US3173791A - Supersensitized photographic silver halide emulsions - Google Patents

Supersensitized photographic silver halide emulsions Download PDF

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Publication number
US3173791A
US3173791A US226591A US22659162A US3173791A US 3173791 A US3173791 A US 3173791A US 226591 A US226591 A US 226591A US 22659162 A US22659162 A US 22659162A US 3173791 A US3173791 A US 3173791A
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dye
silver halide
dyes
imidazole
iodide
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US226591A
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Norman W Kalenda
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Eastman Kodak Co
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Eastman Kodak Co
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Priority to BE637795D priority Critical patent/BE637795A/xx
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Priority to US226591A priority patent/US3173791A/en
Priority to FR948465A priority patent/FR1369855A/fr
Priority to FR948741A priority patent/FR1375313A/fr
Priority to GB38100/63A priority patent/GB1062024A/en
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/28—Sensitivity-increasing substances together with supersensitising substances
    • G03C1/29—Sensitivity-increasing substances together with supersensitising substances the supersensitising mixture being solely composed of dyes ; Combination of dyes, even if the supersensitising effect is not explicitly disclosed
    • 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
    • C09B23/10—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

Definitions

  • This invention relates to photographic silver halide emulsions containing certain benzimidazolocarbocyanine dyes and in particular to silver halide emulsions containing supersensitizing combinations of bcnzimidazolocarbocyanines and bridged naphthimidazolooxacarbocyanine dyes and bridged benzimidazolooxacarbocyanine dyes.
  • the sensitization produced by a given dye varies somewhat with the type of emulsion in which the dye is incorporated.
  • the sensitization produced by a given dye in a given emulsion may be altered by changing the conditions of the emulsion. For example, the sensitization may be increased by increasing the silver ion concentration or decreasing the hydrogen ion concentration or both.
  • sensitization of plates can be increased by bathing plates coated with spectrally sensitized emulsions in water or aqueous solutions of ammonia.
  • Such a process of altering the sensitivity of a sensitized emulsion by increasing the silver ion concentration or decreasing the hydrogen ion concentration is commonly called hypersensitization.
  • Hypersensitized emulsions generally have poor keeping qualities.
  • Another object is to provide such supersensitized emulsions which are characterized by having single mixed aggregate sensitivity maxima at wavelengths between those of the emulsions sensitized with the dyes individually.
  • Another object is to provide a means for preparing such supersensitized emulsions.
  • Y and Y each represent a hydrogen atom, a halogen atom, such as chlorine, bromine, iodine, etc., an
  • R represents an alkyl group, such as methyl, ethyl, propyl, butyl, etc., a carboxyalkyl group, such as carboxyethyl, carboxypropyl, etc.
  • R represents an alkyl group, such as methyl, ethyl, propyl, butyl, etc., and sulfoalkyl, such as 2-sulfoethyl, 3-sulfopropyl, 3-sulfobutyl, 4-sulfobutyl, etc.
  • X represents an acid anion, such as chloride, iodide, bromide, perchlorate, p-toulenesulfonate, ethylsulfate, etc.
  • Z represents the nonmetallic atoms necessary to complete a nucleus of the arimidazole series, such as benzimidazole, 4-chlorobenzimidazole, S-bromobenzimidazole, 6-rnethylbenzimidazo1e, 7-methoxybenzimidazole, 5 acetoxybenzimidazole, 6 acetylbenzimidazole, naphth- (2,3-d)imidazo-le, 4 chloronaphth(2,3 d)imidazole, 5- bromonaphth(2,3 d-imidazole, 7 bromonaphth (25 d)- imidazole, 8 methylnaphth(2,3 d)imidazole, 9 ethylnaphth(2,3 d) imidazole, 5 acetoxynaphth(2,3 d)- imidazole, 6 acetylnaphth(2,3 d) imi
  • benzimidazolocarbocyanine dyes of Formula I are the following typical examples.
  • diethylbenzimidazolocarbocyanine hydroxide Included among the naphthimidazolooxacarbocyanine dyes'of Formula Here the following typical examples.
  • I incorporate in a photographic emulsion one or more of the benzimidazolocarbocyanine dyes represented by Formula I and one or more of the bridged naphthimidazolooxacarbocyanine dyes represented by Formula II.
  • My invention is particularly directed to the ordinarily employed gelatino-silver halide,
  • siiver halide emulsionsin which the carrier or vehicle is other than gelatin, e.g., a resinous material such as polyvinyl alcohol, albumin, etc., or a hydrophilic cellulosic material which has no deleterious effect on the light-sensitive silver halide.
  • concentration of the dyes used in my emulsions can be varied considerably depending upon the particular dyes used, the emulsion and the particular results desired.
  • concentrations and ratio of the dyes in the supersensitizing combination can be determined by methods well .known in the art, in which the sensitivity is determined for a series of test portions of the emulsion desired, each portion containing a different concentration of the dyes.
  • Photographic silver halide emulsions such as those described, containing the supersensitizing combinations of my invention can also contain such addenda as chemical sensitizers, e.g., sulfur sensitizers (e.g., allyl thiocarbamide, thiourea, allylisothiocyanate, cystine, etc.), various gold compounds (e.g., potassium chloroaurate, auric trichloride, etc.) (see Baldsiefen US. Patent 2,540,085, issued February 6, 1951; Damschroder US. Patent 2,597,- 856, issued May 27, 1952, and Yutzy et al. US.
  • additiveenda e.g., sulfur sensitizers (e.g., allyl thiocarbamide, thiourea, allylisothiocyanate, cystine, etc.), various gold compounds (e.g., potassium chloroaurate, auric trichloride, etc.) (see Baldsie
  • Patent 2,597,915, issued May 27, 1952 various palladium compounds, such as palladium chloride (Baldsiefen US. Patent 2,540,086, issued February 6, 1951), potassium chloropalladate (Staufier et al. US. Patent 2,598,079, issued May 27, 1952),, etc., or mixtures of such sensitizers; antifoggants, such as ammonium chloroplatinate (Trivelli et al. US. Patent 2,566,245, issued August 28, 1951), am-.
  • palladium chloride Bodsiefen US. Patent 2,540,086, issued February 6, 1951
  • potassium chloropalladate Staufier et al. US. Patent 2,598,079, issued May 27, 1952
  • antifoggants such as ammonium chloroplatinate (Trivelli et al. US. Patent 2,566,245, issued August 28, 1951), am-.
  • hardeners such as formaldehyde (Miller U.S. Patent 1,763,533, issued June 10, 1930), chrome alum (1,763,- 533), glyoxal (Brunken US. Patent 1,870,354, issued August 9, 1932), dibromacrolein (Block et al. British Patent 406,750, accepted March 8, 1934), etc.; color couplers, such as those described in Salminen et al. US. Pat ent 2,423,730, issued June 7, 1947, Spence and Carroll US. Patent 2,640,776, issued June 2, 1953, etc; or mixtures of such addenda. Dispersing agents for color couplers, such as those set forth in Jelley et al. US. Patent 2,322,027, issued June 15, 1943, and Mannes et al. US. Patent 2,304,940, issued December 15, 1942, can also be employed in the above described emulsions.
  • Example 1 A silver bromoiodide emulsion was made of the type described by Trivelli and Smith, Phot. Journal, vol. 79, 330 (1939). The melted emulsion was divided into separate portions to which were added a solution of the sensitizer or combination of sensitizers indicated in Table 1. After being digested at 50 C. for minutes each of the portions of the sensitized emulsions was coated on a support and dried. The reflectance spectra of the coatings were plotted for light in the visual region with a General Electric Recording Spectrophotometer. The absorption maximums obtained from these curves are listed in the following table.
  • Example 2 p-Methylaminophenol sulfate g 2 Sodium sulfite, desiccated g 90 Hydroquinone g 8 Sodium carbonate monohydrate g 52.5 Potassium bromide g 5 Water to make 1 liter.
  • Example 3 Dye and Concentration (gJmole oi Relative Gamma Fog silver) Speed Example 3 Coatings were made as in Example 1 excepting that sensitize-rs 1, VIII, IX, X and combinations of I with each of the others were used. These coatings were exposed, processed, the density measurements made and the reactive speeds, gammas and fog values determined as in Example 2. These values are listed in Table 3.
  • Example 4 Coatings were made, exposed and processed as in Example 2 excepting that sensitizers II and VII and a combination of them were used. Densitometric measurcments were made and the relative speeds, gammas and fog values are listed in the following table.
  • Example 5 Coatings were made as in Example 1 excepting that the dyes indicated in Tables 5, 6 and 7 were used. These coatings were exposed, processed, and the density measurements made through a yellow Wratten #15 filter for coatings in Table 5 and Table 6, and through a green Wratten #61 filter for coatings in Table 7. The relative speed, gammas, and fog values were determined and are listed in Tables 5, 6 and 7.
  • Dye XI was prepared by the method described hereinafter for Dye VII excepting that an equimolar amount of 5,6 dichloro 3 ethyl 1,2 trimethylenebenzirnidazolium iodide was used in place of 3-ethyl-1,2-trimethylenenaphth[2,3-d]imidazoliurn iodide.
  • Dyes II and IV are described in Van Lare U.S. Patent 2,739,149, issued March 20, 1956, as Examples 2 and 1, respectively.
  • Dyes III and V are described in Brooker et al. US. Patent 2,778,823, issued January 22, 1957, as Examples 3 and 1, respectively.
  • :Dye VI was prepared as follows: 5,6-dichloro-1-ethyl- Z-methylbenzimidazol-e (2 mols, 4.5 g.) and B-iodopropicnic acid (1 mol, 2 :g.) were mixed and heated on a steam bath for four hours at which time the sticky mass that formed was stirred with an excess of ether, the ether was decanted, and the residue disolved in a solution of sodium alcoholate which was prepared by dissolving sodium (25 mols, .58 g.) in absolute ethyl alcohol, 50 mol.
  • FIGS. 1, 2, 3 and 4 further illustrate my invention.
  • FIG. 1 is a wedge spectrogram for a silver bromoiodide emulsion sensitized with Dye I, anhydro-5,5',6,6-tetrachloro-l,l'-diethyl-3,3-di(3 sulfobutyl) benzimidazolo 'carbocyanine hydroxide at a concentration of 0.20 g. per
  • FIG. 2 is a wedge spectrogram for a silver bromoiodide emulsion sensitized with Dye VIII, 3,3'-diethyl-1,10ethylenenapl1th(1,2-d)imidazolooxacarbocyanine iodide-at a concentration of 0.15 g. per mole of silver halide.
  • FIG. 3 is a wedge spectrogram for a silver bromoiodide emulsion containing a supersensitizing combination of Dye I and Dye VIII at concentrations of 0.20 g. and 0.15 g. per mole of silver halide, respectively.
  • FIG. 4 shows curves A, B and C, which relate the percent reflectance of light byv emulsion coatings containing a dye(s) with the wavelength of light being reflected.
  • Curve A shows this relationship for an emulsion with the Dye I at a concentration of 0.20 g. per mole of silver halide.
  • Curve C shows this relationship for an emulsion containing the Dye VIII at a concentration of 0.15 g. per mole of silver halide.
  • Curve B shows this relationship for an emulsion containing a mixture of the dyes represented by Curves A and C, i.e., Dye I at a concentration of 0.20 g. per mole of silver halide and Dye VIII at a concentration of 0.15 g. per mole of silver halide, respectively.
  • My supersensitizing combinations of benzimidazolocarbocyanine dyes with N,u-a-lkylene bridged naphthimidan olooxacarbocyanine dyes are valuable for use in photographic silver halide emulsions.
  • Z represent the nonmetallic atoms necessary to complete a nucleus selected from the class consisting of a benzimidazole, a naphth(2,3-d)imidazole, a naphth(1,2- d)imidazole, and a naphth-(2,1-d)imidazole;
  • R represents a member selected from the class consitsing of an alkyl group and a sulfoalkyl group;
  • R represents an alkyl group;
  • X- represents an acid anion; and
  • n represents an integer of from 2 to 3.
  • R represents a member selected from the class consisting of an alkyl group and a sulfoalkyl group; R represents an alkyl group; X represents an acid anion; and n represents an integer of from 2 to 3.
  • a photographic element comprising a support coated With at least one layer containing a photographic silver halide emulsion of claim 1.
  • a photographic element comprising a support coated with at least one layer containing a photographic silver halide emulsion of claim 2.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
US226591A 1962-09-27 1962-09-27 Supersensitized photographic silver halide emulsions Expired - Lifetime US3173791A (en)

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Application Number Priority Date Filing Date Title
BE637795D BE637795A (en:Method) 1962-09-27
US226591A US3173791A (en) 1962-09-27 1962-09-27 Supersensitized photographic silver halide emulsions
FR948465A FR1369855A (fr) 1962-09-27 1963-09-24 Nouvelle émulsion photographique sursensibilisée
FR948741A FR1375313A (fr) 1962-09-27 1963-09-26 Nouveaux colorants sensibilisateurs utilisables en photographie
GB38100/63A GB1062024A (en) 1962-09-27 1963-09-27 Improvements in sensitized photographic silver halide emulsions

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3282932A (en) * 1962-09-27 1966-11-01 Eastman Kodak Co Merocyanine sensitizers for silver halide
US3364031A (en) * 1963-06-24 1968-01-16 Eastman Kodak Co Supersensitized photographic silver halide emulsions
US3769025A (en) * 1970-06-05 1973-10-30 Fuji Photo Film Co Ltd Spectrally sensitized silver halide photographic emulsion
US3947275A (en) * 1970-05-01 1976-03-30 Fuji Photo Film Co., Ltd. Spectrally sensitized silver halide photographic emulsion
US4003750A (en) * 1973-05-03 1977-01-18 Eastman Kodak Company Silver halide emulsion containing photographic sensitizing dyes

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB587434A (en) * 1939-12-20 1947-04-25 Gevaert Photo Prod Nv Improvements in and relating to the preparation of heterocyclic nitrogen compounds
GB615205A (en) * 1939-12-28 1949-01-04 Gevaert Photo Prod Nv Improvements in and relating to the manufacture of dyes and photographic emulsions sensitised therewith
US2954376A (en) * 1958-04-08 1960-09-27 Gevaert Photo Prod Nv Polymethine dyes containing a 4-(hydroxymethyl)-or 4-(acetoxymethyl)-delta2-thiazoline or oxazoline nucleus, and preparation thereof
US2973264A (en) * 1957-03-06 1961-02-28 Gevaert Photo Prod Nv Sensitized photographic emulsions

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB587434A (en) * 1939-12-20 1947-04-25 Gevaert Photo Prod Nv Improvements in and relating to the preparation of heterocyclic nitrogen compounds
GB615205A (en) * 1939-12-28 1949-01-04 Gevaert Photo Prod Nv Improvements in and relating to the manufacture of dyes and photographic emulsions sensitised therewith
US2973264A (en) * 1957-03-06 1961-02-28 Gevaert Photo Prod Nv Sensitized photographic emulsions
US2954376A (en) * 1958-04-08 1960-09-27 Gevaert Photo Prod Nv Polymethine dyes containing a 4-(hydroxymethyl)-or 4-(acetoxymethyl)-delta2-thiazoline or oxazoline nucleus, and preparation thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3282932A (en) * 1962-09-27 1966-11-01 Eastman Kodak Co Merocyanine sensitizers for silver halide
US3364031A (en) * 1963-06-24 1968-01-16 Eastman Kodak Co Supersensitized photographic silver halide emulsions
US3947275A (en) * 1970-05-01 1976-03-30 Fuji Photo Film Co., Ltd. Spectrally sensitized silver halide photographic emulsion
US3769025A (en) * 1970-06-05 1973-10-30 Fuji Photo Film Co Ltd Spectrally sensitized silver halide photographic emulsion
US4003750A (en) * 1973-05-03 1977-01-18 Eastman Kodak Company Silver halide emulsion containing photographic sensitizing dyes

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GB1062024A (en) 1967-03-15

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