US3630748A - Spectrally sensitized light-sensitive silver halide material - Google Patents

Spectrally sensitized light-sensitive silver halide material Download PDF

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Publication number
US3630748A
US3630748A US24812A US3630748DA US3630748A US 3630748 A US3630748 A US 3630748A US 24812 A US24812 A US 24812A US 3630748D A US3630748D A US 3630748DA US 3630748 A US3630748 A US 3630748A
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United States
Prior art keywords
silver halide
stands
alkyl
sensitizing
spectrally sensitized
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US24812A
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English (en)
Inventor
Johannes Gotze
Karl Lehmer
Erich Bockly
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Agfa Gevaert AG
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Agfa Gevaert AG
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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
    • C09B23/10—The polymethine chain containing an even number of >CH- groups
    • C09B23/102—The polymethine chain containing an even number of >CH- groups two heterocyclic rings linked carbon-to-carbon

Definitions

  • R stands for alkyl
  • R stands for alkyl, cycloalkyl, aryl or aralkyl which groups are preferably substituted with acid groups.
  • the new compounds exhibit no Schwarzschild efi'ect and are useful sensitizers for color photographic silver halide emulsions.
  • the present invention relates to light-sensitive photographic layers, especially silver halide emulsion layers, which have been spectrally sensitized with new types of sensitizing dyes.
  • the absorption of the sensitizers on the silver halide should be so strong that the sensitizing effect will be impaired as little as possible by the other necessary additives such as wetting agents and emulsifiers, stabilizers, color couplers, dyes that can be bleached out, white toners, optical brightening agents, etc. It must also be possible to carry out sensitization under extreme conditions such as elevated temperature and high moisture content. Furthermore, the sensitizing dyes must not increase the fog as is the case with the known basic cyanine dyes. Further there are wanted certain sensitizing properties, for example, in addition to a sufficient sensitizing intensity a decrease of sensitizing towards longer wavelengths, which is as steep as possible. For these reasons, there is considerable interest in finding new sensitizing dyes, which have not these above disadvantages.
  • sensitizing dyes for spectrally sensitizing light-sensitive layers especially silver halide emulsion layers, that do not suffer the above-mentioned disadvantages.
  • Y stands for O, S, N-aryl or N-alkyl
  • R stands for alkyl having up to four carbon atoms, which alkyl may be substituted, for example, with hydroxy, halogen, carboxyl or sulfo;
  • R stands for a hydrocarbon group, for example aklyl having up to four carbon atoms, cycloalkyl such as cyclohexyl, aryl, such as phenyl, or aralkyl, such as benzyl, which hydrocarbon groups may be further substituted, for example with carboxyl or sulfo.
  • This bromination product (191 g.) is reacted with ammonium dithiocarbomate (138 g.) in 1,000 mi. of ethanol.
  • the reaction is slightly exotherm and is completed by heating on a steam-bath for several hours whereas sulfur and ammoniumbromide are separated. After filtration the mixture is concentrated by evaporation until all ammoniumbromide has crystallized out.
  • the solution is again filtered and the filtrate is poured into aqueous 2n solution of sodium hydroxide (500 ml.), again filtered and then mixed with dimethylsulfate g.).
  • the reaction product is extracted with ether.
  • the residue remaining after the evaporation of the ether can be used immediately for the preparation of dyes.
  • the distillation in vacuum which however is accompanied with considerable decomposition is possible (boiling point 0.15 mm./l40-160 C.).
  • sensitizing dyes according to the invention can be performed in principle following the usual methods which are known to an expert having ordinary skill in the chemistry of cyanine dyes.
  • preparation of dye l is described in detail below.
  • the other dyes can be prepared in an analogous manner. In the preparation of dye Vl, however, the use of the pure base which has been distillized is preferred.
  • the new dyes according to the invention are excellent sensitizing dyes which sensitize silver halide emulsions in the blue and blue-green range of the spectrum with a steep decrease of sensitization towards longer wavelengths of the spectrum.
  • the maximum of sensitization which is brought about from the dyes according to the present invention which are derived from 7-oxotetrahydrobenzothiazole is shifted but slightly bathochrome if compared with the sensitizing maximum effected by analogous dyes which are derived from benzothiazole.
  • the dyes according to the invention are distinguished over those benzothiazole dyes by a considerably increase intensity of sensitization.
  • the sensitizing dyes according to the present invention can be used in any silver halide emulsions, Suitable silver halides are silver chloride, silver bromide or mixtures thereof, if desired containing a small amount of silver iodide of up to 10 mols percent.
  • the silver halides may be dispersed in the usually hydrophilic compounds, for example, carboxymethylcellulose, polyvinyl alcohol, polyvinyl pyrrolidone, alginic acid and its salts, esters or amides or preferably gelatin.
  • the sensitizing dyes to be used according to the present invention are advantageously added to the photographic emulsion before the chemical ripening or before casting.
  • the methods employed for this are generally known to persons skilled in this art.
  • the sensitizing dyes are generally incorporated in the emulsion in the form of solutions, e.g., in an alcohol such as methanol or ethanol or acetone or mixtures these solvents with water.
  • the solvents must, of course, be compatible with gelatin and must not have any adverse effects on the photographic properties of the emulsion.
  • the quantity of sensitizing dye added may vary within wide limits, e.g., between 2 and 200 mg. preferably between 10 and 60 mg. per kg. of the silver halide emulsion.
  • the concentration of dye may be adapted to the particular requirements. depending on the type of emulsion, the desired sensitizing effect, etc. The most suitable concentration for any given emulsion can easily be determined by the usual tests employed in the art of emulsion making.
  • the emulsions may also contain chemical sensitizers, e.g., reducing agents such as stannous salts, polyamines such as diethylentriamine, or sulfur compounds as described in US. Pat. No. 1,574,944. Furthermore, salts of noble metals, such as ruthenium, rhodium, palladium, iridium, platinum or gold may be contained in the emulsions for chemical sensitization, as described in the article by R. Koslowsky, Z. Wiss. Phot. 46, 65-72 (1951).
  • the emulsions may also contain, as chemical sensitizers, polyalkylene oxides, especially polyethylene oxide and derivatives thereof.
  • the emulsions according to the present invention may contain the usual stabilizers such as homopolar or salt-type compounds of mercury with aromatic or heterocyclic rings, such as mercaptotriazoles, simple mercury salt, sulfonium mercury double salts and other mercury compounds.
  • suitable stabilizers are azaindenes, especially tetraor pentaazaiedenes, in particular those that are substituted with hydroxyl or amino groups. Compounds of this type are described in the article by Birr, Z. Wiss. Phot. 47, 2-58 (1952).
  • Other suitable stabilizers include heterocyclic mercapto compounds, e.g., phenylmercaptotetrazole, quaternary benzothiazole derivatives and benzotriazole.
  • the sensitivity which is brought about by means of the sensitizing dyes according to the present invention is also maintained in the presence of color couplers it being immaterial whether the couplers have been added to the emulsion in form of an aqueous solution or in an emulsified form.
  • This property as well as the behavior of reciprocity enables the new sensitizers to be used advantageously in color photographic emulsions.
  • the emulsions may be hardened in the usual manner for example, with formaldehyde or by use of halogen-substituted aldehydes which contain a carboxyl group, e.g., mucobromic acid, diketones, methanesulfonic acid esters and dialdehydes.
  • formaldehyde or by use of halogen-substituted aldehydes which contain a carboxyl group, e.g., mucobromic acid, diketones, methanesulfonic acid esters and dialdehydes.
  • EXAMPLE 1 A silver chlorobromide emulsion as commonly used in photographic papers, which contains the usual additives such as formaldehyde as hardening agent and saponine as wetting agent, is divided in 6 parts. Each part is sensitized with one sensitizer of the following table and is subsequently cast on a layer support. After drying the materials are exposed to light in a sensitometer behind a grey step wedge having 2-steps and behind filters which are mentioned in the table. The development is carried out as usual.
  • Dye V has proved to be a sensitizer just as useful as dye [11. This dye after processing does not a least effect a discoloration of the layer, but brings about excellent white tones of paper.
  • EXAMPLE 2 A silver bromide emulsion as commonly used in color photographic papers, which contains per kg. 70 g. of gelatin, 0.4 moles of silver bromide, 15 g. of p-stearoylaminobenzoyl- (3,S-dicarboxy)-acetanilide as a yellow-forming coupler, and the usual additives as 0.35 g. of saponine, 3 ml. of a 5 percent aqueous methanolic solution of N,N',N"-trisacryloyl-hexahydro-1,3,5-triazine and 300 mg. of 1,3,7-triaza-4-hydroxy-6 -methylindolizine, is divided in 4 parts. Three parts are sensitized with one dye of the following table. One part serves as a comparison test.
  • S J s N I CH; III
  • Light-sensitive photographic material comprising at least formed as described in example I.
  • one silver halide emulsion layer which material contains a sensitizing dye of the following formula Agfa-Govacrt-filtor H s Senslti- Y zation maxl- L 489 mum U 449 (spectrum (nm) (blue) minus blue) V N Unsensitlzed emulsion 11 I N wherein: Va 475 13 6 Y stands for 0,8, N-aryl or N-alkyl;
  • R stands for alkyl having up to four carbon atoms, and R stands for alkyl having up to four carbon atoms, cycloalkyl, aryl or aralkyl. 2. Material according to claim 1 wherein Y stands for S and R stands for alkyl having up to four carbon atoms and being 232 1 3 further substituted with carboxyl or sulfo.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US24812A 1969-04-03 1970-04-01 Spectrally sensitized light-sensitive silver halide material Expired - Lifetime US3630748A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE1917163A DE1917163C3 (de) 1969-04-03 1969-04-03 Spektral sensibilisiertes lichtempfindliches Material

Publications (1)

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US3630748A true US3630748A (en) 1971-12-28

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US (1) US3630748A (enrdf_load_stackoverflow)
BE (1) BE747781A (enrdf_load_stackoverflow)
CH (1) CH535971A (enrdf_load_stackoverflow)
DE (1) DE1917163C3 (enrdf_load_stackoverflow)
FR (1) FR2042922A5 (enrdf_load_stackoverflow)
GB (1) GB1264103A (enrdf_load_stackoverflow)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4105454A (en) * 1976-02-05 1978-08-08 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion spectrally sensitized with merocyanine dyes

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2055329A1 (en) * 1990-11-21 1992-05-22 Dietrich M. Fabricius Sensitization of tabular grains with a zeromethine dye and a tetraazaindene

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2157351A (en) * 1934-12-28 1939-05-09 Agfa Ansco Corp Sensitizing dyes for photographic emulsions
US3385707A (en) * 1963-05-18 1968-05-28 Agfa Ag Optically sensitized photographic materials containing neutrocyanine dyes

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2157351A (en) * 1934-12-28 1939-05-09 Agfa Ansco Corp Sensitizing dyes for photographic emulsions
US3385707A (en) * 1963-05-18 1968-05-28 Agfa Ag Optically sensitized photographic materials containing neutrocyanine dyes

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4105454A (en) * 1976-02-05 1978-08-08 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion spectrally sensitized with merocyanine dyes

Also Published As

Publication number Publication date
CH535971A (de) 1973-04-15
DE1917163B2 (de) 1979-08-02
FR2042922A5 (enrdf_load_stackoverflow) 1971-02-12
DE1917163C3 (de) 1980-04-17
DE1917163A1 (de) 1970-11-05
BE747781A (fr) 1970-09-23
GB1264103A (enrdf_load_stackoverflow) 1972-02-16

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