US3764340A - Spectrally sensitized silver halide photographic emulsion - Google Patents

Spectrally sensitized silver halide photographic emulsion Download PDF

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Publication number
US3764340A
US3764340A US00183592A US3764340DA US3764340A US 3764340 A US3764340 A US 3764340A US 00183592 A US00183592 A US 00183592A US 3764340D A US3764340D A US 3764340DA US 3764340 A US3764340 A US 3764340A
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United States
Prior art keywords
dye
silver halide
photographic emulsion
halide photographic
sensitizing dyes
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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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US00183592A
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English (en)
Inventor
A Sato
T Ikeda
K Shiba
H Takei
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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Publication date
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    • 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
    • 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

Definitions

  • This invention relates to a spectrally sensitized silver halide photographic emulsion, and more particularly to a silver halide photographic emulsion which is supersensitized by the combined use of at least two sensitizing dyes resulting in a high red sensitivity.
  • An object of this invention is to provide a silver halide photographic emulsion having a high red sensitivity within the spectrally sensitized wavelength region of 620-685 11m. and a small inherent desensitization by the combined use of two different types of sensitizing dyes.
  • it aims at the improved red sensitivity of blackwhite sensitive material having a sensitive maximum in the vicinity of 630 nm. and the improved spectral sensitivity of black-White sensitive material having a sensitive maximum in a longer wavelength region, i.e. in the region of 640680 nm.
  • R represents a lower alkyl group, e.g., methyl, ethyl, propyl, etc., alkenyl, e.g., vinyl, methyl, etc.
  • R represents a sulfoalkyl group, e.g., 'y-sulfopropyl, -sulfobutyl, fi-sulfobutyl, etc.
  • A represents a lower alkyl group, e.g., methyl, ethyl, etc., or an aryl group, e.g., phenyl, p-methoxyphenyl
  • Z represents nonmetallic atoms re- 3,764,340 Patented Oct.
  • P and Q represent hydrogen atoms or lower alkyl groups or an atomic group capable of being connected to each other to form a heterocyclic ring
  • R and R each represents a lower alkyl group, e.g., methyl, ethyl, propyl, 'y-sulfopropyl, 'y-sulfobutyl, fi-sulfobutyl, fi-carboxybutyl, etc.;
  • A represents a lower alkyl group, e.g., methyl, ethyl, etc., or an aryl group, e.g., phenyl;
  • Z and 2 each represents nonmetallic atoms required to complete a benzothiazole, benzoselenazole or ,B-naphth'othiazole nucleus, which may be substituted by a halogen atom, e.g., chlorine, bromine atom, etc., a lower alkyl group, e.g
  • the cyanine dyes of the general Formula I have a sensitized maximum peak in the range of 620-650 nm. and, compared with the sensitizing dyes of the general Formula II, a very small red sensitivity. Many cyanine dyes of the general Formula II have a sharp J-band and a high red sensitivity. It has been found that the combined use of said sensitizing dyes (I) and (II) having such features improves the red sensitivity of said sensitizing dye of (II), resulting in a silver halide photographic emulsion having a very small inherent densensitization.
  • the combination of said sensitizng dye of (I) and mesomethylthiacarbocyanine among said sensitizng dye (II) is suitable to a black-white sensitive material having a sensitized maximum peak in the vicinity of 630 nm. and shows such eifect that has not been found in the previous art, said effect extending gradually the spectral sensitization region to the longer wavelength without a large shift of sensitive maximum peak.
  • the combination use of a sensitizing dye of the general Formula I and a symmetrical fi-naphthothiacarbocyanine of the general Formula II has a peculiar effect: that is, the sensitized maximum peak may be selected voluntarily in the region of 620- 680 nm.
  • the spectral sensitivity can be highly increased to maintain the red sensitivty at a high level. Said effect is not affected by using at the same time another sensitizer for improving the green sensitivity (for example, 2,2'-cyanine, thia-2-cyanine, etc.) or sensitizers having other spectral sensitization region.
  • another sensitizer for improving the green sensitivity for example, 2,2'-cyanine, thia-2-cyanine, etc.
  • sensitizers having other spectral sensitization region for example, 2,2'-cyanine, thia-2-cyanine, etc.
  • FIGS. 14 show the sensitivities of the dyes described herein when compared with various control samples. A fuller understanding of the drawings can be had by referring to Table 2 and the specific examples reported therein.
  • sensitizing dyes used in this invention are mentioned as follows, but said sensitizing dyes used in this invention are not restricted to these examples.
  • Dye L The sensitizing dyes of the general Formulas I and II, which are used in this invention, can be synthesized by a known method. For example, by reference to U.S. Pat. No. 2,503,776 and German Pat. Nos. 929,080 asd 1,072,- 765, those skilled in the art can synthesize them readily.
  • sensitizing dyes according to this invention can be similarly synthesized.
  • the spectral sensitization process according to this invention is effective for the spectral sensitization of gelatin silver halide photographic emulsion. It can also sensitize sufficiently an emulsion containing hydrophilic colloid other than gelatin, e.g., agar collodion, watersoluble cellulose derivatives, polyvinyl alcohol or other synthetic or natural hydrophilic resins.
  • a mixed silver halide emulsion such as silver iodobromide, chloroiodobromide, etc., are suitable.
  • sensitizing dye of (I) and (II) it is possible to add said sensitizing dye of (I) and (II) to a photographic emulsion in a common manner.
  • the dyes it is convenient to add the dyes as a solution in a suitable solvent such as methanol, ethanol, etc., to the emulsion.
  • the sensitizing dyes (I) and (II) to be contained in the emulsion are used in an amount of 10- to 10- mol/mol of silver halide respectively and the molar ratio of both dyes may be varied within a wide range of from 9:1 to 1:9 corresponding to the etfect desired.
  • the photographic emulsion according to this invention can be applied further with the hyperand other super-sensitization.
  • additives which are generally used, for example, chemical sensitizer, stabilizer, toner, hardener, surface active agent, antifoggant, plasticizer, development accelerator, color developer and fluorescent brightening agent can be contained in the emulsion in a common manner.
  • the photographic emulsion according to this invention can be coated on a suitable base, for example, glass, films of cellulose derivatives, films of synthetic resins, baryta paper or resin-coated paper in a common manner.
  • a suitable base for example, glass, films of cellulose derivatives, films of synthetic resins, baryta paper or resin-coated paper in a common manner.
  • Single sensitizing dye of (I) and (II) used in this invention each was added to a silver iodobromide emulsion (AgI:AgBr7:93 in mol percent) to prepare silver halide photographic emulsions.
  • silver halide photographic emulsions containing the combination of said sensitizing dyes of (I) and (II) used in this invention were prepared. These emulsions were coated respectively on a cellulose triacetate film base, dried, then exposed through a yellow filter (a filter transmitting rays of longer wavelength than 580 nm.) and a blue filter (a filter transmitting rays of 400-490 nm. and having a maximum transmission at 450 nm.) to a daylight of 64 luxes (corresponding to 5,400 K.) and developed.
  • the liquid developer one having the composition shown in Table 1 was used. 1
  • the yellow and red sensitivity are each shown as the relative sensitivity to the sensitivity 100 of said sensitiziug dye H which is exposed in an amount of 4X16- mol/kg. emulsion through the yellow and red filter as mentioned above and the inherent sensitivity is shown as the relative sensitivity to the sensitivity 100 of original emulsion which is exposed through the blue filter.
  • the green sensitizing dyes which may be used in combination with said sensitizing dye of (I) and (II) used in this invention are those having the follownig chemical structures, but they are not restricted only to these sensitizing dyes.
  • R represents a lower alkyl or alkenyl group
  • R represents a sulfoalkyl group
  • A represents a lower alkyl, or aryl group
  • Z represents a n'on'rnetallic atom required to complete a benzothiazole, benzoselenazole or B-naphthothiazole nucleus
  • Z represents a sulfur or selenium atom
  • B represents a phenyl
  • P and Q each represents a hydrogen atom or a lower alkyl group or an atomic group capable of being connected to form a morpholine ring
  • X represents an anion
  • n is 0 or 1, n being 0 for the intermolecular salt
  • A represents a lower alkyl or aryl group
  • Z and Z each represents a nonmetallic atom required to complete a' benzothiazole, benzoselenazole or B-naphthothiazle nucleus
  • X represents an anion
  • m is 0 or 1
  • m being 0 for the intermolecular salt.
  • the sensitizing dye of the general Formula II is a member selected from the group consisting of:
  • Anionic mi 6 (JHDaSOr 132KB 30 6.
  • a photographic light-sensitive material compi'ising a layer containing the photographic emulsion as claimed in claim 1.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Organic Chemistry (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)
US00183592A 1970-09-24 1971-09-24 Spectrally sensitized silver halide photographic emulsion Expired - Lifetime US3764340A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP45083656A JPS4842499B1 (fr) 1970-09-24 1970-09-24

Publications (1)

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US3764340A true US3764340A (en) 1973-10-09

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Country Status (5)

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US (1) US3764340A (fr)
JP (1) JPS4842499B1 (fr)
DE (1) DE2147888C3 (fr)
FR (1) FR2108527A5 (fr)
GB (1) GB1364918A (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4179296A (en) * 1975-12-29 1979-12-18 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
US5316904A (en) * 1992-11-19 1994-05-31 Eastman Kodak Company Amide substituted dye compounds and silver halide photographic elements containing such dyes
US5354651A (en) * 1992-11-19 1994-10-11 Eastman Kodak Company Hydroxyarylacyl dye compounds and silver halide photographic elements containing such dyes
US5492802A (en) * 1992-11-19 1996-02-20 Eastman Kodak Company Dye compounds and photographic elements containing such dyes

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4179296A (en) * 1975-12-29 1979-12-18 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
US5316904A (en) * 1992-11-19 1994-05-31 Eastman Kodak Company Amide substituted dye compounds and silver halide photographic elements containing such dyes
US5354651A (en) * 1992-11-19 1994-10-11 Eastman Kodak Company Hydroxyarylacyl dye compounds and silver halide photographic elements containing such dyes
US5492802A (en) * 1992-11-19 1996-02-20 Eastman Kodak Company Dye compounds and photographic elements containing such dyes

Also Published As

Publication number Publication date
DE2147888C3 (de) 1974-10-31
DE2147888B2 (de) 1974-04-04
GB1364918A (en) 1974-08-29
FR2108527A5 (fr) 1972-05-19
DE2147888A1 (de) 1972-04-13
JPS4842499B1 (fr) 1973-12-13

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