US3793034A - Spectrally sensitized silver halide photographic emulsions - Google Patents

Spectrally sensitized silver halide photographic emulsions Download PDF

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Publication number
US3793034A
US3793034A US00227026A US3793034DA US3793034A US 3793034 A US3793034 A US 3793034A US 00227026 A US00227026 A US 00227026A US 3793034D A US3793034D A US 3793034DA US 3793034 A US3793034 A US 3793034A
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emulsion
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beta
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US00227026A
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English (en)
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A Sato
K Shiba
H Takei
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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
    • G03C1/10—Organic substances
    • G03C1/12—Methine and polymethine dyes
    • G03C1/14—Methine and polymethine dyes with an odd number of CH groups
    • G03C1/18—Methine and polymethine dyes with an odd number of CH groups with three CH groups
    • 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
    • C09B23/0008—Methine or polymethine dyes, e.g. cyanine dyes substituted on the polymethine chain
    • C09B23/005—Methine or polymethine dyes, e.g. cyanine dyes substituted on the polymethine chain the substituent being a COOH and/or a functional derivative thereof
    • C09B23/0058—Methine or polymethine dyes, e.g. cyanine dyes substituted on the polymethine chain the substituent being a COOH and/or a functional derivative thereof the substituent being CN

Definitions

  • Z and Z each represent a group of nonmetallic atoms necessary to complete a benzene ring, the hydrogen atoms of which may be substituted by substituents.
  • the present invention relates to silver halide photographic emulsions containing new sensitizing dyes, and particularly to silver halide photographic emulsions having a high spectral sensitivity at a range of 5 l0 533 mu.
  • the spectral sensitization often is affected by the chemical structure of the sensitizing dyes. Namely, since the formation of a J-aggregate of the sensitizing dyes is influenced by the chemical structure, for example, kinds of heterocyclic nuclei and kinds of substituents, a sensitization of near the spectral sensitization maximum caused by the J-aggregate of the sensitizing dyes adsorbed on the surface of silver halide particles is influenced extremely by the chemical structure of the sensitizing dyes used. Accordingly, selection of the sensitizing dye used is very important in the case of highly sensitizing the desired specified wave length range of the photographic sensitive material.
  • the present inventors have found that the following new sensitizing dyes form the J-aggregate and are useful for high spectral sensitization of a range of 510 533 mp.
  • An object of the present invention is to provide silver halide photographic emulsions having a high spectral sensitivity at about 510 533 my. which do not leave stain after development.
  • the object of the invention has been attained by adding novel sensitizing dyes represented by the following formula (1) to silver halide photographic emulsions.
  • alkylsulfonyl groups e.g., a methylsulfonyl group etc.
  • sulfamyl group alkylaminosulfonyl groups (e-g-;, methylaminosulfonyl group and ethylaminosulfonyl group), dialkylaininosulfonyl groups (e.g., dimethylaminosulfonyl group, diethylaminosulfonyl group, piperidinosulfonyl group, morpholinosulfonyl group and .pyrrolidinosulfonyl group etc.), cyano group, carboxyl group, alkoxycarbony] groups (e.g., methoxy-carbonyl group and ethox-* ycarbonyl group etc.) and acyl groups (e.g., acetyl group and benzo
  • a preferred substituent is the chlorine atom.
  • the substituents of Z include alkyl groups (e.g., methyl group etc.), halogen atoms (e.g., fluorine atom, chlorine'atom and bromine atom etc.) and alkoxy groups (e.g., methoxy group etc.).
  • R, and R which are identical or different each represent an alkyl group preferably having up to 8 carbon atoms [i.e., unsubstituted alkyl group and substituted alkyl 2 group; (e.g., methyl group, ethyl group, n-propyl group, n-butyl group and cyclohexyl group etc.
  • a hydroxyalkyl group e.g., B-hydroxyethyl group, 'y-hydroxypropyl group
  • an acetoxyalkyl group e.g., B-acetoxyethyl group; 'y-acetoxypropyl group
  • an alkyl group containing a carboxy radical e.g., carboxymethyl group, B-carboxyethyl, group, 'y-carboxypropyL group, 8-carboxybutyl group, p-carboxybenzyl group and p-carboxyphenethyl group
  • a cyanoalkyl group e.g., B-cyanoethyl group, 'y-cyanopropyl group, S-cyanobutyl group
  • a carbamoylalkyl group e.g., B-carbamoylethyl group, y-carbamoylpropyl group, o-carbamoyl
  • 'y-sulfamoyl propyl group 'd-sulfamoyl butyl group
  • an aminosulfonyl alkyl group e.g., 'y-N- ethylaminosulfonyl propyl group, 8-N- ethylaminosulfonyl butyl group
  • an alkyl group containing a sulfo radical e.g., B-sulfoethyl group, y-sulfopropyl group, 'y-sulfobutyl group, S-sulfobutyl group, p-sulfobenzyl group and p-sulfophenethyl group
  • an aralkyl group e.g., benzyl group, phenethyl group
  • an ally] group e.g., vinylmethyl group
  • a preferred substituent is the substituted alkyl group containing a sulfo or carboxy radical.
  • one of R and R has a sulfo radical or carboxyl radical as the substituent, for example, in the case of 'y-sulfopropyl group, it is supposed that an inner salt having the following formula (II) is formed.
  • the characteristic of the chemical structure of the sensitizing dyes used in the present invention is that Z, has a benzimidazole nucleus as defined in formula (1).
  • L, I m) wherein 2,, R, and R each represent the same meaning as in formula l X represents an anion (e.g., bromine ion and iodine ion etc.), and n represents 0 or 1 (n 0 when the inner salt)
  • Silver halide photographic emulsions can be spectrally sensitized by the sensitizing dyes used in the present invention. Especially, they are effective for increasing a'sensitive range of the gelatin-silver halide photographic emulsions. Further, photographic emulsions containing a hydrophilic colloid besides gelatin such as agar. agar, collodion, cellulosederivatives, polyvinyl alcohol and synthetic or natural hydrophilic resins can be sensitized by the above-mentioned dyes.
  • silver salts such as silver bromide, silver iodobromide, silver bromochloride and silver iodobromochloride can be used.
  • the sensitizing dyes may be added to the photographic emulsions by any common method.
  • the sensitizing dyes are added to the emulsions as a solution prepared by dissolving in a suitable solvent such as methanol, methyl cellosolve and pyridine etc.
  • the amount "of the sensitizing dyes added to the emulsions can vary in a range of 5-200 mg of dye per kg of the emulsions according to the desirable efiect. However, this amountis not limitative.
  • Known sensitizing dyes may be added additionally to the photographic emulsions of the .present invention.
  • sensitizing agents can be added to the emulsion by any common method.
  • photographic emulsions of the present invention can be applied to suitable supports, for example, glass films of cellulose derivatives, films of synthetic resins, baryta paper, resin coated paper and synthetic paper by any common method.
  • Silver halide photographic emulsions were prepared by adding sensitizing dyes above-mentioned to a gelatin silver iodobromide emulsion (molar ratio: Br I 93 v 7). The emulsions were applied to cellulose triacetate films. After drying, the films were exposed to light through a yellow filter made by Fuji Photo Film Co. (filter through which rays having a wave length of longer than 480 my. pass) using a day-light lamp of 64 5 luxes (corresponding to 5,400K) and developed. The developer having the composition represented in Table l was used. 7
  • spectral sensitivity is represented by a relative sensitivity which is obtained by supposing that the spectral sensitivity of the sensitizing dye (B) is 100 when exposed to light using a yellow filter.
  • the sensitizing dyes used for comparison are those having the following chemical structure. 4
  • the FIGURE shows curves of the spectral sensitivity of the silver halide emulsions containing sensitizing dye 7 which is the typical example of the sensitizing dyes used in the present invention (shown as the solid line) and sensitizing dye for comparison (A) (shown as the dotted line).
  • the sensitizing dyes used in the present invention form the J-aggregate, and the photographic emulsions containing said dyes have excellent photographic characteristics in that they have a high spectral sensitivity and an excellent sharp cut property in a long wave length side.
  • the FIGURE shows curves of the spectral sensitivity.
  • (7) and (A) represent curves of the spectral sensitivity of photographic emulsions containing the sensitizing dye (7) used in the present invention and the dye used for comparison (A), respectively.
  • a silver halide photographic emulsion which contains at least a sensitizing dye represented by the following formula:
  • Z, and Z each represent a group of nonmetallic atoms necessary to complete a benzene ring, and R, and R each represent an identical or different alkyl group.

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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)
  • 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)
US00227026A 1971-02-18 1972-02-17 Spectrally sensitized silver halide photographic emulsions Expired - Lifetime US3793034A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP752571A JPS5434328B1 (https=) 1971-02-18 1971-02-18

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US3793034A true US3793034A (en) 1974-02-19

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JP (1) JPS5434328B1 (https=)
DE (1) DE2207496A1 (https=)
GB (1) GB1376020A (https=)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4960890A (en) * 1985-09-21 1990-10-02 Basf Aktiengesellschaft Methine dyes which have at least one heterocycle containing two nitrogen atoms and preparation thereof
US5294709A (en) * 1989-02-28 1994-03-15 Fuji Photo Film Co., Ltd. Methine compounds and methine dyes
US20080224034A1 (en) * 2005-07-06 2008-09-18 Devlin Stuart Wollstein System and Method for Locating One or More Persons
US10487211B2 (en) * 2017-10-13 2019-11-26 Lanxess Deutschland Gmbh Methine dyes

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2918369A (en) * 1956-06-15 1959-12-22 Gen Aniline & Film Corp Non-ionic benzimidazole cyanine dyes containing in alpha-position a cyano group on the methenyl chain
US3244526A (en) * 1962-02-23 1966-04-05 Gen Aniline & Film Corp Benzimidazole cyanine dyes containing in alpha-position a carboethoxy group on the methine chain
US3656957A (en) * 1970-04-03 1972-04-18 Eastman Kodak Co Photographic silver halide emulsions containing k-substituted carbocyanine dyes

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2918369A (en) * 1956-06-15 1959-12-22 Gen Aniline & Film Corp Non-ionic benzimidazole cyanine dyes containing in alpha-position a cyano group on the methenyl chain
US3244526A (en) * 1962-02-23 1966-04-05 Gen Aniline & Film Corp Benzimidazole cyanine dyes containing in alpha-position a carboethoxy group on the methine chain
US3656957A (en) * 1970-04-03 1972-04-18 Eastman Kodak Co Photographic silver halide emulsions containing k-substituted carbocyanine dyes

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4960890A (en) * 1985-09-21 1990-10-02 Basf Aktiengesellschaft Methine dyes which have at least one heterocycle containing two nitrogen atoms and preparation thereof
US5294709A (en) * 1989-02-28 1994-03-15 Fuji Photo Film Co., Ltd. Methine compounds and methine dyes
US20080224034A1 (en) * 2005-07-06 2008-09-18 Devlin Stuart Wollstein System and Method for Locating One or More Persons
US10487211B2 (en) * 2017-10-13 2019-11-26 Lanxess Deutschland Gmbh Methine dyes

Also Published As

Publication number Publication date
DE2207496A1 (de) 1972-08-24
GB1376020A (en) 1974-12-04
JPS5434328B1 (https=) 1979-10-26

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