US2848329A - Supersensitization with bis-heterocyclic bases - Google Patents

Supersensitization with bis-heterocyclic bases Download PDF

Info

Publication number
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
Authority
US
United States
Prior art keywords
those
series
dye
heterocyclic
emulsion
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US584544A
Other languages
English (en)
Inventor
Chechak Jonas John
Jean E Jones
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eastman Kodak Co
Original Assignee
Eastman Kodak Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to BE557438D priority Critical patent/BE557438A/xx
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Priority to US584544A priority patent/US2848329A/en
Priority to FR1195613D priority patent/FR1195613A/fr
Priority to GB15062/57A priority patent/GB861907A/en
Application granted granted Critical
Publication of US2848329A publication Critical patent/US2848329A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • 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

Definitions

  • 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:

Landscapes

  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Thiazole And Isothizaole Compounds (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
US584544A 1956-05-14 1956-05-14 Supersensitization with bis-heterocyclic bases Expired - Lifetime US2848329A (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
BE557438D BE557438A (en)) 1956-05-14
US584544A US2848329A (en) 1956-05-14 1956-05-14 Supersensitization with bis-heterocyclic bases
FR1195613D FR1195613A (fr) 1956-05-14 1957-05-13 Nouvelle émulsion photographique sursensibilisée par des bases hétérocycliques
GB15062/57A GB861907A (en) 1956-05-14 1957-05-13 Improvements in dye-sensitized photographic emulsions

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US584544A US2848329A (en) 1956-05-14 1956-05-14 Supersensitization with bis-heterocyclic bases

Publications (1)

Publication Number Publication Date
US2848329A true US2848329A (en) 1958-08-19

Family

ID=24337756

Family Applications (1)

Application Number Title Priority Date Filing Date
US584544A Expired - Lifetime US2848329A (en) 1956-05-14 1956-05-14 Supersensitization with bis-heterocyclic bases

Country Status (4)

Country Link
US (1) US2848329A (en))
BE (1) BE557438A (en))
FR (1) FR1195613A (en))
GB (1) GB861907A (en))

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 (zh) * 2013-11-29 2014-02-26 沈阳药科大学 苯并噻唑类化合物及其用途
JPWO2021010340A1 (en)) * 2019-07-12 2021-01-21

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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 (10)

* 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 (zh) * 2013-11-29 2014-02-26 沈阳药科大学 苯并噻唑类化合物及其用途
CN103601698B (zh) * 2013-11-29 2016-08-17 沈阳药科大学 苯并噻唑类化合物及其用途
JPWO2021010340A1 (en)) * 2019-07-12 2021-01-21
WO2021010340A1 (ja) * 2019-07-12 2021-01-21 日本化薬株式会社 発光性化合物又はその塩、ならびにこれを用いた偏光発光素子、偏光発光板、及び表示装置
CN113993854A (zh) * 2019-07-12 2022-01-28 日本化药株式会社 发光性化合物或其盐，以及使用该化合物而得的偏光发光元件、偏光发光板及显示装置
CN113993854B (zh) * 2019-07-12 2025-04-15 日本化药株式会社 发光性化合物或其盐，以及使用该化合物而得的偏光发光元件、偏光发光板及显示装置

Also Published As

Publication number Publication date
FR1195613A (fr) 1959-11-18
GB861907A (en) 1961-03-01
BE557438A (en))

Similar Documents

Publication Publication Date Title
US2688545A (en) Supersensitization of photographic emulsions with benzimidazolocarbocyanine dyes
US3666480A (en) Spectrally sensitized silver halide photographic emulsion
US3482978A (en) Carbocyanine filter dyes and sensitizers for silver halide emulsions
US2933390A (en) Supersensitization of photographic silver halide emulsions
US4046572A (en) Silver halide photographic light sensitive material
US2937089A (en) Supersensitized photographic emulsions containing sulfonated compounds
US2961318A (en) Supersensitization of photographic emulsions containing planar cyanines
US3706566A (en) Photographic emulsion containing optically dye-sensitized silver halide grains of less than 0.2 micron
US2701198A (en) Supersensitized photographic emulsions containing simple cyanine dyes
US2843490A (en) Supersensitizing combinations comprising meso-substituted carbocyanine dyes and polyvalent metal salts
US2848329A (en) Supersensitization with bis-heterocyclic bases
US3922170A (en) Spectrally sensitized silver halide photographic emulsion
US3632349A (en) Silver halide supersensitized photographic emulsion
US2945763A (en) Green sensitization of photographic silver halide emulsions
US3573920A (en) Fine grain silver halide emulsions containing novel dye combinations
US3575869A (en) Supersensitizing combinations of merocyanine dyes
US3933510A (en) Spectrally sensitized silver halide photographic emulsion
US2852385A (en) Supersensitization of photographic emulsions
US3873324A (en) Spectrally sensitized silver halide photographic emulsion
US3669672A (en) Supersensitized silver halide photographic emulsion
US3440053A (en) Silver halide photographic emulsions containing allopolar cyanine dyes
US3930860A (en) Spectrally sensitized color photographic materials suitable for high temperature rapid development
US2860984A (en) Supersensitized photographic emulsions containing polymethine dyes and ketones
US3173791A (en) Supersensitized photographic silver halide emulsions
US2751298A (en) Supersensitization of photographic emulsions with benzimidazolocyanine dyes