US2680686A - Sensitized and supersensitized photographic emulsions - Google Patents

Sensitized and supersensitized photographic emulsions Download PDF

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US2680686A
US2680686A US141601A US14160150A US2680686A US 2680686 A US2680686 A US 2680686A US 141601 A US141601 A US 141601A US 14160150 A US14160150 A US 14160150A US 2680686 A US2680686 A US 2680686A
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formula
emulsion
supersensitized
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silver
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Andre Emile Van Dormael
Nys Jean Marie
Cat Arthur Henri De
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Gevaert Photo Producten NV
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/72—Nitrogen atoms
    • C07D213/75—Amino or imino radicals, acylated by carboxylic or carbonic acids, or by sulfur or nitrogen analogues thereof, e.g. carbamates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
    • C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
    • C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
    • C07D235/24—Benzimidazoles; Hydrogenated benzimidazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
    • C07D235/30—Nitrogen atoms not forming part of a nitro radical
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
    • C07D263/62—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems having two or more ring systems containing condensed 1,3-oxazole rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
    • C07D277/62—Benzothiazoles
    • C07D277/68—Benzothiazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
    • C07D277/82—Nitrogen atoms
    • 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
    • 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
    • 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

  • G A COMPOUND OF FORMULA Y. F 5 HaA DYE OF FORMULA XIII.
  • M A COMPOUND OF FORMULA 1:.
  • N A DYE or: FORMULA 12m.
  • the present invention relates to a process for the production of photographic silver halide emulsions.
  • This invention more particularly relates to the sensitization and supersensitization of photographic silver halide emulsions.
  • An object of the present invention is to provide a new process for sensitizing and supersonsitizing photographic emulsions.
  • a further object is to provide a photographic element comprising an emulsion sensitized or supersensitized according to our new process.
  • R' a member selected from the group consisting of a substituted acyl group, a not substituted acyl-group, a substituted amido group and a not-substituted amido group.
  • the compound of the formula ner A mixture of 2 g. N-methyl-2-imino-dihydrobenzthiazole and 0.8.. g.: ethyl-malonate is heated at 170 C. for 1.hour. .After cooling, the
  • Example 2 55 i' 'lhe spectral sensitivity of-lasilver chloride emulsion is increased by using 50 mg./kg. of the compound of the formula prepared as follows: g. N-phenyl-2-imino-dihydrobenzthiazole in 50 cm. acetic anhydride are heated at boiling temperature. After cooling,
  • Example 4 A silver bromide emulsion, containing per kg. of emulsion 20 mg. cyanine of the formula rig N is supersensitized by simultaneously using 30 mg./kg. of the derivative of the formula S CH:
  • Example 7 A silver chloride emulsion, containing per kg. of emulsion 20 mg. trimethincyanine of the formula which may be prepared as follows: A suspension of 5 g. N-methyl-2-imino-dihydrobenzthiazole in cm. acetic anhydride is refluxed for 15 minutes. After adding 100 cm. diluted alcohol (70%) the mixture is heated once more at boiling temperature for 5 minutes whereafter the product is precipitated by ice-water. Melting point (after recrystallisation from alcohol) Bil-142 C.
  • Emample 5 A silver chloride emulsion, containing per kg. of emulsion 6 mg. trimethincyanine of the formula CHa-CHn-CH:
  • T 02115 prepared as follows: A mixture of 3.3 g. N- 01 01 Brmethyl-2-imino-dihydrobenzthiazole and 0.6 g. 'urea is melted at about 180 C. for 1 hour. After Ha CH3 cooling, the product is extracted by boiling water. Aft cooling, the product obtained is Sucked off is strongly supersensitized by simultaneously and recrystallised from alcohol. Melting point: using mgJkgof the compound of the formula 224-226 C.
  • Example 9 30 A silver chloro-bromide emulsion, containing per kg. of emulsion 10 mg. pentamethincyanine of NH the formula (I:
  • Example13 prepared as follows: A mixture of 4 g.
  • Example 14 2 carhethoxymethyl benzthiazole in l cm.
  • a silver chloro-bromide emulsion, containing Xylene, is heated for 4 h s a boiling e p aper kg. of emulsion 10 mg. trimethincyanine of ture in the presence of 5 drops pyridine.
  • a prodr EHPCHZCHE i 1 I c-on is obtained from a silver chloro-bromide emulsion, containing Xylene, is heated for 4 h s a boiling e p aper kg. of emulsion 10 mg. trimethincyanine of ture in the presence of 5 drops pyridine.
  • a prodr EHPCHZCHE i 1 I c-on on
  • FIG. 1 The specification is accompanied by drawings to illustrate the supersensitizing efiect obtained with five of our new dyestuff combinations used in silver halide emulsions.
  • FIG. 1 to 5 is a diagrammatic reproduction of three spectrograms. In each figure, the sensitivity is represented by a dotted line; the sensitivity of the emulsion containing only the cyanine dye is represented by a dash-dotted line; and the sensitivity of the emulsion containing the compound according to the invention in combination with the cyanine dye is represented by the solid line.
  • a photographic silver halide emulsion containing the compound of the formula 2.
  • a photographic silver halide emulsion containing the combination of the dyestufi of the formula l0 and the dyestuff of the formula than N References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 2,080,049 Kendall May 11, 1937 2,153,930 Kendall Apr. 11, 1939 2,177,635 Carroll et a1 Oct. 31, 1939 2,298,732 Brooker et a1. Oct. 13, 1942 2,312,040 Kendall et a1. Feb. 23, 1943 2,340,882 Kendall Feb. 8, 1944 2,490,745 Carroll et a1 Dec. 6, 1949 2,503,861 Weissberger Apr. 11, 1950 FOREIGN PATENTS Number Country Date I 617,720 Great Britain Feb. 10, 1949

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Cosmetics (AREA)
  • Thiazole And Isothizaole Compounds (AREA)
  • Plural Heterocyclic Compounds (AREA)

Description

June 1954 A. E. VAN DORMAEL ETAL 86 SENSITIZED AND SUPERSENSITIZED PHOTOGRAPHIC EMULSIONS Filed Jan. 51, 1950 2 Sheets-Sheet 1 A=A comouno 0F FORMULA I. F 1B=A DYE OF FORMULA 11.
lg. .cnns comouno OF FORMULA '1 Wm: THE DYE o|= FORMULA x1.
700 no 600 55a 50a 45a 400 11/4 D=A COMPOUND 0F FORMULA EDI.
F E=A 0v: OF FORMULA 2x 1.
{9 arm: COMPOUND OF FORMULA 2111 WITH THE DYE OF FORMULA XII.
G=A COMPOUND OF FORMULA Y. F 5 HaA DYE OF FORMULA XIII.
lg urns COMPOUND OF FORMULA Y WITH Tl-IE nvs OF FORMULA x111.
June 1954 A. E. VAN DORMAEL ETAL 2,680,686
SENSITIZED AND SUPERSENSITIZED PHOTOdRAPI-IIC EMULSIONS Filed Jan. 31, 1950 2 Sheets-Sheet 2 J: A compouno OF FORMULA I. F 4 K=A DYE OF FORMULA m.
19 Lg'l'l-lE COMPOUND OF FORMULA '1 WITH me we or FORMULA m.
700 650 50a 55a 500 450 400 m,
M=A COMPOUND OF FORMULA 1:. N=A DYE or: FORMULA 12m.
19 0.11:1: COMPOUND OF FORMULA 1x WITH THE we or FORMU y In wen/or:
r/Ynar/ fm/ r a Za/vnae/ Jean #74? I Patented June 8, 1954 FICE SENSITIZED AND SUPERSENSITIZED PHOTOGRAPHIC EMULSION S Andr Emile Van Dormael, Heverlee-Louvain, Jean Marie Nys, Louvain, and Arthur Henri De Cat, Kessel-Loo-Louvain, Belgium, assignors to Gevaert Photo-Producten, N. V., Mortsel, Belgium, a Belgian company Application January 31, 1950, Serial No. 141,601
Claims priority, application France February 1, 1949 The present invention relates to a process for the production of photographic silver halide emulsions.
This invention more particularly relates to the sensitization and supersensitization of photographic silver halide emulsions.
An object of the present invention is to provide a new process for sensitizing and supersonsitizing photographic emulsions.
A further object is to provide a photographic element comprising an emulsion sensitized or supersensitized according to our new process.
Other objects will appear from the following description.
We have found that the sensitivity of photographic silver halide emulsions optionally containing optical sensitizers may be improved by incorporating into these emulsions products corresponding to the following general formula Dzthe atoms necessary to complete a member selected from the group consisting of fiveand six-membered heterocyclic nuclei and fiveand six-membered heterocyclic nuclei bearing a fused-on arylene ring,
2 Claims. (Cl. 95-7) or of the corresponding amino-cyclammonium salt corresponding to the formula wherein Xzan acid residue, with an ester, an anhydride or an acid chloride of an aliphatic, aromatic or heterocyclic acid.
The derivatives of the first given general formula wherein R:an amido group may be obtained by causing an. acid chloride or an amide of carbonic acid, such as phosgene, urea or the derivatives of the later, to react upon the products corresponding to the formula The following examples serve to illustrate the invention without limiting, however, the scope thereof.
Example 1 A silver bromo-iodide emulsion, containing per kg. of emulsion 10 mg. trimethincyanine of the n=a positive integer of from 1 to 2, formula l om-cm-om -on= "on o C H so Ni N O 2 a 4 Rza member selected from the group consisting of H, alkyl, substituted alkyl, aryl, alkenyl and alkylene, V
R':a member selected from the group consisting of a substituted acyl group, a not substituted acyl-group, a substituted amido group and a not-substituted amido group.
general formula wherein Rzan acyl group, substituted or not, may be obtained for instance by condensation of a base bearing an imino group and corresponding to the formula r'----' R I-'I(-cH=oH I is strongly supersensitized by simultaneously using 30 ing/kg. of the compound of the formula ner: A mixture of 2 g. N-methyl-2-imino-dihydrobenzthiazole and 0.8.. g.: ethyl-malonate is heated at 170 C. for 1.hour. .After cooling, the
product obtained is sucked off and dried. Melting point (after recrystallisation from alcohol): 262-263 0.
" Example 2 55 i' 'lhe spectral sensitivity of-lasilver chloride emulsion is increased by using 50 mg./kg. of the compound of the formula prepared as follows: g. N-phenyl-2-imino-dihydrobenzthiazole in 50 cm. acetic anhydride are heated at boiling temperature. After cooling,
the product is precipitated by water. Melting point (after recrystallisation from alcohol): 149.5-150.5 C.
Example 3 A silver bromo-iodide emulsion, containing per kg. of emulsion 25 mg. trimethincyanine of the formula on; JJ-CH: -OH=C i i C2115 Cil a is supersensitized by simultaneously using 30 mg./kg. of the compound of the formula in Example 2.
Example 4 A silver bromide emulsion, containing per kg. of emulsion 20 mg. cyanine of the formula rig N is supersensitized by simultaneously using 30 mg./kg. of the derivative of the formula S CH:
4 is strongly supersensitized by simultaneously using 30 mg./ kg. of the derivative of the formula Example 6' A silver bromide emulsion, containing per kg. of emulsion mg. trimethincyanine of the formula is supersensitized by simultaneously using mg./kg. of the compound of the formula JHa prepared in the following manner: A mixture of 3.2 g. N-methyl-2-imino-dihydrobenzthiazole and 4.2 g. benzoyl chloride in cm. xylene is refluxed for 3 hours. After cooling, the precipitate formed is recrystallised from diluted alcohol. Melting point: l56.5-l57.5 C.
Example 7 A silver chloride emulsion, containing per kg. of emulsion 20 mg. trimethincyanine of the formula which may be prepared as follows: A suspension of 5 g. N-methyl-2-imino-dihydrobenzthiazole in cm. acetic anhydride is refluxed for 15 minutes. After adding 100 cm. diluted alcohol (70%) the mixture is heated once more at boiling temperature for 5 minutes whereafter the product is precipitated by ice-water. Melting point (after recrystallisation from alcohol) Bil-142 C.
Emample 5 A silver chloride emulsion, containing per kg. of emulsion 6 mg. trimethincyanine of the formula CHa-CHn-CH:
a an. a.
is supersensitized by simultaneously using 30 mg./kg. of the compound of the formula CH:C O CH:
obtained as follows: A mixture of 3 g. N-methyl- 2-imino-dihydrobenzthiazole and 10 cm. ethyl aceto acetate is refluxed for 2 hours. After cooling, the crystals, formed are sucked off. Melting CgHaS O" point (after recrystallisation from alcohol). benzthiazole and 2.10 g, benzoyl chloride in 30 146-147" C. cm. benzene is heated at boiling temperature for Example 8 3 hours in the presence of 1.2 g. pyridine. After complete evaporation, the residue is washed in an A silver chloride emulsion, containing per 6 ice-cold sodium carbonate solution 5% and finally of emulsion 20 mg. trimethincyanine of the recrystallised from alcohol. Melting point: formula 18618'l C.
is supersensitized by simultaneously using 30 mg./kg. of the compound of the formula Example 11 r A silver bromo-iodide emulsion, containing per -s NH: kg. of emulsion mg. trimethincyanine of the L J: formula 20 (1311. T 02115 prepared as follows: A mixture of 3.3 g. N- 01 01 Brmethyl-2-imino-dihydrobenzthiazole and 0.6 g. 'urea is melted at about 180 C. for 1 hour. After Ha CH3 cooling, the product is extracted by boiling water. Aft cooling, the product obtained is Sucked off is strongly supersensitized by simultaneously and recrystallised from alcohol. Melting point: using mgJkgof the compound of the formula 224-226 C.
Example 9 30 A silver chloro-bromide emulsion, containing per kg. of emulsion 10 mg. pentamethincyanine of NH the formula (I:
=NC=0 S S \N/ oH=oH-oH=oH-oH=J 1k NZ 7 N prepared as follows: A mixture of 2.1 g. 2-amino- L 5 40 naphthimidazole and 1.4 g. benzoyl chloride m 50 cm. xylene is heated at boiling temperature for 3 hours in the presence of 0.3 g. pyridine. After complete evaporation, the residue is washed in an ice-cold sodium carbonate solution 5% and recrystallised from alcohol. Melting .point: 244-245 0.
is strongly supersensitized by simultaneously using 30 mg./kg. of the derivative of the formula NH J Example 12 A silver bromo-iodide emulsion, containing per kg. of emulsion 30 mg. trimethincyam'ne of the e formula prepared according to Pierrons indications (Ann.
Chim. (8) 15 (1908) Se CH3 Se Example 10 A? i B A silver chloro-bromide emulsion, containing M \N 7 per kg. of emulsion 20 mg. trimethincyanine of A) the formula 01H, 2H5
om-om-om I O-OH= CH C'HISOF NZ N is strongly supersensitized by simultaneously as is supersensitized by simultaneously using 30 using 30 mg./kg. of the derivative of formula mg./ kg. of the compound of theformula 76 prepared according to sei de s indications (Ber. 58 prepared as follows: A mixture of 2.25 g. 2-amino- (1925) 354) Example13 prepared as follows: A mixture of 4 g. N- A silver bromo-iodide emulsion, containing per methyl'z'lmmo'dihydmbenzthiazole and i i lrdro uinone-diacet lchloride in 45 cm k of emulsion 20 m trimetnmc anme the cm 9 y g g y f xylene 1s refluxed for '3 hours. After cooling, the
formula crystalline product is separated and recrystal- S o H lised from cyclohexanone. Melting point: 276- I 277 C. 01 Cl Example 16 g 5 I 10 A silver chloride emulsion, containing per kg. of emulsion mg. c'yanine according to the is supersensitized by simultaneously using 30 mg./kg. of the compound of the formula formula is supersensitized by simultaneously using 30 m ./k of the com ound of the formula prepared as follows: A mixture of 1.4 g. 2-aminog a p loenzoxazole (according to Skraup, Ann. 419
(1919) 68) and 1.4 g. benzoylchloride in cm. 0 dry benzene, is refluxed for minutes. Then 0.8 5 it g. pyridine are added to the reaction mixture \N/ \N which is further refluxed for 3 hours. After fil- L trating while still warm, the filtrate is cooled and H1 (1133 the precipitate formed is filtrated. Melting point (after recrystallisation from alcohol) 214-215 C. 30 prepared F follows: A m x of methyl-2-1m1no-dihydrobenzth1azo1e and 1.1 g.
Example 14 2 carhethoxymethyl benzthiazole in l cm. A silver chloro-bromide emulsion, containing Xylene, is heated for 4 h s a boiling e p aper kg. of emulsion 10 mg. trimethincyanine of ture in the presence of 5 drops pyridine. After the formula '35 cooling and recrystallising from butanol, a prodr EHPCHZCHE i 1 I c-on: on
is supersensitized by simultaneously using 30 not is obtained, melting at 172-173" (3., and cormg'./kg. of the compound of formula responding to the formula EH3 s s fi =0 L=N-OOCH2 L N N l l 1 V Hs N 2 g. of this compound and 1.12 g. methyliodide are A heated at 100 C. for 48 hours in a sealed tube and a product of the formula prepared according to Camps, Archiv der Pharmazie,240 (1902) 363. g T
0-011 GN=C Example 15 6 1 N I A silver chloro-bromide emulsion, containing 1 5 per kg. of emulsion 10 mg. trimethincyanine of Y a the formula is obtained. Melting point: 253-254 C. (with decm-oHT-om w 3 N -c11= g OH c N 0211580;
is supersensitized by simultaneously using 30 composition). 1 g. of the latter product is dismg./kg. of the compound of the formula solved in 50 cm. phenol and 50 cm. anhydrous S o o S Jags-d-cmm-Oo-om-A-zwl: N \N a.
9 alcohol. After adding 2 g. KOH dissolved in 20 cm. ethanol, the reaction mixture is refluxed for 2 hours. On pouring out into sodium hydroxide N, the azaketomethylene compound corresponding to the formula (EH3 precipitates. Melting point (after recrystallisation from isoamyl alcohol) 326327 C.
The specification is accompanied by drawings to illustrate the supersensitizing efiect obtained with five of our new dyestuff combinations used in silver halide emulsions. Each of the Figs. 1 to 5 is a diagrammatic reproduction of three spectrograms. In each figure, the sensitivity is represented by a dotted line; the sensitivity of the emulsion containing only the cyanine dye is represented by a dash-dotted line; and the sensitivity of the emulsion containing the compound according to the invention in combination with the cyanine dye is represented by the solid line.
We claim:
1. A photographic silver halide emulsion containing the compound of the formula 2. A photographic silver halide emulsion containing the combination of the dyestufi of the formula l0 and the dyestuff of the formula than N References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 2,080,049 Kendall May 11, 1937 2,153,930 Kendall Apr. 11, 1939 2,177,635 Carroll et a1 Oct. 31, 1939 2,298,732 Brooker et a1. Oct. 13, 1942 2,312,040 Kendall et a1. Feb. 23, 1943 2,340,882 Kendall Feb. 8, 1944 2,490,745 Carroll et a1 Dec. 6, 1949 2,503,861 Weissberger Apr. 11, 1950 FOREIGN PATENTS Number Country Date I 617,720 Great Britain Feb. 10, 1949

Claims (1)

1. A PHOTOGRAPHIC SILVER HALIDE EMULSION CONTAINING THE COMPOUND OF THE FORMULA
US141601A 1949-02-01 1950-01-31 Sensitized and supersensitized photographic emulsions Expired - Lifetime US2680686A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2848329A (en) * 1956-05-14 1958-08-19 Eastman Kodak Co Supersensitization with bis-heterocyclic bases
US2852385A (en) * 1956-05-14 1958-09-16 Eastman Kodak Co Supersensitization of photographic emulsions

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2080049A (en) * 1934-08-03 1937-05-11 Ilford Ltd Production of dyes of the cyanine type
US2153930A (en) * 1935-05-08 1939-04-11 Ilford Ltd Sensitized photographic emulsion
US2177635A (en) * 1937-05-29 1939-10-31 Eastman Kodak Co Photographic emulsion
US2298732A (en) * 1940-12-16 1942-10-13 Eastman Kodak Co Polymethine base
US2312040A (en) * 1938-07-22 1943-02-23 Ilford Ltd Production of colored photographic images by color development and composition therefor
US2340882A (en) * 1935-08-16 1944-02-08 Ilford Ltd Sensitized photographic material
GB617720A (en) * 1944-03-21 1949-02-10 Dastman Kodak Company Improvements in or relating to photography
US2490745A (en) * 1948-01-13 1949-12-06 Eastman Kodak Co Cellulose carboxylic ester silver halide emulsions sensitized with benzothiazole and benzoselenazole quaternary salts
US2503861A (en) * 1949-03-02 1950-04-11 Eastman Kodak Co 2-(mercaptoacetamido)-benzothiazole and its s-acetyl derivative

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2080049A (en) * 1934-08-03 1937-05-11 Ilford Ltd Production of dyes of the cyanine type
US2153930A (en) * 1935-05-08 1939-04-11 Ilford Ltd Sensitized photographic emulsion
US2340882A (en) * 1935-08-16 1944-02-08 Ilford Ltd Sensitized photographic material
US2177635A (en) * 1937-05-29 1939-10-31 Eastman Kodak Co Photographic emulsion
US2312040A (en) * 1938-07-22 1943-02-23 Ilford Ltd Production of colored photographic images by color development and composition therefor
US2298732A (en) * 1940-12-16 1942-10-13 Eastman Kodak Co Polymethine base
GB617720A (en) * 1944-03-21 1949-02-10 Dastman Kodak Company Improvements in or relating to photography
US2490745A (en) * 1948-01-13 1949-12-06 Eastman Kodak Co Cellulose carboxylic ester silver halide emulsions sensitized with benzothiazole and benzoselenazole quaternary salts
US2503861A (en) * 1949-03-02 1950-04-11 Eastman Kodak Co 2-(mercaptoacetamido)-benzothiazole and its s-acetyl derivative

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2848329A (en) * 1956-05-14 1958-08-19 Eastman Kodak Co Supersensitization with bis-heterocyclic bases
US2852385A (en) * 1956-05-14 1958-09-16 Eastman Kodak Co Supersensitization of photographic emulsions

Also Published As

Publication number Publication date
NL72814C (en)
GB684166A (en) 1952-12-10
DE812872C (en) 1951-09-06
FR979853A (en) 1951-05-04

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