US2566167A - Photographic silver halide emulsion supersensitized with a benzimidazole base - Google Patents

Photographic silver halide emulsion supersensitized with a benzimidazole base Download PDF

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US2566167A
US2566167A US663763A US66376346A US2566167A US 2566167 A US2566167 A US 2566167A US 663763 A US663763 A US 663763A US 66376346 A US66376346 A US 66376346A US 2566167 A US2566167 A US 2566167A
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groups
benzimidazole
emulsion
silver
carbon
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US663763A
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Burt H Carroll
Spence John
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Eastman Kodak Co
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Eastman Kodak Co
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Priority to US663763A priority patent/US2566167A/en
Priority to GB10453/47A priority patent/GB635366A/en
Priority to FR950098D priority patent/FR950098A/fr
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/28—Sensitivity-increasing substances together with supersensitising substances

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  • This invention relates to sensitized photographic emulsions and to a process for preparing the same.
  • This application is a continuationin-part of our copending application Serial No. 466,796, led November 24, 1942 (now United States Patent 2,398,778, dated April 23, 1946).
  • a photographic silver halide emulsion other than a chloride emulsion e. g. silver chlorobromide (which may contain small amounts of silver iodide), silver bromide or silver bromiodide emulsions, spectrally sensitized with a (at least one) cyanine dye is supersensitized by incorporating in the emulsion one or more benzimidazole bases.
  • a photographic silver halide emulsion other than a chloride emulsion e. g. silver chlorobromide (which may contain small amounts of silver iodide), silver bromide or silver bromiodide emulsions, spectrally sensitized with a (at least one) cyanine dye is supersensitized by incorporating in the emulsion one or more benzimidazole bases.
  • Our invention is Vdirected principally to emulsions of such grain size that the emulsions give a substantially neutral-toned image in Eastman Kodak Companys D-76 developer, and should not be confused with prior proposals to obtain blueblack tones in line-grain emulsions by means of Moreover, our invention involves incorporation of the benzimidazole bases in the emulsion before exposure of the emulsion and should not be confused with 10 Claims. (Cl. 95--7) proposals to develop with color-forming developers silver salt images, in the presence of certain heterocyclic nitrogen bases which contain a reactive methyl group.
  • benzimidazole bases advantageously employed in practicing our invention are of a specinc type and can be defined as benzimidazole (benziminazole) bases selected from the group consisting of benzimidazole and benzimidazole containing a substituent (i. e. at least one substituent) selected from the group consisting of alkyl groups, alkoxyl groups, hydroxyalkyl groups, aryl groups, aryloxyl groups, alkylmercapto groups, arylmercapto groups, acyl groups, acyloxyl groups and halogen atoms.
  • a substituent i. e. at least one substituent
  • substituents are: methyl, ethyl, methoxyl, ethoxyl, hydroxyethyl, phenyl, phenoxyl, ,methylmercaptd ethylmercapto, phenylmercapto, acetyl, propionyl, benzoyl, acetoxyl (acetoxy), propionoxyl (propionoxy) and benzoxy groups, and chlorine, bromine and iodine atoms.
  • cyanine dyes which are supersensitized by the benzimidazole bases are charterized by the fact that the dyes produce two types of sensitization depending upon conditions.
  • diierent types of sensitization are described by Leermakers, Carroll and Staud, J. Chem. Physics 5, 878 (1937), and by Schwarz, Sci. et Ind. Phot. 10, 233 (1939).
  • a cyanine dye of this type When a cyanine dye of this type is used as a sensitizer in low concentration, it exhibits a sensitizing maximum displaced about 20 to 50 mu. toward the red from the absorption maximum in ethyl alcohol solution.
  • a second maximum of sensitization develops ⁇ at longer wavelengths, which may be accompanied by 'an increase in total optical sensitization.
  • a decrease in sensitivity at the first maximum can be detected.
  • the eiect appears to correspond to a more complete conversion than has ever been obtained without a supersensitizer, Vand in any c ase the long Wavelength sensitivity is better than can be obtained from the same concentration or" dye without the benzimidazole base.
  • 3lrdiethyl-6'-rnethoXy-2'-cyanine iodide 3,3-diethyl-Q-methylthiacarbocyanine bromide. 9-ethyl-3,3'-dimethylthiacarbocyanine bromide. 5ch1oro3,3,9-triethylthiacarbocyanine iodide. 5,5 -dichloro3,3 ,9 -triethylthiacarbocyanine iodide. 35,3 -diethyl-9-methyl-4,5,4 ,5 -dibenzothiacarbo cyanine bromide. 3,3-diethyl-Q-methylselenathiacarbocyanine bromide.
  • the sensitizing dyes can be employed in -any desired concentration. Ordinarily from l0 to 30 mg. of dye per liter of emulsion will suiiice to produce the optimum sensitizing effect.
  • the methods of incorporating sensitizing dyes in emulsions are well known'to those skilled in the art. Ordinarily it is preferable to ⁇ dissolve the dye in a water-miscible solvent, such as methanol or ethanol, beforeillorporating in the emulsion.
  • a water-miscible solvent such as methanol or ethanol
  • the amount of benzimidazole base employed is not critical. Usually the full supersensitizing effect is developed at a concentration of 0.10 to 1.5 grams per liter of emulsion. At these concentrations practically none of the benzimidazole bases has an appreciable eiect on the pH of the emulsion.
  • the benzimidazole bases can be added to the emulsions with, before or after the sensitivzing Clye or dyes. More than one benzimidazole base can be employed.
  • the benzimidazole bases are preferably, but not necessarily, diluted with a water-miscible, solvent, such as methanol, before incorporation in the emulsions.
  • the sensitizing dye or dyes and the benzimidazole. base or bases 'Call be added to the emulsions at any convenient stage of their preparation, but preferably to the washed, finished emulsions before coating.
  • Example 2 A fast negative gelatino'-silver-bromiodide developing-out emulsion was sensitized with 3,3"- diethyl-9-methylselenacarbocyanine bromide (20 mg. per liter of emulsion) and to a portion of the spectrally sensitized emulsion was added 2- methylbenzimidazole. A portion of the spectrally sensitized emulsion without the Z-methylbenzimidazole and a portion containing it were exposed through red (Wratten No. 25) and minus blue (Wratten No. 12) iilters. The results are tabulated below:
  • the accompanying drawing illustrates graphically the supersensitizing eiect obtained with two ⁇ of our new combinations in a gelatino-silverbromiodide emulsion.
  • Each ligure in the drawing is a diagrammatic reproduction of two spectrograms.
  • Curve A represents the sensitivity ofl a gelatine-silver-bromiodide emulsion containing 3,3-dietnyl-Q-methylselenacarbocyanine bromide in a concentration of 20 mg. per liter of emulsion.
  • Curve B represents the Sensitivity of the saine emulsion containing 3,3 diethyl-9-methylselenacarbocyanine bromide in a concentration of about 20 mg. lper liter of emulsion and containing, in addition, benzimidazole in a concentration of about 0.58 g. per liter of emulsion. It will be observed that with the benzimidazole in the emulsion, a new sharp maximum appears at about 640 ma and the red speed is considerably increased. In Fig.
  • Curve C represents the sensitivity of a gelatinosilver-bromiodide emulsion containing4 3,3diethyl-Q-methylselenacarbocyanine bromide in a ⁇ concentration of 20 mg. per liter ofy emulsion.
  • Curve D represents the sensitivity oi the same emulsion containing 3,3-diethyl-9-methylselenacarbocyanine bromide in a concentration of about 20 mg. per liter of emulsion and containing, in addition, Z-methylbenzimidazole in a concentration of about 0.25 g. per liter of emulsion.
  • Our invention is primarily directed to the customarily employed gelatino-silver-halide developing-out emulsions, such as gelatina-silverchlorobromide, gelatino-silver-bromi-de and gelatino silver bromiodide developing out emulsions, especially emulsions for development to black-and-White images by means of non-colorforming developers, e. g. hydroquinone-N-methylp-amino-phenol developers.
  • non-colorforming developers e. g. hydroquinone-N-methylp-amino-phenol developers.
  • Emulsions prepared in accordance with our invention can be coated in the usual manner upon any desired support, such as cellulose nitrate support, cellulose acetate support, polyvinyl acetal resin support, metal support, glass support or paper support.
  • Cyanine dyes are des-cribed and defined, e. g. in The Theory of the Photographic Process, by C. E. K. Mees, The MacMillan Company, New York, 1942.
  • a photographic silver halide emulsion selected from the group consisting of silver chlorobromide, silver bromide and silver bromiodide developing-out emulsions spectrally sensitized with av sensitizing cyanine dye and containing, as a supersensitizer, a benzimidazole base selected from the group consisting of benzimidazole and benzimidazole containing a substituent selected from the group consisting of halogen atoms, alkyl groups, alkoxyl groups, hydroxyalkyl groups, aryl groups containing only carbon and hydrogen atoms, aryloxyl groups in which the aryl portion contains only carbon and hydrogen atoms, alkylmercapto groups, arylmercapto groups in which the aryl portion contains only carbon and hydrogen atoms, acyl groups containing only carbon and hydrogen atoms plus one oxygen atom, and acyloxyl groups containing only carbon and hydrogen atoms plus two oxygen atoms.
  • a photographic gelatino-silver-halide developing-out emulsion selected from the group consisting of silver chlorobromide, silver bromide and silver bromiodide developing-out emulsions spectrally sensitized with a sensitizing cyanine dye and containing, as a supersensitizer, a benzimidazole base selected from the group consisting of benzimidazole and benzimidazole containing a substituent selected from the group consisting of halogen atoms, alkyl groups, alkoxyl groups, hydroxyalkyl groups, aryl groups containing only carbon and hydrogen atoms, aryloxyl groups in which the aryl portion contains only carbon and hydrogen atoms, alkylmercapto groups, arylmercapto groups in which the aryl portion contains only carbon and hydrogen atoms, acyl groups containing only carbon and hydrogen atoms plus one oxygen atom, and acyloxyl groups containing only carbon and hydrogen atoms plus
  • a photographic gelatino-silver-halide developing-out emulsion selected from the' group consisting of silver chlorobromide, silver bromide and silver bromiodide developing-out emulsions spectrally sensitized with a sensitizing cyanine dye and containing, as a supersensitizer, 2-methylbenzimidazole which has the formula:
  • a photographic neglectn-Silverman@ developing-out emulsion selected from the group consisting of silver chlorobromide, silver bromide and silver bromiodide developing-out emulsions spectrally sensitized with a sensitizing cyanine dye which produces a maximum of spectral sensitivity in the emulsion at one concentration and at a higher concentration, or upon digestion of the emulsion containing the dye at the lower concentration, produces a second maximum of sensitivity at a wavelength longer than that of the-first maximum, the emulsion containing, as a supersensitizer, a benzimidazole base selected from the group consisting of benzimidazole and benzimidazole containing a substituent selected from the group consisting of halogen atoms, alkyl groups, alkoxyl groups, hydroxyalkyl groups, aryl groups containing only carbon and hydrogen atoms, aryloxyl groups in which the aryl portion contains only carbon and
  • a photographic gelatino-silver-halide developing-out emulsion selected from the group consisting of silver chlorobromide, silver bromide and silver bromiodide developing-out emulsions spectrally sensitized with a sensitizing cyanine dye which produces a maximum of spectral sensitivity in the emulsion at one concentration and at a higher concentration, or upon digestion of the emulsion -containing the dye at the lower concentration, produces a maximum of sensitivity at a wavelength longer than that of the rst maximum, the emulsion containing, as :a supersensitizer, benzimidazole having the formula:
  • the emulsion containing, as a supersensitizer, Z-methylbenzimid'az'ole having the formula:
  • a photographic gelatino-silver-halide developing-out emulsion selected from the group consisting of silver chlorobromide, silver bromide and silver bromiodide developing-out emulsions spectrally sensitized with a sensitizing cyanine dye and containing, as a supersensitizer, benzimidazole which has the formula;
  • a photographic gelatino-silver-halide developingout emulsion selected from the group consisting of silver chlorobromide, silver bromide and silver bromiodide developing-out emulsions s pectrally sensitized with a sensitizing cyanine dye which produces a maximum of spectral sensitivity in the emulsion at one concentration and at a higher concentration, or upon digestion of the emulsion containing the dye at the lower concentration, produces a maximum of sensitivity at a wavelength longer than that of the irst ⁇ Ii'aximufn, the emulsion containing, as a supersens't'izer, 2-mthylben ⁇ zimidazole having the formula:

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
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US663763A 1946-04-20 1946-04-20 Photographic silver halide emulsion supersensitized with a benzimidazole base Expired - Lifetime US2566167A (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
BE474543D BE474543A (en, 2012) 1946-04-20
US663763A US2566167A (en) 1946-04-20 1946-04-20 Photographic silver halide emulsion supersensitized with a benzimidazole base
GB10453/47A GB635366A (en) 1946-04-20 1947-04-18 Sensitive photographic emulsions
FR950098D FR950098A (fr) 1946-04-20 1947-07-24 Perfectionnements aux émulsions photographiques

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3248220A (en) * 1961-11-22 1966-04-26 Grinten Chem L V D Two-component diazotype material
US4030927A (en) * 1975-01-16 1977-06-21 Fuji Photo Film Co., Ltd. Supersensitizing combinations of halogen substituted benzotriazoles and cyanine dyes

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2066099A (en) * 1928-01-31 1936-12-29 Agfa Ansco Corp Photographic emulsion
US2158882A (en) * 1937-01-16 1939-05-16 Eastman Kodak Co Photographic emulsion
US2296306A (en) * 1938-10-26 1942-09-22 Eastman Kodak Co Nondiffusing metallic salt coupler compound
US2353754A (en) * 1942-11-07 1944-07-18 Eastman Kodak Co Color photography using metallic salt coupler compounds

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2066099A (en) * 1928-01-31 1936-12-29 Agfa Ansco Corp Photographic emulsion
US2158882A (en) * 1937-01-16 1939-05-16 Eastman Kodak Co Photographic emulsion
US2296306A (en) * 1938-10-26 1942-09-22 Eastman Kodak Co Nondiffusing metallic salt coupler compound
US2353754A (en) * 1942-11-07 1944-07-18 Eastman Kodak Co Color photography using metallic salt coupler compounds

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3248220A (en) * 1961-11-22 1966-04-26 Grinten Chem L V D Two-component diazotype material
US4030927A (en) * 1975-01-16 1977-06-21 Fuji Photo Film Co., Ltd. Supersensitizing combinations of halogen substituted benzotriazoles and cyanine dyes

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FR950098A (fr) 1949-09-16
BE474543A (en, 2012)
GB635366A (en) 1950-04-05

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