US2848329A - Supersensitization with bis-heterocyclic bases - Google Patents

Supersensitization with bis-heterocyclic bases Download PDF

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US2848329A
US2848329A US584544A US58454456A US2848329A US 2848329 A US2848329 A US 2848329A US 584544 A US584544 A US 584544A US 58454456 A US58454456 A US 58454456A US 2848329 A US2848329 A US 2848329A
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Chechak Jonas John
Jean E Jones
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Eastman Kodak Co
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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

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  • This invention relates to photographic silver halide emulsions useful in color photography and photographic silver halide emulsions containing dicarbocyanine dyes, and as supersenitizers therefor, certain heterocyclic bases.
  • the sensitization produced by a given dye varies somewhat with the type of emulsion in which the dye is incorporated.
  • the sensitization of a given emulsion by a given dye may be altered by varying the conditions in the emulsion. For example, the sensitization may be increased by increasing the silver ion concentration or decreasing the hydrogen ion concentration (i. e., increasing the alkalinity) or both.
  • sensitization can be increased by bathing plates, coated with a spectrally sensitized emulsion, in Water or in acqueous solutions of ammonia.
  • Such a process of altering the sensitivity of a sensitized emulsion by increasing the silver ion concentration and/or by decreasing the hydrogen ion concentration is commonly called hypersensitization.
  • Hypersensitized emulsions have generally poor keeping qualities.
  • a heterocyclic nucleus of the benzoxazole series e. g., benzoxazole, S-hydroxybenzoxazole, 6-hydroxybenzoxazole, S-chlorobenzoxazole, S-methoxybenzoxazole, o-methoxybenzoxazole, S-phenylbenzoxazole, S-bromobenzoxazole, etc.
  • a heterocyclic nucleus of the naphthoxazole series e.
  • a heterocyclic nucleus of the Z-quinoline series e. g., Z-quinoline, 6-methyl-2-quinoline, 7-methyl-2-quinoline, 8-methy1-2-quinoline, 6-chlo ro-2-quinoline, 8-chloro-2-quinoline, 4-chloro-2-quinoline, 5 ethoxy-Z-quinoline, 6 ethoxy-Z-quinoline, 7-ethoXy-2- quinoline, fi-hydroxy-Z-quinoline, 7-hydroXy-2-quinoline, 6-methoxy-2-quinoline, etc.), a heterocyclic nucleus of the 4-quinoline series (e.
  • benzimidazole e.g., 4-quinoline, 6-methoxy-4- quinoline, 7-methyl-4-quinoline, 8-methyl-4-quinoline, etc.
  • a heterocyclic nucleus of the benzimidazole series e. g., benzimidazole, S-chlorobenzimidazole, 5,6-dichlorobenzimidazole, 1,7-trimethylenebenzimidazole, etc.
  • a heterocyclic nucleus of the 5,6-benzoquinoline series e.
  • heterocyclic bases useful in practicing our invention comprise heterocyclic nitrogen bases containing from 1 to 2 nitrogen atoms and having a substituent attached thereto which contains at least four carbon atoms.
  • Such heterocyclic bases comprise those advantageously represented by the following general formula: (II) Zg I N b-Rz wherein Z; represents the non-metallicatoms necessary to 7 complete a heterocyclic nucleus containing from 1 to 2 quinoline series, etc.), and R represents an organic radi-' cal containing at least 4 carbon atoms, said radical hav- 3 ing a molecular weight of at least 71.
  • Embraced by the above general Formula II are the bis-heterocyclyl compounds represented by the following general formula:
  • D represents a divalent organic radical, such as dithiaalkylene (e. g., u,w cliihiaalkylene groups, such as u,w-dithiapropylene, a,wdithiabutylene, a,w-dithiapentylene,' etc., especially such groups containing from 1 to carbon atoms), alkylene (e.
  • dithiaalkylene e. u,w cliihiaalkylene groups, such as u,w-dithiapropylene, a,wdithiabutylene, a,w-dithiapentylene,' etc., especially such groups containing from 1 to carbon atoms
  • alkylene e.
  • Typical bisheterocyclyl compounds represented by Formula III include the following:
  • R represents an alkyl group (e. g., amyl, heXyl, octyl, decyl, dodecyl, etc., especially an alkyl group containing from 5 to 12 carbon atoms), an aryl group (e. g., phenyl, m-, and p-tolyl, 0-, m-, and p-anisyl, 0-, rn-, and p-arninophenyl, p-dimethylaminophenyl, p-diethylaminophenyl, etc., especially a mononuelear aromatic group of the benzene series), an aralkyl group (e.
  • alkyl group e. g., amyl, heXyl, octyl, decyl, dodecyl, etc., especially an alkyl group containing from 5 to 12 carbon atoms
  • an aryl group e.
  • Bases ernbraced by Formula IV include the following:
  • halogen atoms such as chlorine, bromine, ete., alkoxyl
  • ' 7 groups such as methoxyl, ethoxyl, etc., hydroxyl, amino, etc.
  • our invention we incorporate one or more of the dicarbocyanine dyes represented by Formula I above with one or more heterocyclic bases, such as those represented by Formulas II, III or IV above.
  • Our invention is particularly directed to the ordinarily employed gelatino-silver-halide emulsions.
  • the carrier is other than gelatin, e. g., a resinous substance or cellulosic material which has no deteriorating effect on the light-sensitive materials.
  • the dicarbocyanine dyes and heterocyclic bases can be employed in various concentrations depending upon the eifects desired.
  • the optimum or near optimum concentration of the dicarbocyanine dyes which we employ in practicing our invention is of the order of from 0.010 to 0.30 g. per mol. of silver halide in the emulsion.
  • heterocyclic bases which we employ in our invention can advantageously be employed at a concentration of from about 0.05 to 1.0 g. per mol. of silver halide in the emulsion.
  • the ratio of concentration of dicarbocyanine dye to heterocyclic base can vary rather widely in our combinations, e. g., from 1:5 to 1:100 (by weight) in many cases.
  • the methods of incorporating sensitizing dyes and heterocyclic bases in silver halide emulsions are well known to those skilled in the art. While the dicarbocyanine dyes and heterocyclic bases can be directly dispersed in the emulsions, it is convenient to add the same in the form of solutions in appropriate solvents. Methanol, ethanol, pyridine, and the like have proven satisfactory for many of the dyes of Formula I and bases of Formulas II, III and IV. Mixtures of solvents, e. g., pyridine diluted with methanol or acetone, can also be used. The dicarbocyanine dyes and heterocyclic bases are dispersed in the finished emulsions and should be uniformly distributed throughout the emulsions.
  • Our invention is primarily directed to the ordinarily employed gelatino-silver-halide developing-out emulsions, e. g., gelatino-silver-chloride, -chlorobromide, -ch1oroiodide, -chlorobromiodide, -bromide and -bromidide developing-out emulsions.
  • Emulsions which form the latent image mostly inside the silver halide grains such as the emulsions set forth in U. S. Patent 2,456,956, dated December 21, 1948, can also be employed in practicing our invention.
  • emulsions prepared in accordance with our invention can be coated in the usual manner on any suitable support, e. g., glass, cellulose nitrate film, cellulose acetate film, polyvinyl-acetal resin film, paper or metal.
  • suitable support e. g., glass, cellulose nitrate film, cellulose acetate film, polyvinyl-acetal resin film, paper or metal.
  • Photographic silver halide emulsions such as those listed above, containing the supersensitizing combinations of our invention can also contain such addenda as chemical sensitizers, e. g., sulfur sensitizers .(e. g., allyl thiocarbamide, thiourea, allylisothiocyanate, cystine, etc),
  • chemical sensitizers e. g., sulfur sensitizers .(e. g., allyl thiocarbamide, thiourea, allylisothiocyanate, cystine, etc)
  • various gold compounds e. g., potassium chloroaurate, auric trichloride, etc.
  • various palladium compounds such as palladium chloride (U. S. 2,540,086), potassium chloropalladate (U. 2,598,079), etc., or mixtures of such sensitizers
  • anti-foggants such as ammonium chloroplatinate (U. S. 2,566,245), ammonium chloroplatinite (U. S. 2,566,263), benzotriazole, nitrobenzimidazole, 5- nitroindazole, benzidine, mercaptans, etc.
  • Such silver halide emulsions can also contain thiazolidones or other ultraviolet absorbing compounds, such as those described in Sawdy U. S. Patent 2,739,888, issued March 27, 1956. While certain emulsion addenda, such as certain ultraviolet compounds, and certain color-forming compounds cause desensitization or un-sensitizing effects, it has been found that the new combinations of our invention largely overcome such effects.
  • Typical color-forming compounds which can he so employed include those in U. S. Patent 2,322,027 and the following:
  • amylphenoxy acetanilide The following table and examples will serve to illustrate the beneficial effects of our new supersensitizing combinations when employed in a photographic emulsion containing a dispersion of a coupler or color-forming compound.
  • Table II these effects are illustrated for an ordinary photographic gelatino-silver-bromiodide emulsion containing 3,3'-diethyloxathiadicarbocyanine iodide (50 mg./mol. AgX).
  • To one portion of the sensitized emulsion was added a coupler dispersion containing coupler No. 5 of the above list, while no coupler dispersion was added to the second portion.
  • each of the emulsions was then digested for a short time at 50 C., coated, chill set and exposed in an Eastman Type lb sensitomcter through a Wratten No. 25 filter as in the case of the coatings for Table I.
  • the coatings containing the coupler dispersion were held at 40 C. for one-half hour before coating onto the film base and subsequent exposure.
  • the exposed coatings were then developed for about 3 minutes in a developer having the composition indicated above with respect to Table 1. After exposure and development of the coatings, the relative red speed, gamma, and fog for the coatings was measured. The results are given in Table II below.
  • the bis compounds represented by Formula III above are to be distinguished from his compounds containing a substituent on the nitrogen atom shown in Formula 111, such as the following compounds:
  • Such compounds as 3740 above have chemical properties distinct from the heterocyclic bases of our invention. It is to be further understood that in ascertaining the heterocyclic bases of our invention as set forth above, such heterocyclic bases contain not more than 2 nitrogen atoms in any heterocyclic ring, i. e., from 1 to 2 nitrogen atoms in any heterocyclic ring.
  • R of Formula IV can represent an alkylmercapto group, such groups including butylmercapto, hexylmercapto, octylmercapto, decylmercapto, dodecylmercapto, etc., (especially alkylmercapto groups containing from 4 to 12 carbon atoms).
  • R of Formula IV can also represent an arylmercapto group as noted above, including phenylmercapto, tolylmercapto, etc., (especially an arylmercapto group containing from 4 to 7 carbon atoms).
  • Particularly useful substituted imino groups (R of Formula IV include (heterocyclylidene) ethylidene groups wherein the heterocyclic nucleus is the same or difierent type of heterocyclic nucleus represented by Z
  • the accompanying drawing illustrates the supersentitizing eifect obtained with three of our new combinations in gelatino-silver-bromiodide emulsions. Each figure of the drawing is a diagrammatic reproduction of two spectrograms.
  • the sensitivity of the emulsion containing only the dicarbocyanine dye of Formula I is represented by the solid curve, while the sensitivity of the same emulsion containing both a dicarbocyanine dye of Formula I and a heterocyclic base, such as is represented by Formulas II, III or IV, is represented by the broken line. No curve representing the sensitivity of the heterocyclic base alone is shown, since numerous coatings at the concentrations shown in the table have indicated that these heterocyclic bases have little or no measurable sensitizing action of their own.
  • curve A represents the sensitivity of an ordinary gelatino-silver-bromiodide emulsion sensitized with 3,3-diethylthiadicarbocyanine iodide
  • curve B represents the sensitivity of the same emulsion sensitized with 3,3'-diethylthiadicarbocyanine iodide and 1,4-bis[2-(5 phenyloxazolyl)]benzene. Sensitometric measurements for these coatings are given in Example 21 of Table I.
  • curve C represents the sensitivity of an ordinary gelatino-silver-bromiodide emulsion sensitized with 3,3'-diethylthiadicarbocyanine iodide
  • curve D represents the sensitivity of the same emulsion sensitized with 3,3-diethylthiadicarbocyanine iodide and 1,2-bis(2- benzothiazolyl)ethylene. Sensitometric measurements for these coatings are given in Example of Table I.
  • curve B represents the sensitivity of an ordinary gelatino-silver-bromiodide emulsion sensitized with 3,3'-diethyloxadicarbocyanine iodide
  • curve F represents the sensitivity of the same emulsion sensitized with 3,3-diethyloxadicarbocyanine iodide with 1,4-bis [2- (5phenyloxazolyl)lbenzene. Sensitometric measurements for these coatings are given in Example of Table I.
  • Example A -2- [4- (2-amin0-5-methylphenylazo) phenyl] benzothiazole
  • a solution of 0.8 g. of sodium nitrite in 5 ml. of Water was added dropwise to a cold (5 C.) suspension of 2.26 g. of 2-p-aminophenylbenzothiazole in 50 ml. of water containing 4 ml. of concentrated hydrochloric acid.
  • the reaction mixture was allowed to stand in the cold for one hour, then diluted to 500 ml. with ice water and 0.5 g. of urea was added.
  • the reaction mixture was filtered and the clear cold filtrate was added to 1.07 g. of ptoluidine dissolved in 5 ml. of pyridine. After standing for several hours the crystals were collected on a filter.
  • the yield of product was 81% crude and 50% after two recrystallizations from benzene.
  • the yellow crystals had M. P. l191 C. with de
  • Example B N,N'-bis(2-benz0thiaz0lyl) oxumide
  • a mixture of 1.5 g. of Z-aminobenzothiazole and 1.46 g. of diethyl oxalate was heated under reflux for about two minutes.
  • the solid product was removed from the flask and washed with methyl alcohol. After two recrystallizations from pyridine, the colorless crystals melted above 320 C.
  • Example C.2-(Z-benzotlziazolylhydrazono methylbenzothiazole A solution of 1.7 g. (1 mol.) of beuzothiazole-Z- carboxaldehyde and 1.7 g. (1 mol.) of Z-hydrazinobenzothiazole in 25 ml. of absolute ethyl alcohol was heated at the refluxing temperature for 30 minutes. After chilling, the product was collected on a filter and washed with ethyl alcohol. After two recrystallizations from a mixture of 30 percent pyridine and 70 percent ethyl alcohol, the yield was 37 percent, and the yellow crystals melted at 271272 C. with decomposition.
  • Example D 1,5-bis(Z-benzothiazolylthio) pentane
  • a mixture of 8.35 g. (0.05 mol.) of mercaptobenzothiazole and 5.75 g. (0.025 mol.) of pentamethylene bromide was heated for two hours at C.
  • a homogeneous liquid first formed but soon solidified to a glassy solid.
  • the mixture was retained at 135 C. for two hours.
  • the solid product was dissolved in methanol, decolorized with decolorizing carbon, filtered, and chilled.
  • the solid that separated (4 g.) melted at 6 C.
  • the higher melting solid is the salt which loses hydrogen bromide readily.
  • a reaction carried out in methanol in the presence of sodium methoxide gave the same product.
  • Compound 16 can be prepared according to the method described in U. S. Patent 2,726,246, issued December 6, 1955.
  • Compound 21 was prepared in the manner shown in Example D above, by eacting together Z-mercaptobenzimidazole and ethylene bromide.
  • Compound 24 was prepared as follows: 3.7 g. of 2- aminobenzothiazole was mixed with 2.1 ml. of diketene and allowed to stand. In about minutes, a vigorous reaction took place. The mixture liquified and then turned to a solid. This solid was crystallized from alcohol to give a quantitative yield of product melting at Compound 36 was prepared as follows: 6.0 g. of the sodium salt of Compound were dissolved in 100 ml. of water containing 5 g. of sodium carbonate. Phosgene was led into this solution at 5 0 C. with a period of 1.5 hours. When the reaction mixture gave a negative diazo reaction, heating was discontinued and the desired product recovered from the reaction mixture by the addition of an equal volume of saturated salt solution. The yield of product was 4.3 g.
  • Compound 37 can be prepared by condensing 3-ethyl- 2(3)-benzothiazolone hydrozone (Chem. Abs, 22, 1358) with terephthalic aldehyde.
  • R and R each represents an alkyl group containing from 1 to 2 carbon atoms, n represents a positive integer of from 1 to 2,
  • X represents an acid radical
  • Z represents the non-metallic atoms necessary to complete a heterocyclic nucleus selected from the group consisting of those of the benzothiazole series, those of the naphthothiazole series, those of the benzoselenazole series, those of the naphthoselenazole series, those of the benzoxazole series, those of the naphthoxazole series, those of the 2-quinoline series, those of the 4-quinoline series, and those of the benzimidazole series, and Z represents the non-metallic atoms necessary to complete a heterocyclic nucleus selected from the group consisting of those of the benzoxazole series, those of the naphthoxazole series, those of the benzoselenazole series, those of the naphthoselenazole series, those of the benzothiazole series
  • R and R each represents an alkyl group containing from 1 to 2 carbon atoms
  • X represents an acid radical
  • Z represents the non-metallic atoms necessary to complete a heterocyclic nucleus of the benzothiazole series, and at least one heterocyclic base selected from those represented by the following general formula:
  • Z represents the non-metallic atoms necessary to complete a heterocyclic nucleus selected from the group consisting of those of the thiazole series, those of the benzothiazole series, those of the naphthothiazole series, those of the oxazole series, those of the benzoxazole series, those of the naphthoxazole series, those of the selenazole series, those of the benzoselenazole series, those of the naphthoselenazole series, those of the benzimidazole series, and those of the Z-quinoline series
  • a represents a positive integer of from 1 to 2
  • D represents a divalent organic radical selected from the group consisting of a dithiaalkylene group containing from 1 to 5 carbon atoms, an alkylene group containing from 1 to 10 carbon atoms, an arylene group containing from 6 to 13 carbon atoms, a vinylene group, a thio group, and an oxydirnethylene group.
  • R and R each represents an alkyl group containing from 1 to 2 carbon atoms
  • X represents an acid radical
  • Z represents the non-metallic atoms necessary to complete a heteroeyclic nucleus of the benzothiazole series, and at least one heterocyclic base selected from those represented by the following general formula:
  • I Iii-R1 X wherein R and R each represents an alkyl group containing from 1 to 2 carbon atoms, X represents an acid radical, Z represents the non-metallic atoms necessary to complete a heterocyclic nucleus of the benzothiazole series, and Z represents the non-metallic atoms necessary to complete a heterocyclic nucleus of the benzoxazole series, and at least one heterocyclic base selected from those represented by the following general formula:
  • Z represents the non-metallic atoms necessary to complete a heterocyclic nucleus selected from the group consisting of those of the thiazole series, those of the benzothiazole series, those of the naphthothiazole series, those of the oxazole series, those of the benzoxazole series, those of the naphthoxazole series, those of the selenazole series, those of the benzoselenazole series, those of the naphthoselenazole series, those of the benzimidazole series, and those of the Z-quinoline series, va!
  • D represents a positive integer of from 1 to 2
  • D represents a divalent organic radical selected from the group consisting of a dithiaalkylene group containing from 1 to 5 carbon atoms, an alkylene group containing from 1 to carbon atoms, an arylene group containing from 6 to 13 carbon atoms, a vinylene group, a thio group, and an oxydimethylene group.
  • Z represents the non-metallic atoms necessary to complete a heterocyclic nucleus of the benzothiazole series and D represents a bis(phen lene)methyl group.
  • R and R each represents an alkyl group containing from 1 to 2 carbon atoms
  • X represents an acid radical
  • Z represents the non-metallic atoms necessary to complete a heterocyclic nucleus of the benzoselenazole series, and at least one heterocyclic base selected from those represented by the following general formula:
  • Z represents the non-metalic atoms necessary to complete a heterocyclic nucleus selected from the group consisting of those of the thiazole series, those of the benzothiazole series, those of the naphthothiazole series, those of the oxazole series, those of the benzoxazole series, those of the naphthoxazole series, those of the selenazole series, those of the benzoselenazole series, those of the naphthoselenazole series, those of the benzirnidazole series, and those of the Z-quinoline series
  • d represents a positive integer of from 1 to 2
  • D represents a divalent organic radical selected from the group consisting of a dithiaalkylene group containing from 1 to 5 carbon atoms, an alkylene group containing from 1 to 10 carbon atoms, an arylene group containing from 6 to 13 carbon atoms, a vinylene group, a thio group, and an
  • R and R each represents an alkyl group containing from 1 to 2 carbon atoms
  • X represents an acid radical
  • Z represents the non-metallic atoms necessary to complete a heterocyclic nucleus of the benzoselenazole series, and at least one heterocyclic base selected from those represented by the following general formula:

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Description

g-' 1958' J. J. CHECHAK ETAL 2,848,329
SUPERSENSI-TIZATIONWITH BIS-HETEROCYCLIC BASES Filed May 14, 1956 A: 5,5; DIETHYLTHIA DICARBOCYANINE IODIDE a.= 5,3 DIETHYLTHIADICARBOCYANINE IODIDE WITH |,4-[2- (-5 PHENYLOXAZOLYU] BENZENE v C2D 'llll HLWMH 1m m m 300 4-00 '4 500 600 700 c=s,s- DIETHYlIHIADICARBOCYANINE IODIDE =3,3'- DIETHYIJ'HIADICARBOCYANINE IODIDE WITH L215 (2- a ENZOTHIAZOLYL) ETHYLEN E =3,3:- DIETHYLOXAIDICARBOCYANINE IODIDE F 3,3 DIETHYLOXADICARBOCYANINE IODIDE WITH |,4- BIS [2- (5- PHENYLOXAZOLYD] BENZENE 76120811 C/zechak J e an E. Jones INVENTORS moRNm llnitd tates SUPERSENSITIZATIGN WITH BlS-HETEROCYCLIC BASES Jonas John Chechak and Jean E. Jones, Rochester, N. Y., assignors to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey Application May 14, 1956, Serial No. 584,544
10 Claims. (Cl. 96-104) This invention relates to photographic silver halide emulsions useful in color photography and photographic silver halide emulsions containing dicarbocyanine dyes, and as supersenitizers therefor, certain heterocyclic bases.
It is known in the art of making photographic emulsions that certain dyes of the cyanine class alter the sensitivity of photographic emulsions of the gelatinosilver-halide kind, when the dyes are incorporated in the emulsions. It is also known that the sensitization produced by a given dye varies somewhat with the type of emulsion in which the dye is incorporated. Furthermore, the sensitization of a given emulsion by a given dye may be altered by varying the conditions in the emulsion. For example, the sensitization may be increased by increasing the silver ion concentration or decreasing the hydrogen ion concentration (i. e., increasing the alkalinity) or both. Thus, sensitization can be increased by bathing plates, coated with a spectrally sensitized emulsion, in Water or in acqueous solutions of ammonia. Such a process of altering the sensitivity of a sensitized emulsion by increasing the silver ion concentration and/or by decreasing the hydrogen ion concentration is commonly called hypersensitization. Hypersensitized emulsions have generally poor keeping qualities.
We have now found another means of altering the sensitivity in emulsions containing dicarbocyanine dyes. Since the conditions in the emulsion, i. e., the hydrogen ion and/or the silver ion concentration undergo little or no change in our method, we shall designate our method as a kind of supersensitization.
It is, therefore, an object of our invention to provide photographic emulsions containing dicarbocyanine dyes and, as supersensitizers therefore, certain heterocyclic bases. Another object is to provide a process for preparing these supersensitized emulsions. Other objects will become apparent from a consideration of the following description and examples.
The dicarbocyanine dyes which are useful in practicing our invention include those represented by the following general formula:
2,848,329 Patented Aug. 19, 1958 ice benzothiazole, 6-chlorobenzothiazole, 7-chlorobenzothia zole, 4-methylbenzothiazole, S-methylbenzothiazole, 6- methylbenzothiazole, 5 bromobenzothiazole, 6 bromobenzothiazole, 4-phenylbenzothiazole, 5-phenylbenzothiazole, 4-methoxybenzothiazole, 5 -methoxybenzothiazole, 6 methoxybenzothiazole, 6 iodobenzothiazole, 5 iodobenzothiazole, 4-ethoxybenzothiazole, S-ethoxybenzothiazole, 5,6-dimethylbenzothiazole, S-hydroxybenzothiazole, 6-hydroxybenzothiazole, etc.), a heterocyclic nucleus of the naphthothiazole series (e. g., or naphthothiazole, B-naphthothiazole, 7-methoxy-tx-naphthothiazole, S-methoxy a naphthothiazole, 5 methoxy-{B-naphthothiazole, S-ethoxy-a-naphthothiazole, etc.), a heterocyclic nucleus of the benzoselenazole series (e. g., benzoselenazole, 5 chlorobenzoselenazole, 6 methoxybenzoselenazole, S-methoxybenzoselenazole, etc.), a heterocyclic nucleus of the naphthoselenazole series (e. g., wnaphthoselenazole, fi-naphthoselenazole, etc.), a heterocyclic nucleus of the benzoxazole series (e. g., benzoxazole, S-hydroxybenzoxazole, 6-hydroxybenzoxazole, S-chlorobenzoxazole, S-methoxybenzoxazole, o-methoxybenzoxazole, S-phenylbenzoxazole, S-bromobenzoxazole, etc.), a heterocyclic nucleus of the naphthoxazole series (e. g., ot-naphthoxazole, fi-naphthoxazole, etc.), a heterocyclic nucleus of the Z-quinoline series (e. g., Z-quinoline, 6-methyl-2-quinoline, 7-methyl-2-quinoline, 8-methy1-2-quinoline, 6-chlo ro-2-quinoline, 8-chloro-2-quinoline, 4-chloro-2-quinoline, 5 ethoxy-Z-quinoline, 6 ethoxy-Z-quinoline, 7-ethoXy-2- quinoline, fi-hydroxy-Z-quinoline, 7-hydroXy-2-quinoline, 6-methoxy-2-quinoline, etc.), a heterocyclic nucleus of the 4-quinoline series (e. g., 4-quinoline, 6-methoxy-4- quinoline, 7-methyl-4-quinoline, 8-methyl-4-quinoline, etc.), a heterocyclic nucleus of the benzimidazole series (e. g., benzimidazole, S-chlorobenzimidazole, 5,6-dichlorobenzimidazole, 1,7-trimethylenebenzimidazole, etc.), a heterocyclic nucleus of the 5,6-benzoquinoline series (e. g., 5,6-benzo-2-quinoline, etc.), etc., and-Z represents the non-metallic atoms necessary to complete a heterocyclic nucleus selected from the group consisting of those of the quinoline series (e.g., such as those defined by Z above), those of the benzoxazole series (e. g., such as those defined by Z above), those of the naphthoXazole series (e. g., such as those defined by Z above), those of the benzoselenazole series (e. g., such as those defined by Z above), those of the naphthoselenazole series (e. g., such as those defined by Z above), those of the benzothiazole series (e. g., such as those defined by Z above), those of the naphthothiazole series (e. g., such as those defined by Z above), etc. Other dicarbocyanine dyes can also be employed in our invention.
The heterocyclic bases useful in practicing our invention comprise heterocyclic nitrogen bases containing from 1 to 2 nitrogen atoms and having a substituent attached thereto which contains at least four carbon atoms. Such heterocyclic bases comprise those advantageously represented by the following general formula: (II) Zg I N b-Rz wherein Z; represents the non-metallicatoms necessary to 7 complete a heterocyclic nucleus containing from 1 to 2 quinoline series, etc.), and R represents an organic radi-' cal containing at least 4 carbon atoms, said radical hav- 3 ing a molecular weight of at least 71. Embraced by the above general Formula II are the bis-heterocyclyl compounds represented by the following general formula:
(III) ,Z, //Z2\\ bi C(D)d-1 iv wherein Z has the values given above, d represents a positive integer of from 1 to 2, and D represents a divalent organic radical, such as dithiaalkylene (e. g., u,w cliihiaalkylene groups, such as u,w-dithiapropylene, a,wdithiabutylene, a,w-dithiapentylene,' etc., especially such groups containing from 1 to carbon atoms), alkylene (e. g., methylenqethylene, propylene, butylene, pentylene, hexylene, etc., especially such groups containing from 1 to carbon atoms), arylene (e. g., phenylene, biphenylene, benzylene, bis(phenylene)methyl, etc., especially such groups containing from 6 to 13 carbon atoms), vinylene, thio, oxyclimethylene, etc. Typical bisheterocyclyl compounds represented by Formula III include the following:
1 ,5-bis (2-benzothiazo1y1thio) pentane 1,2-bis Z-benzothiazolyl) ethane C-CHzCHzCHr-C 1,3-bis (2-benzothiazolyl propane 1 ,4-bis (2-benzothiazo1y1) butane 1,5-bis (2-benzothiazo1y1) pentane N N Bis (2-benzothiazo1y1thio) methane 1,2-bis (2-benzothiazo1ylthio) ethane 0-8-0 Q Bis (2-benzoth1azoly1) sulfide (9) Bis [4 (2-benzothiazoly1) phenyl] methane 1,4-bis 2-a-naphthothiazo1yl) butane n R n HHH/ 1 Bis (Z-a-naphthothiazolyl) methane p,a-Bis 2-benzothiazo1yl) toluene 1,4bis (Z-benzimidazolyl benzene 1,2-bis (2-benzimid azolyi) ethylene 2- (2-benzothiazolyl)benzothiazole 1,5-b1s (2-benzoxazo1y1) pentane 1,2-bis (2-benzimidazo1y1thio) ethane hydrobromide 1,2-bis (2-benzothiazolyl) ethylene Also embraced by Formula 11 above are heterocyclic bases selected from those represented by the following general formula:
wherein Z has the values given above and R represents an alkyl group (e. g., amyl, heXyl, octyl, decyl, dodecyl, etc., especially an alkyl group containing from 5 to 12 carbon atoms), an aryl group (e. g., phenyl, m-, and p-tolyl, 0-, m-, and p-anisyl, 0-, rn-, and p-arninophenyl, p-dimethylaminophenyl, p-diethylaminophenyl, etc., especially a mononuelear aromatic group of the benzene series), an aralkyl group (e. g., benzyl, ,Ci-phenylethyl, etc.), an aryloxyalkyl group (e. g., phenoxymethyl, fiphenoxyethyl, etc.), an acylamido group (e. g., amido toluarnido, acetacetarnido, valerarnido, benzamido, etc., especially an acylamido group containing from 4 to 9 carbon atoms), alkylmercapto, arylrnercapto, a substituted amino group (e. g., butylarnino, anilino, tolylamino, etc.), and a substituted imino group. Bases ernbraced by Formula IV include the following:
( s Q t 2- (p-anisylybenzothiaz ole O-CsHs Z-phenylbenzothiazole 24 S O O H ll C-N-CC Hr-C-C Ha N 2-acetacetamidobenzothiazole C-CHsCHz-CaHa N 2- (B-phenylethyl benzothiazole C-CHz-O-CaHa 2-phenoxymethy1benzothiazole butyr- 2- [-1-(2-amin0-5-methy1phenylaz0)pheny1]benzothiaz 1e 2- 4-dimethy1aminophenyl benzothiazole C-N=O HO H=O Cells 2- (3-ethy1-2(3H)-benzothiazolylidene)ethylideneJaminobenzothiazole C S C aHs 2-pheny1mercaptobenzoxazole C S C EH11 2-n-octylmereaptob enzothiazole f N S 03H 2-(4-amino-3-sulfopheny1)-6-methy1benzothiazo1e 4,4=-his 2- (G-methylbenzothiazolyl) ]-N,N-diphenylurea-2,2' disulfonic acid As shown above, the heterocyclic nuclei represented by Z of Formula II above can have substituents thereon which do not interfere with the photographic emulsion. Such substituents can be alkyl groups, such as methyl, ethyl, etc., aryl groups, such as phenyl, tolyl, etc.,
halogen atoms, such as chlorine, bromine, ete., alkoxyl,
' 7 groups, such as methoxyl, ethoxyl, etc., hydroxyl, amino, etc.
According to our invention, we incorporate one or more of the dicarbocyanine dyes represented by Formula I above with one or more heterocyclic bases, such as those represented by Formulas II, III or IV above. Our invention is particularly directed to the ordinarily employed gelatino-silver-halide emulsions. However, our supersensitizing combinations can be employed in silver halide emulsions in which the carrier is other than gelatin, e. g., a resinous substance or cellulosic material which has no deteriorating effect on the light-sensitive materials. The dicarbocyanine dyes and heterocyclic bases can be employed in various concentrations depending upon the eifects desired.
Ordinarily, the optimum or near optimum concentration of the dicarbocyanine dyes which we employ in practicing our invention is of the order of from 0.010 to 0.30 g. per mol. of silver halide in the emulsion.
The heterocyclic bases which we employ in our invention can advantageously be employed at a concentration of from about 0.05 to 1.0 g. per mol. of silver halide in the emulsion.
In general, the ratio of concentration of dicarbocyanine dye to heterocyclic base can vary rather widely in our combinations, e. g., from 1:5 to 1:100 (by weight) in many cases.
The methods of incorporating sensitizing dyes and heterocyclic bases in silver halide emulsions are well known to those skilled in the art. While the dicarbocyanine dyes and heterocyclic bases can be directly dispersed in the emulsions, it is convenient to add the same in the form of solutions in appropriate solvents. Methanol, ethanol, pyridine, and the like have proven satisfactory for many of the dyes of Formula I and bases of Formulas II, III and IV. Mixtures of solvents, e. g., pyridine diluted with methanol or acetone, can also be used. The dicarbocyanine dyes and heterocyclic bases are dispersed in the finished emulsions and should be uniformly distributed throughout the emulsions. The following procedure is satisfactory: Stock solutions of the dicarbocyanine dyes and heterocyclic bases are prepared by dissolving the same in appropriate solvents as described above. Then, to the flowable gelatino-silver-halide emulsion, the desired amounts of the stock solution of one of the dyes (or heterocyclic bases) are slowly added. While stirring the emulsion. Stirring is continued until the dye is thoroughly incorporated in the emulsion. Then the desired amount of the stock solution of the heterocyclic base (or dye, if heterocyclic base has been added first) is slowly added to the emulsion, while stirring. Stirring is continued until the second solution is thoroughly incorporated. The supersensitized emulsion can then be coated out on a suitable support. such as glass, cellulose derivative film, resin film, or paper, to a suitable thickness and allowed to dry. The details of such coating methods are well known to those skilled in the art. The foregoing procedures and proportions are to be regarded only as illustrative. Clearly, our invention is directed to any silver halide emulsion containing a combination of the alforesaid dicarbocyanine dyes and heterocyclic bases whereby a supersensitizing efiect is obtained.
The following examples will serve to illustrate further the manner of practicing out invention.
In Table I below, to difierent portions of the same batch of photographic gelatino-silver-bromiodide emulsion were added (1) a dicarbocyanine dye, such as those represented by Formula I above, and (2) a combination of the dicarbocyanine dye and heterocyclic base. Then the emulsions were held at about 5052 C. for a short time and coated on a support, chill set, and dried. After exposure through a Wratten No. 25 filter, i. e., a filter which transmits substantially no light of wavelength shorter than about 580 mu. in an Eastman Type lb sensis tometer, the film strips were processed for 3 minutes in a developer having the following composition:
Water to make 1 liter.
The speed (red), gamma and fog for each of the coatings was then measured. The results are recorded in Table I. I
TABLE I Red Light Exposure sensitizing Dye and Base (gJmol. Example AgX) Bil/E Gam- Fog Speed ma (a) 3,3'-diethyloxathiadicarbocya 4.35 1.54 .06
nine iodide (.045 (b) dye (a) (.045) plus base 1 (.30)..- 10.6 2. 48 06 {(0) dye (d) (.045) 3. 85 1.21 .06 (d) dye (a) (.045) plus base 6 (.15).-. 7. 55 1. .06 (e) dye ((1 (.045) plus base 7 (.15) 8. 2. l6 06 (I) dye (a) (.045) plus base 28 (.15) 29. 5 3. 18 .00 (g) dye (a) (.045) plus base 8 (.15)-.. 10.4 2.40 .06 (h) dye (a) (.045) plus base 9 (.15)... 15.4 2. 70 .06 (2') dye (a) (.045) plus base 10 (.15). 8. 25 2.48 .06 (j) dye (a) (.045) plus base 11 (15).. 15.8 1.92 .06 {(k) dye (a) (.045) 4. 25 1. 52 .06 (I) dye (a) (.045) plus base 29 (.15)-.. 27. 5 2. 62 .06 (m) dye (a) (.045) plus base 12 (.15). 11.4 2. 64 .06 (n) dye (a) (.045) plus base 13 (.15). 11.4 2. 72 .06 (o) dye (a) (.045) plus base 14 (15).. 9. 5 2.10 .06 {(p) dye (11) (.045) 4.05 1.30 .06 (q) dye (a) (.045) plus base 2 (.15)-.. 5. 6 1.84 .06 (r) dye (a) (.045) plus base 3 (15).... 12. 5 2.7 .06 (s) dye (a) (.045) plus base 4 (.15).. 7. 2 2.1 .06 (t) dye (a) (.045) plus base 5 (.15). 7.9 2.32 .06 (u) dye (a) (.045) 5.8 2.0 .06 (v) dye (a) (.045) plus base 17 (.15)... 7. 2 2.0 .06 (w) 3,3'-di-B-hydroxyethylthiadicar- (i. 40 1. 05
boeyaniue bromide (.045). (I) dye (w) (.045) plus base 29 (15).. 13. 7 2. 40 06 (y) dye (to) (.045) plus base 28 (.15)- 19.0 2. 70 .05 (z) 3,3-diethylthiadicarbocyanine 5.6 2.1 .05
iodide (.045). (a) dye (z) (.045) plus base 21a (.15).. 7.6 2. 7 .05 (b') dye (z) (.045) plus base 16 (.15)-.. 25. 5 3.1 .05 (c) 3,3'-diethylseleuadicarbocyauine- 2. 7 2. 9 .06 iodide (.045).
(d') dye (c) (.045) with base 21a (.15). 6.0 2. 4 .05 (e) dye (6) (.045) with base 16 (.15).. 10. 9 3. 1 05 (f) 3,3-dicthyl-4,5,4,5-dibsnzo- 5.6 3.1 .10
thiadioarboeyanine iodide (.045). (g') dye (f) (.045) plus base 16 (.15).. 20. 5 3. 0 .07 (h') 3,3-diethyloxadicarbocyanine 7. 6 3. 2 .07
iodide (.045). (i') dye (h) (.045) plus base 16 (.15).. 15. 8 3.1 .07 (j 1,1-dimethyl-2,2-dicarbocyaui.ue 2.8 2. 4 .34
romide (.045). (1.1) dye (3") plus base 16 (.15) 8.8 2.8 .12 {(1') dye (a) (.045)... 4.05 1. 30 .06 (m) dye (a) (.045) plus base 30 (15).. 14. 7 2. 60 06 (n) dye (a) (.045) plus base 31 (.15).. 15.4 3. 1 .06 {(0') dye (a) (.045) 4.15 1.89 .08 (p) dye (a) (.045) plus base 32 (.15) 6.9 1. 30 .06 {(q) dye (a) (.045) 4. 6 1. 9 .06 (I') dye (a) (.045) plus base 22 (15).. 17. 3 2. 6 .06 (s') dye (a) (.045) plus base 19 (.15).. 6.3 2. 2 .05 (t) dye (a) (.045) plus base 20 (.15).- 9. 3 3.0 .06 {(u') dye (a) (.045) 4. 0 2. 3 00 (v) dye (a) (.045) plus base 23 (15).. 7.0 2. 2 .05 (w) dye (a) (.045) plus base 24 (.15). 7. 4 2. 4 .06 (I) dye (a) (.045) plus base 25 (.15).. 14. 4 3. 1 .06 (y) dye (a) (.045) plus base 26 (.15).. 45. 5 2.9 .06 (2) dye (a) (.045) plus base 21 (15).. 9.9 2.4 .06 (11") dye (a) (.045) plus base 15 (15).. 16. 9 2. 8 .06 (0) dye (a) (.045) plus base 27 (.l5). l0. 4 2. 3 .06 {(c) dye (a) (.045) 2.0 50 .05 (d") dye (a) (.045) plus base 18 (.32) 18. 0 1. 8 06 In the above table, the coatings of Examples 2, 3, -4, 5, 6, 7, and 8 were made from the same batch of emulsion, the coatings of Examples 9, 10, 11, and 12 were made from the same batch of emulsion, the coatings of Examples 13, 14, 15, and 16 were made from the same batch of emulsion, the coatings of Examples 18 and 19 were made from the same batch of emulsion, the coatings of Examples 20 and 21 were made from the same batch of emulsion, the coatings of Examples 22 and 23 were made from the same batch of emulsion, the coatings of Examples 27 and 28 were made from the same batch of emulsion, the coatings of Examples 30, 31, and 32 were made from the same batch of emulsion, and the coatings of Examples 33 to 39 were made from the same batch of emulsion. No measurements of coatings containing only the heterocyclic bases of Formula II alone are given, since numerous coatings at the concentration used in the table have shown that these bases alone have little or no measurable sensitizing effect on the emulsions.
Our invention is primarily directed to the ordinarily employed gelatino-silver-halide developing-out emulsions, e. g., gelatino-silver-chloride, -chlorobromide, -ch1oroiodide, -chlorobromiodide, -bromide and -bromidide developing-out emulsions. Emulsions which form the latent image mostly inside the silver halide grains, such as the emulsions set forth in U. S. Patent 2,456,956, dated December 21, 1948, can also be employed in practicing our invention.
The emulsions prepared in accordance with our invention can be coated in the usual manner on any suitable support, e. g., glass, cellulose nitrate film, cellulose acetate film, polyvinyl-acetal resin film, paper or metal.
Photographic silver halide emulsions, such as those listed above, containing the supersensitizing combinations of our invention can also contain such addenda as chemical sensitizers, e. g., sulfur sensitizers .(e. g., allyl thiocarbamide, thiourea, allylisothiocyanate, cystine, etc),
various gold compounds (e. g., potassium chloroaurate, auric trichloride, etc.) (see U. S. Patents 2,540,085; 2,597,856 and 2,597,915), various palladium compounds, such as palladium chloride (U. S. 2,540,086), potassium chloropalladate (U. 2,598,079), etc., or mixtures of such sensitizers; anti-foggants, such as ammonium chloroplatinate (U. S. 2,566,245), ammonium chloroplatinite (U. S. 2,566,263), benzotriazole, nitrobenzimidazole, 5- nitroindazole, benzidine, mercaptans, etc. (see Mees--- The Theory of the Photographic Process, Macmillan Pub., 1942, page 460), or mixtures thereof; hardeners, such as formaldehyde (U. S. 1,763,533), chrome alum (U. S. 1,763,533), glyoxal U. S. 1,870,354), dibromacrolein (Br. 406,750), etc; color couplers, such as those described in U. S. Patent 2,423,730, Spence and Carroll U. S. Patent 2,640,776, etc.; or mixtures of such addenda. Dispersing agents for color couplers, such as those set forth in U. S. Patents 2,322,027 and 2,304,940, can also be employed in the above-described emulsions.
Such silver halide emulsions can also contain thiazolidones or other ultraviolet absorbing compounds, such as those described in Sawdy U. S. Patent 2,739,888, issued March 27, 1956. While certain emulsion addenda, such as certain ultraviolet compounds, and certain color-forming compounds cause desensitization or un-sensitizing effects, it has been found that the new combinations of our invention largely overcome such effects. Typical color-forming compounds which can he so employed include those in U. S. Patent 2,322,027 and the following:
Coupler:
(l) l-hydroxy-2-[8-(2,4'-di-tert.amylphenoxy) nbutyll-naphthamide (U. S. Patent 2,474,293) (2) 1-hydroxy-4-phenylazo-4'-(p tert. butylphenoxy)-2-naphthanilide (U. S. Patent 2,521,908) (3) 2-(2,4-di-tert.-amylphenoxyacetamino)-4,6 dichloro-S-methyl phenol (Graham U. S. Patent 2,725,291)
(4) 2-(u-di-tert.amylphenoxy-mbutyrylamino) 4,6-
dichloro-t-methyl phenol (5) 6-{0L-{4i:0L-(2,4 di tert.amylphenoxy)butyramido]-phenoxy}acetamido} 2,4 dichloro 3- methyl phenol (6) 2-[3 (2",4 diamylphenoxy) acetamidolbenzamido4-chloro-5-methyl phenol (7) *1-(2,4,6'-trichlorophenyl)-3 [3"(2',4"-ditert.amylphenoxyacetamido) benzamidol 5- pyrazolone (U. S. Patent 2,600,788)
(8) 1-(2',4,6-trichlorophenyl)-3-[3"-(2,4 ditertampylphenoxyacetamido)-benzamidol-4 (pmethoxyphenylazo) -5 -pyr azolone (9) N-(4 benzoylacetaminobenzenesulfonyl) N- (y-phenylpropyl) p toluidine (U. S. Patent 2,298,443)
('10) a-o-methoxybenzoyl-a-chloro 4-[u (2,4 ditert.-amylphenoxy)-n butyramido] acetanilide (McCrossen, U. S. Patent 2,728,658)
(11) ot-{3 [a (2,4 di tert.amylphenoxy)acetamido] -benzoyl}-2-methoxyacetanilide (12) 3-benzoylacetamido-4-methoxy-2',4' di tert.
amylphenoxy acetanilide ("13) 4-benzoylacetamido-3-metl1oxy-2,4 di tert.-
amylphenoxy acetanilide The following table and examples will serve to illustrate the beneficial effects of our new supersensitizing combinations when employed in a photographic emulsion containing a dispersion of a coupler or color-forming compound. In Table II, these effects are illustrated for an ordinary photographic gelatino-silver-bromiodide emulsion containing 3,3'-diethyloxathiadicarbocyanine iodide (50 mg./mol. AgX). To one portion of the sensitized emulsion was added a coupler dispersion containing coupler No. 5 of the above list, while no coupler dispersion was added to the second portion. To an aliquot of each of these portions of emulsion was added a heterocyclic base as identified in the following table. Each of the emulsions was then digested for a short time at 50 C., coated, chill set and exposed in an Eastman Type lb sensitomcter through a Wratten No. 25 filter as in the case of the coatings for Table I. The coatings containing the coupler dispersion were held at 40 C. for one-half hour before coating onto the film base and subsequent exposure. The exposed coatings were then developed for about 3 minutes in a developer having the composition indicated above with respect to Table 1. After exposure and development of the coatings, the relative red speed, gamma, and fog for the coatings was measured. The results are given in Table II below.
Speed Gamma Fog Speed Gamma Fog none 3 7 .04 21 46 .12 35 (4.0) 535 5 1 .04 3.0 .07 none 100 2 9 .05 36 2.0 .14 36 (0.4) 395 3 6 .05 280 2.7 .12
The bis compounds represented by Formula III above are to be distinguished from his compounds containing a substituent on the nitrogen atom shown in Formula 111, such as the following compounds:
C H3 CH3 Bis (3-1nethyl-2 (3H -benzothiazolylldene) acetone (39) I S N CN s C=CH CC H=C I r C2Hs C2 [Bis (3-ethy1-2 (3H -be.nzothiazolylidene) is opropylidene] malonitrile (40) S /S (I l CH3 C a 1,4-bis[ (3-methyl-2 (3H) -benzothiazolylidene) amino] benzene Compounds 37-40 above can also be employed advantageously in combination with the dicarbocyanine dyes of our invention, such as dye (a) of Table I. Such compounds as 3740 above have chemical properties distinct from the heterocyclic bases of our invention. It is to be further understood that in ascertaining the heterocyclic bases of our invention as set forth above, such heterocyclic bases contain not more than 2 nitrogen atoms in any heterocyclic ring, i. e., from 1 to 2 nitrogen atoms in any heterocyclic ring. As noted above, R of Formula IV can represent an alkylmercapto group, such groups including butylmercapto, hexylmercapto, octylmercapto, decylmercapto, dodecylmercapto, etc., (especially alkylmercapto groups containing from 4 to 12 carbon atoms). R of Formula IV can also represent an arylmercapto group as noted above, including phenylmercapto, tolylmercapto, etc., (especially an arylmercapto group containing from 4 to 7 carbon atoms). Particularly useful substituted imino groups (R of Formula IV include (heterocyclylidene) ethylidene groups wherein the heterocyclic nucleus is the same or difierent type of heterocyclic nucleus represented by Z The accompanying drawing illustrates the supersentitizing eifect obtained with three of our new combinations in gelatino-silver-bromiodide emulsions. Each figure of the drawing is a diagrammatic reproduction of two spectrograms. The sensitivity of the emulsion containing only the dicarbocyanine dye of Formula I is represented by the solid curve, while the sensitivity of the same emulsion containing both a dicarbocyanine dye of Formula I and a heterocyclic base, such as is represented by Formulas II, III or IV, is represented by the broken line. No curve representing the sensitivity of the heterocyclic base alone is shown, since numerous coatings at the concentrations shown in the table have indicated that these heterocyclic bases have little or no measurable sensitizing action of their own.
In Fig. 1, curve A represents the sensitivity of an ordinary gelatino-silver-bromiodide emulsion sensitized with 3,3-diethylthiadicarbocyanine iodide, while curve B represents the sensitivity of the same emulsion sensitized with 3,3'-diethylthiadicarbocyanine iodide and 1,4-bis[2-(5 phenyloxazolyl)]benzene. Sensitometric measurements for these coatings are given in Example 21 of Table I.
In Fig. 2, curve C represents the sensitivity of an ordinary gelatino-silver-bromiodide emulsion sensitized with 3,3'-diethylthiadicarbocyanine iodide, while curve D represents the sensitivity of the same emulsion sensitized with 3,3-diethylthiadicarbocyanine iodide and 1,2-bis(2- benzothiazolyl)ethylene. Sensitometric measurements for these coatings are given in Example of Table I.
In Fig. 3, curve B represents the sensitivity of an ordinary gelatino-silver-bromiodide emulsion sensitized with 3,3'-diethyloxadicarbocyanine iodide, while curve F represents the sensitivity of the same emulsion sensitized with 3,3-diethyloxadicarbocyanine iodide with 1,4-bis [2- (5phenyloxazolyl)lbenzene. Sensitometric measurements for these coatings are given in Example of Table I.
Many of the heterocyclic bases represented by Formulas II, III and IV above have been previously described in the prior art. Listed below are references describing the method whereby a number of these compounds can be prepared, together with the melting point of these products in certain cases.
Chem. Abs, 47 (1953), 2750 Ber. 13, 21 and Ber. 46, 97
.T.A. .s.,73,(1951 1093 U. S. 2,739,96 L
The following examples describe the preparation of a number of these heterocyclic bases which can be employed in our invention.
Example A .-2- [4- (2-amin0-5-methylphenylazo) phenyl] benzothiazole A solution of 0.8 g. of sodium nitrite in 5 ml. of Water was added dropwise to a cold (5 C.) suspension of 2.26 g. of 2-p-aminophenylbenzothiazole in 50 ml. of water containing 4 ml. of concentrated hydrochloric acid. The reaction mixture was allowed to stand in the cold for one hour, then diluted to 500 ml. with ice water and 0.5 g. of urea was added. The reaction mixture was filtered and the clear cold filtrate was added to 1.07 g. of ptoluidine dissolved in 5 ml. of pyridine. After standing for several hours the crystals were collected on a filter. The yield of product was 81% crude and 50% after two recrystallizations from benzene. The yellow crystals had M. P. l191 C. with decomposition.
Example B.N,N'-bis(2-benz0thiaz0lyl) oxumide A mixture of 1.5 g. of Z-aminobenzothiazole and 1.46 g. of diethyl oxalate was heated under reflux for about two minutes. The solid product was removed from the flask and washed with methyl alcohol. After two recrystallizations from pyridine, the colorless crystals melted above 320 C.
Example C.2-(Z-benzotlziazolylhydrazono methylbenzothiazole A solution of 1.7 g. (1 mol.) of beuzothiazole-Z- carboxaldehyde and 1.7 g. (1 mol.) of Z-hydrazinobenzothiazole in 25 ml. of absolute ethyl alcohol was heated at the refluxing temperature for 30 minutes. After chilling, the product was collected on a filter and washed with ethyl alcohol. After two recrystallizations from a mixture of 30 percent pyridine and 70 percent ethyl alcohol, the yield was 37 percent, and the yellow crystals melted at 271272 C. with decomposition.
Example D.1,5-bis(Z-benzothiazolylthio) pentane A mixture of 8.35 g. (0.05 mol.) of mercaptobenzothiazole and 5.75 g. (0.025 mol.) of pentamethylene bromide was heated for two hours at C. A homogeneous liquid first formed but soon solidified to a glassy solid. The mixture was retained at 135 C. for two hours. The solid product was dissolved in methanol, decolorized with decolorizing carbon, filtered, and chilled. The solid that separated (4 g.) melted at 6 C. The higher melting solid is the salt which loses hydrogen bromide readily. A reaction carried out in methanol in the presence of sodium methoxide gave the same product.
Compound 16 can be prepared according to the method described in U. S. Patent 2,726,246, issued December 6, 1955.
Compound 21 was prepared in the manner shown in Example D above, by eacting together Z-mercaptobenzimidazole and ethylene bromide.
Compound 24 was prepared as follows: 3.7 g. of 2- aminobenzothiazole was mixed with 2.1 ml. of diketene and allowed to stand. In about minutes, a vigorous reaction took place. The mixture liquified and then turned to a solid. This solid was crystallized from alcohol to give a quantitative yield of product melting at Compound 36 was prepared as follows: 6.0 g. of the sodium salt of Compound were dissolved in 100 ml. of water containing 5 g. of sodium carbonate. Phosgene was led into this solution at 5 0 C. with a period of 1.5 hours. When the reaction mixture gave a negative diazo reaction, heating was discontinued and the desired product recovered from the reaction mixture by the addition of an equal volume of saturated salt solution. The yield of product was 4.3 g.
Compound 37, can be prepared by condensing 3-ethyl- 2(3)-benzothiazolone hydrozone (Chem. Abs, 22, 1358) with terephthalic aldehyde.
What we claim as our invention and desire secured by Letters Patent of the United States is:
1. A photographic gelatino-silver-halide developingout emulsion sensitized with a supersensitizing combination of at least one dicarbocyanine dye selected from those represented by the following general formula:
1'; wherein R and R each represents an alkyl group containing from 1 to 2 carbon atoms, n represents a positive integer of from 1 to 2, X represents an acid radical, Z represents the non-metallic atoms necessary to complete a heterocyclic nucleus selected from the group consisting of those of the benzothiazole series, those of the naphthothiazole series, those of the benzoselenazole series, those of the naphthoselenazole series, those of the benzoxazole series, those of the naphthoxazole series, those of the 2-quinoline series, those of the 4-quinoline series, and those of the benzimidazole series, and Z represents the non-metallic atoms necessary to complete a heterocyclic nucleus selected from the group consisting of those of the benzoxazole series, those of the naphthoxazole series, those of the benzoselenazole series, those of the naphthoselenazole series, those of the benzothiazole series, those of the naphthothiazole series, and those of the Z-quinoline series, and at least one heterocyclic base selected from those represented by the following general formula:
good stirring for wherein R and R each represents an alkyl group containing from 1 to 2 carbon atoms, X represents an acid radical, and Z represents the non-metallic atoms necessary to complete a heterocyclic nucleus of the benzothiazole series, and at least one heterocyclic base selected from those represented by the following general formula:
wherein Z represents the non-metallic atoms necessary to complete a heterocyclic nucleus selected from the group consisting of those of the thiazole series, those of the benzothiazole series, those of the naphthothiazole series, those of the oxazole series, those of the benzoxazole series, those of the naphthoxazole series, those of the selenazole series, those of the benzoselenazole series, those of the naphthoselenazole series, those of the benzimidazole series, and those of the Z-quinoline series, a represents a positive integer of from 1 to 2, D represents a divalent organic radical selected from the group consisting of a dithiaalkylene group containing from 1 to 5 carbon atoms, an alkylene group containing from 1 to 10 carbon atoms, an arylene group containing from 6 to 13 carbon atoms, a vinylene group, a thio group, and an oxydirnethylene group.
3. A photographic gelatino-silver-halide developingout emulsion sensitized with a supersensitizing combination of at least one dicarbocyanine dye selected from those represented by the following general formula:
wherein R and R each represents an alkyl group containing from 1 to 2 carbon atoms, X represents an acid radical, and Z represents the non-metallic atoms necessary to complete a heteroeyclic nucleus of the benzothiazole series, and at least one heterocyclic base selected from those represented by the following general formula:
in I Iii-R1 X wherein R and R each represents an alkyl group containing from 1 to 2 carbon atoms, X represents an acid radical, Z represents the non-metallic atoms necessary to complete a heterocyclic nucleus of the benzothiazole series, and Z represents the non-metallic atoms necessary to complete a heterocyclic nucleus of the benzoxazole series, and at least one heterocyclic base selected from those represented by the following general formula:
wherein Z represents the non-metallic atoms necessary to complete a heterocyclic nucleus selected from the group consisting of those of the thiazole series, those of the benzothiazole series, those of the naphthothiazole series, those of the oxazole series, those of the benzoxazole series, those of the naphthoxazole series, those of the selenazole series, those of the benzoselenazole series, those of the naphthoselenazole series, those of the benzimidazole series, and those of the Z-quinoline series, va! represents a positive integer of from 1 to 2, D represents a divalent organic radical selected from the group consisting of a dithiaalkylene group containing from 1 to 5 carbon atoms, an alkylene group containing from 1 to carbon atoms, an arylene group containing from 6 to 13 carbon atoms, a vinylene group, a thio group, and an oxydimethylene group.
6. A photographic gelatino-silver-halide developingout emulsion sensitized with a supersensitizing combination of at least one dicarbocyanine dye selected from those represented by the following general formula:
wherein Z represents the non-metallic atoms necessary to complete a heterocyclic nucleus of the benzothiazole series and D represents a bis(phen lene)methyl group.
7. A photographic g'elatino-silvcr-halide developingout emulsion sensitized with a supersensltizing combination of 3,3'-diethyloxathiadicarbocyanine iodide and bis- [4-(2-benzothiazolyl) -phenyl] methane.
8. A photographic gelatino-silver-halide developingout emulsion sensitized with a supersensitizing combination of at least one dicarbocyanine dye selected from those represented by the following general formula:
wherein R and R each represents an alkyl group containing from 1 to 2 carbon atoms, X represents an acid radical, and Z represents the non-metallic atoms necessary to complete a heterocyclic nucleus of the benzoselenazole series, and at least one heterocyclic base selected from those represented by the following general formula:
bl Exam-we wherein Z represents the non-metalic atoms necessary to complete a heterocyclic nucleus selected from the group consisting of those of the thiazole series, those of the benzothiazole series, those of the naphthothiazole series, those of the oxazole series, those of the benzoxazole series, those of the naphthoxazole series, those of the selenazole series, those of the benzoselenazole series, those of the naphthoselenazole series, those of the benzirnidazole series, and those of the Z-quinoline series, d represents a positive integer of from 1 to 2, D represents a divalent organic radical selected from the group consisting of a dithiaalkylene group containing from 1 to 5 carbon atoms, an alkylene group containing from 1 to 10 carbon atoms, an arylene group containing from 6 to 13 carbon atoms, a vinylene group, a thio group, and an oxydimethylene group.
9. A photographic gelatino-silver-halide developingout emulsion sensitized with a supersensitizing combination of at least one dicarbocyanine dye selected from those represented by the following general formula:
l b-R1 wherein R and R each represents an alkyl group containing from 1 to 2 carbon atoms, X represents an acid radical, and Z represents the non-metallic atoms necessary to complete a heterocyclic nucleus of the benzoselenazole series, and at least one heterocyclic base selected from those represented by the following general formula:
References fitted in the file of this patent UNITED STATES PATENTS 2,680,686 Van Dormael et al June 8, 1954

Claims (1)

1. A PHOTOGRAPHIC GELATINO-SILVER-HALIDE DEVELOPINGOUT EMULSION SENSITIZED WITH A SUPERSENITIZING COMBINATION OF AT LEAST ONE DICARBOCYANINE DYE SELECTED FROM THOSE REPRESENTED BY THE FOLLOWING GENERAL FORMULA:
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2937089A (en) * 1956-03-30 1960-05-17 Eastman Kodak Co Supersensitized photographic emulsions containing sulfonated compounds
US3994733A (en) * 1973-12-10 1976-11-30 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
EP1103847A1 (en) * 1999-11-26 2001-05-30 Agfa-Gevaert N.V. Silver halide photographic film material exhibiting increased covering power and "colder" blue-black image tone
US6342338B1 (en) 1999-11-26 2002-01-29 Agfa-Gevaert Silver halide photographic material exhibiting increased covering power and “colder” blue-black image tone
CN103601698A (en) * 2013-11-29 2014-02-26 沈阳药科大学 Benzothiazole compounds and application thereof
WO2021010340A1 (en) * 2019-07-12 2021-01-21 日本化薬株式会社 Luminescent compound or salt thereof, and polarized light emitting element, polarized light emitting plate and display device each using same

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GB2161160B (en) * 1984-07-06 1989-05-24 Fisons Plc Heterocyclic sulphinyl compounds

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2680686A (en) * 1949-02-01 1954-06-08 Gevaert Photo Producten Sensitized and supersensitized photographic emulsions

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2680686A (en) * 1949-02-01 1954-06-08 Gevaert Photo Producten Sensitized and supersensitized photographic emulsions

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2937089A (en) * 1956-03-30 1960-05-17 Eastman Kodak Co Supersensitized photographic emulsions containing sulfonated compounds
US3994733A (en) * 1973-12-10 1976-11-30 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
EP1103847A1 (en) * 1999-11-26 2001-05-30 Agfa-Gevaert N.V. Silver halide photographic film material exhibiting increased covering power and "colder" blue-black image tone
US6342338B1 (en) 1999-11-26 2002-01-29 Agfa-Gevaert Silver halide photographic material exhibiting increased covering power and “colder” blue-black image tone
CN103601698A (en) * 2013-11-29 2014-02-26 沈阳药科大学 Benzothiazole compounds and application thereof
CN103601698B (en) * 2013-11-29 2016-08-17 沈阳药科大学 Benzothiazole compound and application thereof
WO2021010340A1 (en) * 2019-07-12 2021-01-21 日本化薬株式会社 Luminescent compound or salt thereof, and polarized light emitting element, polarized light emitting plate and display device each using same
CN113993854A (en) * 2019-07-12 2022-01-28 日本化药株式会社 Luminescent compound or salt thereof, and polarized light-emitting element, polarized light-emitting panel, and display device using same

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