US3708302A - Silver halide emulsion sensitized with thioamine-glutaraldehyde or acrylic aldehyde adduct - Google Patents

Silver halide emulsion sensitized with thioamine-glutaraldehyde or acrylic aldehyde adduct Download PDF

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US3708302A
US3708302A US00104768A US3708302DA US3708302A US 3708302 A US3708302 A US 3708302A US 00104768 A US00104768 A US 00104768A US 3708302D A US3708302D A US 3708302DA US 3708302 A US3708302 A US 3708302A
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adduct
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glutaraldehyde
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J Plakunov
J Koller
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Eastman Kodak Co
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Eastman Kodak Co
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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
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/09—Noble metals or mercury; Salts or compounds thereof; Sulfur, selenium or tellurium, or compounds thereof, e.g. for chemical sensitising

Definitions

  • compositions comprising a hydrophilic colloid and an adduct of a first compound which is a thioamine with a second compound which is glutaraldehyde or acrylic aldehyde.
  • the compositions when coated upon photographic materials effect a significant speed increase without detrimentally affecting the other sensitometric properties of said materials.
  • This invention relates to radiation sensitive, imageforming materials and methods for increasing the photographic speed of said materials.
  • this invention relates to a hydrophilic, water permeable overcoat for photographic materials, said overcoat having dispersed therein an adduct of a thioamine with glutaraldehyde or acrylic aldehyde.
  • this invention relates to image-forming materials, such as photographic silver halide elements, and especially to high speed negative materials such as X-ray films or light sensitive material employed in making color material especially color separation negatives, containing a distinct layer'comprising said adduct.
  • this invention relates to the rapid processing of high speed negative materials said material containing a distinct layer comprising said adduct.
  • cysteine or aldehydes to photographic systems, i.e., photographic elements and photographic developers, it has not been taught heretofore that one may incorporate into a photographic element the combination of an aminothiol with a dicarbonyl or dicarboxy compound or an nap-unsaturated aldehyde.
  • Aldehydes as hardeners are well known addenda for photographic system, for example, see US. Pats. 3,220,- 849 of Baden and Bard issued Nov. 30, 1965; 3,418,132 of Ketze, Ir. issued Dec. 24, 1968; and 2,247,569 of Brunken et al. issued 1941; 2,279,411 of Peterson issued Apr. 14, 1942; and 3,232,764 of Allen and Burness, issued Feb. 1, 1966.
  • the increase in photographic speed with respect to development provides several degrees of freedom not ordinarily available, for example, one may decrease the silver halide coverage, the processing time for the exposed film can be decreased, or with regard to radiography, the patient may be exposed to small amounts of radiation.
  • novel photographic elements which exhibit a marked increase in the sensitivity of the element accompanied by uniformity throughout the material upon processing in the presence of a hardening or non-hardening developer.
  • the photographic element comprises a support, a silver halide layer and a distinct layer containing an adduct of a thioamine with glutaraldehyde or acrylic aldehyde.
  • a coating comprising an adduct of a thioamine with glutaraldehyde or acrylic aldehyde.
  • the adduct is dispersed in water permeable hydrophilic colloid vehicle.
  • the water permeable hydrophilic coating so provided is coated over a photographic silver halide element.
  • Thioamine should be understood to be an amine compound containing a sulfur atom having an oxidation state of two.
  • thioamines which may advantageously be utilized are aminothiols, aminodisulfides and thiolactones.
  • the first of said compounds of their salts and preferably the hydrochloride salts which are preferably employed in the formation of the adducts fall into two general classes.
  • Compounds illustrative of Class I each contain at least one sulfur atom having an oxidation state of two, a carboxy group or its lactone, and an amine group.
  • Compounds illustrative of Class I are cysteine or its homologues and other amino acids containing a sulfur atom having an oxidation state of two.
  • Compounds of Class II contain an amino group and a sulfur atom having an oxidation state or two.
  • the following list is illustrative of first compounds suitably employed in forming the adduct of this invention:
  • the first compounds employed in forming the adducts of this invention are those of Class I.
  • cysteine, penicillamine, homocysteinethiolactone and 2-aminoethanethiol-HC1 are employed as first compounds utilized in forming the adduct.
  • cysteine is employed as a first compound in forming the adduct.
  • the second of said compounds employed in the formation of the adducts employed in this invention is a glutaraldehyde or acrylic aldehyde.
  • adducts employed in this invention are described in co-filed Amering application Ser. No. 104,690 entitled Novel Compositions and Photographic Processes.
  • the adducts of a thioamine, for example crysteine, and glutaraldehyde are prepared in the same manner as the adducts described in Amering.
  • the adducts are readily formed by adding the first compound to the second compound, or vice versa, in a suitable solvent, preferably an aqueous solvent.
  • Illustrative of the adducts which may be employed in this invention are the products obtained by mixing: cysteine and glutaraldehyde, glutaraldehyde and DL-penicillamine, glutaraldehyde and DL-homocysteinethiolactone, glutaraldehyde and Z-aminoethanethiol.
  • Preferred adducts are those formed from glutaraldehyde and one of L-cysteine.HCl DL-penicillamine, DL-homocysteinethiolactone .HCl, and Z-aminoethanethioLI-ICI.
  • the speed increases and fog levels obtained are dependent upon the amount of first compound employed in forming the adduct as well as the ratio of said first compound to said second compound. With increased use of cysteine, one obtains greater speed increases.
  • the useful ratios of first compound to second compound can vary over a wide range, said ranges being easily determined through routine experimentation.
  • a preferred range of ratios, in terms of moles, is from 1:1 to about 1:8 of said first compound to said second compound.
  • Another preferred range of ratios is 1:1 to about 1:4.
  • this invention comprises a water permeable coating composition comprising a hydrophilic colloid and the adduct.
  • the hydrophilic colloid vehicles for said adduct can include both naturally-occurring substances such as protein, for txample, gelatin, gelatin derivatives, cellulose derivatives, polysaccharides such as dextr-an, gum arabic and the like; and synthetic polymeric substances such as water soluble polyvinyl compounds, for example, poly (vinylpyrrolidone), acrylamide polymers and the like.
  • the vehicle or binder for the adduct can also comprise alone or in combination with hydrophilic water permeable colloids, other synthetic polymeric compounds such as dispersed vinyl compounds 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.
  • the adduct can be added to the hydrophilic colloid by means well known in the art, for example, the adduct may be added from water solutions or suitable organic solvent solutions.
  • the adducts can be added using various procedures including those described in Collins et al. U.S. Pat. 2,912,343 issued Nov. 10, 1959; McCrossen et al. U.S. Pat. 3,342,605 issued Sept. 19, 1967; Audran U.S. Pat. 2,996,287 issued Aug. 15, 1961 and Johnson et al. U.S. Pat. 3,425,835 issued Feb. 4, 1969.
  • the concentration of the adduct in the water permeable colloid can vary widely. The most desirable concentrations for a particular silver halide element can be determined by experimentation. The change in concentration will naturally affect the photographic speed. Suitable results appear to be obtained when the adduct is present at about .001 mg./ft. to about 5 mg./ft. of water permeable colloid. The preferred concentration is in a range of about .005 mg./ft. to about .5 mg./ft. of water permeable colloid.
  • the water permeable colloid coating compositions comprising the adducts as described hereinabove are utilized as an overcoat for a photographic element, especially a high-speed photographic element, for example, an X-ray photographic elementor a color separation photographic film.
  • the coating comprising the Water permeable colloid and the adduct may be coated according to various coating procedures well known in the art, for example, dip coating, air knife coating, curtain coating, or extrusion coating using hoppers of the type described in Belguin U.S. Pat. 2,681,294 issued June 15, 1954.
  • dip coating air knife coating
  • curtain coating or extrusion coating using hoppers of the type described in Belguin U.S. Pat. 2,681,294 issued June 15, 1954.
  • This invention also can be used for silver halide layers coated by vacuum evaporation as described in British Fat. 968,- 453 and LuValle et al. U.S. Pat. 3,219,451 issued Nov. 23, 1965.
  • the coating composition comprising the water permeable colloid and the adduct may also contain any of the addenda normally utilized in photographic products.
  • the coating composition of this invention can contain other speed increasing compounds such as polyalkylene glycols, cationic surface active agents and thioethers or combinations of these as described in Piper U.S. Pat.
  • the coating composition of this invention comprising the Water permeable colloid and the adduct can contain antifoggants and stabilizers.
  • Suitable antifoggants and stabilizers each used alone or in combination include thiazolium salts described in Brooker et al. U.S. Pat. 2,131,038 issued Sept. 27, 1938, and Allen et al. U.S. Pat. 2,694,716 issued Nov. 16, 1954; the azaindenes described in Piper U.S. Pat. 2,886,437 issued May 12, 1959, and Heimbach et al. U.S. Pat. 2,444,605 issued July 6, 1948; the mercury salts as described in Allen et al. U.S. Pat. 2,728,663 issued Dec.
  • the coating composition of this invention comprising the Water permeable colloid and the adduct may contain incorporated developing agents such as hydroquinones, catechols, aminophenols, 3-pyrazolidones, ascorbic acid and its derivatives, reductones and phenylendiamines. Combinations of developing agents can be employed in the practice of the invention.
  • the developing agents can be in a silver halide emulsion and/or in another suitable location in the photographic element.
  • the developing agents may be added from suitable solvents or in the form of dispersions as described in Yackel U.S. Pat. 2,592,368 issued Apr. 8, 1952, and Dunn et al. French Pat. 1,505,778.
  • the coating composition of this invention comprising the water permeable colloid and the adduct may contain plasticizers and lubricants such as polyalcohols e.g., glycerin and diols of the type described in Milton et al. U.S. Pat. 2,960,404 issued Nov. 1, 1966; fatty acids or esters such as those described in Robijns U.S. Pat. 2,588,- 765 issued Mar. 11, 1952, and Duane U.S. Pat. 3,121,060 issued Feb. 11, 1964, and silicone resins such as those described in Du Pont British Pat. 955,061.
  • plasticizers and lubricants such as polyalcohols e.g., glycerin and diols of the type described in Milton et al. U.S. Pat. 2,960,404 issued Nov. 1, 1966; fatty acids or esters such as those described in Robijns U.S. Pat. 2,588,- 765 issued Mar. 11, 1952, and Duane U.S. Pat
  • the photographic layers employed in the practice of this invention may contain surfactants such as saponin;
  • anionic compounds such as the alkyl aryl sulfonates described in Baldsiefen U.S. Pat. 2,600,831 issued June 17, 1962; amphoteric compounds such as those described in Ben-Ezra U.S. Pat. 3,138,816 issued May 19, 1964; and Water soluble adducts of glycidol and an alkyl phenol such as those described in Olin Mathieson British Pat. 1,022,878.
  • the various layers, including the photographic layers, employed in the practice of this invention can contain light absorbing materials and filter dyes such as those described in Sawday U.S. Pat. 3,253,921 issued May 31, 1966; Gaspar U.S. Pat. 2,274,782 issued Mar. 3, 1942; Silberstein et al. U.S. Pat. 2,527,583 issued Oct. 31, 1950, and Van Campen U.S. Pat. 2,956,879 issued Oct. 18, 1960.
  • the dyes can be mordanted, for example, as described in Jones et al. U.S. Pat. 3,282,699 issued Nov. 1, 1966.
  • the addenda described hereinabove may also be incorporated in any of the other layers of a photographic element.
  • the overcoat of this invention can be located in a variety of physical positions with reference to the electromagnetic radiation sensitive silver salt layer.
  • the overcoat can be the upper and outermost layer or any of the internal layers. Any layer contiguous to the silver halide layers can contain the adduct.
  • the only limitation on the location of the adduct containing emulsion layer is that it should preferably not contain electromagnetic radiation sensitive silver halides since the adduct will tend to fog the silver and/or decrease the speed of the silver salt.
  • X-ray materials which can be developed in. the presence of a hardening developer or a non-hardening developer.
  • the X-ray materials comprise a support, at least one image recording layer such as a coarse-grained silver bromoiodide gelatin emulsion of the type employed in medical radiography, and the adduct containing hydrophilic colloid layer.
  • the X-ray products normally contain a phosphor containing screen as an integral or separate part of element, said phosphors emitting in the ultraviolet region of the spectrum.
  • the phosphors which may be employed in the X-ray elements of this invention are well known in the art.
  • Phosphors which may be suitably employed in the X-ray products of this invention are disclosed, for example, in Belgium Pat. No. 703,998 of Luckey issued Mar. 18, 1968.
  • Illustrative of the typical phosphors employed in radiography are, for example, lead activated barium sulfate, europium activated barium sulfate, europium activated barium strontium sulfate, lead sulfate and the like.
  • novel coatings of this invention can be employed in combination with color sensitive material.
  • photographic films for making color separations said film comprising a support, a coarsed-grained silver halide emulsion and an overcoat comprising the above described adducts.
  • Typical photographic materials for making color separations are described in copending Sales in U.S. application Ser. No. 609,357 filed Jan. 16, 1967.
  • Processing of the photographic elements of this invention can be effected in a variety of ways including the multi-tank manual methods but preferably in a continuous machine processing system wherein the photographic element is processed by passing through rollers or otherwise in one continuous motion by transporting it into and out of at least one processing solution in the manner shown, for example, by U.S. Pats. 3,025,779 of Russell and Kunz issued Mar. 20, 1962; 3,078,024 of Sardeson issued Feb. 19, 1963; 3,122,086 of Fitch issued Feb. 25, 1964; 3,149,551 of Cramer issued Feb. 22, 1964; 3,156,173 of Meyer issued Nov. 10, 1964; and 3,224,356 of Fleisher and Hixon issued Feb. 21, 1965.
  • a typical roller type processing apparatus employed in the fast processing of X-ray materials is described in Belgian Pat. 700,301 issued Aug. 31, 1967, to Barnes et al.
  • the silver halide emulsions used with this invention can comprise silver chloride, silver bromide, silver bromoiodide, silver chlorobromoiodide or mixtures thereof.
  • the emulsions may 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 al. U.S. Pat. 2,222,264 issued Nov. 4, 1940; Illingsworth U.S. Pat. 3,320,069 isued May 15, 1967; and McBride U.S.
  • Pat. 3,271,157 isued Sept. 16, 1966.
  • Surface image emulsions may be used or internal image emulsions such as those described in Davey et al. U.S. Pat. 2,592,250 issued Apr. 8, 1952; Porter et al. U.S. Pat. 3,206,313 issued Sept. 14, 1965 Berriman U.S. Pat. 3,367,778 issued Feb. 6, 1968, and Bacon et al. U.S. Pat. 3,447,927 issued June 3, 1969.
  • mixtures of surfaces and internal image emulsions may be used as described in Luckey et al. U.S. Pat. 2,996,382 issued Apr. 15, 1961.
  • Negative type emulsions may be used or direct positive emulsions such as those described in Leermakers U.S. Pat. 2,184,013 issued Dec. 19, 1939; Kendall et al. U.S. 2,541,472 issued Feb. 13, 1951;,Berriman U.S. Pat. 3,367,778 issued Feb. 6, 1968; Schouwenaars British Pat. 723,019; Illingsworth et al. French Pat. 1,520,821; Ives U.S. Pat. 2,563,785 issued Aug. 7, 1951; Knott et al. U.S. Pat. 2,456,953 issued Dec. 21, 1968, and Land U.S. Pat. 2,861,885 issued Nov. 25, 1958.
  • the emulsions may be regular grain emulsions such as the type described in Klein and Moisar, J. Phot. Sci., vol. 12, No. S, Sept/Oct. 1964, pp. 242251.
  • the silver halide emulsions used with this invention may be unwashed or washed to remove soluble salts.
  • the soluble salts may be removed by chillsetting and leaching or the emulsion may be coagulation washed, e.g., by the procedures described in Hewitson et al. U.S. Pat. 2,618,556 issued Nov. 18, 1972; Yutzy et al. U.S. 'Pat. 2,614,928 issued Oct. 21, 1952; Yackel US. Pat. 2,565,418 issued Aug. 21, 1951; Hart et al. U.S. Pat. 3,241,969 issued Mar. 22, 1966; and Waller et al. U.S. Pat. 2,489,341 issued Nov. 29, 1949.
  • the emulsions used with this invention may be sensitized with chemical sensitizers, such as with reducing agents; sulfur, selenium or tellurium compound; gold, platinum or palladium compounds; or combinations of these.
  • chemical sensitizers such as with reducing agents; sulfur, selenium or tellurium compound; gold, platinum or palladium compounds; or combinations of these.
  • Suitable procedures are described in Sheppard et al. U.S. Pat. 1,623,499 issued Apr. 5, 1927; Waller et al. U.S. Pat. 2,399,083 issued Apr. 23, 1946; McVeigh U.S. Pat. 3,297,447 issued Jan. 10, 1967; and Dunn US. Pat. 3,297,- 446 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 oxyguargum 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,
  • 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, gelatin, gelatin 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 lavers 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. 3,142,568 issued July 28, 1964; White U.S. Pat. 3,193,386 issued July 6, 1965; Houck et al. U.S. Pat. 3,062,674 issued Nov. 6, 1962; Houck et al. U.S. 3,220,844 issued Nov. 30, 1965; Ream et al. U.S. Pat.
  • the photographic elements used with this invention may contain antistatic or conducting layers, such layers may comprise soluble salts, e.g., chlorides, nitrates, etc., evaporated metal layers, ionic polymers such as those described in Minsk U.S. Pat. 2,861,056 issued Nov. 18, 1958, and Sterrnan et al. U.S. Pat. 3,206,312 issued Sept. 14, 1965 or insoluble inorganic salts such as those described in Trevoy U.S. Pat. 3,428,451 issued Feb. 18, 1969.
  • soluble salts e.g., chlorides, nitrates, etc.
  • evaporated metal layers ionic polymers such as those described in Minsk U.S. Pat. 2,861,056 issued Nov. 18, 1958, and Sterrnan et al. U.S. Pat. 3,206,312 issued Sept. 14, 1965 or insoluble inorganic salts such as those described in Trevoy U.S. Pat. 3,428,451 issued Feb. 18, 1969.
  • Typical supports include cellulose nitrate film, poly(ethylene terephthalate) film, polycarbonate film and related films or resinous materials, as well as glass, paper, metal and the like.
  • a flexible support is employed, especially a paper support, which can be partially acetylated or coated with baryta and/ or an alpha-olefin polymer, particularly a polymer of an alpha-olefin containing 2 to 10 carbon atoms such as polyethylene, polypropylene, ethylenebutene copolymers and the like.
  • the photographic elements used in this invention may contain brightening agents including stilbenes, triazines, oxazoles and coumarin brightening agents.
  • Water soluble brightening agents may be used such as those described in Albers et al. German Pat. 972,067 and McFall et al. U.S. 'Pat. 2,933,390 issued Apr. 19, 1960, or dispersions of brighteners may be used such as those described in Jansen German Pat. 1,150,274, Oetiker et al. US. Pat. 3,406,070 issued Oct. 15, 1968, and Heidke French Pat. 1,530,244.
  • Spectral sensitizing dyes can be used conveniently to confer additional sensitivity to the light sensitive silver halide emulsion of the multilayer photographic elements of the invention.
  • additional spectral sensitization can be obtained by treating the emulsion with a solution of a sensitizing dye in an organic solvent or the dye may be added in the form of a dispersion in Owens et al. British Pat. 1,154,781.
  • the dye may either be added to the emulsion as a final step or at some earlier stage.
  • Sensitizing dyes useful in sensitizing such emulsions are described, for example, in Brooker et al. U.S. Pat. 2,526,632 issued Oct. 24, 1950; Sprague U.S. Pat. 2,503,- 776 issued Apr. 11, 1950; Brooker et al. U.S. Pat. 2,493,- 748 issued Jan. 10, 1950; and Taber et al. U.S. Pat. 3,384,- 486 issued May 21, 1968.
  • Spectral sensitizers which can be used include the cyanines, merocyanines, complex (tri or tetranuclear) merocyanines, complex (tri or tetranuclear) cyanines, holopolar cyanines, styryls, hemicyanines (e.g. enamine hemicyanines), oxonols and hemioxonols.
  • Dyes of the cyanine classes may contain such basic nuclei as the thiazolines, oxazolines, pyrrolines, pyridines, oxazoles, thiazoles, selenazoles and imidazoles.
  • Such nuclei may contain alkyl, alkylene hydroxyalkyl, sulfoalkyl, carboxyalkyl, aminoalkyl and enamine groups and may be fused to carbocyclic or heterocyclic ring systems either unsubstituted or substituted with halogen, phenyl,
  • the dyes may be symmetrical or unsymmetrical and may contain alkyl, phenyl, enarnine or heterocyclic substituents on the methine or polymethine chain.
  • the merocyanine dyes may contain the basic nuclei mentioned above as well as acid nuclei such as thiohydantoins rhodanines, oxazolidenediones, thiazolidenediones, barbituric acids, thiazolineones, and malononitrile. These acid nuclei may be substituted with alkyl, alkylene,
  • phenyl carboxyalkyl, sulfoalkyl, hydroxyalkyl, alkoxyalkyl, akyamino groups, or heteroeyclic nuclei. Combinations of these dyes may be used, if desired.
  • supersensitizing addenda which do not absorb visible light may be included, for example, ascorbic acid derivatives,
  • This invention may be used with elements designed for colloid transfer processes such as described in Yutzy et al. U.S. Pat. 2,716,059 issued Aug. 23, 1955; silver salt diffusion transfer processes such as described in Rott U.S. Pat. 2,352,014 issued June 20, 1944, Land U.S. Pat. 2,543,181 issued Feb. 27, 1951, Yackel et al. U.S. Pat.
  • EXAMPLE 1-7 A coarse-grained silver bromoiodide gelatin photographic emulsion of the type used in medical X-ray films is coated on a poly(ethyleneterephthalate) film support at a coverage of 435 mg. of silver/ft? and 288 mg. of gelatin/ft ⁇ . Over the emulsion layer is coated a gelatin layer at a coverage of 130 mg. of gelatin/ft. containing the ingredients listed in Table I. The samples are exposed on an intensity scale sensitometer and processed in an automatic processing machine of the type described in U.S. Pat. 3,147,090 using a hardening developer of the type described in U.S. Pat. 3,232,761 with a total processing time of seconds.
  • Example 4-7 an adduct of L-cysteine and glutaraldehyde is prepared by combining desired ratios of the two compounds in an aqueous solution at a pH of 5.6 and holding the mixture for 24 hours before addition to gelatin solutions.
  • This invention may be used with elements designed for 55 color photography, for example, elements containing color-forming couplers such as those described in Frohlich et al. U.S. Pat. 2,376,679 issued May 22, 1945, Jelley et al. U.S. Pat. 2,322,027 issued June 15, 1943; Fierke et al. U.S. Pat. 2,801,171 issued July 30, 1957, Godowsky 60 U.S. Pat. 2,698,794 issued Jan. 4, 1966, Barr et al. U.S. Pat. 3,227,554 issued Jan. 4, 1966, and Graham et al. U.S. Pat.
  • the silver halide emulsions used with this invention can be used for making lithographic printing plates such as by the colloid transfer of undeveloped and unhardened areas of an exposed and developed emulsion to a suitable support as described in Clark et a1.
  • U.S. Pat. 2,763,533 75 EXAMPLES 8-12 Examples of the photographic elements prepared in the same manner as in Examples 1-7 are processed for 6 minutes in a conventional Elon-hydroquinone developer containing no hardening agent, fixed and washed. The results are summarized in Table II.
  • A L-cysteine
  • B Glutaraldehyde
  • C Adduct of L-cysteine and glutaraldehyde.
  • the overcoat layer can contain a mixture of gelatin and hydrophilic colloids such as disclosed in Belgian Pat. 731,212.
  • taining the described green-light absorbing dye is coated containing a preformed adduct of L-cysteine and acrylic on a polyethylene terephthalate support at 775 mg. of aldehyde.
  • the samples are exposed on an intensity sensilver/ft. and 850 mg. of gelatin/ft. 1O sitometer and processed in an automatic processing ma-
  • the emulsion layer is overcoated with a gelatin layer chine of the type described in U.S. Pat. 3,147,090 using at 82 mgjftfi. either a hardening or non-hardening developer.
  • a film, identified as B in Table III, is prepared in the The adduct is prepared by combining, at a ratio of 1:4, manner of the above film except to the gelatin overcoat L-cysteine and acrylic aldehyde in an aqueous solution layer is added the adduct of L-cysteine (0.045 mg./ft. at a pH of 5.6 and aging the mixture for 24 hours before and glutaraldehyde (0.105 mg./ft. addition to gelatin solutions.
  • the developed separation films are washed, fixed in a conventional alkali metal thiosulfate fixing bath, washed and dried. Sensitometric measurements are made of each of the separation images with the results summarized in Table III.
  • the above table illustrates that the advantages obtained through incorporating the adduct in an overcoat are lost when the adduct is added to the silver halide emulsion.
  • the table illustrates that when the adduct is added at a high level, excessive fog results and when the adduct is added at lower levels, no speed advantage is obtained.
  • a photographic element comprising a support bearing at least one electromagnetic radiation-sensitive silver halide layer, the improvement being wherein said element contains on the same side of the support as said layer, a distinct layer comprising an adduct of a first compound which is cysteine, DL-penicillamine, DL- homocysteine-thiolactone or 2-aminoethanethiol with a second compound which is glutaraldehyde or acrylic aldehyde.
  • a photographic element of claim 1 wherein said second compound is glutaraldehyde.
  • a photographic element of claim 1 wherein said preformed adduct comprises from about 1 to about 8 mole equivalents of said second compound to about 1 mole equivalent of said first compound.
  • said radiation-sensitive silver halide layer comprises a coarsegrained silver bromoiodide emulsion.
  • said silver bromide layer comprises a black-and-white panchromatically sensitized silver bromoiodide emulsion.
  • a black-and-white photographic element adapted for color separation materials comprising a support, a silver halide emulsion and a' layer distinct from the silver halide emulsion, the improvement wherein said layer comprises L-cysteineglutaraldehyde adduct.
  • a radiographic element comprising a support bearing at least one image recording layer and a layer distinct from said image recording layer, the improvement wherein said distinct layer contains a L-cysteine-glutaraldehyde adduct.

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  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US00104768A 1971-01-07 1971-01-07 Silver halide emulsion sensitized with thioamine-glutaraldehyde or acrylic aldehyde adduct Expired - Lifetime US3708302A (en)

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US (1) US3708302A (de)
BE (1) BE777730A (de)
CA (1) CA976022A (de)
DE (1) DE2200504A1 (de)
IT (1) IT946347B (de)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4145218A (en) * 1976-09-02 1979-03-20 Konishiroku Photo Industry Co., Ltd. Process for developing light-sensitive silver halide photographic materials
US4230796A (en) * 1978-01-18 1980-10-28 E. I. Du Pont De Nemours And Company High speed lithographic film element
US4243748A (en) * 1979-05-29 1981-01-06 E. I. Du Pont De Nemours And Company Light-sensitive silver halide reproduction material
US4314024A (en) * 1979-08-04 1982-02-02 Agfa-Gevaert Aktiengesellschaft Stabilized photographic emulsion, a process for its preparation and stabilized photographic materials
EP0084403A2 (de) * 1982-01-04 1983-07-27 E.I. Du Pont De Nemours And Company Silberhalogenidemulsion die eine Fraktion eines gereinigten Cysteine-Glutaraldehyd-Polymers enthält
US4514492A (en) * 1983-12-15 1985-04-30 E. I. Du Pont De Nemours And Company Elimination of defects in cysteine-sensitized emulsions
DE4422181A1 (de) * 1994-06-28 1996-01-04 Du Pont Deutschland Verfahren zur Herstellung von photographischen Aufzeichnungsmaterialien für die medizinische Radiographie
US6682868B1 (en) 2003-03-26 2004-01-27 Eastman Kodak Company Radiographic imaging assembly with blue-sensitive film
US6686118B1 (en) 2003-03-26 2004-02-03 Eastman Kodak Company Blue-sensitive film for radiography and imaging assembly and method
US6686119B1 (en) 2003-05-29 2004-02-03 Eastman Kodak Company Blue-sensitive film for radiography and imaging assembly and method
US6686116B1 (en) 2003-03-26 2004-02-03 Eastman Kodak Company Blue spectrally sensitized film for radiography, imaging assembly and method
US6686117B1 (en) 2003-03-26 2004-02-03 Eastman Kodak Company Blue-sensitive film for radiography with reduced dye stain

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1535042A (en) * 1975-04-09 1978-12-06 Agfa Gevaert Preparation of photographic silver halide emulsions

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4145218A (en) * 1976-09-02 1979-03-20 Konishiroku Photo Industry Co., Ltd. Process for developing light-sensitive silver halide photographic materials
US4230796A (en) * 1978-01-18 1980-10-28 E. I. Du Pont De Nemours And Company High speed lithographic film element
US4243748A (en) * 1979-05-29 1981-01-06 E. I. Du Pont De Nemours And Company Light-sensitive silver halide reproduction material
US4314024A (en) * 1979-08-04 1982-02-02 Agfa-Gevaert Aktiengesellschaft Stabilized photographic emulsion, a process for its preparation and stabilized photographic materials
US4481359A (en) * 1982-01-04 1984-11-06 E. I. Du Pont De Nemours And Company Silver halide emulsion containing a purified cysteine-glutaraldehyde polymer fraction and process of making
EP0084403A3 (en) * 1982-01-04 1983-12-14 E.I. Du Pont De Nemours And Company Silver halide emulsion containing a purified cysteine-glutaraldehyde polymer fraction
EP0084403A2 (de) * 1982-01-04 1983-07-27 E.I. Du Pont De Nemours And Company Silberhalogenidemulsion die eine Fraktion eines gereinigten Cysteine-Glutaraldehyd-Polymers enthält
US4514492A (en) * 1983-12-15 1985-04-30 E. I. Du Pont De Nemours And Company Elimination of defects in cysteine-sensitized emulsions
DE4422181A1 (de) * 1994-06-28 1996-01-04 Du Pont Deutschland Verfahren zur Herstellung von photographischen Aufzeichnungsmaterialien für die medizinische Radiographie
US5576154A (en) * 1994-06-28 1996-11-19 Sterling Diagnostic Imaging, Inc. Photographic recording materials for medical radiography
US6682868B1 (en) 2003-03-26 2004-01-27 Eastman Kodak Company Radiographic imaging assembly with blue-sensitive film
US6686118B1 (en) 2003-03-26 2004-02-03 Eastman Kodak Company Blue-sensitive film for radiography and imaging assembly and method
US6686116B1 (en) 2003-03-26 2004-02-03 Eastman Kodak Company Blue spectrally sensitized film for radiography, imaging assembly and method
US6686117B1 (en) 2003-03-26 2004-02-03 Eastman Kodak Company Blue-sensitive film for radiography with reduced dye stain
US6686119B1 (en) 2003-05-29 2004-02-03 Eastman Kodak Company Blue-sensitive film for radiography and imaging assembly and method

Also Published As

Publication number Publication date
DE2200504A1 (de) 1972-07-20
IT946347B (it) 1973-05-21
BE777730A (fr) 1972-05-02
CA976022A (en) 1975-10-14

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