US3527641A - Supersensitized photographic silver halide emulsion - Google Patents

Supersensitized photographic silver halide emulsion Download PDF

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Publication number
US3527641A
US3527641A US588710A US3527641DA US3527641A US 3527641 A US3527641 A US 3527641A US 588710 A US588710 A US 588710A US 3527641D A US3527641D A US 3527641DA US 3527641 A US3527641 A US 3527641A
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US
United States
Prior art keywords
dye
group
silver halide
emulsion
halide emulsion
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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US588710A
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English (en)
Inventor
Yoshiuki Nakazawa
Masanao Hinata
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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Publication of US3527641A publication Critical patent/US3527641A/en
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    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/005Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08Sensitivity-increasing substances
    • G03C1/28Sensitivity-increasing substances together with supersensitising substances
    • G03C1/29Sensitivity-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

Definitions

  • a photographic composition comprising a silver halide emulsion sensitized with a combination of two dilferent cyanine dyes.
  • the combination of two difierent sensitizing dyes results in an increase in the sensitization of the silver halide emulsion above that which can be obtained with either dye employed alone.
  • the present invention relates to a silver halide emulsion sensitized by sensitizing dyes and more particularly it relates to a photographic silver halide emulsion super-dyesensitized by the combination of two types of sensitizing dyes.
  • an object of the present invention is to provide a photographic silver halide emulsion sensitized by sensitizing dyes, not accompanied by the above-mentioned drawback, and without the necessity of varying the conditions in the emulsion, e.g., the silver ion concentration and/or the hydrogen ion concentration.
  • Another object of the present invention is to increase the sensitivity of a photographic silver halide emulsion without the above-mentioned drawback and further without varying the conditions in said emulsion.
  • the inventors have found that by incorporation in a photographic silver halide emulsion the two types of sensitizing dyes, shown below, a higher sensitivity is obtained by the interaction of the two sensitizing dyes as compared with the case of using each sensitizing dye individually.
  • the sensitivity of a photographic silver halide emulsion is increased by incorporating therein the halogen-substituted mesoethyl thiacarbocyanin having the following general Formula I,
  • W and W each represents a halogen atom
  • R and R each represents an alkyl group (such as a methyl group, an ethyl group, or a propyl group), a substituted alkyl group (such as a B-hydroxyethyl group, a B-acetoxyethyl group, a 'y-acetoxypropyl group, an ethylsulfate group, and a propylsulfate group), a carboxyalkyl group or a derivative thereof (such as a carboxymethyl group, a fi-carboxyethyl group, and a 2-(2-carboxyethoxy) ethyl group), a sulfoalkyl group or a derivative thereof (such as a fi-sulfoethyl group, a 'y-sulfopropyl group, a a-sulfobutyl group, a Z-hydroxy-l-sulf
  • the photographic silver halide emulsion of the present invention contains therein at least one sensitizing dye represented by the above-mentioned general Formula I and at least one sensitizing dye represented by the abovementioned general Formula II.
  • the emulsion to be employed in our invention there may be used the usual gelatino silver halide emulsions, but protective colloids other than gelatin, such as a resinous material or a cellulose derivative which have no bad influence on the photographic properties of the light sensitive element may also be used.
  • protective colloids other than gelatin such as a resinous material or a cellulose derivative which have no bad influence on the photographic properties of the light sensitive element may also be used.
  • sensitizing dyes of this invention may be used in various concentrations, but a particularly elTective proportion of sensitizing dye (I) or sensitizing dye (II) is from 0.02 to 0.4 g. per one gram molecule of the silver halide.
  • concentration ratio of dye (I) to dye (II) is preferably from 10:1 to 1:10.
  • the sensitizing dyes may be incorporated in the emulsion in a conventional manner. For example, they may be added therein as a solution thereof in an organic solvent, such as methanol or ethanol, or in water. It is convenient to add sensitizing dye (I) and sensitizing dye (H) to the silver halide emulsion before coating. Further, sensitizing dye (I) may be incorporated in the silver halide emulsion before or after the addition of dye (II), or a mixed solution of dye (I) and dye (II) may be added to the emulsion.
  • an organic solvent such as methanol or ethanol
  • the silver halide emulsion to be used in the present invention may contain further usual additives, such as a. chemical sensitizer, an anti-foggant, a hardening agent, a wetting agent, a stabilizer, a developing promoter, an anti-bronzing agent, a coupler, a fluorescent whitening agent, and an air-fog preventing agent.
  • a chemical sensitizer such as a. chemical sensitizer, an anti-foggant, a hardening agent, a wetting agent, a stabilizer, a developing promoter, an anti-bronzing agent, a coupler, a fluorescent whitening agent, and an air-fog preventing agent.
  • the photographic silver halide emulsion sensitized by the sensitizing dyes of this invention may be provided with highly sensitive color sensitivity, in compliance with the purpose, by increasing the green sensitivity with the addition of pseudocyanin, oxacarbocyanin, imidacarbocyanin or merocyanin, color sensitization for black and white light sensitive elements, using various silver halide emulsions, can be easily conducted.
  • the present invention in the case of applying the present invention to a silver halide light sensitive emulsion for a red sensitive layer of a photographic light sensitive color element, by reducing the addition amount of sensitizing dye (II) as compared with that of sensitizing dye (I), the color sensitization for high red sensitivity can be conducted without increasing the green sensitivity so much.
  • a coupler may be incorporated in the emulsion together with the sensitizing dyes.
  • the silver halide emulsion sensitized by the sensitizing dyes of the present invention may be applied in a conventionally employed manner to a suitable support such as a glass plate, a film of cellulose derivative, a synthetic resin film or a paryta paper.
  • the sensitivity of the thus coated light sensitive film was shown by the read sensitivity exposed through Fuji No. 7 Filter (transmitting light having a wave length longer than 590 m and made by Fuji Shashin Film Co.).
  • the thus exposed film was developed in a developer having the following composition for 7 minutes at 20 C.;
  • the results are shown in the following table.
  • the sensitivity was shown by M.U.D. (a reciprocal of the amount of exposure necessary for giving the 4 density of fog plus 0.1, multiplied by 10).
  • the numerical value shown in the parentheses appearing after the name of sensitizing dye is the proportion of the sensitizing dye shown by the number of milli-liter of mol solution thereof per kg. of emulsion.
  • Examples 1-7 employed the same batch of a silver iodo-bromide emulsion (iodine 5.0 mol percent).
  • Examples 8-20 employed the same batch of a silver iodo-bromide emulsion (iodine 7.0 mol percent).
  • a photographic composition comprising: a sliver halide emulsion sensitized with a combination at least one sensitizing dye selected from the group consisting of those represented by the following general Formula I;
  • R represents an alkyl group
  • a photographic silver halide light sensitive element comprising:
  • a silver halide emulsion photographic layer sensitized with a combination of at least one sensitizing dye selected from the group consisting of those represented by the following general Formula I;
  • R2 (I) wherein W and W each represents a halogen atom;
  • R and R each represents a member selected from the group consisting of alkyl, hydroxyalkyl, alkoxyalkyl, sulfoxyalkyl, carboxyalkyl, (carboxyalkoxy) alkyl, sulfoalkyl, (hydroxy) sulfoalkyl, (alkoxy) sulfoalkyl, (sulfoalkoxy) alkyl, (hydroxy) (sulfoalkoxy) alkyl, (alkoxy) (sulfoalkoxy) alkyl, allyl, aryl and aralkyl;
  • X represents an anion; and n is 1 or 2, said It being 1 when an inner salt is formed, and
  • At least one sensitizing dye selected from the group consisting of those represented by the following general Formula II;
  • R represents an alkyl group

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US588710A 1965-10-22 1966-10-24 Supersensitized photographic silver halide emulsion Expired - Lifetime US3527641A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP6443765 1965-10-22

Publications (1)

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US3527641A true US3527641A (en) 1970-09-08

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BE (1) BE688777A (enrdf_load_html_response)
GB (1) GB1128418A (enrdf_load_html_response)

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3808009A (en) * 1971-08-14 1974-04-30 Konishiroku Photo Ind Light-sensitive super-sensitized silver halide photographic emulsions
EP0143424A2 (en) 1983-11-25 1985-06-05 Fuji Photo Film Co., Ltd. Heat-developable light-sensitive materials
EP0147854A2 (en) 1983-12-29 1985-07-10 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive materials
EP0209118A2 (en) 1985-07-17 1987-01-21 Konica Corporation Silver halide photographic material
US4710631A (en) * 1984-08-28 1987-12-01 Fuji Photo Film Co., Ltd. Temperature compensation for a semiconductor light source used for exposure of light sensitive material
EP0256537A2 (en) 1986-08-15 1988-02-24 Fuji Photo Film Co., Ltd. Color print and a method for producing the same
US4818676A (en) * 1985-09-12 1989-04-04 Mitsubishi Paper Mills, Ltd. Silver halide photographic emulsion
EP0562476A1 (en) 1992-03-19 1993-09-29 Fuji Photo Film Co., Ltd. A silver halide photographic emulsion and a photographic light-sensitive material
EP0563708A1 (en) 1992-03-19 1993-10-06 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion and light-sensitive material using the same
US5306598A (en) * 1990-02-28 1994-04-26 International Paper Company Silver halide photographic emulsions and elements for use in helium/neon laser and light-emitting diode exposure
US5332657A (en) * 1991-12-27 1994-07-26 Konica Corporation Silver halide color photographic light-sensitive material offering excellent color reproduction
WO1996013755A1 (en) 1994-10-26 1996-05-09 Eastman Kodak Company Photographic emulsions of enhanced sensitivity
US5582957A (en) * 1995-03-28 1996-12-10 Eastman Kodak Company Resuspension optimization for photographic nanosuspensions
US5597687A (en) * 1990-08-16 1997-01-28 Eastman Kodak Company Sensitizing dye combination for photographic materials
EP0777153A1 (en) 1995-11-30 1997-06-04 Fuji Photo Film Co., Ltd. Silver halide color photographic light-sensitive material
US20050281798A1 (en) * 2004-06-16 2005-12-22 Glen Gong Targeting sites of damaged lung tissue using composition
EP1624337A2 (en) 2004-08-02 2006-02-08 Fuji Photo Film Co., Ltd. Silver halide holographic sensitive material and system for taking holographic images by using the same
EP1691237A2 (en) 2005-02-15 2006-08-16 Fuji Photo Film Co., Ltd. Holographic recording material and holographic recording method
EP1914594A2 (en) 2004-01-30 2008-04-23 FUJIFILM Corporation Silver halide color photographic light-sensitive material and color image-forming method

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2075048A (en) * 1932-11-04 1937-03-30 Eastman Kodak Co Photographic emulsion containing supersensitized carbocyanines
US2206076A (en) * 1939-04-22 1940-07-02 Eastman Kodak Co Photographic emulsion
US2422080A (en) * 1943-12-08 1947-06-10 Ilford Ltd Photographic emulsions containing supersensitizing dye combinations
US3338714A (en) * 1963-08-26 1967-08-29 Ilford Ltd Photographic supersensitized silver halide emulsions

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2075048A (en) * 1932-11-04 1937-03-30 Eastman Kodak Co Photographic emulsion containing supersensitized carbocyanines
US2206076A (en) * 1939-04-22 1940-07-02 Eastman Kodak Co Photographic emulsion
US2422080A (en) * 1943-12-08 1947-06-10 Ilford Ltd Photographic emulsions containing supersensitizing dye combinations
US3338714A (en) * 1963-08-26 1967-08-29 Ilford Ltd Photographic supersensitized silver halide emulsions

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3808009A (en) * 1971-08-14 1974-04-30 Konishiroku Photo Ind Light-sensitive super-sensitized silver halide photographic emulsions
EP0143424A2 (en) 1983-11-25 1985-06-05 Fuji Photo Film Co., Ltd. Heat-developable light-sensitive materials
EP0147854A2 (en) 1983-12-29 1985-07-10 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive materials
US4710631A (en) * 1984-08-28 1987-12-01 Fuji Photo Film Co., Ltd. Temperature compensation for a semiconductor light source used for exposure of light sensitive material
EP0209118A2 (en) 1985-07-17 1987-01-21 Konica Corporation Silver halide photographic material
US4818676A (en) * 1985-09-12 1989-04-04 Mitsubishi Paper Mills, Ltd. Silver halide photographic emulsion
EP0256537A2 (en) 1986-08-15 1988-02-24 Fuji Photo Film Co., Ltd. Color print and a method for producing the same
US5306598A (en) * 1990-02-28 1994-04-26 International Paper Company Silver halide photographic emulsions and elements for use in helium/neon laser and light-emitting diode exposure
US5597687A (en) * 1990-08-16 1997-01-28 Eastman Kodak Company Sensitizing dye combination for photographic materials
US5332657A (en) * 1991-12-27 1994-07-26 Konica Corporation Silver halide color photographic light-sensitive material offering excellent color reproduction
EP0563708A1 (en) 1992-03-19 1993-10-06 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion and light-sensitive material using the same
EP0562476A1 (en) 1992-03-19 1993-09-29 Fuji Photo Film Co., Ltd. A silver halide photographic emulsion and a photographic light-sensitive material
WO1996013755A1 (en) 1994-10-26 1996-05-09 Eastman Kodak Company Photographic emulsions of enhanced sensitivity
US5582957A (en) * 1995-03-28 1996-12-10 Eastman Kodak Company Resuspension optimization for photographic nanosuspensions
EP0777153A1 (en) 1995-11-30 1997-06-04 Fuji Photo Film Co., Ltd. Silver halide color photographic light-sensitive material
EP1914594A2 (en) 2004-01-30 2008-04-23 FUJIFILM Corporation Silver halide color photographic light-sensitive material and color image-forming method
US20050281798A1 (en) * 2004-06-16 2005-12-22 Glen Gong Targeting sites of damaged lung tissue using composition
EP1624337A2 (en) 2004-08-02 2006-02-08 Fuji Photo Film Co., Ltd. Silver halide holographic sensitive material and system for taking holographic images by using the same
EP1691237A2 (en) 2005-02-15 2006-08-16 Fuji Photo Film Co., Ltd. Holographic recording material and holographic recording method

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BE688777A (enrdf_load_html_response) 1967-03-31
GB1128418A (en) 1968-09-25

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