US3684517A - Photographic emulsion containing new benzimidazole compounds as sensitizing dyes - Google Patents

Photographic emulsion containing new benzimidazole compounds as sensitizing dyes Download PDF

Info

Publication number
US3684517A
US3684517A US86328A US3684517DA US3684517A US 3684517 A US3684517 A US 3684517A US 86328 A US86328 A US 86328A US 3684517D A US3684517D A US 3684517DA US 3684517 A US3684517 A US 3684517A
Authority
US
United States
Prior art keywords
nucleus
mol
methyl
mixture
dye
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
US86328A
Other languages
English (en)
Inventor
Leslie G S Brooker
Earl J Van Lare
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
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Application granted granted Critical
Publication of US3684517A publication Critical patent/US3684517A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
    • C09B23/08—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups more than three >CH- groups, e.g. polycarbocyanines
    • C09B23/083—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups more than three >CH- groups, e.g. polycarbocyanines five >CH- groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
    • C09B23/04—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups one >CH- group, e.g. cyanines, isocyanines, pseudocyanines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
    • C09B23/06—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups three >CH- groups, e.g. carbocyanines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/10—The polymethine chain containing an even number of >CH- groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/10—The polymethine chain containing an even number of >CH- groups
    • C09B23/105—The polymethine chain containing an even number of >CH- groups two >CH- groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/10—The polymethine chain containing an even number of >CH- groups
    • C09B23/107—The polymethine chain containing an even number of >CH- groups four >CH- groups
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/10—Organic substances
    • G03C1/12—Methine and polymethine dyes

Definitions

  • This invention relates to new 'benzimidazole compounds useful in the preparation of new cyanine and merocyanine dyes, to photographic silver halide emulsions sensitized with these dyes and to photographic elements containing the new photographic silver halide emulsions.
  • polymethine dyes such as those of the cyanine and merocyanine classes from intermediates comprising methyl substituted nitrogenous heterocyclic nuclei the methyl groups of which can be made reactive by quaternization of the heterocyclic nuclei. It is also known that the photographic characteristics of the resulting dyes, with respect to photographic elements comprising silver halide emulsions, vary with the nuclei involved and their substituent groups. Accordingly, because of the constant demands of modern photographic processes for new and improved polymethine dyes, there is a continuing search for new heterocyclic nuclei and derivatives thereof from which such dyes can be prepared.
  • the new benzimidazole compounds of our invention include those represented by the following general formula:
  • R and R are selected from the group consisting of hydrogen and chlorine atoms and Q represents the non-metallic atoms necessary to complete a heterocyclic nucleus containing 5 atoms in the heterocyclic ring such as those selected from the group consisting of a thiazole nucleus (e.g., thiazole, 4-methylthiazole, S-methylthiazole, 4-phenylthiazole, S-phenylthiazole, 4,5-dimethylthiazole, 4,5-diphenylthiazole, 4-(2-thienyl)thiazo1e, etc.), a thiazoline nucleus (e.g., thiazoline, 4-methylthiazoline, etc.), a benzothiazole nucleus (e.g., benzothiazole, 4-chloro- 3,684,517. Patented Aug. 15, 1972 hce (III) S (CHaCO)zO H Formula (I) Q, C-N- R;
  • Q represents the non-metallic
  • the residue was diluted with a small amount of ethyl alcohol, cooled, and the solid filtered 01f and washed with ethyl alcohol. This solid did not give a dye. The fitrate and washings were combined and concentrated as far as possible.
  • the residue was treated with a small amount of diethyl ether and 8 g. (26%) of 1-(2-benzothiazolyl)-5,6-dichloro-2-methylbenzimidazole, M.P. 95-98 C., was filtered off and washed with ether. On concentrating the ether solution an additional 4.2 g. (13 of product was obtained.
  • EXAMPLE 4 1-(2-benzothiazolyl)-5-chloro-2-methylbenzimidazole -CH3 or A mixture of 15 g. (1 mol.) of Z-aminobenzothiazole, 19.2 g. (1 mol.) of 1,4-dichloro-Z-nitrobenzene, and 60 ml. of dimethylacetarnide was heated for 17 days at C; The cooled react-ion mixture was poured into 400 ml.
  • the acetic acid and the excess acetic anhydride were distilled otf slowly until the residue reached a temperature of 220 C.
  • the mixture was chilled and then boiled for 2 hours with 40 ml. of 4 N hydrochloric acid, ifiltered and cooled.
  • the filtrate was made alkaline with aqueous sodium carbonate, cooled, and extracted with diethyl ether.
  • the ether extract was dried and the ether removed.
  • the oily residue of 1-(Z-benzothiazolyl)-5-chloro-2-meth ylbenzimidazole (5 g., 48%) was used without further purification in the preparation of dyes.
  • R represents an alkyl group, preferably an alkyl group having 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, octyl, decyl, etc., a carboxyalkyl group such as carboxymethyl, carboxyethyl, carboxypropyl or carboxybutyl, for example a sulfoalkyl group such as Z-sulfoethyl, 3-sulfopropyl or 4-sulfobutyl, for example, etc.; and X represents an acid anion such as chloride, bromide, iodide, methylsulfate, ethylsulfate, benzenesulfonate, p-toluenesulfonate, thiocyanate, perchlorate, and sulfamate, for example
  • R, R R Q and X are as defined previously; d represents a positive integer of from l-3; n represents a positive integer of from 1-2; and Z represents the nonmetallic atoms necessary to complete a 5- to fi-membered heterocyclic nucleus selected from the group consisting of a thiazole nucleus (e.g., thiazole, 4-methylthiazole, 4- phenylthiazole, 5- methylthiazole, 5-phenylthiazole, 4,5- dimethylthiazole, 4,5-diphenylthiazole, 4-(2-thienyl)thiazole, etc.); a benzothiazole nucleus (e.g., benzothiazole, 4-chlorobenzothiazole, 5-chl0robenzothiazole, 6-chlorobenzothiazole, 7-chlorobenzothiazole, 4-methylbenzothiazole, S-methylbenzothiazole, 6-methylbenzothiazole, 5- bromobenzothi
  • the new cyanine dyes of our invention can be prepared from cyclammonium salts having the general Formula VI by a variety of methods, e.g., unsymmetrical cyanines having the general Formula VII can be prepared by condensing cyclammonium salts having the Formula VI with compounds having the general formula:
  • R.-1g cH-o mn-l-o-a, x
  • R X, Z and n are as defined previously and R is a reactive group such as a halogen atom, e.g., chloro, bromo or iodo, analkylmercapto group such as methylmercapto, for example, an arylmercapto group, such as phenylmercapto, for example, an alkoxy group such as methoxy or ethoxy, for example, the S-anilinovinyl group, a B-acetanilido-vinyl group, etc.
  • a reactive group such as a halogen atom, e.g., chloro, bromo or iodo
  • analkylmercapto group such as methylmercapto
  • an arylmercapto group such as phenylmercapto
  • an alkoxy group such as methoxy or ethoxy
  • EXAMPLE 8 I-(Z-benzothiazolyl)-3'-ethyl-3-methylbenzimidazolothiacarbocyanine iodide A mixture of 1.3 g. (1 mol.) of l-(2-benzothiazolyl) 2-methylbenzimidazole and 1.86 g. (l mol.+l% excess) of methyl p-toluenesulfonate was heated at 175 C. for 3 minutes. To the cooled melt were added 2.25 g. (1 mol.) of Z-B-acetanilidovinyl-3-ethylbenzothiazolium iodide, 10 ml. of pyridine, and 1 g.
  • R, R R Q and d have the meaning previously assigned to them and L represents the non-metallic atoms required to complete a 5- to 6-membered heterocyclic nucleus such as those selected from the class consisting of a 2-pyrazolin-5-one nucleus (e.g., 3-methyl-1-phenyl-2- pyrazolin-S-one, 1-phenyl-Z-pyrazolin-S-one, 1-(2-benzothiazolyl)-3-methyl-2-pyrazolin-5-one, etc.), an isoxazolone nucleus (e.g., 3-phenyl-5(4H)-isoxazolone, 3-methyl- 5-(4H)-isoxazolone, etc.), an oxindole nucleus (e.g., 1- alkyl-2-, 3-dihydro-2-oxindoles, etc.), a 2,4,6-triketohexahydropyrimidine nucleus (e.g., barbituri
  • a rhodanine nucleus i.e., 2-thio-2,4-thiazolidinedione series
  • rhodanine such as rhodanine, 3-alky1rhodanines (e.g., 2-methylrhodanine, 3-ethylrhodanine, etc.), 3-allyl rhodanine, 3-carboxyalkylrhodanines (e.g., 3-(2-carboxyethyl)rhodanine, 3-(4-carboxybutyl)rhodanine, etc.), 3- sulfoalkylrhodanines (e.g., 3-(2-sulfoethyl)rhodanine, 3- (3-sulfopropyl)rhodanine, 3 (4 sulfobutyl)rhodanine, etc.), or 3-arylrhodanines (e.g., 3-phenylrhodanine, etc.),
  • R represents a hydrogen atom or an acyl group such as formyl, acetyl, propionyl, butyryl, benzoyl, otoluoyl, m-toluoyl, or p-toluoyl, for example, and R represents an aryl group such as phenyl, methylphenyl e.g. (o-, m-, p-tolyl), chlorophenyl, bromophenyl, alkoxyphenyl such as methoxyphenyl and ethoxyphenyl, for example, sulfophenyl and naphthyl.
  • acyl group such as formyl, acetyl, propionyl, butyryl, benzoyl, otoluoyl, m-toluoyl, or p-toluoyl, for example
  • R represents an aryl group such as phenyl, methylphenyl e.
  • Examples 15-22 hereinafter illustrate the preparation of the new merocyanine dye compounds of the invention but are not limitative of our new merocyanine dye compounds or their preparation.
  • the dye was filtered off and washed lightly 14 with cold ethyl alcohol.
  • the dye was purified by precipitation from a pyridine solution with methyl alcohol.
  • the yield of pure dye, as fine orange needles, was 0.2 g. (9% M.P. 293294 C. (dec.).
  • EXAMPLE 16 5- ⁇ l- (Z-benzothiazolyl -5 ,6-dichloro-3 -methyl2-benzimidazolinylidene] ethylidene ⁇ -3-ethylrhodanine
  • To the cooled melt were added 1.6 g. (1 mol.) of 5-acetanilidomethylene-3-ethylrhodanine, 10 ml.
  • naphthimidazole derivatives similar to the hereinbefore described benzimidazole derivatives can be prepared by employing o-nitronaphthyl halides such as 2-ch1oro-3- nitro-naphthalene, 1-chloro-2-nitronaphthalene, and 2- chloro-l-nitronaphthalene, for example, as the o-nitroaryl halide reactants in Equation 1, hereinbefore. It will be equally obvious that these naphthimidazole derivatives can then be employed to prepare cyanine and merocyanine dyes which are benzologs of the dyes represented by Formulas VII, VIII, and X.
  • the new cyanine and mercocyanine dyes of our invention having the Formulas VII, VIII, and X, are spectral sensitizers for photographic silver halide emulsions being particularly useful in manufacturing photographic gelatinsilver halide emulsions of the developing out type.
  • the dyes are advantageously incorporated into washed, finished, emulsions and should, of course, be uniformly distributed throughout the emulsions.
  • the methods of incorporating dyes into photographic emulsions are simple and well known to those skilled in the art of emulsion making.
  • the dyes can i be added from solutions in appropriate organic solvents which are compatible with the emulsions and free from deleterious effects on the light sensitive materials.
  • Methanol, isopropanol, and pyridine, alone or in admixture, have proven satisfactory as solvents for the dyes.
  • the types of silver halide emulsions that can be sensitized with the new dyes of this invention include those prepared from hydrophilic colloids that are known to be satisfactory vehicles for dispersed silver halides, for example, emulsions comprising natural materials such as gelatin, gelatin derivatives, agar-agar, albumin, gum arabic, alginic acid, etc., and synthetic resins such as poly- (vinyl alcohol), poly(vinyl pyrrolidone), polyacrylamide, cellulose ethers and carboxylated derivatives thereof, partially hydrolyzed cellulose acetate, certain copolymers of acrylic and methacrylic acids, polymeric hydrosols or 1atexes, mixtures of these, and the like.
  • hydrophilic colloids that are known to be satisfactory vehicles for dispersed silver halides
  • emulsions comprising natural materials such as gelatin, gelatin derivatives, agar-agar, albumin, gum arabic, alginic acid, etc.
  • the concentration of the new dyes in the emulsion can vary widely, e.g., from about 5 to about 100 mg. per liter of flowable emulsion.
  • the specific concentration will vary according to the type of light sensitive material in the emulsion and the effects desired.
  • the suitable and most economical concentration for a given emulsion will be apparent to those skilled in the art upon making the tests and observations customarily used in the art of emulsion making.
  • a gelatin-silver halide emulsion sensitized with one of the dyes of this invention the following procedure is satisfactory: A quantity of the dye is dissolved in a suitable solvent and a quantity of this solution containing from 5 to 100 mg. of dye is slowly added to one liter of a gelatin-silver halide emulsion. With most of the dyes, 10 to 20 mg. of dye per liter of emulsion sufiices to produce the maximum sensitizing eifect with the ordinary gelatin-silver bromide (including bromoiodide and chlorobromide) emulsions.
  • Photographic silver halide emulsions containing the sensitizing dyes of this invention can also contain other addenda such as chemical sensitizers, e.g., sulfur sensitizers such as allyl thiocarbamide, thiourea, allyl isothiocyanate, cystine, etc., selenium and tellurium sensitizers, various gold compounds such as potassium chloroaurate, auric trichloride, etc. (see US. Pats. 2,540,085; 2,597,- 856, and 2,597,915), various palladium compounds such as palladium chloride (US. Pat. 2,540,086), potassium chloropal1adate(U .S. Pat.
  • chemical sensitizers e.g., sulfur sensitizers such as allyl thiocarbamide, thiourea, allyl isothiocyanate, cystine, etc., selenium and tellurium sensitizers
  • gold compounds such as potassium chloro
  • antifoggants such as ammonium chloroplatinate (US. Pat. 2,566,263), benzonitrazole, nitrobenzimidazoles, S-nitroindazole, mercaptans, etc., (see Mees, The Theory of the Photographic Process, Macmillan Pub., 1942, p. 460); or mixtures thereof.
  • Photographic silver halide emulsion layers and other layers present in the photographic elements made according to the invention may contain developing agents such as hydroquinones, catechols, 1,3-pyrazolidones, aminophenols, etc.; and the layers can be hardened with any suitable hardener such as aldehyde hardeners, aziridine hardeners, hardeners which are derivatives of dioxane, oxypolysaccharides, mixtures of these, and the like.
  • the layers present in photographic elements made according to the invention may also contain color couplers, such as those described in US. Pats. 2,423,730 and 2,640,776, et al., or mixtures of such addenda. Dispersing agents for color couplers such as those set forth in US. Pats.
  • the photographic emulsions can also contain additional additives, particularly those known to be beneficial in photographic emulsions, including stabilizers, for example, particularly the water soluble inorganic acid salts of cadmium, cobalt, manganese, and zinc such as disclosed in U.S. Pat. 2,829,404, and the substituted triazaindolizines such as those disclosed in US. Pats.
  • stabilizers for example, particularly the water soluble inorganic acid salts of cadmium, cobalt, manganese, and zinc such as disclosed in U.S. Pat. 2,829,404, and the substituted triazaindolizines such as those disclosed in US. Pats.
  • the dyes dissolved in suitable solvents, were added to separate portions of either a silver bromoiodide (99.3:0.65) or a silver chlorobromide (40- 60) emulsion, as indicated in the table, at the concentrations indicated.
  • a silver bromoiodide 99.3:0.65
  • a silver chlorobromide 40- 60
  • the emulsions were coated on a cellulose acetate film support at a coverage of 459 mg., of silver and 1040 mg., of gelatin per square foot.
  • a sample of each coating was then exposed on an Eastman 1B 'Sensitometer and to a wedge spectrograph, processed for 3 minutes in Kodak. Developer D49, fixed, washed, and dried.
  • SENSITIZIN G DATA Dye of Dye cone. sensitizing sensitizing example Emulsion (grams per range maximum numbertype mole) (m to-- (m 0.08 600 560 0. 1a 610 540, 575- 0. O8 560 515 0. 13 580 535 0. 08 540 515 0. 13 545 515 0. 08 670 540, 600 0. 13 660 560, 605 0. 08 625 595 0. 13 630 595 0.08 600 560 0. 13 600 560 0. 08 720 555, 665 0. 13 720 665 0. 08 690 565 0. 08 660 590 0. 13 635 560 0.08 640 555 O. 08 640 530, 580 0. 13 635 500, 570 O. 08 630 580 0.
  • the photographic silver halide emulsions may be coated advantageously on any of the support materials commonly used in photographic elements including glass, metals, paper, cellulose nitrate, and synthetic film forming resinous materials such as polystyrene, polyolefins, polyesters, polyamides, polycarbonates, poly(vinyl acetals), etc., supports such as papers which are partially acetylated or coated with an a-olefin polymer, particularly a polymer derived from an a-olefin containing 2-10 carbon atoms as exemplified by polyethylene and polypropylene, ethylene-butene copolymers, and the like, also give good results.
  • filter-eel refers to a diatomaceous earth filter aid. Any inert diatomite filter aid can be employed such as that sold by Johns-Manville under the registered trade-mark Celite,
  • the invention has been described in detail with reference to particular embodiments thereof, but it will be understood that variations and modifications can be eifected within the spirit and scope of the invention as described hereinbefore and as defined in the appended claims.
  • R and R each represents the same or different member selected from the group consisting of a hydrogen atom or a chlorine atom
  • Q represents the nonmetallic atoms required to complete a S-membered heterocyclic nucleus selected from the group consisting of a thiazole nucleus, a thiazoline nucleus, a benzothiazole nucleus and a naphthothiazole nucleus.
  • a photographic element comprising a support having thereon at least one layer containing a photographic emulsion according to claim 1.
  • R and R each represents the same or different member selected from the group consisting of a hydrogen atom or a chlorine atom;
  • R represents a member selected from the group consisting of an alkyl group, a carboxyalkyl group, a sulfoalkyl group and a phenyl group;
  • d represents a positive integer of from 1 to 3;
  • n represents a positive integer of from 1 to 2;
  • Q represents the nonmetallic atoms required to complete a S-membered heterocyclic nucleus selected from the group consisting of a thiazole nucleus, at thiazoline nucleus, a benzothiazole nucleus and a naphthothiazole nucleus;
  • Z represents the nonmetallic atoms required to complete a 5- to 6-membered heterocyclic nucleus selected from the class consisting of a thiazole nucleus, a benzothiazole nucleus, 3.
  • naphthothiazole nucleus a thianaphtheno-7', 6, 4,5-thiazole nucleus, an oxazole nucleus, a benzoxazole nucleus, at naphthoxazole nucleus, a selenazole nucleus, a benzoselenazole nucleus, at naphthoselenazole nucleus, a thiazoline nucleus, a Z-pyridine nucleus, a 4-pyridine nucleus, a 2- quinoline nucleus, a 4-quinoline nucleus, al-isoquinoline nucleus, a 3-isoquinoline nucleus, a 3,3-dialkylindolenine nucleus, an imidazole nucleus, a benzimidazole nucleus, and .a-naphthimidazole nucleus;
  • L represents the nonmetallic atoins required to complete a heterocyclic nucleus selectedfrom the class
  • a photographic silver halide emulsion according to claim 4 wherein said compound has the formula:
  • a photographic silver halide emulsion according to 8 A photographic element comprising a support and having thereon at least one layer containing a silver halide emulsion according to claim 4.
  • a photographic element comprising a support and at least one layer coated thereon containing silver halide and a compound selected from the formulae:
  • R and R each represents the same or different member selected from the group consisting of a hydrogen atom or a chlorine atom;
  • R represents a member selected from the group consisting of an alkyl group, a carboxyalkyl group, a sulfoalkyl group and a phenyl group;
  • d represents a positive integer of from 1 to 3;
  • n represents a positive integer of from 1 to 2;
  • Q represents the nonmetallic atoms required to complete a S-membered heterocyclic nucleus selected from the group consisting of a thiazole nucleus, a thiazoline nucleus, at benzothiazole nucleus and a naphthothiazole nucleus;
  • Z represents the nonmetallic atoms required to complete a 5- to 6-membered heterocyclic nucleus selected from the class consisting of a thiazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus,
  • naphthoxazole nucleus a selenazole nucleus, a benzoselenazole nucleus, 9. naphthoselenazole nucleus, a thiazoline nucleus, a Z-pyridine nucleus, a 4-pyridine nucleus, a 2 quinoline nucleus, a 4 quinoline nucleus, at 1 isoquinoline nucleus, a 3 isoquinoline nucleus, a 3,3 dialkylindolenine nucleus, an imidazole nucleus, a benzimidazole nucleus, and a naphthimidazole nucleus;
  • L represents the nonmetallic atoms required to complete a heterocyclic nucleus selected from the class consisting of a 2-pyraz0lin-5-one nucleus, an isoxazolone nucleus, an oxindole nucleus, at barbituric acid nucleus, a Z-thiabarbituric acid nu
  • a photographic element according to claim 9 wherein said compound is 1,1'-di(2-lbenzothiazoly)-3,3'-dimethylbenzimidazolocarbocyanine iodide.
  • a photographic element according to claim 9 wehein said compound is I-(Z-benzothiazolyl)*3'-ethyl-3- methylbenzimidazolothiacarbocyanine iodide.
  • a photographic element according to claim 9 wherein said compound is 5- ⁇ [1-(2-benzothiazolyl)-5- chloro 3 methyl 2 benzimidazolinylidene]ethylidene ⁇ -3-ethylrhodanine.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Thiazole And Isothizaole Compounds (AREA)
US86328A 1970-11-02 1970-11-02 Photographic emulsion containing new benzimidazole compounds as sensitizing dyes Expired - Lifetime US3684517A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US8632870A 1970-11-02 1970-11-02

Publications (1)

Publication Number Publication Date
US3684517A true US3684517A (en) 1972-08-15

Family

ID=22197853

Family Applications (1)

Application Number Title Priority Date Filing Date
US86328A Expired - Lifetime US3684517A (en) 1970-11-02 1970-11-02 Photographic emulsion containing new benzimidazole compounds as sensitizing dyes

Country Status (4)

Country Link
US (1) US3684517A (enExample)
CA (1) CA964266A (enExample)
FR (1) FR2113436A5 (enExample)
GB (1) GB1363718A (enExample)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4138551A (en) * 1975-03-18 1979-02-06 Ciba-Geigy Ag Spectral sensitization of photographic material and new spectral sensitizers
JPWO2021141078A1 (enExample) * 2020-01-10 2021-07-15

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4138551A (en) * 1975-03-18 1979-02-06 Ciba-Geigy Ag Spectral sensitization of photographic material and new spectral sensitizers
JPWO2021141078A1 (enExample) * 2020-01-10 2021-07-15
WO2021141078A1 (ja) * 2020-01-10 2021-07-15 富士フイルム株式会社 光電変換素子、撮像素子、光センサ
JP7308984B2 (ja) 2020-01-10 2023-07-14 富士フイルム株式会社 光電変換素子、撮像素子、光センサ
US12329025B2 (en) 2020-01-10 2025-06-10 Fujifilm Corporation Photoelectric conversion element, imaging element, and optical sensor

Also Published As

Publication number Publication date
FR2113436A5 (enExample) 1972-06-23
CA964266A (en) 1975-03-11
GB1363718A (en) 1974-08-14

Similar Documents

Publication Publication Date Title
US2734900A (en) Chxgh
US3482978A (en) Carbocyanine filter dyes and sensitizers for silver halide emulsions
US3639127A (en) Silver halide emulsions containing a dye derived from 4,6-diaryl substituted picolinium salts as desensitizer
US2955939A (en) Holopolar cyanine dyes and photographic emulsions containing them
US3194805A (en) Merocyanine and holopolar dyes containing arylene-chain substitution
US2776280A (en) Optical sensitizing dyes containing a n-carbamylmethyl group
US3384486A (en) Merocyanine dyes for photographic elements containing an extracyclic tertiary amino group
US3326688A (en) Photographic sensitizing dyes
US2882159A (en) Merocyanine sensitizing dyes and photographic emulsions containing them
US3468661A (en) Photographic material sensitized with a trimethine dye containing a benzoyl substituted benzimidazole nucleus
US3632808A (en) Cyanine dyes containing an imidazo (4 5-b)quinoxaline nucleus
US3469985A (en) Light-absorbing dyes derived from barbituric and 2 - thiobarbituric acid compounds useful for photography and their preparation
US3337540A (en) Methine dyes
US2778823A (en) Benzimidazolocarbocyanine dyes
US3684517A (en) Photographic emulsion containing new benzimidazole compounds as sensitizing dyes
US3539349A (en) Fogold direct positive silver halide emulsions containing quaternated merocyanine dyes
US3140182A (en) Non-ionized polymethine sensitizing dyes
US3440052A (en) Sensitized silver halide emulsions with holopolar dyes containing a dilactone ring
US2748114A (en) Merocyanine dyes containing a sulfone group
US3384489A (en) Sensitized silver halide emulsions containing n, alpha-alkylene bridged sensitizing dyes
US3140951A (en) Desensitizing dyes and photographic processes and materials
US2743274A (en) Merocyanine dyes containing the triazolo [4, 3-a]-quinoline or tetrazolo [a] quinoline nucleus
US3725398A (en) Process for preparing 9-aryloxycarbocyanine compounds
US3483196A (en) Imidazo(4,5-b) quinolinium salts and cyanine,merocyanine and styryl photographic sensitizing dyes derived therefrom
US3579344A (en) Novel dyes and direct positive photographic emulsions