US2882158A - Photographic sensitizing dyes and emulsions containing them - Google Patents

Photographic sensitizing dyes and emulsions containing them Download PDF

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US2882158A
US2882158A US585946A US58594656A US2882158A US 2882158 A US2882158 A US 2882158A US 585946 A US585946 A US 585946A US 58594656 A US58594656 A US 58594656A US 2882158 A US2882158 A US 2882158A
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those
series
mol
dye
pyridine
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Leslie G S Brooker
Donald W Heseltine
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Eastman Kodak Co
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Eastman Kodak Co
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Priority to US585946A priority patent/US2882158A/en
Priority to GB15056/57A priority patent/GB868797A/en
Priority to GB15055/57A priority patent/GB862443A/en
Priority to FR1192173D priority patent/FR1192173A/fr
Priority to GB16183/57A priority patent/GB868798A/en
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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
    • G03C1/10—Organic substances
    • G03C1/12—Methine and polymethine dyes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/18—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
    • C07D207/20—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • 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
    • C09B23/0091—Methine or polymethine dyes, e.g. cyanine dyes having only one heterocyclic ring at one end of the methine chain, e.g. hemicyamines, hemioxonol
    • 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
    • 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 certain cyanine :dyes useful in optically sensitizing photographic silver halide emulsions, and to photographic silver halide emulsions sensitized with these cyanine dyes.
  • the dyes of our invention can advantageously be reprea carbalkoxyl group, such as carbometh'oxyl, carbethoxyl,
  • Z represents the non-metallic atoms necessary to complete a heterocyclic nucleus containing from-5 (n is 1') to 6 (n is 2) atoms in the heterocyclic ring, such as those selected from the group consisting of those of the thiazole series (e.g., thiazole, 4-methylthiazole, S-methylthiazole, 4-phenylthiazole, 5-phenylthiazole,.
  • thiazole series e.g., thiazole, 4-methylthiazole, S-methylthiazole, 4-phenylthiazole, 5-phenylthiazole,.
  • 4,5-dimethylthiazole 4,5 diphenylthiazole, 4-(2-thienyl)thiazole, etc.
  • those of the benzothiazole series e.g., benzothiazole, 4-methylbenzothiazol e, 5-methylbenzothiazo1e,.
  • naphthothiazole series e.g., naphtho[2,1]thiazole,
  • thoseof the naphthoxa-zole series e.g., naphth[2,1.] oxazole, naphth[1,2]oxazole, etc.
  • those of the selenazole series. e.g., 4wmethylselenazole, 4-phenylse1enazole, etc.
  • those of the benzoselenazole series e.g., benzoselenazole, 5-methoxybenzoselenazole, 5-hydroxybenzoselenazole, tetrahydrobenzoselenazole, etc.
  • those of the naphthoselenazole series e.g., naphtho[2,1]selenazole, naphtho[1,2] selenazole, etc.
  • those of the thiazoline series e.g., thiaz'oline, 4-methylthiazoline, etc.
  • those of. the 2-quinoli-ne series e.g.,
  • R can represent an aryl group, such as phenyl, tolyl, etc. (e.g., a monocyclic aryl group of. the benzene: series).
  • the instant invention provides methods for making the dyes represented by Formula I above by condensing a cyclammon'ium quaternary salt selected from those represented by the following general formula:
  • R, n and Z each have the values given above
  • X represents an acid radical, such as chloride, bromide, iodide, thiocyanate, p-t'oluenesullfonate, benzenesulfonate, ethylsulfate, etc
  • R represents an alkylmercapto group (e.g., methylmercapto, ethylmercapto, etc.), and arylmercapto group (e.g.,-phenylmercapto, tolylmercapto, etc.), or a fl-acylanilidovinyl group (e.g., B-acetanilidovinyl, B-benzoylanilidovinyl, etc.),, with a compound selected from those represented by the following general formula:
  • R, R R R R n, d and Z have the values given above.
  • the condensations of the intermediates of Formula H with the compounds of Formula III (or IIIa) can be accelerated by basic condensing agents, such as the trialkylamines (e.g., triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, etc.), N,N-dialkylanilines (e.g., N,N-d imethylaniline, N,N-diethylaniline, etc.), N-alkylpiperidines (e.g. N-methylpiperidine, N-ethylpiper'idine, etc.), etc.
  • trialkylamines e.g., triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, etc.
  • N,N-dialkylanilines e.g., N,N-d imethylaniline, N,N-diethylaniline, etc.
  • the condensations can be carried outin the presence of an inert diluent, such as the lower alcohols (e.g., ethanol, n-propanol, isopropanol, n-hutanol, etc.), pyridine, quinoline, 1,4-dioxane, etc.
  • an inert diluent such as the lower alcohols (e.g., ethanol, n-propanol, isopropanol, n-hutanol, etc.), pyridine, quinoline, 1,4-dioxane, etc.
  • Example 1 -2-[ (3-dicyanomethylene-5,5-dimethyl- 1 -cyclohexene-1 -yl)methylene]-3-methylthiaz0lidine 3-methyl-2-thiothiazolidinone (4 g., 1 mol.+200%) and methyl p-toluenesulfonate (7.44 g., 1 mol.
  • Example 2 -2-[(S-dicyanomethylene-5,5dimethyl-1- cyclohexen-I -yl) -methylene] -3-methylbenzoxazoline 2-methylmercaptobenzoxazole (4.95 g., 1 mol.+200%) and methyl p-toluenesulfonate (5.6 g., 1 mol.+200%) were mixed and heated to reflux over a free flame and then allowed to cool slowly to room temperature.
  • 3-dicyanomethylene 1,5,5 trimethyl 1 cyclohexene (0.93 g., 1 mol.), 3-methyl-2-methylmercaptobenzoselenazolium p-toluenesulfonate (2.07 g., 1 mol.) and triethylamine (1.4 ml., 1 mol.+l00%) were dissolved in pyridine (10 ml.) and heated under reflux for ten minutes.
  • the crude dye was thrown out of solution by the addition with stirring of methyl alcohol (100 ml.). After chilling overnight, the crude dye was filtered oif, washed with methyl alcohol and dried. The yield of purified dye after two recrystallizations from ethyl alcohol was 0.89 g. (47%), M.P. 183-4 C.
  • Example 5 --2-[(3-dicyan0methylene 5,5 dimethylcyclohexen-I-yl)-methylene] 1 methylnaphtho[1,2] thiazoline 3-dicyanomethylene 1,5,5, trimethyl 1 cyclohexene (0.93 g., 1 mol.), 1-methyl-Z-methylmercaptonaphtho [1,2lthiaz0liurn p-toluenesulfonate (2.09 g., 1 mol.) and triethylarnine (1.4 ml., 1,,mol.+100%) were dissolved in pyridine (15 ml.) and the mixture heated under reflux for ten minutes.
  • the crude dye was thrown out of solution by the addition with stirring of methyl alcohol (100 ml.). After chilling overnight, the crude dye was filtered off, washed with methyl alcohol and dried. The yield of purified dye after three recrystallizations from pyridine and methyl alcohol, was 1.45 g., (77%), M.P. 243-4 C. with dec.
  • the crude dye was thrown out of solution by the addition with stirring of methyl alcohol (100 ml.). After chilling overnight, the crude dye was filtered off, washed with a little methyl alcohol and dried. The yield of purified dye after two recrystallizations from ethyl alcohol was 1.10 g. (31%), M.P. 2034 C. with dec.
  • the crude dye was thrown out of solution by the addition with stirring of water (100 ml.). The aqueous solution was then decanted and the residue stirred with methyl alcohol until it became crystalline. After chilling overnight, the crude dye was filtered ofli, washed with a little methyl alcohol and dried. After two recrystallizations from ethyl alcohol, the yield of purified dye was 0.39 g., (11%), M.P. 195-6" C. with dec.
  • Example 9.2- (3-dicyan0methylene-5.5-dimethyI-1-cyclohexen-I -yl methylene] -1 -phenylpyrr0lidine 3 dicyanomethylene 1,5,5 trimethyl 1 cyclohexene (1.86 g., 1 mol.), 2-methylmercapto-l-phenylpyrrolidinium p-toluenesulfonate (3.63 g., 1 mol.) and triethylamine (2.8 ml., 1 mol.+%) were dissolved in pyridine (15 ml.) and heated under reflux for fifteen minutes. The crude product was thrown out of solution by the addition with stirring of water (100 ml.).
  • Example I2 -2-[(J-dicyanomethylene-S-methyl-I-cyclohexen-1-yl)-methylene]-3-methylbenzoxazoline 3 dicyanomethylene 1,5 dimethyl 1 cyclohexene (0.86 g., 1 mol.), 3-methyl-2-methylmercaptobenzoxazolium p-toluenesulfonate (6.72 g., 1 mol.+l%) and triethylamine (2.8 ml., 1 mol.+300%) were dissolved in pyridine ml.) and heated under reflux for ten minutes. The crude dye was thrown out of solution by the addition with stirring of water (50 ml.).
  • Example 13 2- (3-dicyanomethylene-I -cyclohexen-1- yl) methylene]-3-methylbenzolhiaz0line B-dicyanomethylene-l-methyl-1-cyclohexene (0.79 g., 1 mol.), 3-methyl-2-methylmercaptobenzothiazolium ptoluenesulfonate (3.67 g., l mol.+l00%) and triethylamine 1.4 ml., 1 mol.+l00%) were dissolved in pyridine (10 ml.) and heated under reflux for ten minutes. The crude dye was thrown out of solution by the addition with stirring of water (100 ml.).
  • the crude dye was thrown out of solution by the addition with stirring of water (100 ml.). The aqueous solution was decanted and the residue dissolved in a little methyl alcohol and chilled with occasional stirring for one week. The crude dye was then filtered otf, washed with a little methyl alcohol and dried. After two recrystallizations from pyridine and methyl alcohol, the yield of pure dye was 0.65 g. (swans/ 1 ,185-36 C. with dec..
  • the crude dye was precipitated by the addition with stirring of water (100 ml.). The aqueous solution was decanted and the residue stirred with methyl alcohol until crystalline. After chilling overnight, the crude dye was, filtered off, washed with a little methyl alcohol and dried. After two recrystallizations from ethyl alcohol, the yield of pure dye was 1.12 g. (30%), M.P. 179180 C. with dec.
  • the intermediates selected from those represented by Formulas III and HM can advantageously be prepared by the method of Widequist (Acta. Chem. Scand., vol. 3:, pp. 3034304, 1949) by condensing a 3-methyl-2-cyclohexen-l-one, with an intermediate of the formula:
  • Malononitrile (19.8 g., 1 mol.) and isophorone (46 g., 1 mol.+10%) were dissolved in chloroform and ammonium acetate (2.5 g.) and acetic acid (4 ml.) were added.
  • the mixture was then heated under reflux for one hour in a system fitted for continuous removal of water.
  • the chloroform solution was then washed with two ml. portions of water and the chloroform removed by distillation. The residue was then distilled under vacuum yielding 30.2 g. (54%), B.P. -6 C./l9 mm., M.P. 7980 C.
  • Example 25 -6- carbethoxy 3 dicyanomethylene-lmethyl-1 -cyclh exene 4-carbethoxy-3-methyl-2-cyclohexen-1-one (18.1 g., 1 mol.) and malononitrile (7.3 g., 1 mol.+10%) were dissolved in chloroform (40 m1.) and ammonium acetate (2.5 g.) and acetic acid (4 ml.) were added. The reaction mixture was then heated under reflux for four hours in an apparatus designed for the continuous removal of water. The chloroform solution was then washed with two 25 ml. portions of water and the chloroform removed by distillation. The residue was then distilled under vacuum yielding 15.6 g. (68%) of product, B.P. 200-201" C./9 mm.
  • All of the dyes of our invention are particularly useful in manufacturing photographic, silver halide emulsions, serving to alter the sensitivity thereof. Sensitizationby means of our new dyes is, of course, directed primarily to the ordinarily employed, gelatino-silverhalide, developing-out emulsions.
  • the dyes are advantageously incorporated in the washed, finished emulsion and should, of course, be uniformly distributed throughout the emulsion. In the preparation of photographic emulsions containing our'new .dyes, it is only necessary to disperse the dyes in the emulsions.
  • the methods of incorporating dyes in emulsion are simple and well known to those skilled in the art of emulsion making.
  • concentration of our new dyes in the emulsion can vary widely, i.e., from about to about 100 mgs. per liter of flowable emulsion.
  • concentration of the dye will vary according to the type of light-sensiitve material in the emulsion and according to the effects desired.
  • suitable and most economical concentration for any given emulsion will be apparent to those skilled in the art upon :making the ordinary tests and observations customarily used in the art of emulsion making.
  • the dyes can be incorporated by bathing a plate or film upon which an emulsion has been coated, in the solution of the dye, in an appropriate solvent. Bathing methods, however, are not to be preferred ordinarily.
  • Photographic silver halide emulsions which can advantageously be sensitized by means of the new dyes of our invention comprise the customarily employed gelatino-silver-chloride, gelatino-silver-chlorobromide, gelatino-silver-bromide, and gelatino-silver bromiodide developing-out emulsions.
  • Photographic silver halide emulsions such as those listed above, containing the sensitizing dyes 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.S.
  • chemical sensitizers e.g., sulfur sensitizers (e.g., allyl thiocarbamide, thiourea, allylisothiocyanate, cystine, etc.)
  • gold compounds e.g., potassium chloroaurate, auric
  • 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., 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.
  • 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.
  • the 2-methylmercapto-l-phenylpyrrolidinium p-toluene sulfonate employed in Example 9 above was prepared as follows: 1-phenyl-2-thiopyrrolidone (1.77 g., 1 mol.) and methyl p-toluene-sulfonate (1.86 g., 1 mol.) were fused and heated on a steam bath for one hour. The solid quaternary salt was used in dye condensations without further purification.
  • the 1-phenyl-2-thiopyrrolidone used above was prepared as follows: l-phenyl-Z-pyrrolidone (26 g., 1 mol.) [Spath and Lintner Ber., 69B, 2727 (1936)] and phosphorous pentasulfide (18 g., 1 mol. +50%) were dissolved in pyridine ml.) and heated to reflux. After ten minutes the reaction mixture was poured into water 0. .9 i hsti r n -T .e oi y p odu w extracted .wi et and the ethereal solution concentrated and the residue distilled at l95-l9 7 C./ 8 mm. After recrystallization of the solid distillate from ethanol, the yield of pale yellow crystals was 17 g. (59%), MP. 73-5 C.
  • a photographic silver halide emulsion sensitized with a polymethine dye selected from those represented by the following general formula:
  • R represents an alkyl group containing from 1 to 4 carbon atoms
  • d represents a positive integer of from 1 to 2
  • Q represents the atoms necessary to complete a cyclohexene ring.
  • a photographic silver halide emulsion sensitized with a polymethine dye selected from those represented by the following general formula:
  • R represents an alkyl group containing from 1 to 4 carbon atoms
  • d represents a positive integer of from 1 to 2
  • Q represents the atoms necessary to complete a cyclohexene ring.
  • R represents an alkyl group containing from 1 to 4 carbon atoms
  • d represents a positive integer of from 1 to 2
  • Q represents the atoms necessary to complete a cyclohexene ring.
  • a photographic silver halide emulsion sensitized with a polymethine dye selected from those represented by the following general formula:
  • R represents an alkyl group containing from 1 to 4 carbon atoms
  • R represents a member selected from the group consisting of a cyano group and a carbalkoxyl group containing from 2 to 3 carbon atoms
  • R represents a member selected from the group consisting of a hydrogen atom and a carbalkoxyl group containing from 2 to 3 carbon atoms
  • R and R each represents a member selected from the group consisting of a hydrogen atom and an alkyl group containing from 1 to 2 carbon atoms
  • n and d each represents a positive integer of from 1 to 2
  • 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 thianaphtheno-7',6',4,5-thiazole series, those of the oxazole series, those of the benzoxazole
  • a photographic silver halide emulsion sensitized with 9 A photographic silver halide emulsion sensitized with the polymethine dye represented by the following formula:
  • R represents an alkyl group containing from 1 to 4 carbon atoms
  • R represents a member selected from the group consisting of a cyano group and an alkoxy carbonyl group containing from 2 to 3 carbon atoms
  • Q rep resents the non-metallic atoms necessary to complete a cyclohexene ring
  • n and d each represents a positive integer of from 1 to 2
  • 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 thianaphtheno-7,6',4,5- thiazole 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

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  • 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)
  • Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
US585946A 1956-05-21 1956-05-21 Photographic sensitizing dyes and emulsions containing them Expired - Lifetime US2882158A (en)

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BE557656D BE557656A (en, 2012) 1956-05-21
US585946A US2882158A (en) 1956-05-21 1956-05-21 Photographic sensitizing dyes and emulsions containing them
GB15056/57A GB868797A (en) 1956-05-21 1957-05-13 Improvements in dye-sensitized photographic emulsions
GB15055/57A GB862443A (en) 1956-05-21 1957-05-13 Improvements in dye-sensitized photographic emulsions
FR1192173D FR1192173A (fr) 1956-05-21 1957-05-15 Nouvelles cyanines et leurs applications notamment en photographie
GB16183/57A GB868798A (en) 1956-05-21 1957-05-21 Improvements in photographic sensitizing dyes

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3124584A (en) * 1964-03-10 Process for the production of hetero-
US3305558A (en) * 1967-02-21 And y-cyanobenzimidazole derivatives
US3852321A (en) * 1972-10-13 1974-12-03 J Babler 3,3-dimethylcyclohexylideneacetonitriles
EP0349139A3 (en) * 1988-06-29 1990-05-30 Ici Americas Inc. Ultraviolet radiation absorbing cyclohexenylidene compositions
WO2000059872A1 (en) * 1999-04-02 2000-10-12 Hrl Laboratories, Llc Dopants for liquid-crystal devices
JP2006527765A (ja) * 2003-06-18 2006-12-07 インダストリアル リサーチ リミティド 双性イオン性非線形オプトフォアおよびそれらが組み込まれているデバイス

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Publication number Priority date Publication date Assignee Title
JPS6079348A (ja) * 1983-10-06 1985-05-07 Fuji Photo Film Co Ltd ハロゲン化銀写真感光材料
US5213956A (en) * 1991-07-22 1993-05-25 Eastman Kodak Company Solid particle dispersions of filter dyes for photographic elements
DE4401912A1 (de) * 1994-01-24 1995-07-27 Basf Ag Methinfarbstoffe in der nichtlinearen Optik
US5464736A (en) * 1994-04-28 1995-11-07 Eastman Kodak Company Photographic elements containing particular sensitizing dyes
DE10203939A1 (de) * 2002-02-01 2003-08-21 Few Chemicals Chemiepark Bitte Merocyaninfarbstoff und Initiatorsystem für die Photopolymerisation

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US2697707A (en) * 1950-12-05 1954-12-21 Ilford Ltd Process of producing cyanine dyestuffs
US2721799A (en) * 1950-10-19 1955-10-25 Eastman Kodak Co Sensitized photographic emulsions
US2756227A (en) * 1953-12-28 1956-07-24 Eastman Kodak Co Quaternary salts and method of preparation
US2766233A (en) * 1953-12-11 1956-10-09 Gen Aniline & Film Corp Polymethine dyes for synthetic fibers
US2773869A (en) * 1954-06-21 1956-12-11 American Cyanamid Co Alkenyl bisimidazole optical bleaching agents

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US2721799A (en) * 1950-10-19 1955-10-25 Eastman Kodak Co Sensitized photographic emulsions
US2697707A (en) * 1950-12-05 1954-12-21 Ilford Ltd Process of producing cyanine dyestuffs
US2766233A (en) * 1953-12-11 1956-10-09 Gen Aniline & Film Corp Polymethine dyes for synthetic fibers
US2756227A (en) * 1953-12-28 1956-07-24 Eastman Kodak Co Quaternary salts and method of preparation
US2773869A (en) * 1954-06-21 1956-12-11 American Cyanamid Co Alkenyl bisimidazole optical bleaching agents

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3124584A (en) * 1964-03-10 Process for the production of hetero-
US3305558A (en) * 1967-02-21 And y-cyanobenzimidazole derivatives
US3852321A (en) * 1972-10-13 1974-12-03 J Babler 3,3-dimethylcyclohexylideneacetonitriles
EP0349139A3 (en) * 1988-06-29 1990-05-30 Ici Americas Inc. Ultraviolet radiation absorbing cyclohexenylidene compositions
WO2000059872A1 (en) * 1999-04-02 2000-10-12 Hrl Laboratories, Llc Dopants for liquid-crystal devices
US6852248B1 (en) 1999-04-02 2005-02-08 Hrl Laboratories, Llc Dopants for liquid-crystal devices
JP2006527765A (ja) * 2003-06-18 2006-12-07 インダストリアル リサーチ リミティド 双性イオン性非線形オプトフォアおよびそれらが組み込まれているデバイス

Also Published As

Publication number Publication date
FR1192173A (fr) 1959-10-23
GB868798A (en) 1961-05-25
GB862443A (en) 1961-03-08
BE557656A (en, 2012)
GB868797A (en) 1961-05-25

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