US3492123A - Direct positive silver halide emulsions containing carbocyanine dyes having a carbazole nucleus - Google Patents

Direct positive silver halide emulsions containing carbocyanine dyes having a carbazole nucleus Download PDF

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US3492123A
US3492123A US609740A US3492123DA US3492123A US 3492123 A US3492123 A US 3492123A US 609740 A US609740 A US 609740A US 3492123D A US3492123D A US 3492123DA US 3492123 A US3492123 A US 3492123A
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silver halide
silver
emulsion
direct positive
photographic
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John D Mee
Donald W Heseltine
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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
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/825—Photosensitive materials characterised by the base or auxiliary layers characterised by antireflection means or visible-light filtering means, e.g. antihalation
    • G03C1/83—Organic dyestuffs therefor
    • G03C1/832—Methine or polymethine dyes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/58—[b]- or [c]-condensed
    • C07D209/60—Naphtho [b] pyrroles; Hydrogenated naphtho [b] pyrroles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
    • C07D241/38—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with only hydrogen or carbon atoms directly attached to the ring nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
    • C07D241/38—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with only hydrogen or carbon atoms directly attached to the ring nitrogen atoms
    • C07D241/40—Benzopyrazines
    • C07D241/44—Benzopyrazines with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the hetero ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/06—Peri-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
    • C09B23/04—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups one >CH- group, e.g. cyanines, isocyanines, pseudocyanines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
    • C09B23/06—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups three >CH- groups, e.g. carbocyanines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
    • C09B23/08—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups more than three >CH- groups, e.g. polycarbocyanines
    • C09B23/083—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups more than three >CH- groups, e.g. polycarbocyanines five >CH- groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
    • C09B23/08—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups more than three >CH- groups, e.g. polycarbocyanines
    • C09B23/086—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups more than three >CH- groups, e.g. polycarbocyanines more than five >CH- groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/10—The polymethine chain containing an even number of >CH- groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/10—The polymethine chain containing an even number of >CH- groups
    • C09B23/105—The polymethine chain containing an even number of >CH- groups two >CH- groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/10—The polymethine chain containing an even number of >CH- groups
    • C09B23/107—The polymethine chain containing an even number of >CH- groups four >CH- groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/14—Styryl dyes
    • C09B23/145—Styryl dyes the ethylene chain carrying an heterocyclic residue, e.g. heterocycle-CH=CH-C6H5
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/10—Organic substances
    • G03C1/12—Methine and polymethine dyes
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/10—Organic substances
    • G03C1/12—Methine and polymethine dyes
    • G03C1/14—Methine and polymethine dyes with an odd number of CH groups
    • G03C1/18—Methine and polymethine dyes with an odd number of CH groups with three CH groups
    • 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
    • G03C1/485—Direct positive emulsions
    • G03C1/48515—Direct positive emulsions prefogged
    • G03C1/48523—Direct positive emulsions prefogged characterised by the desensitiser
    • G03C1/4853—Direct positive emulsions prefogged characterised by the desensitiser polymethine dyes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/001—Electric or magnetic imagery, e.g., xerography, electrography, magnetography, etc. Process, composition, or product
    • Y10S430/102—Electrically charging radiation-conductive surface

Definitions

  • This invention relates to novel direct positive photographic materials, and more particularly to new and improved fogged, direct positive photographic silver halide emulsions containing certain unsymmetrical syanine dyes containing a carbazole nucleus.
  • an object of this invention to provide a new class of improved and novel, direct positive photographic silver halide emulsions, and more particularly fogged emulsions of this type, containing at least one of the unsymmetrical cyanine dyes of the invention.
  • Another object of this invention is to provide novel emulsions as above containing, in addition, a photographic color former.
  • Another object of this invention is to provide novel light-sensitive photographic elements comprising a support material having thereon at least one layer of the novel emulsions of the invention.
  • emulsions in accordance with this invention, we prepare our new class of improved and novel, direct positive photographic silver halide emulsions by incorporating one or more of the unsymmetrical dyes of the invention into a suitable fogged silver halide emulsion.
  • the emulsion can be fogged in any suitable manner, such as by light or with chemical fogging agents, e.g., stannous chloride, formaldehyde, thiourea dioxide and the like.
  • the emulsion may be fogged by the addition thereto of a reducing agent such as thiourea dioxide and a compound of a metal more electropositive than silver such as a gold salt, for example, potassium chloroaurate, as described in British Patent 723,019 (1955).
  • Typical reducing agents that are useful in providing such emulsions include stannous salts, e.g., stannous chloride, hydrazine, sulfur compounds such as thiourea dioxide, phosphonium salts as tetra (hydroxymethyl) phosphonium chloride, and the like.
  • Typical useful metal ICC compounds that are more electropositive than silver include gold, rhodium, platinum, palladium, iridium, etc, preferably in the form of soluble salts thereof, e.g., potassium chloroaurate, auric chloride, (NH PdCl and the like.
  • reducing agent and metal compound e.g., metal salt
  • concentrations of reducing agent and metal compound can be varied over a considerable range.
  • good results are obtained using about .05 to 40 mg. reducing agent per mole of silver halide, and 0.5 to 15.0 mg, metal compound per mole of silver halide. Best results are obtained at lower concentration levels of both reducing agent and metal compound.
  • the concentration of added dye can vary widely, e.g., from about 50 to 2000 mg. and preferably from about 400 to 800 mg. per mole of silver halide in the direct positive emulsions.
  • fogged refers to emulsions containing silver halide grains which produce a density of at least 0.5 when developed, Without exposure, for 5 minutes at 68 F. in developer Kodak DK-SO having the composition set forth below, when the emulsion is coated at a silver coverage of 50 mg. to 500 mg. per square foot.
  • the dyes of this invention are also advantageously incorporated in direct positive emulsions of the type in which a silver halide grain has a water-insoluble silver salt center and an outer shell composed of a fogged water insoluble silver salt that develops to silver without exposure.
  • the dyes of the invention are incorporated, preferably, in the outer shell of such emulsions.
  • These emulsions can be prepared in various ways, such as those described in Berriman U.S. patent application Ser. No. 448,467, filed Apr. 15, 1965 now U.S. Patent No. 3,367,- 778.
  • the shell of the grains in such emulsions may be prepared by precipitating over the core grains a light-sensitive water-insoluble silver salt that can be fogged and which fogv is removable by bleaching.
  • the shell is of suflicient thickness to prevent access of the developer used in processing the emulsions of the invention to the core.
  • the silver salt shell is surface fogged to make developable to metallic silver with conventional surface image developing compositions.
  • the silver salt of the shell is sufficiently fogged to produce a density of at least about 0.5 when developed for 6 minutes at 68 F. in Developer A below when the emulsion is coated at a silver coverage of mg. per square foot.
  • Such fogging can be effected by chemically sensitizing to fog with the sensitizing agents described for chemically sensitizing the core emulsion, high intensity light and the like fogging means well known to those skilled in the art. While the more need not be sensitized to fog, the shell is fogged. Fogging by means of a reduction sensitizer, a noble metal salt such as gold salt plus a reduction sensitizer, a sulfur sensitizer, high pH and low pAg silver halide precipitating conditions, and the like can be suitably utilized. The shell portion of the subject grains can also be coated prior to fogging.
  • the core emulsion is first chemically or physically treated by methods previously described in the prior art to produce centers which promote the deposition of photolytic silver, i.e., latent image nucleating centers.
  • centers can be obtained by various techniques as described herein. Chemical sensitization techniques of the type described by Antoine Hautot and Henri Saubeneir in Science et Industries Photographiques, vol. XXVIII, January 1957, pages 1 to 23 and January 1957, pages 57 to 65 are particularly useful.
  • Such chemical sensitization includes three major classes, namely, gold or noble metal sensitization, sulfur sensitization such as by a labile sulfur compound, and reduction sensitization, e.g., treatment of the silver halide with a strong reducing agent which introduces small specks of metallic silver into the silver salt crystal or grain.
  • the dyes of this invention are highly useful electron acceptors in high speed direct positive emulsions comprising fogged silver halide grains and a compound which accepts electrons, as described and claimed in Illingsworth U.S. patent application Ser. No. 609,794 filed Jan. 17, 1967, now abandoned and continuation-in-part 619,- 936, filed Mar. 2, 1967, and titled Photographic Reversal Materials III.
  • the fogged silver halide grains of such emulsions are such that a test portion thereof, when coated as a photographic silver halide emulsion on a support to give a maximum density of at least about one upon processing for six minutes at about 68 F.
  • Kodak DK-SO developer in Kodak DK-SO developer, has a maximum density which is at least about 30% greater than the maximum density of an identical coated test portion which is processed for six minutes at about 68 F. in Kodak DK-SO developer 4 after being bleached for about 10 minutes at about 68 F in a bleach composition of:
  • the grains of such emulsions will lose at least about and generally at least about of their fog when bleached for ten minutes at 68 F. in a potassium cyanide bleach composition as described herein.
  • This fog loss can be illustrated by coating the silver halide grains as a photographic silver halide emulsion on a support to give a maximum density of at least 1.0 upon processing for six minutes at about 68 F. in Kodak DK-SO developer and comparing the density of such a coating with an identical coating which is processed for six minutes at 68 F. in Kodak DK- developer after being bleached for about 10 minutes at 68 F. in the potassium cyanide bleach composition.
  • the maximum density of the unbleached coating will be at least 30% greater, generally at least greater, than the maxi mum density of the bleached coating.
  • the silver halides employed in the preparation of the photographic emulsions useful herein include any of the photographic silver halides as exemplified by silver bromide, silver iodide, silver chloride, silver chlorobromide, silver bromoiodide, and the like.
  • the silver halide grains can be regular and can be any suitable shape such as cubic or octahedral, as described and claimed in Illingsworth US.
  • Such grains advantageously have a rather unrform diameter frequency distribution, as described and claimed in Illingsworth US. patent application Ser. No. 609,790 filed Jan. 17, 1967, now abandoned, and continuation-in-part Ser. No. 619,948 filed Mar. 2, 1967, and titled Photographic Reversal Emulsions II.
  • at least by weight, of the photographic silver halide grains can have a diameter which is within about 40%, preferably within about 30% of the mean grain diameter.
  • Mean grain diameter i.e., average grain size
  • Mean grain diameter can be determined using conventional methods, e.g., as shown in an article by Trivelli and Smith entitled Empirical Relations Between Sensitometric and Size-Frequency Characteristics in Photographic Emulsion Series in The Photographic Journal, vol. LXXIX, 1949, pages 330-338.
  • the fogged silver halide grains in these directpositive photographic emulsions of this invention produce a density of at least 0.5 when developed without exposure for five minutes at 68 F. in Kodak DK-SO developer when such an emulsion is coated at a coverage of 50 to about 500 mg. of silver per square foot of support.
  • the preferred photographic silver halide emulsions comprise at least 50 mole percent bromide, the most preferred emulsions being silver bromoiodide emulsions, particularly those containing less than about ten mole percent iodide.
  • the photographic silver halides can be coated at silver coverages in the range of about 50 to about 500 milligrams of silver per square foot of support.
  • the dyes, reducing agents and metal compounds of the invention are advantageously incorporated in the washed, finished silver halide emulsion and should, of course, be uniformly distributed throughout the emulsion.
  • the methods of incorporating dyes and other addenda in emulsions are relatively simple and well known to those skilled in the art of emulsion making. For example, it is convenient to add them from solutions in appropriate solvents, in which case the solvent selected should be completely free from any deleterious elfect on the ultimate light-sensitive materials. Methanol, isopropanol, pyridine, water, etc., alone or in admixtures, have proven satisfactory as solvents for this purpose.
  • the type of silver halide emulsions that can be sensitized with the new dyes include any of those prepared with hydrophilic colloids that are known to be satisfactory for dispersing silver halides, for example, emulsions comprising natural materials such as gelatin, albumin, agar-agar, gum arabic, alginic acid, etc., and hydrophilic synthetic resins such as polyvinyl alcohol, polyvinyl pyrrolidone, cellulose ethers, partially hydrolyzed cellulose acetate, and the like.
  • the dyes, reducing agents and metal compounds of the invention can be used with emulsions prepared with any of the light-sensitive silver halide salts including silver chloride, silver bromide, silver chlorobromide, silver bromoiodide, silver chlorobromoiodide, etc. Particularly useful for direct positive fogged emulsions in which the silver salt is a silver bromohalide comprising more than 50 mole percent bromide. As indicated previously, certain dyes of this invention are also useful in emulsions which contain color formers. This is unexpected since related prior art dyes cannot be used in emulsions containing a color former.
  • novel emulsions of this invention may be coated on any suitable photographic support, such as glass, film base such as cellulose acetate, cellulose acetate butyrate, polyesters such as polyethylene terephthalate, paper, baryta coated paper, polyolefin coated paper, e.g., polyethylene or polypropylene coated paper, which may be electron bombarded to promote emulsion adhesion, to produce the novel photographic elements of the invention.
  • film base such as cellulose acetate, cellulose acetate butyrate
  • polyesters such as polyethylene terephthalate, paper, baryta coated paper, polyolefin coated paper, e.g., polyethylene or polypropylene coated paper, which may be electron bombarded to promote emulsion adhesion, to produce the novel photographic elements of the invention.
  • Suitable unsymmetrical cyanine dyes for practicing our invention include those represented by the following general formula:
  • R represents a substituent selected from the group consisting of an alkyl radical, an aryl radical, an acyl radical and an organic sulfonyl radical, e.g., an alkyl substituent (including substituted alkyl) and preferably containing from about 1 to 8 carbon atoms, such as methyl, ethyl, propyl, butyl, octyl, sulfoalkyl such as sulfopropyl or sulfobutyl, sulfatoalkyl such as sulfatopropyl or sulfatobutyl, or carboxyalkyl such as carboxyethyl or carboxybutyl, or an aryl group, e.g., phenyl, sulfophenyl, carboxyphenyl, tolyl, etc., or an acyl group containing from about 1 to 10 carbon atoms, e.
  • an alkyl substituent including substituted alky
  • Dyes wherein Z represents the atoms required to complete an imidazo[4,5-b]quinoxaline nucleus are especially useful.
  • a preferred class of dyes are those wherein Z represents the atoms necessary to complete a desensitizing nucleus.
  • desensitizing nucleus refers to those nuclei which, when converted to a symmetrical carbocyanine dye and added to a gelatin silver chlorobromide emulsion containing 40 mole percent chloride and 60 mole percent bromide, at a concentration of from 0.01 to 0.2 gram dye per mole of silver, cause by electron trapping at least about an percent loss in the blue speed of the emulsion when sensitometrically exposed and developed three minutes in Kodak developer D-l9 at room temperature.
  • the desensitizing nuclei are those which, when converted to a symmetrical carbocyanine dye and tested as just described, essentially completely desensitize the test emulsion to blue radiation (i.e., cause a loss of more than about to loss of speed to blue radiation).
  • unsymmetrical cyanine dyes of the invention can be conveniently prepared by condensing the appropriate carbazole-3-carboxaldehyde, preferably having the general formula:
  • n, R X and Z are as previously defined, in an inert dehydrating medium such as, for example, acetic anhydride, at elevated temperatures and preferably at refluxing temperatures of the reaction mixtures.
  • an inert dehydrating medium such as, for example, acetic anhydride
  • the dye compounds separate from the mixture and are purified by one or more recrystallizations from suitable solvents such as an alkanol alone or in admixture with a phenol, for example, from methanol or mixture of methanol and cresol.
  • suitable solvents such as an alkanol alone or in admixture with a phenol, for example, from methanol or mixture of methanol and cresol.
  • the reactants can be employed with a small excess of one or the other, i.e., greater than the stoichiometrically calculated equivalents, but preferably in the approximately equimolar proportions for the best results.
  • a gelatin silver bromoiodide emulsion (2.5 mole percent of the halide being iodide) and having an average grain size of about 0.2 micron is prepared by adding an aqueous solution of potassium bromide and potassiume iodide, and an aqueous solution of silver nitrate, simultaneously to a rapidly agitated aqueous gelatin solution at a temperature of 70 C. over a period of about minutes.
  • the emulsion is chill-set, shredded and washed by leaching with cold water in the conventional manner.
  • the emulsion is reduction-gold fogged by first adding 0.2 mg. of thiourea dioxide per mole of silver and heating for 60 minutes at 65 C. and then adding 4.0 mg.
  • a sample of the coated support is then exposed on an Eastman Ib sensitometer using a tungsten light source and processed for 6 minutes at room temperature in Kodak D-19 developer which has the following composition:
  • the dye of this example has a minimum density in exposed areas of only 0.05, a sensitivity range up to 650 m and a maximum sensitivity at 575 m Whereas the control sample similarly prepared and tested but containing no spectral sensitizing dye increases in density with expo sure. This result indicates that the dye compound of the above example is especially well suited to function as both an electron acceptor and spectral sensitizer. It thus provides excellent quality direct positive photographic silver halide emulsions.
  • Example 2.3-methyl-2-,B-(9-methyl-3-carbazolyl)vinyl- 6-nitro-benzothiazoliump-toluenesulfonate 9-methylcarbazole-3-carboxaldehyde (1.05 g., 1 mol.) and 2,3-dirnethyl 6 nitrobenzothiazolium p toluenesulfonate (1.90 g., 1 mol.) in acetic anhydride (25 ml.) are refluxed for five minutes, during which time much dye separates. The mixture is transferred to a beaker with the aid of a little acetic acid and cooled. The solid is collected and washed with ether. After two recrystallizations from cresol/methanol, the yield of purified dye is 1.67 g. (59%), M.P. 300. In the above formula, pts stands for the p-toluene sulfonate radical.
  • the above prepared dye compound is photographically tested by the exact procedure of Example I. Referring to Table I, it will be seen that the dye of this example has a minimum density in the exposed areas of only 0.04, a sensitivity range up to 630 Ill/L, and a maximum sensitivity at 550 my, whereas the control sample similarly prepared and tested, but containing no spectral sensitizing dye, increases in density with exposure. Accordingly, the dye of this example provides especially useful direct positive materials.
  • Example 3.5-chloro-3-methyl-2-B-(9-methylcarbazolyl) vinyl-6-nitrobenzothiazolium p-toluenesulfonate N02 CH CHC ⁇ 01 N (I: C pts 9-methylcarbazole-carboxaldehyde (1.05 g., 1 mol) and 5 chloro-Z,3-dimethyl-6-nitrobenzothiazolium p-toluenesulfonate (2.08 g., 1 mol) in acetic anhydride (20 ml.) are refluxed for 5 minutes, as much dye separated. The cooled mixture is diluted with ether and the solid collected and washed with ether. After two recrystallizations from cresol/methanol, the yield of purified dye is 1.40 g. (46%), M.P. 297 C. dec.
  • the photographic silver halide emulsion and other layers present in the photographic elements made according to the invention can be hardened with any suitable hardener, including aldehyde hardeners such as formaldehyde, and mucochloric acid, aziridine hardeners, hardeners which are derivatives of dioxane, oxypolysaccharides such as oxy starch or my plant gums, and the like.
  • the emulsion layers can also contain additional additives, particularly those known to be beneficial in photographic emulsions, including, for example, lubricating materials, stabilizers, speed increasing materials, absorbing dyes, plasticizers, and the like. These photographic emulsions can also contain in some cases additional spectral sensitizing dyes.
  • these emulsions can contain color forming couplers or can be developed in solutions containing couplers or other color generating materials.
  • useful color formers are the monomeric and polymeric color formers, e.g. pyrazolone color formers, as well as phenolic, heterocyclic and open chain couplers having a reactive methylene group.
  • the color forming couplers can be incorporated into the direct positive photographic silver halide emulsion using any suitable technique, e.g., techniques of the type shown in Ielley et al. US. Patent 2,322,027, issued Jan. 15, 1943, Fierke et al. US. Patent 2,801,171, issued July 30, 1957, Fisher 10' US.
  • n represents a positive integer of from 1 to 2
  • R represents a substituent selected from the group consisting of an alkyl radical, an aryl radical, an acyl radical and an organic sulfonyl radical
  • R represents an alkyl radical
  • R and R each represents a member selected from the group consisting of hydrogen, an alkyl radical, an aryl radical, a carboxyl group, a sulfo group, a nitro group, a cyano group and a halogen atom
  • X represents an acid anion
  • Z represents the nonmetallic atoms required to complete a 5- to 6-membered heterocyclic nucleus.
  • Z represents the atoms necessary to complete a nucleus selected from the class consisting of a thiazole nucleus, an oxazole nucleus, a selenazole nucleus, a thiazoline nucleus, a pyridine nucleus, a quinoline nucleus and an imidazole nucleus; and, R represents a member selected from the group consisting of an alkyl group, an aryl group, an acyl group, and an alkane-sulfonyl group and an arylsulfonyl group.
  • a photographic element comprising a support coated with at least one layer containing a direct positive photographic silver halide emulsion of claim 1.
  • a photographic element comprising a support coated with at least one layer containing a direct positive photographic silver halide emulsion of claim 6.
  • a direct positive, photographic emulsion in accordance with claim 1 which comprises fogged silver halide grains, said grains being such that a test portion thereof, when coated as a photographic silver halide emulsion on a support to give a maximum density of at least about 1 upon processing for 6 minutes at about 68 F. in Kodak DK-SO developer, has a maximum density which is at least about 30% greater than the maximum density of an identical coated test portion which is processed for 6 minutes at about 68 F. in Kodak DK50 developer after being bleached for about 10 minutes at about 68 F. in a bleach composition of:
  • a direct positive, photographic emulsion in accordance with claim 1 which comprises fogged silver halide grains, at least 95%, by weight, of said grains having a size which is within about 40% of the average grain.
  • a direct positive, photographic emulsion in accordance with claim 2 which comprises fogged silver halide grains, said grains being such that a test portion thereof,
  • a direct positive, photographic emulsion in accordance with claim 2 which comprises fogged silver halide grains, at least by weight, of said grains having a size which is within about 40% of the average grain.

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  • Physics & Mathematics (AREA)
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  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Indole Compounds (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
US609740A 1966-03-11 1967-01-17 Direct positive silver halide emulsions containing carbocyanine dyes having a carbazole nucleus Expired - Lifetime US3492123A (en)

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US53345566A 1966-03-11 1966-03-11
US57169566A 1966-08-11 1966-08-11
US57318366A 1966-08-18 1966-08-18
US60979267A 1967-01-17 1967-01-17
US60976167A 1967-01-17 1967-01-17
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3816121A (en) * 1971-09-04 1974-06-11 Fuji Photo Film Co Ltd Direct positive photographic material containing a color coupler under one micron in size and fogged silver halide grains with substantially no internal sensitivity having absorbed on the surface a desensitizing dye containing a solubilizing group
US3933506A (en) * 1973-05-18 1976-01-20 Agfa-Gevaert N.V. Spectral sensitization of direct-positive silver halide emulsions
EP0829753A1 (en) * 1996-09-12 1998-03-18 Fuji Photo Film Co., Ltd. Photographic silver halide photosensitive material
US20100261698A1 (en) * 2008-06-27 2010-10-14 Christopher Adams Organic compounds

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3650758A (en) * 1970-07-20 1972-03-21 Eastman Kodak Co Direct-positive print-out silver halide emulsion fogged to visible density
DE2132937A1 (de) * 1971-07-02 1973-01-18 Agfa Gevaert Ag Spektral sensibilisierte direkt-positiv-emulsionsschichten
GB1453833A (en) * 1973-01-25 1976-10-27 Agfa Gevaert Direct-positive silver halide emulsions
US4009041A (en) * 1974-10-03 1977-02-22 Polaroid Corporation Fogged, direct-positive silver halide emulsion containing a gallium sulfide semiconductor
US4355098A (en) * 1981-02-11 1982-10-19 E. I. Du Pont De Nemours And Company Supersensitizing direct positive dye combinations
US5049483A (en) * 1989-06-08 1991-09-17 Konica Corporation Direct positive silver halide photographic light-sensitive material and a processing method therefor
US5240828A (en) * 1989-12-22 1993-08-31 Eastman Kodak Company Direct reversal emulsions
US6566044B2 (en) * 2000-03-27 2003-05-20 Fuji Photo Film Co., Ltd. Silver halide photographic material

Citations (2)

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Publication number Priority date Publication date Assignee Title
GB760739A (en) * 1953-03-28 1956-11-07 Agfa Ag Process for the production of antihalation and filter layers
US3326688A (en) * 1963-06-10 1967-06-20 Eastman Kodak Co Photographic sensitizing dyes

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GB723019A (en) * 1952-02-05 1955-02-02 Gevaert Photo Prod Nv Improvements in or relating to the manufacture of photographic material
BE555921A (xx) * 1956-03-19

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB760739A (en) * 1953-03-28 1956-11-07 Agfa Ag Process for the production of antihalation and filter layers
US3326688A (en) * 1963-06-10 1967-06-20 Eastman Kodak Co Photographic sensitizing dyes

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3816121A (en) * 1971-09-04 1974-06-11 Fuji Photo Film Co Ltd Direct positive photographic material containing a color coupler under one micron in size and fogged silver halide grains with substantially no internal sensitivity having absorbed on the surface a desensitizing dye containing a solubilizing group
US3933506A (en) * 1973-05-18 1976-01-20 Agfa-Gevaert N.V. Spectral sensitization of direct-positive silver halide emulsions
EP0829753A1 (en) * 1996-09-12 1998-03-18 Fuji Photo Film Co., Ltd. Photographic silver halide photosensitive material
US5869229A (en) * 1996-09-12 1999-02-09 Fuji Photo Film Co., Ltd. Photothermographic material
US20100261698A1 (en) * 2008-06-27 2010-10-14 Christopher Adams Organic compounds
US20110082129A1 (en) * 2008-06-27 2011-04-07 Christopher Adams Organic compounds
US8030334B2 (en) 2008-06-27 2011-10-04 Novartis Ag Organic compounds
US8791141B2 (en) 2008-06-27 2014-07-29 Novartis Ag Organic compounds
US9242963B2 (en) 2008-06-27 2016-01-26 Novartis Ag Organic compounds

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NO129424B (xx) 1974-04-08
SE345170B (xx) 1972-05-15
FR1513840A (fr) 1968-02-16
DE1547792A1 (de) 1969-12-04
GB1186720A (en) 1970-04-02
DE1597528B2 (de) 1976-11-25
BE695367A (xx) 1967-09-11
DE1597528A1 (de) 1971-11-25
CH474086A (fr) 1969-06-15
BR6787702D0 (pt) 1973-01-18
ES337856A1 (es) 1968-08-16
DE1547793A1 (de) 1969-11-20
GB1186714A (en) 1970-04-02
BE695360A (xx) 1967-09-11
GB1190031A (en) 1970-04-29
JPS521300B1 (xx) 1977-01-13
DE1547779A1 (de) 1970-07-23
BE695364A (xx) 1967-09-11
US3501310A (en) 1970-03-17

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