silver bromide, silver bromoiodide, silver chlorobromoiodide or mixtures thereof.
  • the emulsions can be coarse or fine grain and can be prepared by any of the well-known procedures, e.g., single jet emulsions, double jet emulsions, such as Lippmann emulsions, ammoniacal emulsions, thiocyanate or thioether ripened emulsions such as those described in Nietz et a1.
  • Negative type emulsions can be used or direct positive emulsions such as those described in Leermakers U.S. Pat.'N o.2,184,013 issued Dec. 19, 1939; Kendall et al., U.S. Pat. No. 2,541,472 issued Feb. 13, 1951; Berriman U.S. Pat. No. 3,367,778 issued Feb. 6, 1968; Schouwenaars British Patent 723,019 issued Feb. 2, 1955; lllingsworth et al. French Patent 1,520,821 issued Mar. 4 1968; Ives US. Pat. No. 2,563,785 issued Aug.
  • the emulsions can be regular grain emulsions such as the type described in Klein and Moisar, J. Phat. Sci., Vol. 12, No. 5, Sept/Oct, 1964, pp 242-251.
  • the emulsions used this invention can be sensitized with chemical sensitizers, such as with reducing agents; sulfur, selenium or tellurium compounds; gold, platinum or palladium compounds; or combinations of these. Suitable procedures are described in Sheppard et a1. U.S. Pat. No. 1,623,499 issued Apr. 5, 1927; Waller et al. U.S. Pat. No. 2,399,083'issued Apr. 23, 1946; McVeigh U.S.Pat. No. 3,297,447 issued Jan. 10, 1967;
  • the photographic and other hardenable layers used in the practice of this invention can be hardened by various organic or inorganic hardeners, alone or in combination, such as the aldehydes, and blocked aldehydes, ketones, carboxylic and carbonic acid derivatives, sulfonate esters sulfonyl halides and vinyl sulfonyl ethers, active halogen compounds, epoxy compounds, aziridines, active olefins, isocyanates, carbodiimides, mixed function hardeners and polymeric hardeners such as oxidized polysaccharides like dialdehyde starch and oxyguar gum and the like.
  • various organic or inorganic hardeners such as the aldehydes, and blocked aldehydes, ketones, carboxylic and carbonic acid derivatives, sulfonate esters sulfonyl halides and vinyl sulfonyl ethers, active halogen compounds, epoxy compounds, aziridines, active
  • the photographic emulsions and elements described in the practice of this invention can contain various colloids alone or in combination as vehicles, binding agents and various layers.
  • Suitable hydrophilic materials include both naturally occurring substances such as proteins, for example, gelatine, gelatine derivatives, cellulose derivatives, polysaccharides such as dextran, gum arabic and the like; and synthetic polymeric substances such as water soluble polyvinyl compounds like poly(vinylpyrrolidone), acrylamide polymers and the like.
  • the described photographic emulsion layers and other layers of a photographic element employed in the practice of this invention can also contain alone or in combination with hydrophilic, water permeable colloids, other synthetic polymeric compounds such as dispersed vinyl compounds such as in latex form and particularly those which increase the dimensional stability of the photographic materials.
  • Suitable synthetic polymers include those described, for example, in Nottorf U.S. Pat. No. 3,142,568 issued July 28, 1964; White U.S. Pat. No. 3,193,386 issued July 6, 1965; Houck ct al. U.S. Pat. No. 3,062,674 issued Nov. 6, 1962; Houck et al U.S. Pat. No. 3,220,844 issued Nov. 30, 1965; Ream et a1.
  • Nottorf U.S. Pat. No. 3,142,568 issued July 28, 1964 White U.S. Pat. No. 3,193,386 issued July 6, 1965; Houck ct al. U.S. Pat. No. 3,062,674 issued Nov
  • Typical supports include cellulose nitrate film, cellulose ester film, poly(vinyl acetal) film, polystyrene film, poly(ethylene terephthalate) film.
  • polycarbonate film and related olefin polymer particularly a polymer of an alphaolefin containing two to 10 carbon atoms such as polyethylene, polypropylene, ethylenebutene copolymers and the like.
  • the photographic layers employed in the practice of this invention can contain plasticizers and lubricants such as polyalcohols, e.g., glycerin and diols of the type described in Milton et al, U.S. Pat. No. 2,960,404 issued Nov. 1, 1966; fatty acids or esters such as those described in Robijns U.S. Pat. No. 2,588,765 issued Apr. 11, 1952, and Duane U.S. Pat. No. 3,121,060 issued Feb. 11,1964; and silicone resins such as those described in DuPont British Patent 955,061 issued Apr.
  • plasticizers and lubricants such as polyalcohols, e.g., glycerin and diols of the type described in Milton et al, U.S. Pat. No. 2,960,404 issued Nov. 1, 1966; fatty acids or esters such as those described in Robijns U.S. Pat. No. 2,588,765 issued Apr. 11, 1952, and Duane U.
  • the emulsions containing a compound obtained in accordance with this invention can be used in diffusion transfer processes which utilize the undeveloped silver halide in non-image areas of the negative to form a positive by dissolving the undeveloped silver halide and precipitating it on a silver layer in close proximity to the original silver halide emulsion layer.
  • the emulsions can also be used in diffusion transfer of an imagewise distribution of developer, coupler, or dye, from a lightsensitive layer to a second layer, while the two layers are in close proximity to one another.
  • a flexible support is em-
  • emulsion and coating are employed as in Example 1 and the processing system is as described herein.
  • 4-(amidinoseleno) butyric acid 'Elon is a trademark of the Eastman Kodak Company for its methylated-paru-aminophenol.
  • Example 1 The same emulsion,c0ating and processing system as It can be seen from the preceeding table that the in Example 1. Some coatings are also processed in a compounds of the invention (2-iminoselenazolidine methylated-p-aminophenol hydroquinone developer 4-one and imino-S-methylselenazolidine-4-one) lower for 12 minutes at C. fog and stabilize photographic speed.
  • Y- is a divalent organic moiety selected from the group consisting of ether moieties, thioether moieties and keto moieties or TABLE VI Storage at 50% RH. 48C
  • isoselenouronium compounds described by formula I include those compounds where the divalent linking organic radical can be alkylene, such as an alkylene chain having from one to l0 carbon atoms such as methylene, ethylene, trimethylene and the like and including in that chain, atoms such as ether oxygen atorns thioether, ketoand the like interrupting groups or a xylylene ring.
  • the use of up to three oxygen atoms is preferred but more or less and even no oxygen atoms can be employed.
  • the xylylene rings include those attached at ortho, meta or para positions and the rings can be substituted, e.g., by alkyl groups like lower alkyl of one to four carbons such as methyl xylylene groups and the like.
  • a photographic element comprising a support bearing a light sensitive silver halide-containing layer and, in a fog-stabilizing concentration'from about 0.005 to about 1.0 g/mole silver halide, an organic compound having the structural formula:
  • each R. R, R. R and R is hydrogen, hydrocar bon or an acid residue selected from the group consist- (I) 1 mm E SeC ⁇ lJ. ⁇ w
  • the element of claim 1 comprising the compound of formula I in which said formula corresponds to 3- (amidinoseleno-l-propanesulfonic acid or 4'(N,N- dimethyl-amidinoselenoJ- l -butanesulfonic acid.
  • a silver halide gelatin-containing photographic emulsion stabilized against fog by the presence in a concentration range of from about 0.005 to about 1.0
  • each of R, R R, R and R is hydrogen, a hydrocarbon or an acid residue selected from the group consisting of carboxylic, sulfuric and sulfonic residues and their correspondingderivatives or a selenourea group or its salts and L, L and L can be hydrogen or organic residue groups which can be linked together to form a completed heterocyclic ring;
  • m is an integer of about 0 to about 4;
  • n is an integer of from about 0 to about 4 and the combined total of m and n is-a positive integer of not more than about 8;
  • -Y is a divalent organic moiety selected from the group consisting as a free base or its salts in which R, R, R and R are each hydrogen or a hydrocarbon or functionally substituted hydrocarbon group.
  • the emulsion of claim 4 further comprising a coumary amine silver halide color-developing agent. pler compound of a phenolic-, a pyrazoloneor open 6.
  • the emulsion of claim 4 further comprising develchain reactive methylene compound capable of formopment modifiers. ing a dye with the oxidation product of an aromatic pri-

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  • Physics & Mathematics (AREA)
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US00139942A 1971-05-03 1971-05-03 Silver halide emulsion stabilized with isoselenoureas or ketoselenozolidines Expired - Lifetime US3811896A (en)

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US00139942A US3811896A (en) 1971-05-03 1971-05-03 Silver halide emulsion stabilized with isoselenoureas or ketoselenozolidines
CA138,915A CA976410A (en) 1971-05-03 1972-04-05 Fog stabilization of compositions
FR7214463A FR2135176B1 (index.php) 1971-05-03 1972-04-24
BE782639A BE782639A (fr) 1971-05-03 1972-04-25 Stabilisation des produits photographiques contre la formation du voil
GB2065172A GB1390661A (en) 1971-05-03 1972-05-03 Sensitive silver halide photographic material

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GB (1) GB1390661A (index.php)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3947274A (en) * 1973-05-15 1976-03-30 Fuji Photo Film Co., Ltd. Silver halide photographic material containing an isourea derivative as antifoggant
US4607001A (en) * 1985-04-04 1986-08-19 Eastman Kodak Company Divalent chalcogenide fog inhibiting agents for silver halide photography

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4607000A (en) * 1985-04-04 1986-08-19 Eastman Kodak Company Amido substituted divalent chalcogenide fog inhibiting agents for silver halide photography
EP0198277B1 (de) * 1985-04-12 1989-05-03 A. Nattermann & Cie. GmbH Diselenobis-benzoesäureamide primärer und sekundärer Amine, Verfahren zu ihrer Herstellung und diese enthaltende pharmazeutische Präparate

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3947274A (en) * 1973-05-15 1976-03-30 Fuji Photo Film Co., Ltd. Silver halide photographic material containing an isourea derivative as antifoggant
US4607001A (en) * 1985-04-04 1986-08-19 Eastman Kodak Company Divalent chalcogenide fog inhibiting agents for silver halide photography

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BE782639A (fr) 1972-08-16
FR2135176A1 (index.php) 1972-12-15
CA976410A (en) 1975-10-21
FR2135176B1 (index.php) 1976-01-16
GB1390661A (en) 1975-04-16

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