US3873323A - Spectrally sensitized silver halide photographic emulsions - Google Patents

Spectrally sensitized silver halide photographic emulsions Download PDF

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Publication number
US3873323A
US3873323A US365677A US36567773A US3873323A US 3873323 A US3873323 A US 3873323A US 365677 A US365677 A US 365677A US 36567773 A US36567773 A US 36567773A US 3873323 A US3873323 A US 3873323A
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United States
Prior art keywords
silver halide
halide photographic
photographic emulsion
silver
dye
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Expired - Lifetime
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US365677A
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English (en)
Inventor
Yasuharu Nakamura
Yoshiyuki Nakazawa
Tohru Sueyoshi
Akira Sato
Tadashi Ideda
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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
    • G03C1/22—Methine and polymethine dyes with an even number of CH groups

Definitions

  • This invention relates to a silver halide photographic emulsion containing novel sensitizing dyes, and particularly to a silver halide photographic emulsion having a high spectral sensitivity in the vicinity of 460 490 mu.
  • the spectrally sensitized wave length region and the spectral sensitivity of silver halide photographic emulsions containing sensitizing dyes are influenced by the chemical structure of the sensitizing dyes and, especially, by the kinds of hetero rings and the substituents on the sensitizing dyes.
  • Sensitizing dyes ofen display spectral sensitizations' which are not expected at all due to a slight difference in chemical structure, and the sensitization due to the J-aggregate (J-band) of sensitizing dyes depends on the chemical structures of the sensitizing dyes.
  • the sensitization due to the J-aggregate of a sensitizing dye is effective for the spectral sensitization in the region of a specified wave length, and it is very important to develop sensitizing dyes which form the J aggregate in order to highly sensitize a specified wave length region desired in the silver halide photographic sensitive material.
  • the energy distribution of a light source used in the facsimile field has a peak in the vicinity of 480 my. Therefore, it is desirable that a photographic emulsion used in the facsimile art has a maximum sensitization in the vicinity of its peak, e.g., about 460 490 mu.
  • the object of this invention is to provide a silver halide photographic emulsion having high spectral sensitivity in the vicinity of 460 490 m J., and it has been accomplished by adding to a silver halide photographic emulsion novel sensitizing dyes of the following general wherein R and R each represents identical or different alkyl groups as are conventionally used in cyanine dyes, i.e., both substituted and unsubstituted alkyl groups such as methyl, ethyl, n-propyl, n-butyl, carboxyalkyl (for example, carboxymethyl, B-carboxyethyl, 'y-carboxypropyl, 8-carboxybutyl,etc.), alkoxyalkyl groups (for example, B-methoxyethyl), hydroxyalkyl groups (for example, B-hydroxyethyl etc.), acyloxyul kyl groups (for example, y-acetoxypropyl), sultoal
  • aralkyl groups for example, benzyl, phenethyl, p-carboxyphenethyl). vinylmethyl; and R and R may be identical or different and each represents an acyl group, i.e., aromatic acyl group (e.g., benzoyl, etc.) or an aliphatic acyl group, preferably having up to 3 carbon atoms (e.g., acetyl, propionyl, etc.) or an alkoxycarbonyl group (for example, methoxycarbonyl, ethoxycarbonyl, etc.).
  • aromatic acyl group e.g., benzoyl, etc.
  • an aliphatic acyl group preferably having up to 3 carbon atoms (e.g., acetyl, propionyl, etc.) or an alkoxycarbonyl group (for example, methoxycarbonyl, ethoxycarbonyl, etc.).
  • any alkyl moiety which is present contains up to 4 carbon atoms, except for the alkyl moiety of the alkoxy or alkoxy carbonyl group, which preferably contain up to 3 carbon atoms.
  • sensitizing dyes used in this invention reside in the fact that they have a 5,6-dichlorobenzimidazole nucleus as a hetero ring and an acyl or alkoxycarbonyl group as the terminal group.
  • Those dyes having such a chemical structure readily form the J-aggregate and are effective to increase the spectral sensitivity in the vicinity of 460 490 mu.
  • FIG. 1 shows spectral sensitivity curves, in which (a) shows the spectral sensitivity curve of a silver halide photographic emulsion containing sensitizing dye (I) used in this invention and (b) shows the spectral sensitiviy curve of an otherwised identical emulsion where dye (I) is replaced with control sensitizing dye A.
  • the sensitizing dyes used in this invention can spectrally sensitize silver halide photographic emulsions and are especially effective to expand the sensitivity region ol gclatino-silver halide photographic emulsions.
  • gelatin derivatives such as acetylated gelatin, phthalated gelatin, etc.
  • hydrophilic colloids other than gelatin derivatives such as cellulose 5 derivatives (e.g., carboxymethyl cellulose, cellulose ether, partially hydrolyzed cellulose), polyvinyl alcohol, polyvinyl pyrrolidone, copolymers of maleic anhydride and phthalic acid and other synthetic or natural hydrophilic high molecular substances.
  • any photographic binder can be used with success in the present invention.
  • silver halide photographic emulsion used in this invention various kinds of silver salts such as silver bromide, silver iodobromide, silver chlorobromide, silver chloroidobromide, etc., can be used and especially silver bromide and silver iodobromide emulsions are used effectively. So long as the silver halide is photosensitive, it can be used with success in the present inen ion.
  • most preferred emulsions are those wherein the weight ratio of silver halide to binder is from about 4 about 1 to about 1 about 4.
  • the present invention is very effective when the silver halide used has particles which are normal or ultra linc grains (for example, those with an average particle diameter in number, measured by the projected area method, of less than about 0.1 u).
  • the effect of this invention is more remarkable for the ultra fine grains.
  • the sensitizing dye can be dissolved in a suitable solvent such as methanol, ethanol, methylcellosolve, etc., and added as solution to a silver halide photographic emulsion in the manner commonly used in this art.
  • suitable solvents are easily selected, the primary considerations entering into the selection of the solvent being that the solvent is easy to handle, inexpensive, does not harm photographic properties and is not injurious to the health.
  • Organic solvents miscible with water are generally used.
  • the amount of sensitizing dye contained in a silver halide photographic emulsion can be varied within, for example, a range of about 1 X 10 to about 1 X 10 mol/mol of silver. Especially excellent results are obtained when the amount of sensitizing dye is about 5.8 X 10 mols/mol of silver.
  • any known sensitizing dye may be added to the silver halide photographic emulsion according to this invention.
  • any commonly used chemical sensitizer, toner, film-hardener, antifogging agent, surface active agent, thickener, plasticizer, lubricant, development accelerator, color coupler, UV-absorbent, irradiation inhibitor, matting agent, etc. may be added at proportions as are common in this art using any general addition technique.
  • the silver halide photographic emulsion according to this invention may be coated by any technique commonly used in the art onto a suitable substrate such as, for example, glass, a film of cellulose derivatives (triacetyl cellulose, etc.), a film ofa synthetic resin (polyethylene terephthalate, etc.), baryta paper, a resin-coated paper, synthetic paper and the like.
  • a suitable substrate such as, for example, glass, a film of cellulose derivatives (triacetyl cellulose, etc.), a film ofa synthetic resin (polyethylene terephthalate, etc.), baryta paper, a resin-coated paper, synthetic paper and the like.
  • any photographic substrate can be used with success in the present invention.
  • a given amount (8 ml per 100 g of emulsion) of a methanolic solution (1/l,000 mol of dye per liter of methanolic solution) of one of the above mentioned sensitizing dyes used in this invention was individually added to 100 g of a gelatino silver iodobromide emulsion ((I: Br ratio 3:97 molar): ratio of silver halide:- binder 1:2 (weight); silver halide particle size of 0.08 mu), which was prepared in a known method. 7 ml of the resulting silver halide photographic emulsion was coated on a glass plate of cabinet size and dried to prepare a sample.
  • the sample was exposed through a No. 2 filter (Fuji Photo Co., through which light of a wave length longer than 450 mu passes) with an optical wedge by means of a tungsten lamp having a color temperature of 2,666K (2,000 lux, 20 seconds) and then developed at 20C for 5 min with a liquid developer of the following formulation:
  • FIG. 1 shows the spectral sensitivity curve of dye (I) of this invention and of control dye A based upon the data derived in this example.
  • the spectral sensitivity is shown under the heading Sensitization Degree" as a specific sensitivity where the sensitivity of sensitizing dye A used as a control is set as 100.
  • FIG. ll shows the spectral sensitivity curves of silver halide photographic emulsions which contain novel sensitizing dye (I) used in this invention and control sensitizing dye A, respectively.
  • sensitizing dye (I) used in this invention forms the J-aggregate and has a high spectral sensitivity at 460 490 m,u.
  • R and R each represents an alkyl or substituted alkyl radical selected from the group consisting of carboxyalkyl, alkoxyalkyl, hydroxyalkyl, acyloxyalkyl, sulfoalkyl and aralkyl, and R and R each represents an acyl or alkoxycarbonyl radical.

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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)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
US365677A 1972-05-31 1973-05-31 Spectrally sensitized silver halide photographic emulsions Expired - Lifetime US3873323A (en)

Applications Claiming Priority (1)

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JP47054497A JPS4911320A (US06566495-20030520-M00011.png) 1972-05-31 1972-05-31

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US3873323A true US3873323A (en) 1975-03-25

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US (1) US3873323A (US06566495-20030520-M00011.png)
JP (1) JPS4911320A (US06566495-20030520-M00011.png)
FR (1) FR2186673B1 (US06566495-20030520-M00011.png)
GB (1) GB1389381A (US06566495-20030520-M00011.png)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4309500A (en) * 1977-02-04 1982-01-05 Fuji Photo Film Co., Ltd. Silver halide color photographic light-sensitive material
US4845023A (en) * 1985-03-26 1989-07-04 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive material

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2112162A (en) * 1935-05-25 1938-03-22 Iiford Ltd Manufacture of substituted malonic esters
US2411507A (en) * 1943-12-20 1946-11-26 Ilford Ltd Photographic material
US3629274A (en) * 1966-07-22 1971-12-21 Eastman Kodak Co Merocyanine dyes and photographic materials prepared therewith

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2112162A (en) * 1935-05-25 1938-03-22 Iiford Ltd Manufacture of substituted malonic esters
US2411507A (en) * 1943-12-20 1946-11-26 Ilford Ltd Photographic material
US3629274A (en) * 1966-07-22 1971-12-21 Eastman Kodak Co Merocyanine dyes and photographic materials prepared therewith

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4309500A (en) * 1977-02-04 1982-01-05 Fuji Photo Film Co., Ltd. Silver halide color photographic light-sensitive material
US4845023A (en) * 1985-03-26 1989-07-04 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive material

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Publication number Publication date
GB1389381A (en) 1975-04-03
FR2186673B1 (US06566495-20030520-M00011.png) 1976-11-12
FR2186673A1 (US06566495-20030520-M00011.png) 1974-01-11
JPS4911320A (US06566495-20030520-M00011.png) 1974-01-31

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