US3669672A - Supersensitized silver halide photographic emulsion - Google Patents

Supersensitized silver halide photographic emulsion Download PDF

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Publication number
US3669672A
US3669672A US1837A US3669672DA US3669672A US 3669672 A US3669672 A US 3669672A US 1837 A US1837 A US 1837A US 3669672D A US3669672D A US 3669672DA US 3669672 A US3669672 A US 3669672A
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United States
Prior art keywords
group
silver halide
emulsion
halide photographic
photographic emulsion
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Expired - Lifetime
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US1837A
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English (en)
Inventor
Keisuke Shiba
Reiichi Ohi
Tadao Shishido
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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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
    • 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
    • C09B23/0066—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain being part of a carbocyclic ring,(e.g. benzene, naphtalene, cyclohexene, cyclobutenene-quadratic acid)
    • 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

Definitions

  • This invention relates to a spectrally sensitized silver halide photographic emulsion and more particularly to a silver halide photographic emulsion sensitized by at least one sensitizing dye and an organic compound in a super sensitizing combination.
  • a red-sensitive silver halide photographic emulsion is required in a light-sensitive material for color photography.
  • pentamethinecyanine dyes are used in order to obtain a silver halide photographic emulsion having no sensitivity in the green-sensitive region and a high red-sensitivity only.
  • pentamethinecyanine dyes tend to cause fogging more readily and have a lower spectral sensitivity than monomethinecyanine dyes and trimethinecyanine dyes.
  • pentamethinecyanine dyes have a sensitivity in the green-sensitive region also due to the H-aggregate.
  • the cyanine dye of the pentamethine type is represented by the following General Formula I:
  • GENERAL FORMULA I in which Z and Z each represents the atoms necessary to complete a heterocyclic nucleus such as a benzothiazole nucleus, a benzoselenazole nucleus, a naphthoxazole nucleus, a naphthothiazole nucleus and naphthoselenazole nucleus, and the like, L L L L and L are methine groups, R and R are substituted or non-substituted alkyl or aryl groups, R, and L or R and L may be bridged b an alkylene group, L and L may form a ring with carbon chain, X" is an anion and n is 0 or 1.
  • the organic heterocyclic compound is represented by the following General Formula II:
  • GENERAL FORMULA II in which Z represents the atoms necessary to complete aromatic rings, Y is an oxygen atom, a sulfur atom, a selenium atom or R and R are alkyl or aralkyl groups.
  • the heterocyclic nucleus completed by Z or Z can be substituted or unsubstituted. If substituted the substitution can be with an alkyl group, an aralkyl group, hydroxyl group, alkoxy group or halogen atom, R or R is an alkyl group such as a methyl, an ethyl, a propyl, or a butyl group, a substituted alkyl group such as a B-hydroxyethyl, a fl-acetoxyethyl, an ethylsulfate, a carboxymethyl, a 2-(2-carboxyethoxy)ethyl, a B-sulfoethyl, an asulfopropyl, a 3-methoxy-2-(3-sulfopropoxy)propyl, a benzyl group, or an aryl group.
  • R or R is an alkyl group such as a methyl, an ethyl, a prop
  • the feature of the chemical structure lies in that it is an aromatic heterocyclic compound having a thio-keto structure.
  • the aromatic nucleus completed by Z; is a benzene or naphthalene nucleus, e.g., the carbon atoms in Z can form a benzene or naphthalene ring.
  • This nucleus if substituted, can be substituted with an alkyl group, a halogen atom, a hydroxyl group, an alkoxyl group, a carboxyl group or a sulfonate group.
  • the organic heterocyclic compound represented by General Formula II acts specifically to supersensitize the dye represented by General Formula I raising the spectral sensitivity of the dye without increasing fog formation, or fogging. On the contrary, fog formation is often reduced. Another feature is that this organic heterocyclic compound can reduce the desensitization of the sensitizing dye.
  • the sensitizing dye and organic heterocyclic compound used in the invention can be added to a silver halide photographic emulsion separately or together, dissolved in a water-soluble organic solvent such as methanol, ethanol or butanol.
  • a water-soluble organic solvent such as methanol, ethanol or butanol.
  • the amounts or proportions of these components can be varied depending on the properties of the other additives and the emulsion used.
  • the added amount of the sensitizing dye represented by General Formula I to an emulsion generally ranges from -10 mole per 1 mole of silver halide in the emulsion.
  • the proportion of the sensitizing dye and organic heterocyclic compound added to an emulsion is suitably Within a range of from 1:0.1 to 1:4, on a molar basis.
  • Typical of the silver halide photographic emulsions used in the invention are silver chloride, silver chlorobromide, silver bromide and silver iodobromide emulsions.
  • emulsions can be prepared conventionally and coated onto a suitable support, such as a cellulose derivative film, a polyethylene terephthalate film, a baryta paper, other plastic films such as resin coated paper, synthetic paper or dry plate glass.
  • Examples of the pentamethine dye represented by General Formula I and the organic heterocyclic compound represented by General Formula II are given as follows. These examples are merely exemplary and not limiting.
  • the pentamethine type cyanine dyes are known compounds.
  • Methods of preparing the foregoing organic heterocyclic compounds, which can be used in the invention, are as follows.
  • Compound I I-A can be obtained by a known method as disclosed in Nippon Yakugaku Zasshi (Journal of Japan Pharmacy), 74, 1365-1369 (1954), i.e., by reacting 2-methylthiobenzimidazole, obtained by heating under reflux Z-mercaptobenzimidazole and methyl iodide in equimolar amounts in methanol for 6 hours and then neutralizing with caustic potash, with methyl iodide in equimolar amount at 110 C. for 48 hours in a sealed tube and then heating under reflux with pyridine for 1 hour.
  • Z-mercaptobenzimidazole (or a 4-substituted-2-mercaptobenzimidazole obtained by reaction of 4-substituted- 1,2-diaminobenzene with carbon disulfide) and benzyl bromide in equimolar amounts are heated under reflux in methanol for 6 hours and neutralized with alkali to obtain the 2-benzylthiobenzimidazole (or the corresponding 4-substituted-2-benzylthiobenzimidazole).
  • This material is heated under reflux with benzyl bromide in equimolar amounts in xylene for 6 hours. Then the xylene is distilled off under reduced pressure.
  • EXAMPLE 3 (COMPOUND II-C) 2-propylthiobenzimidazole obtained by heating under reflux 2-mercaptobenzimidazole and propyl iodide in equimolar amounts in ethanol for 6 hours in a manner similar to that described in Example 2 is heated and refluxed with propyl iodide in equimolar amounts in dioxane for 12 hours. After distilling off the dioxane, pyridine is added to the mixture and the mixture is heated and refluxed for 1 hour.
  • the pyridine is distilled off under reduced pressure and the resulting yellow oily material is subjected to separation on Florisil (a synthetic resin) by column chromatography to give a colorless and transparent liquid with n-hexane used as an elutent.
  • EXAMPLE 5 100 g. of a silver chlorobromide emulsion prepared conventionally was placed in a beaker and melted, to which a given amount of a solution of one sensitizing dye represented by General Formula I in methanol was then added. The resulting emulsion was allowed to stand at 40 C. for 15 minutes with agitation and coated onto a glass support for a dry plate in a proportion of 7 ml. of the emulsion per cabinet size, followed by drying.
  • the resulting photographic materials were subjected to optical wedge exposure through a Fuji Filter No. 12 (manufactured by Fuji Photo Film Co., Ltd.), a yellow filter permitting the transmission of light having longer Wavelengths than 500 mp, developed at 20 C. for 10 minutes with a black-and-white developer, fixed, washed with water and dried. Then, the density was measured to determine the spectral sensitivity.
  • the results obtained are shown in Table l.
  • the standard spectral sensitivity is 100 in the case in which 4 ml. of a solution of sensitizing dye I-B having a concentration of 5 X 10* mol./ 1., is added to 100 g. of the foregoing emulsion.
  • the photographic material was exposed as described in Example 1 and subjected to color forming development at C. for 10 minutes, a first fixing, bleaching and second fixing to obtain a cyan negative image. Its density was measured by the use of red light to obtain the spectral sensitivity and the results are shown in Table 2.
  • Z and Z each represent the atoms necessary to complete a substituted or unsubstituted heterocyclic nucleus selected from the group consisting of a benzothiazole nucleus, a benzoselenazole nucleus, a naphthoxazole nucleus, a naphthothiazole nucleus or a naphthoselenazole nucleus, wherein said substituent is selected from the group consisting of an alkyl group, an aralkyl group, a hydroxyl group, an alkoxyl group and a halogen atom; wherein L L L L and L each are methine groups; wherein R and R each represents a member selected from the group consisting of an alkyl group, a hydroxyalkyl group, an acetoxyalkyl group, an alkyl sulfate group, a carboxyalkyl group, a carboxyalkoxyalkyl group, a sulfoalkyl group, an alk
  • a photographic light-sensitive element comprising a support having thereon at least one layer of the silver halide photographic emulsion of claim 1.
  • a method of increasing the spectral sensitivity in the red-sensitive region without increasing fog formation of a photographic emulsion comprising incorporating into said emulsion the cyanine dye of claim 1 and the heterocyclic compound of claim 1.
  • R and R each represents a member selected from the group consisting of:
  • a substituted alkyl group selected from the group consisting of a beta-hydroxyethyl group, a betaacetoxyethyl group, an ethylsulfate group, a carboxymethyl, a 2-(2-carboxyethoxy)ethyl group, a betasulfoethyl group, an alpha-sulfopropyl group and a 3-methoxy-2-(3-sulfopropoxy)propyl group; and

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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)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
US1837A 1969-01-10 1970-01-09 Supersensitized silver halide photographic emulsion Expired - Lifetime US3669672A (en)

Applications Claiming Priority (1)

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JP194769 1969-01-10

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DE (1) DE2000897B2 (enrdf_load_stackoverflow)
FR (1) FR2028083A1 (enrdf_load_stackoverflow)
GB (1) GB1291554A (enrdf_load_stackoverflow)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3994733A (en) * 1973-12-10 1976-11-30 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
US4105451A (en) * 1976-12-22 1978-08-08 Eastman Kodak Company Photothermographic material, composition and process
US4207108A (en) * 1976-11-04 1980-06-10 Eastman Kodak Company Silver halide photothermographic element, composition and process
US4607006A (en) * 1983-10-06 1986-08-19 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive material containing non-spectral sensitizing electron donative silver halide adsorptive compound
EP0794456A1 (en) 1996-03-07 1997-09-10 Agfa-Gevaert N.V. Method of reproducing an electronically stored medical image on a light-sensitive photographic material
EP2929882A1 (en) * 2014-04-10 2015-10-14 Mifcare MIF inhibitors

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3994733A (en) * 1973-12-10 1976-11-30 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
US4207108A (en) * 1976-11-04 1980-06-10 Eastman Kodak Company Silver halide photothermographic element, composition and process
US4105451A (en) * 1976-12-22 1978-08-08 Eastman Kodak Company Photothermographic material, composition and process
US4607006A (en) * 1983-10-06 1986-08-19 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive material containing non-spectral sensitizing electron donative silver halide adsorptive compound
EP0794456A1 (en) 1996-03-07 1997-09-10 Agfa-Gevaert N.V. Method of reproducing an electronically stored medical image on a light-sensitive photographic material
EP2929882A1 (en) * 2014-04-10 2015-10-14 Mifcare MIF inhibitors
WO2015155358A1 (en) * 2014-04-10 2015-10-15 Mifcare Mif inhibitors
JP2017510657A (ja) * 2014-04-10 2017-04-13 ミフカレ Ｍｉｆ阻害剤
US10160732B2 (en) 2014-04-10 2018-12-25 Mifcare MIF inhibitors

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Publication number Publication date
DE2000897B2 (de) 1973-02-15
FR2028083A1 (enrdf_load_stackoverflow) 1970-10-09
DE2000897A1 (de) 1970-07-30
GB1291554A (en) 1972-10-04

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