US3808008A - Spectrally sensitized silver halide photographic emulsion - Google Patents

Spectrally sensitized silver halide photographic emulsion Download PDF

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Publication number
US3808008A
US3808008A US00179391A US17939171A US3808008A US 3808008 A US3808008 A US 3808008A US 00179391 A US00179391 A US 00179391A US 17939171 A US17939171 A US 17939171A US 3808008 A US3808008 A US 3808008A
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United States
Prior art keywords
dye
silver halide
mol
forming
alkyl group
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Expired - Lifetime
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US00179391A
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English (en)
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K Shiba
A Sato
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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
    • 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

Definitions

  • ABSTRACT A photographic silver halide emulsion which comprises silver halide and the combination of at least one sensitizing dye represented by the general formula (1) which may be the same or different, each represents a sulfur atom or a selenium atom; 2 represents an atomic group required for forming a naphthol ring; Z represents an atomic group required for forming a naphthol ring or a benzene ring; R, and R each represent a lower alkyl group, at least one member selected from the group consisting of R and R being an alkyl group substituted with a sulfo radical; X is an acid anion; and p is 1 or 2, p being 1 when said dye has a betaine structure; and at least one sensitizing dye represented by the general formula 11) 5 Claims, 3 Drawing Figures [451 Apr. 30, 1974 PAI EmPR30-
  • This invention relates to spectrally sensitized silver halide photographic emulsions, and more particularly to superpanchromatically sensitized silver halide photographic emulsions obtained by employing a combination of at least two selected sensitizing dyes.
  • An object of the present invention is to provide a photographic light-sensitive element having a high sensitivity extending uniformly over the wavelength range of 400 mp. to 700 mp.
  • at least two sensitizing dyes in combination are employed and in this case, it is usual that the maximum sensitivity obtained by employing a combination of at least two sensitizing dyes is lower than that obtained by employing each dye alone.
  • a high spectral sensitivity can be superadditively obtained by the use of more than two sensitizing dyesin specific combination, and this phenomenon is known assupersensitization.
  • the object of the present invention will be accomplished by finding a combination of a group consisting of sensitizing dyes particularly giving a supersensitizing effect and imparting a high sensitivity over a wavelength range of from 680 my. to 550 mu.
  • a dye having a spectral absorption and which sensitizes an emulsion over a long wavelength region has many disadvantages as compared to another dye having its spectral absorption and sensitization in a short wavelength region.
  • these disadvantages are such that the desensitization with respect to intrinsic absorption of light of a silver halide emulsion is more remarkable, the efficiency of sensitization is liable to be reduced, and fog is also likely to occur.
  • the maximum absorption wavelength of an isolated molecule of the dye itself relates to a short wavelength, it is considered that such a dye having an absorption peak in the longer wavelength region, when it is adsorbed on the above-described silver halide grains, particularly a dye which forms a J-band when adsorbed on the silver halide grains in the emulsion, is advantageous for the object of the present invention.
  • the dye which has the sensitivity peak in the longest wavelength region in a group of dyes to be combined must be most likely to form a J-band, and in this case, the J-band must not be destroyed by the other combined dyes or other additives.
  • a suitable forming function of the J-band is required, that is, in the case where the forming function is too remarkable, there is a tendency such that a supersensitizing function is hard to achieve and a uniformly high spectral sensitivity distribution is also hard to obtain.
  • A represents a lower alkyl group, such as methyl, ethyl or n-propyl; Y and Y which may be the same or different, each represents a sulfur atom or a selenium atom; Z represents an atomic group required for forming a naphthol ring; Z represents an atomic group required for forming a naphthol ring or a benzene ring, each of which may be substituted by, for example, a lower alkyl group such as methyl and/or ethyl, a halogen atom such as chlorine or bromine, a hydroxy group, an alkoxy group, an alkoxycarbonyl group, a carbonyl group or a carboxyl group; R and R represent lower alkyl groups (such as methyl, ethyl, npropyl, allyl, or substituted alkyls having a sulfo radical such as sulfoethyl, sulfopropyl,
  • A represents a hydrogen atom or a lower alkyl group
  • Z represents an atomic group required for forming a benzoselenazole ring nucleus
  • 2. represents an atomic group required for forming a benzothiazole ring nucleus or a benzoselenazole ring nucleus, either of which may be substituted or unsubstituted, respectively (for example, the heterocyclic ring may be substituted by a lower alkyl group such as methyl or ethyl, a halogen atom such as chlorine or bromine, phenyl alkoxycarbonyl, carboxyl, hydroxyl, or alkoxy);
  • R and R represent lower alkyl groups (such as methyl, ethyl, and n-propyl, B-hydroxyethyl, fi -carboxyethyl, a-carboxypropyl, S-carboxybutyl, B-sulfoethyl, a-sulf
  • FIGS. 1, 2 and 3 are spectograms of combinations of dyes shown in Example 1.
  • the combination which is preferred according to the present invention comprises at least one sensitizing dye of the general formula (III) and at least one sensitizing dye of the general formula (IV):
  • the sensitizing dye represented by the above general formula (I) has the following three characteristic features. That is, the first characteristic feature resides in the fact that at least one member of the two cyanine heterocyclic nuclei is a B-naphthothiazole nucleus or a B-naphthoselenazole nucleus.
  • the second characteristic feature resides in the fact that the sensitizing dye easily forms a J-band and particularly, the maximum sensitivity thereof is between a wavelength ranging from 650 mu to 700 mu, and in the case where this second feature is satisfied, the heterocyclic ring nuclei may be substituted or unsubstituted, respectively.
  • the third characteristic feature resides in the fact that at least one of R and R has a sulfo radical, the betaine structure probably being fonned with this sulfo radical, and it is, therefore, considered that the J-band is liable to be formed.
  • the characteristic feature of the sensitizing dye represented by the general formula (II) resides in the fact that at least one of the heterocyclic ring nuclei formed by Z, and 2,, respectively, is a benzoselenazole nucleus.
  • the supersensitizing function obtained by the combination use with the dyes represented by the general formula (I) is not only more remarkable, but also a more uniform spectral distribution of the sensitivity is obtained.
  • the invention according to Japanese Patent Publication No. 4933/68 was remarkably improved.
  • monomethine dyes such as 2,2- quinocyanine dyes and pseudocyanine dyes, preferably of the general formula (VI), may be added to the photographic emulsion of the present invention.
  • Z represents an atomic group required for fonning a benzene-series ring
  • Z represents an atomic group required for forming a quinoline-series ring, a benzthiazole-series ring or a benzselenazole-series ring
  • R R X and r have the same meaning as R;,, R X and q of the general formula (II), respectively.
  • Dye A or B as shown hereinbelow may be employed in combination with the sensitizing dyes of the present invention.
  • sensitizing dyes represented by the general formulae (l) and (II) can be synthesized by well-known processes, for example, by referring to the specifications of U.S. Pat. No. 2,503,776, British Pat. No. 742,] 12, West German Pat. No. 1,072,765, West German Pat. No. 1,163,671 and US. Pat. No. 3,177,210, respectively, the dyes can be easily synthesized by those skilled in the art.
  • the sensitizing dye employed for the present invention is dissolved in an aqueous solution or water soluble organic solvent, for example, methanol, ethanol, acetone, methyl cellosolve, or pyridine and is mixedly or separately added to a silver halide emulsion.
  • an aqueous solution or water soluble organic solvent for example, methanol, ethanol, acetone, methyl cellosolve, or pyridine
  • the sensitizing dye may be dissolved or dispersed in an oil having a solubility of less than 10 percent with respect to water, the resulting dispersion or solution being added to the emulsion.
  • ultrasonic vibration may be adopted for the dissolution of the sensitizing dye.
  • the amount added, and order for adding the sensitizing dye, or the timing of preparing the emulsion to be added, and the method for the addition thereof can be suitably changed in accordance with its purpose. In general, it ispreferable that the amount, to be employed, of the sensitizing dye of the general formula (l) or (11) is within a range for from 1 X 10? mol to X mol per 1 mol of silver halide.
  • EXAMPLE 1 One kg of a silver chlorobromide emulsion (Br content; l7 mol percent) which was prepared in accordance with an ordinary process and chemically sensitized was warmed to melt it.
  • the sensitizing dye represented by the general formula (1) or (11) was added to the emulsion in an amount (added in the form of a dyemethanol solution) in the concentration shown in the Table l, and was sufficiently agitated.
  • Each of the resulting mixtures was maintained for 10 minutes after adding each solution thereto at a temperature of C, an anionic wetting agent and a hardening 'agent were added thereto, and the thus-obtained mixture was applied onto a film and dried, to thereby obtain samples of a light-sensitive element.
  • Each of the resulting light-sensitive elements was cut into two pieces, one of which was subjected to wedge exposure through aNoiit-Tiyiiowrfnr (manufactured by Fuji Photo Film Co., Ltd.) by employing a sensitometer having a light source of 5400K obtained by applying a DG (Davis-Gibson) converting filter to a 5 light source of a color temperature of 2666K.
  • DG Downlink-Gibson
  • H w M H H m Wm is within a range of from 1:10 to 10:4, in molar ratio.
  • the amount to be added of the monomethme dye is Anhydrous Sodium sulme 40 g within the range of from 10 mol to 10 mol per 1 mol q i ne 4 g of the dye of the general formula (1).
  • EXAMPLE 2 developed by employing the following color developing Instead of the emulsion employed in Example I, 1 Kg of a silver iodobromide emulsion (1" content; 4 mol percent) was employed and the coloring matters were similarly added thereto, respectively.
  • Example 1 the resulting light--ens ti e QEEQHEMELQEHFJSEWEL (Q1111QSPPEQGFPSI as ptfgfl mii itqsata tqmgsetsts f 2291-.
  • a superpanchromatically sensitized photographic silver halide emulsion which comprises silver halide and the combination of at least one sensitizing dye pr fint stmt a snie istm le,
  • A represents a lower alkyl group: Y and Y which may be same or different, each represents a sulfur atom or a selenium atom;
  • Z represents an atomic group required for forming a naphthol ring;
  • Z represents an atomic group required for forming a naphthol ring or a benzene ring;
  • R and R each represent a lower alkyl group, at least one member selected from the group consisting of R and R being an alkyl group substituted with a sulfo radical;
  • X is an acid anion; and
  • p is l or 2, p being 1 when said dye has a betaine structure, at least one sensitizing dye represented b1 the eneral tqrgal (1L a benzoselenazole nucleus;
  • R and R each represent a wherein Z represents an atomic group required for forming a ring of the benzene series;
  • Z represents an atomic group required for forming a
  • 3-,IhQCmlllSiQlLQfJllfliHLlWhQIEllllhfijlIlQl-lllllflbfi added of the monomethine dye is within the range of from 1 X 10' mol to l X 10" mol per 1 mol of silver halide.
  • a photographic light-sensitive material which comprises a support having thereon the emulsion layer Qt im 1.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US00179391A 1970-09-10 1971-09-10 Spectrally sensitized silver halide photographic emulsion Expired - Lifetime US3808008A (en)

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Application Number Priority Date Filing Date Title
JP45079515A JPS4842496B1 (me) 1970-09-10 1970-09-10

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JP (1) JPS4842496B1 (me)
CA (1) CA977598A (me)
DE (1) DE2145407A1 (me)
FR (1) FR2107458A5 (me)
GB (1) GB1366118A (me)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3955979A (en) * 1970-10-16 1976-05-11 Fuji Photo Film Co., Ltd. Flash exposure of supersensitized silver halide photographic light-sensitive material
US4042400A (en) * 1975-01-14 1977-08-16 Konishiroku Photo Industry Co., Ltd. Light-sensitive silver halide photographic material
US5219723A (en) * 1991-10-10 1993-06-15 Eastman Kodak Company Green sensitizing dyes for variable contrast photographic elements

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS51129497U (me) * 1975-04-07 1976-10-19

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3459553A (en) * 1965-10-11 1969-08-05 Polaroid Corp Photosensitive elements
US3573920A (en) * 1967-11-30 1971-04-06 Eastman Kodak Co Fine grain silver halide emulsions containing novel dye combinations
US3667960A (en) * 1969-03-27 1972-06-06 Fuji Photo Film Co Ltd Spectrally supersensitized silver halide photographic emulsion
US3679428A (en) * 1969-07-23 1972-07-25 Fuji Photo Film Co Ltd Spectrally sensitized photographic emulsions
US3681080A (en) * 1969-07-23 1972-08-01 Fuji Photo Film Co Ltd Silver halide photographic emulsion

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3459553A (en) * 1965-10-11 1969-08-05 Polaroid Corp Photosensitive elements
US3573920A (en) * 1967-11-30 1971-04-06 Eastman Kodak Co Fine grain silver halide emulsions containing novel dye combinations
US3667960A (en) * 1969-03-27 1972-06-06 Fuji Photo Film Co Ltd Spectrally supersensitized silver halide photographic emulsion
US3679428A (en) * 1969-07-23 1972-07-25 Fuji Photo Film Co Ltd Spectrally sensitized photographic emulsions
US3681080A (en) * 1969-07-23 1972-08-01 Fuji Photo Film Co Ltd Silver halide photographic emulsion

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3955979A (en) * 1970-10-16 1976-05-11 Fuji Photo Film Co., Ltd. Flash exposure of supersensitized silver halide photographic light-sensitive material
US4042400A (en) * 1975-01-14 1977-08-16 Konishiroku Photo Industry Co., Ltd. Light-sensitive silver halide photographic material
US5219723A (en) * 1991-10-10 1993-06-15 Eastman Kodak Company Green sensitizing dyes for variable contrast photographic elements

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FR2107458A5 (me) 1972-05-05
CA977598A (en) 1975-11-11
GB1366118A (en) 1974-09-11
JPS4842496B1 (me) 1973-12-13
DE2145407A1 (de) 1972-03-16

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