US3753721A - Photographic materials - Google Patents

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US3753721A
US3753721A US00063606A US3753721DA US3753721A US 3753721 A US3753721 A US 3753721A US 00063606 A US00063606 A US 00063606A US 3753721D A US3753721D A US 3753721DA US 3753721 A US3753721 A US 3753721A
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silver halide
gold
grains
sensitized
silver
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A Millikan
M Brizee
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Eastman Kodak Co
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    • 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
    • C09B23/0066—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain being part of a carbocyclic ring,(e.g. benzene, naphtalene, cyclohexene, cyclobutenene-quadratic acid)
    • 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
    • C09B23/02—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
    • C09B23/08—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
    • C09B23/086—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 more than 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
    • C09B23/10—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
    • G03C1/09—Noble metals or mercury; Salts or compounds thereof; Sulfur, selenium or tellurium, or compounds thereof, e.g. for chemical sensitising
    • 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 materials, and more particularly to fine grain silver halide photographic materials.
  • Glafkides Photographic Chemistry, published by the Fountain Press, London, 1958, states at page 320 that gold sensitization is mainly effective with large silver halide grains, which have higher sensitivity to light than fine silver halide grains (i.e., up to 0.2 micron in size). Glafkides also statesat page 319 that gold sensitization frequently results in substantial increases in fog and causes emulsion instability, which often results in the emulsion becoming useless after being kept for a few days.
  • Fine grain silver halide emulsions must be used instead of faster large grain silver halide emulsions for various purposes, for example in photographic applications where high resolution is essential, such as holography and microphotography. Hence,1it appears highly desirable to provide stable emulsions comprising fine silver halide grains which have low fog and high speeds.
  • One object of this invention is to provide photographic silver halide grains which exhibit increased speed to blue radiation.
  • Another object of this invention is to provide chemically sensitized photographic silver halide emulsions which are stable and exhibit increased speed to blue radiation.
  • a further object of this invention is to providephotographic silver halide emulsions which are particularly useful in applications requiring high resolving power, such as holography and microphotography.
  • Still another object of this invention is to provide spectrally sensitized photographic silverhalide emulsions.
  • Another object of this invention is to provide spectrally sensitized fine grain silver halide emulsions having higher speeds in the region of spectral sensitivity.
  • light-sensitive silver halide grains having an average grain size up to about 0.2 micron are sensitized with the combination of a noble metal sensitizer, at a concentration of about at least 50 milligrams noble metal per mole of silver,
  • the silver halide grains are spectrally sensitized with a photographic spectral sensitizing methine dye.
  • Silver halide grains employed in the practice of this invention can comprise silver chloride, silver bromide, silver bromoiodide, silver chlorobromoiodide or mixtures thereof.
  • the silver halide grains can range in-size up to 0.2 micron, and preferably upto 0.15 or 0.1 pm. Grains in the range of about 0.02 up to 0.09 micron give excellent results.
  • Such silver halide grains can be prepared by any of the well-known procedures. Very fine grain emulsions known in the art as Lippmann" emulsions are useful herein.
  • the noble metal sensitizers useful in this invention include the well-known gold sensitizers and other noble metals such as palladium and platinum, including any of the noble metal sensitizers described in Smith et al U.S. Pat. No. 2,448,060 issued Aug. 31, 1948.
  • Typical useful gold sensitizers are described in Waller et al U.S. Pat. No. 2,399,083 issued Apr. 23, 1946, Baldesiefen U.S. Pat. Nos. 2,540,085 and 2,540,086 both issued Feb. 6, 1951; Damschroder U.S. Pat. No. 2,597,856 issued May 27, 1952 and Damschroder et al. U.S. Pat. No. 2,642,361 issued June 16, 1953.
  • the noble metal sensitizer is employed in accordance with the invention in a concentration of from at least about 50 milligrams of noble metal per mole of silver, and preferably from about 125 to 175 milligrams noble metal sensitizer per mole of silver. Note that concentrations of noble metal are expressed in terms of noble metal and are not based on the total weight of the compound containing the noble metal.
  • the noble metal sensitizer is employed at concentrations lower than which causes substantial fog, such as fog levels over 3. Generally, there is no advantage in employing over 200 mg. noble metal per mole of silver.
  • the silver halide grains are chemically sensitized with a sulfur sensitizer.
  • Sulfur sensitizers are well known in the art and are described, for example, by Damschroder et al. US. Pat. No. 2,642,36! issued June 16, I953, columns 3 and 4.
  • Typical sulfur sensitizers are thiourea, allylisothiocyanate, thiosinamine (allylthiourea), cystine and B-ethyl xanthate propionic acid.
  • methyl or ammonium thiocyanates such as alkali metal thiocyanates (e.g., sodium or potassium thiocyanate) or alkaline earth metal thiocyanates (e.g., calcium thiocyanine, strontium thiocyanate, etc.), cadmium thiocyanate and ammonium thiocyanate.
  • alkali metal thiocyanates e.g., sodium or potassium thiocyanate
  • alkaline earth metal thiocyanates e.g., calcium thiocyanine, strontium thiocyanate, etc.
  • cadmium thiocyanate e.g., calcium thiocyanine, strontium thiocyanate, etc.
  • ammonium thiocyanate e.g., sodium or potassium thiocyanate
  • cadmium thiocyanate e.g., calcium thiocyanine, strontium thiocyanate, etc.
  • Sulfur sensitizers are employed herein at a weight ratio of sulfur to noble metal of about 1:15 to l:75, and preferably about 1:30 to about 1:50.
  • the amount of labile sulfur is used in calculating the useful concentrations of sulfur.
  • certain sulfur sensitizers e.g., sodium thiosulfate
  • sulfur sensitizers contain two sulfur atoms, but only one of those sulfur atoms is labile. These compounds are used in concentrations calculated on the basis of the one labile sulfur atom therein.
  • Any methine (including polymethine) photographic spectral sensitizing dye can be employed in the practice of this invention.
  • the most useful methine dyes are the cyanine, merocyanine, hemicyanine and hemioxonol dyes.
  • the dyes can be used in widely varying concentrations, with optimum concentrations being determined by any suitable means previously described in the art. Generally, about to 2,000 mg. dye per mole of silver provide good results, although larger or smaller amounts produce useful results depending on the particular dye and silver halide used.
  • Typical useful cyanine dyes have the following general formula:
  • thiazole 4-methylthiazole, 4-phenylthiazole, 5- methylthiazole, S-phenyl-thiazole, 4,5- dimethylthiazole, 4,5-diphenylthiazole, 4-(2- thienyl)thiazole, benzothiazole, 4-cholorbenzothiazole,
  • dimethoxy benzothiazole dimethoxy benzothiazole, 5,6-dioxymethylenebenzothiazole, S-hydroxy benzothiazole, 6- hydroxybcnzothiazole, naphtholZJ-dlthiazolc, naphtho[ 1,2-d1thiazole, 5-methoxynaphtho[2,3-dlthiazole, S-ethoxynaphthol2,3-d]thiazole, 8- methoxynaphthol2,3-d]thiazole, 7- methoxynaptho[2,3-d]thiazole, 4-methoxythianaphtheno7',6-4,5-thiazole, etc.; an oxazole nucleus, e.g., 4-methyloxazole, S-methyloxazole, 4-phenyloxazole, 4,5-diphenyloxazole, 4-ethyloxazole, 4,5- dimethyloxazole, S-phenylox
  • a quinoline nucleus e.g., 2- quinoline, 3-methyl-2-quinoline, 5-ethyl-2-quinoline, 6-chloro-2-quinoline, 8-chloro-2quinoline, 6-methoxy- 2-quinoline, 8-ethoxy-2-quinoline, 8-hydroxy-2- quinoline, 4quinoline, 6-methoxy-4-quinoline, 7-methyI-4-quinoline, 8-chloro-4-quinoline, 1- isoquinoline, 3 ,4-dihydrol -isoquinoline, 3- isoquinoline, etc; a 3,3-dialkylindolenine nucleus, e.g., 3,3-dimethylindolenine, 3,3,S-trimethylindolenine, etc.; and, an imidazole nucleus, e.g., imidazole, 1- alkylimidazole, l-alkyl-4 phenylimidazo1
  • the acid anion, represented by X in the above formula, is included in the substituent represented by R such as dyes containing the betaine type structurev
  • Some specific cyanine dyes that can be used in the process of this invention include the following: l'3-diethylthia-2'-cyanine chloride 1, l -diethyl-2,2'-cyanine chloride 3,3'-diethyloxacarbocyanine iodide 5,5-dichloro-3,3 -diethylthiacarbocyanine iodide 1,1'-diethyl-2,2'-carbocyanine iodide 3,3'-diethylthiazolocarbocyanine iodide 3,3'-diethyl-4,4'-diphenylthiazolocarbocyanine iodide 6 3,3-diethyl-9-methylthiacarbocyanine iodide 1,3,3 triethylbenzimi
  • Cyanine dyes which have at least one nucleus selected from a 5- or 6-dichlorobenzimidazole nucleus, a 5- or 6- methoxy-substituted benzothiazole nucleus or a 5- or 6-trifluoromethylbenzimidazole nucleus provide particularly good results.
  • Supersensitization of these dyes with a sulfonated polynuclear aromatic organic supersensitizer, an azaindeneor a silver halide reducing agent e.g., those described below.
  • a particularly useful class of cyanine dyes are tricarbocyanine dyes in which the meso carbon atom of the methine linkage of the dye is attached to the nitrogen atom of an amino group which forms an enamine with the methine linkage of the tricarbocyanine dye.
  • the term tricarbocyanine denotes. dyeshaving the ammidinium-ion chromophoric system (see Mees and James, The Theory of the Photographic Process, Third Edition, 1966, page 201).
  • such dyes have two nitrogen-containing heterocyclic nuclei which are joined by a straight chain methine linkage having seven methine groups.
  • the carbon atom of the central methine group of the methine linkage is referred to herein as the meso carbon atom of the methine linkage.
  • the preferred enamine tricarbocyanine dyes-used herein have the following formula:
  • a and b each represents an integer of from 1 to 2;
  • X represents an acid anion, such as those mentioned above;
  • R and R each represents a value given for R and R above;
  • Z and Z are each selected from a value given for Z and Z above;
  • Q represents a divalent linkage, such as ethylene, trimethyl, orthophenylene, which linkage can be substituted, for example, with halogen, an alkyl or an alkoxy group of one to four carbon atoms; and R and R taken separately each represents a member selected from the group consisting of alkyl and aryl, and, taken together R and R represent the non-metallic atoms required to complete a heterocyclic ring containing from 5 to 6 atoms, e.g., a morpholino group, a thiomorpholino group, a piperidino group, a piperazinyl group, (preferably a 4-alkyl-lpiperazinyl group such as methyl, ethy
  • Z and Z each represents a benzoxazole, a naphthothiazole nucleus, or a benzothiazole nucleus;
  • Q represents an ethylene linkage; and, R and R are taken together and represents a piperazinyl group, 4-ethoxycarbonyl-l-piperazinyl being preferred.
  • the enamine tricarbocyanine dyes employed in this invention can be prepared by reacting one mol of an intermediate having formula III below:
  • Typical useful merocyanine dyes have the following formula:
  • R-,, L and Z represents a value selected from those given above for R,, L and Z, respectively; c represents an integer of from 1 to 2; p represents an integer of from 1 to 3; and, Q represents the non-metallic atoms necessary to complete a 5- or 6-membered nucleus of the type used in merocyanine dyes typically containing a hetero atom selected from nitrogen, sulfur, selenium, and oxygen, such as a 2-pyrazolin-5-one nucleus, e.g., 3-methyl-l-phenyl-2-pyrazolin-S-one, l-phenyl-2-pyrazoline-5-one, l-(2-benzothiazolyl)-3- methyl-2-pyrazolin-5-0ne, etc.; an isoxazolone nucleus, e.g., 3-phenyl-5(4H)-isoxazolone, 3-methyl-5(4H) -isoxazolone, etc.; an oxindole
  • a 2-thio-2,4-oxazolidinedione nucleus i.e., those of the 2-thio-2,4(3H, 5H)-oxazoledione series) e.g., 3-ethyl-2 -thio-2,4-oxazolidinedione, 3-(2- thianaphthenone, etc.
  • a 2-thio-2,S-thiazolidinedione nucleus i.e., the 2-thio-2,5-(3H,4H)-thiazoledi0ne seimidazolidinedione, v l,3-diethyl 2,4- imidazolidinedione, l-ethyl-3-phenyl-2,4- imidazolidinedione, l-ethyl-3-a-nap
  • nuclei wherein Q represents the non-metallic atoms required to complete a heterocyclic nucleus containing five to six atoms in the heterocyclic ring, three to four of said atoms being carbon, and two of said atoms being selected from the group consisting of nitrogen, oxygen, and sulfur, and at least one of said two atoms being a nitrogen atom.
  • Typical useful merocyanine dyes are described in Brooker et al. US. Pat. No. 2,493,747 and 2,493,748, both issued Jan. 10, 1950, and Knott US. Pat. No. 2,839,403 issued June 17, 1958.
  • methine dyes include those comprising first and second! nuclei joined by a double bond or methine linkage (including one or more methine groups); the first of said nuclei being selected from the groupd consisting of l a nitrogen-containing heterocyclic nucleus of the type used in cyanine dyes having from 5to 6 non-metallic atoms in the heterocyclic ring, and (2) a nitrogen-containing heterocyclic ketomethylene nucleus of the type used in merocyanine dyes having from 5 to 6 non-metallic atoms in the heterocyclic ring, joined in each instance by a carbon atom of l) or (2) to said linkage; and said second nucleus being an enamine group selected from the group consisting of a l-(3,4,4a,5,6,7-hexahydro-2-naphthyl)- pyrrolidine group, a l-(3,3a,4,5-tetrahydro-2H-inden- 6-yl)pyrold
  • Methine dyes of this type can be conveniently prepared in a number of ways. For example, a number of the dyes defined by formula VIII above are advantageously prepared by heating a mixture of l a heterocyclic salt of the formula:
  • l-(2-norbornylidene)pyrrolidinium salt e.g., the chloride, bromide, iodide, perchlorate, p-toluenesulfonate, etc. salt, or a 1-( l-indanylidene)pyrrolidinium salt, e.g., the chloride, bromide, iodide, perchlorate, p-toluenesulfonate, etc.
  • a solvent medium such as ethanol, pyridine, N,N-dimethylacetamide, acetic anhydride, etc.
  • a basic condensing agent such as triethylamine is used with the acetic anhydride reaction medium.
  • the dyes are then separated from the reaction mixtures and purified by one or more recrystallizations from appropriate solvents such as methanol, mixtures of pyridine and methanol, and the like.
  • the dyes wherein the value offis 1 in formula VI" above are advantageously prepared with l) a heterocyclic salt of the formula:
  • g, R X and Z are as previously defined and R represents an alkyl or aryl group, e.g., methyl, butyl, phenyl, etc., and (2) an enamine intermediate above defined, under generally similar reaction conditions and purification of the dyes as described in the preceding procedure.
  • the dyes defined by formula [V above are also prepared by the above procedure described for the dyes of formula Vlll using the same enamine intermediates except that the heterocyclic salt of formula X is replaced by a ketomethylene heterocyclic compound of the formula:
  • Enamine dyes containing a double bond remote from the chromophoric chain can be prepared in a manner similar to the preparation of the enamine dyes of formulas ll, VIII and IX above, but using one of the following starting materials:
  • lsophorone (41.4 g), 3-pyrroline (31.0 g), p-toluene sulfonic acid (0.5 g) and benzene (90 ml) are placed in an apparatus designed for the continuous removal of water and heated at reflux for 1 hour. After evaporating under reduced pressure, the residue is distilled in vacuum. Decomposition takes place during the distillation with 12.1 g (21 percent) of the desired material being obtained. (b.p.
  • the yield of purified dye is 0.5 g (25 percent), m.p. 262-263 C dec.
  • the yield of purified dye is 0.5 g (22 percent), m.p. 267-268 C dec. 3-Ethyl-2-[4-(3-pyrrolin-l-yl)-1 ,3-pentadienyl1benzoxazolium perchlorate l-Ispropylidene-B-pyrrolinium perchlorate (2.3 g), 2-( 2-acetanilidovinyl )-3-ethylbenzoxazolium iodide (4.3 g), acetic anhydride (1.0 ml) and triethylamine (1.7 ml) are dissolved in ethanol (20 ml) and heated at reflux for minutes.
  • the crude dye is collected on a filter and then recrystallized from methanol.
  • the yield of purified dye is 0.9 g (21 percent), m.p. 214-2l5 C dec. 3-Ethyl-2-[4-( l ,2,5 ,6-tetrahydr0- l -pyridyl )-3,4- trimethylene-l ,3 butadienyllbenzothiazolium perchlorate l-Cyclopentylidenel ,2,5 ,6-tetrahydropyridinium perchlorate (2.7 g), 2-( 2-acetanilidovinyl)-3-ethylbenzothiazolium iodide (4.5 g) and triethylamine (1.5 ml) are dissolved in acetic anhydride (20 ml) and the mixture stirred at room temperature for l A hours.
  • the crude dye is collected on a filter, rinsed with ethanol and then recrystallized twice from methanol.
  • the yield of purified dye is 1.0 g (23 percent), m.p. 227-228 C dec. 3,3 '-Diethyl-l0,1Z-ethylene-l l-( l ,2,5,6-tetrahydrol pyridyl)-oxatricarbocyanine perchlorate 5 (37 percent), m.p. 25l-252 C dec.
  • Preferred supersensitizers are the polynuclear aromatic compounds containing at least one sulfo group.
  • polynuclear aromatic as used herein is intended to mean 2 or more benzene rings fused together (for example, as in naphthalene, pyrene, etc) or at least 2 benzene rings or aromatic rings directly joined together (for example, as in diphenyl, terphenyl, quaterphenyl, etc) or through an aliphatic linkage.
  • Such sulfonated derivatives can conveniently be presented by the following general formula: XIV.
  • T-SO M wherein T represents a polynuclear aromatic group as defined above and M represents a hydrogen atom or a water-soluble cation salt group (e.g., sodium, potasslum, ammonium, triethylammonium, triethanolammonium, pyridinium, etc).
  • a water-soluble cation salt group e.g., sodium, potasslum, ammonium, triethylammonium, triethanolammonium, pyridinium, etc.
  • T represents a 1,3,5-triazin-6-ylamino group
  • T represents an aromatic group (i.e., benzene or substituted benzene) and M has the values given above.
  • T represents a 1,3,5-triazin-2-ylamino group (i.e., a 1,3.5-triazin-2-ylamino group)
  • T represents a 1,3,5-triazin-2-ylamino group (i.e., a 1,3.5-triazin-2-ylamino group)
  • T represents a 1,3,5-triazin-2-ylamino group (i.e., a 1,3.5-triazin-2-ylamino group)
  • R R R R each represents a hydrogen atom or a substituent group, such as hydroxyl, aryloxyll (e.g., phenoxyl, otoloxyl, p-sulfophenoxyl, etc.), alkoxyl(e.g., methoxyl, ethoxyl, etc.), a halogen atom (e.g., chlorine, bromine, etc.), a heterocyclic radical (e.g., morpholinyl, piperidyl, etc.), an alkylthio group (e.g., methylthio, ethylthio, etc.), an arylthio group (e.g., phenylthio, tolylthio, etc.), a heterocyclylthio group (e.g., benzothiazylthio, etc.) an amino group, an alkylamino group (e.g., methylamino
  • R R R and/or R each represents a heterocyclylamino group (e.g., 2-benzothiazoleamino, Z-pyridylamino, etc.) can also be used in practicing my invention.
  • R is an acylamido group (e.g., acetamido,
  • sulfobenzzmido 4-methoxy-3-sulfobenzamido, 2- ethoxybenzamido, 2,4-diethoxy, benzamido, ptolylamido, 4-methyl-Z-methoxybenzamido, naphthoylamino, 2-naphthoylamino, 2,4- dimethoxybenzamido, L Z-phenylbenzamido, 2-
  • R represents an acylamido group (e.g., as defined by R above), or a sulfoaryl group (e.g., sulfophenyl, p-sulfodiph enyl, etc.) and R represents a hydrogen atom or a sulfo group, said compound containing at least one sulfo group.
  • the dibenzothiophenedioxide compounds of Formula XVII have, in general, been previously described in the prior art. See, for example, US Pat. Nos. 2,573,652; 2,580,234; and 2,563,493. Further examples of the preparation of such compounds are given in J. E. Jones, J. Spence, and J.A. VanAllan, US. Pat. No. 2,937,089, issued May 17, 1960. Still other examples of compounds represented by Formula XIV above which can be used in my invention have been previously described in B. H. Carroll, J. E. Jones, and J. Spence, U.S. Pat. No. 2,950,196, issued Aug. 23, 1960. (See, in particular, the compounds of Formulas 11, Ill and [V of that patent).
  • a sulfonated triazolostilbene e.g., of the type shown in U.S. Pat. No. 2,713,057.
  • Phenanthrene-3-sulfonic acid sodium salt 18. 2,3-dimethylnaphthalene-l-sulfonic acid sodium salt 19. 4-[4-phenoxy-6 (B-hydroxyethylamino)-striazin2-ylamino]4-[4-chloro-6-di(B- hyd roxyethyl )amino-s-traizin-2-ylamino -stilbene- 2,2'-disulfonic acid 20. 2,8-bis[4-(4-sulfoanilino)-6-hydroxy-s-triazin-2- ylamino] carbazole 21.
  • disulfodibenzothiophene-S,5-dioxide sodium salt As can be seen above, many of the sulfonated derivatives are employed in the form of their water-soluble salts, such as alkali metal (e.g., sodium, potassium, etc.) salts, or ammonium or amine (e.g., triethylamine, triethanolamine, pyiridine, aniline, etc.) salts. By thus using these derivatives, they can be added to the emulsions in substantially neutral aqueous solutions without distrubing the pH of the emulsions.
  • alkali metal e.g., sodium, potassium, etc.
  • ammonium or amine e.g., triethylamine, triethanolamine, pyiridine, aniline, etc.
  • any reducing agent i.e., a material capable of reducing silver halide
  • a material capable of reducing silver halide can be employed which supersensitizes photographic silver halide emulsions containing methine dyes of the type employed herein.
  • dihydroxy substituted reducing agents Typical dihydroxy compounds which can be employed in the practice of this invention are selected from the group consisting of the benzenes, gammalactones, pyronimides, tetronimides, furans and pyrroles, which contain at least two hydroxyl groups.
  • Typical useful dihydroxy substituted compounds which can be utilized include hydroquinone, resorcinol, pyrocatechol, 3-methylpyrocatechol, toluhydro- 25 mides; 3,4,5-trihydroxy-5,6-dihydro-pyronimides; and amino hexose reductones wherein the moiety comprising the subject reductones can be represented by the following formula wherein R and R can be an alkyl radical, preferably having one to eight carbon atoms or together the necessary atoms to make a heterocyclic radical with the nitrogen atom, preferably having a 5 to 6 atom nucleus and including a second nitrogen atom or an oxygen atom such as morpholino, piperazino, pyrrolino, pyridino, pyrimidino, piperidino and the like.
  • CoHa- NH 5-(4-Carboxyphenyl)-3 hydroxy tetronimide, 5-(3,4-Dimethoxyphenyl)-3-hydroxy tetronimide, 5-(n-Butyl)-3-hydroxy tetronimide 5-(2-Furyl)-3-hydroxy tetronimide (5-a-Furyl-3 ,4-dihyd roxy-2-imino-2,S-dihydrbfuran), and the like; 5,6-Diphenyl-3,4,5-trihydroxy-5,fi-dihydro-pyronimide 5,6-Di-n butyl-3,4,51trihydroxy-5,6-dihydropyronimide, 5,6-Di-morpholino-3,4,5-trihydroxy-5,-dihydropyronimide, y 5,6-(2-Sulfophenyl)3,4,5-trihydroxy5,6-dihydro pyronimide, and the like;
  • Dimethylamino hexose reductone Di-n-butylamino hexose reductone Di-n-hexylamino hexose reductone Morpholino hexose reductone Piperazino hexose reductone Pyrrolino hexosereductone Piperidino hexose reductone and the like.
  • tetronimides an pyronimides such as mentioned above may be prepared by the methods described in British Pat. No. 782,304, Swiss Pat. No. 322,985, and in Helv. Chim. Acta, 39, 1780 (1956).
  • the above, and still other 3-hydroxy tetronimides and 3,4,5-trihydroxy- 5,6-dihydro-pyronimides that are suitable, are disclosed in Salminen, U.S. Pat. No. 3,330,655, issued July 11, 1967.
  • the amino hexose reductones of the invention are derived from sugars, especially D-gluccse, although other six carbon or hexose reducing sugars such ad D- galactose, D-mannose, D-fructose, L-sorbose or the like can be used.
  • a typical method for preparing the subject reductones comprises heating in a reaction medium substantially free of water a hcxosc reducing. sugar and an aliphatic or cyclic secondary amine in the presence of an acidic reductone-forming catalytic agent such as phosphoric acid, boric acid, acetic acid, succinic acid or the like.
  • Emulsions containing a methine: dye of the type described above can be supersensitized with an azain dene, such as a triazaindene, a tetraazaindene or a pentaazaindene. Hydroxy and amino substituted azaindenes are especially useful. Representative useful azaindenes include those described in the following references:
  • R is an alkyl group, e.g., methyl, ethyl, propyl, butyl, etc.
  • the azaindene in some emulsions, is advantageously used in combination with reducing agent, or preferably sulfonated organic compound supersensitizer, to produce emulsions having the best overall characteristics in terms of inherent emulsion speed, sensitized speed, low fog and storage stability.
  • one or more of the sulfonated organic compounds or one or more of the azaindenes or one or more of the reducing agents, and one or more of the methine dyes are added separately or together to light-sensitive photographic silver halide emulsions to supersensitize the emulsions.
  • Particularly good results are frequently obtained when both sulfonated organic compound and reducing agent are employed.
  • excellent results are obtained with the combination of an azaindene with a sulfonated organic compound supersensitizer.
  • the dyes most effectively supersensitized with the compounds described above are the cyanines, particularly the carbocyanine, dicarbocyanine and tricarbocyanine dyes.
  • the enamine tricarbocyanine dyes described herein, such as those of Formula 11 above, are particularly effective when used with supersensitizer.
  • the optimum concentration of methine dye and supersensitizer can be determined in a manner well known to those skilled in the art by measuring the sensitivity of test portions of the same emulsion, each portion containing a different concentration of dye and supersensitizer or mixture of supersensitizers.
  • good results are obtained with about 100 to 2,000 mg dye per mole of silver and about 25 to 2,000 mg and preferably 50 to 1,000 mg per mole of silver of the sulfonated organic supersensitizer.
  • the silver halide emulsions described herein can be unwashed or washed to remove soluble salts. in the latter case the soluble salts can be removed by chillsetting and leaching or the emulsion can be coagulation washed, e.g., by the procedures described in Hewitson et a1 U.S. Pat. No. 2,618,556; Yutzy et al. U.S. Pat. No. 2,614,928; Yackel U.S. Pat. No. 2,565,418; Hart et al. U.S. Pat. No. 3,241,969; and Waller et al. U.S. Pat. No. 2,489,341.
  • the noble metal and sulfur sensitizers can be added to the emulsion by conventional procedures, such as those described by Smith et al. in U.S. Pat. No. 2,448,0- 60 issued Aug. 31, 1948. Generally, the sensitizers are added at the completion of Ostwald ripening and prior to final digestion.
  • the silver halide emulsions of this invention can contain speed increasing compounds such as polyalkylene glycols, cationic surface active agents and thioethers or combinations of these as described in Piper U.S. Pat. No. 2,886,437; Chechak U.S. Pat. No. 3,046,134; Carroll et al. U.S. Pat. No. 2,944,900; and Goffe U.S. Pat. No. 3,294,540.
  • Silver halide emulsions of this invention can be protected against the production of fog and can be stabilized against loss of sensitivity during keeping.
  • Suitable antifoggants and stabilizers which can be used alone or in combination, include the thiazolium salts described in Staud U.S. Pat. N0. 2,131,038 and Allen U.S. Pat.
  • Photographic elements including emulsions prepared in accordance with this invention can contain incorporated developing agents such as hydroquinones, catechols, aminophenols, 3-pyrazolidones, ascorbic acid and its derivatives, reductones and phenylenediamines, or combinations of developing agents.
  • the developing agents can be in a silver halide emulsion and/or in another suitable location in the photographic element.
  • the developing agents can be added from suitable solvents or in the form of dispersions as described in Yackel U.S. Pat. No. 2,592,368 and Dunn et al. French Pat. No. 1,505,778.
  • Silver halide grains sensitized in accordance with the invention can be dispersed in colloids that can be hardened by various organic or inorganic hardeners, alone or in combination, such as the aldehydes, and blocked aldehydes, ketones, carboxylic and carbonic acid derivatives, sulfonate esters, sulfonyl halides and vinyl sulfones, active halogen compounds, epoxy compounds, aziridines, active olefins, isocyanates, carbodiimides, mixed function hardeners and polymeric hardeners such as oxidized polysaccharides, e.g., dialdehyde starch, oxyguargum etc.
  • various organic or inorganic hardeners such as the aldehydes, and blocked aldehydes, ketones, carboxylic and carbonic acid derivatives, sulfonate esters, sulfonyl halides and vinyl sulfones, active halogen compounds, epoxy compounds,
  • Photographic emulsions sensitized in accordance with this invention can contain various colloids alone or in combination as vehicles or binding agents.
  • Suitable hydrophilic materials include both naturallyoccurring substances such as proteins, for example, gel atin, gelatin derivatives, cellulose derivatives, polysaccharides such as dextran, gum arabic and the like; and synthetic polymeric substances such as water soluble polyvinyl compounds, e.g., poly(vinyl-pyrrolidone) acrylamide polymers or other synthetic polymeric compounds such as dispersed vinyl compounds in latex form, and particularly thosewhich increase the dimensional stability of the photographic materials.
  • Suitable synthetic polymers include those described, for example, in U.S. 'Pat. No.
  • Emulsions supersensitized in accordance with this invention can be used in photographic elements which contain antistatic or conducting layers, such as layers that comprise soluble salts, e.g., chlorides, nitrates, etc., evaporated metal layes, ionic polymers such as those described in Minsk U.S. Pat. No. 2,861,056 and 3,206,312 or insoluble inorganic salts such as those described in Trevoy U.S. Pat. No. 3,428,451.
  • soluble salts e.g., chlorides, nitrates, etc.
  • evaporated metal layes ionic polymers such as those described in Minsk U.S. Pat. No. 2,861,056 and 3,206,312
  • insoluble inorganic salts such as those described in Trevoy U.S. Pat. No. 3,428,451.
  • Photographic emulsions containing the supersensitizing combinations of the invention can be coated on a wide variety of supports.
  • Typical supports include cellulose nitrate film, cellulose ester film, poly(vinyl acetal) film, polystyrene film, poly(ethylene terephthalate) film, polycarbonate film and related films or resinous materials, as well as glass, paper, metal and the like.
  • a flexible support is employed, especially a paper support, which can be partially acetylated or coated with baryta and/or an alpha-olefin polymer, particularly a polymer of an'alpha-olefin containing two to carbon atoms such as polyethylene polypropylene, ethylenebutene copolymers and the like.
  • Sensitized emulsions of the invention can contain plasticizers and lubricants such as polyalcohols, e.g.,
  • glycerin and diols of the type described in Milton U.S. Pat. No. 2,960,404; fatty acids or esters such as those described in Robijns U.S. Pat. No. 2,588,765 and Duane U.S. Pat. No. 3,121,060; and silicone resins such as those described in DuPont British Pat. No.
  • the photographic emulsions sensitized as described herein can contain surfactants such as saponin, anionic compounds such as the alkyl aryl sulfonates described in Baldsiefen U.S. Pat. No. 2,600,831 and amphoteric compounds such as those described in Ben-Ezra U.S. Pat. No. 3,133,816.
  • surfactants such as saponin, anionic compounds such as the alkyl aryl sulfonates described in Baldsiefen U.S. Pat. No. 2,600,831 and amphoteric compounds such as those described in Ben-Ezra U.S. Pat. No. 3,133,816.
  • Photographic elements containing emulsion layers sensitized as described herein can contain matting agents such as starch, titanium dioxide, zinc oxide, silica, polymeric beads including beads of the type described in Jelley et a1.
  • matting agents such as starch, titanium dioxide, zinc oxide, silica, polymeric beads including beads of the type described in Jelley et a1.
  • Sensitized silver halide emulsions of the invention can be utilized in photographic elements which contain brightening agents including stilbene, triazine, oxazole and coumarln brightening agents.
  • Brightening agents including stilbene, triazine, oxazole and coumarln brightening agents.
  • Water soluble brightening agents can be used such as those described in Albers et al. German Pat. No. 972,067 and McFall et al. U.S. Pat. No. 2,933,390 or dispersions of brighteners can be used such as those described in Jansen German Pat. No. 1,150,274 and Oetiker et al. U.S. Pat. No. 3,406,070.
  • Photographic elements containing emulsion layers sensitized by the invention can be used in photographic elements which contain light absorbing materials and filter dyes such as those described in Sawdey U.S. Pat. NO. 3,253,921; Gaspar U.S. Pat. No. 2,274,782; Carroll et al. U.S. Pat. No. 2,527,583 and Van Campen U.S. Pat. No. 2,956,879.
  • the dyes can be mordanted, for example, as described in Milton and Jones U.S. Pat. No. 3,282,699.
  • the sensitizing dyes can be added to the photographic emulsions from water solutions or suitable organic solvent solutions, for example with the procedure described in Collins et al. U.S. Pat. No. 2,912,343; Owens et a1 U.S. Pat. NO. 3,342,605; Audran U.S. Pat. No. 2,996,287 or Johnson et al. U.S. Pat. No. 3,425,835.
  • the dyes can be dissolved separately or together, and the separate or combined solutions can be added to a silver halide emulsion, or a silver halide emulsion layer can be bathed in the solution of dye or dyes.
  • Photographic emulsions of this invention can be coated by various coating procedures including dip coating, air knife coating, curtain coating, or extrusion coating using hoppers of the type described in Beguin U.S. Pat. No. 2,681,294. If desired, two or more layers may be coated simultaneously by the procedures described in Russell U.S. Pat. No. 2,761,791 and Wynn British Pat. No. 837,095.
  • Emulsions sensitized as described herein are useful in colloid transfer processes such as described in Yackel et al. U.S. Pat. No. 2,716,059; silver salt diffusion transfer processes such as described in Rott U.S. Pat. No. 2,352,014, Land U.S. Pat. No. 2,543,181, Yackel U.S. Pat. No. 3,020,155 and Land U.S. Pat. No. 2,861,885; color image transfer processes such as described in Rogers U.S. Pat. No. 3,087,817; 3,185,567; and 2,983,606; Weyerts U.S. Pat. No. 3,253,915, Whitmore et al. US. Pat. No.
  • Silver halide emulsions containing the sensitizer combinations of this invention can be used in elements designed for color photography, for example, elements containing color-forming couplers such as those described in Frolich et al. U.S. Pat. NO. 2,376,679; Vittum et al. U.S. Pat. No. 2,322,027; Fierke et al. U.S. Pat- No. 2,801,171; Godowsky U.S. Pat. No. 2,698,794; Barr et al. U.S. Pat. No. 3,227,554 and Graham U.S. Pat. No.
  • Exposed photographic emulsions of this invention can be processed by various methods including processing in alkaline solutions containing conventional developing agents such as hydroquinones, catechols, aminophenols, 3-pyrazolidones, phenylen-ediamines, ascorbic acid derivatives, hydroxylamines, hydrazines and the like; web processing such as described in Tregillus et al. U.S. Pat. No.
  • the photographic emulsions of this invention can be processed in hardening developers such as those described in Allen et a1 U.S. Pat. No. 3,232,761; in roller transport processors such as those described in Russell U.S. Pat. No. 3,025,779; or by surface application processing as described in Example 3 of Kitze U.S. Pat. No. 3,418,132.
  • the silver halide emulsions sensitized by this inven tion can be used for making lithographic printing plates such as by the colloid transfer of undeveloped and unhardened areas of an exposed and developed emulsion to a suitable support as described in Clark et a] U.S. Pat. No. 2,763,553; to provide a relief image as described in Woodward U.S. Pat. No. 3,402,045 or Spencer U.S. Pat. No. 3,053,658; to prepare a relief printing
  • lithographic printing plates such as by the colloid transfer of undeveloped and unhardened areas of an exposed and developed emulsion to a suitable support as described in Clark et a] U.S. Pat. No. 2,763,553; to provide a relief image as described in Woodward U.S. Pat. No. 3,402,045 or Spencer U.S. Pat. No. 3,053,658; to prepare a relief printing
  • lithographic printing plates such as by the colloid transfer of undeveloped and unhard
  • EXAMPLES 1-8 A set of examples are prepared with four variables in order to illustrate optimum conditions of noble metal and sulfur sensitization of a very fine grain gelatino silver iodobromide (2.5 mole percent iodide) Lippmann emulsion of 0.05 m grain size.
  • the four variables are (l level of noble metal sensitization, (2) level of sulfur sensitization, (3) length of time of the chemical sensitization at 65 C, and (4) the level of Dye A with which the emulsion was spectrally sensitized before coating (see structure and name below).
  • Each emulsion is exposed for seconds to a tungsten 500W light source in an Eastman 1B Sensitometer and developed for 4 minutes in Kodak D-l9 developer.
  • the coatings are made at approximately 250 mg silver and 600 mg gelatin per square foot on a cellulose acetate support. The results are shown in Table I below.
  • Example 1 shows the sensitivity of the primitive emulsion without chemical or spectral sensitization.
  • Example 2 shows a marked decrease in speed upon gold and sulfur sensitization at levels in a range customarily used in the art. Upon spectral sensitization (Example 3), a notable speed increase is observed.
  • Example 4 a substantially higher level of gold sensitization compared with Example 3 gives a relative speed increase from 100 to 363, accompanied by a small increase in fog.
  • An intermediate but still high level of gold sensitization is indicated in Examples 5 and 6 with lower levels of sulfur sensitization and dye.
  • the relative speeds of these emulsions are high but not as high as in Example 4.
  • Example 7 shows that an increase in sulfur sensitization actually causes a decrease in speed when compared to Example 6. The higher the gold level, the greater the speed.
  • the speed generally varies inversely with the sulfur and the dye levels.
  • Example 8 compared with Example 3 shows little change in speed when a lower level of dye was used. However, the speed drops
  • Dye A Anhydr0-3,9-diethyl-5,5 '-dimethoxy-3 '-(3- sulfopropyl)thiacarbocyanine hydroxide, the red sensitizer used in the examples above.
  • EXAMPLE 9 A series of gelatino silver iodobonomide Lippmann emulsions with varying iodide content from 0 to 18.8 mole percent is prepared. The grain size decreases as the iodide content increases.
  • the emulsions are treated in three ways (A) given no further chemical sensitization, (8) chemically sensitized with 176 mg. sodium thiosulfate (23 mg. sulfur) plus 88 mg. potassium tetrachlorate (42 mg. gold) in the range 0 to 10 minutes at 65 C, and (C) chemically sensitized with 30 mg. sodium thiosulfate (3.9 mg. sulfur) plus 300 mg. potassium tetrachloraurate (144 mg.
  • the relative speeds are based on the same scale as Table l.
  • a series of Lippman gelatin silver bromoiodide (2.5 mole percent of the halide being iodide) emulsions are prepared and coated on a cellulose acetate support at a concentration of 250 mg. silver per square foot and 1041 mg. gelatin per square foot.
  • the emulsions are chemically sensitized with potassium tetrachloroaurate and sodium thiosulfate, with 10 minute digestion at 65 C after addition of the chemical sensitizers.
  • Various dyes, identified in Table T below, are added to the emulsions, which have the grain size and contain the concentration of chemical sensitizer given in the following tables.
  • Supersensitizer A is 4,4'-bis[4,6-bis-ochloroanilino-s-triazin-2-yl amino]-2,2'-stilbenedisulfonic acid, sodium salt in amounts of 1,000 mg. per mole of silver and Supersensitizer B (ascorbic acid) in amounts of 500 mg. per mole of silver are added as is described in the tables below.
  • Each emulsion is exposed and developed as described in Examples 1-9 above, except that an exposure is made through Kodak Wratten Filters 35 and 28 to record the blue (365 line) exposure.
  • Silver halide grain size 0.09; 300 mg. potassium tetrachloroaurate per mole of silver (about 150 mg. gold per mole of silver) and 30 mg. sodium thiosulfate (about 4 mg. sulfur per mole of silver): Sensiti- Mg.
  • Emulsions employed for such purposes advantageously contain a high concentration of at least one removable and substantially photographically inert light absorbing dye, as described in Stevens British Pat. No. 1,139,062. Since these materials are generally exposed to a mercury vapor source which emits in the blue region of the spectrum at 405 nm and 436 nm and in the green region at 547 nm. it is desirable that the sliver halide exhibit high sensitivity to all three line exposures.
  • a particularly useful sensitizer is 3-ethyl-5-(3-ethyl- Z-benzothiazolinylidene )-2-thio-2,4-oxazolidine-dione, which can be used effectively at concentrations of about 600 to 800 mg. per mole of silver.
  • An effective green sensitizer is 3,3-diethyl-4'-methyloxathiazolocarbocyanine iodide, which can be used effectively at 400, and preferablyv at 800 mg. per mole of silver..
  • the combination of such sensitizers provides good blue and green speeds when the emulsion is exposed to a mercury vapor illuminant.
  • cyanine, merocyanine or hemicyanine dyes having a tertiary aminoalkyl group substituted on a heterocyclic nitrogen atom of the dye such as 6-chloro-3,3'-diethyl-l-(2- morpholinoethyl)benzimidazolooxacarbocyanine iodide.
  • dyes and dye combinations include anhydro-9-ethyl-3 ,3 -di( 3-sulfopropyl)-4,5 ;4',5 dibenzothiacarbocyanine hydroxide, sodium salt; anhydro-3-ethyl-9-methyl-3 3-sulfobutyl )thiacarbocyanine hydroxide; anhydro-l -ethyl-3-( 3-sulfobutyl)thia- 2'-cyanine hydroxide; 3-ethyl-5-(3-ethyl-2- benzothiazolinylidene)-2-thi0-2,4-oxazolidinedione; 3,3'-diethyl-4'-methyloxathiazolocarbocyanine iodide; anhydro-3,9-diethyl-5,5-dimethoxy-3'(3-sulfopropyl)-thiacarbocyanine hydroxide; or, anhydro-9- ethy
  • dyes can be used alone, or in combination with other dyes, such as 3,3-diethyl-6,6'- dimethoxythiadi carbocyanine p-toluenesulfonate.
  • dyes whether used alone or in combination with other dyes, can be supersensitized, e.g., with a polynuclear aromatic compound containing at least one sulfo group (such as 4,4'-bis[4,6-bis-o-chloroanilino-striazin-Z-yl amino]-2,2'-stilbenedisulfonic acid, sodium salt), and/or a reducing agent (such as ascorbic acid).
  • a polynuclear aromatic compound containing at least one sulfo group such as 4,4'-bis[4,6-bis-o-chloroanilino-striazin-Z-yl amino]-2,2'-stilbenedisulfonic acid, sodium salt
  • a reducing agent such as ascorbic
  • a photographic silver halide emulsion comprising light-sensitive silver halide grains having an average grain size up to about 0.2 micron; said silver halide grains being sensitized with the combination of a gold sensitizer, at a concentration of about 50 to 200 milligrams gold per mole of silver, and a sulfur sensitizer at a weight ratio of sulfur to gold of from 1:15 to 1:75; and, said silver halide being spectrally sensitized with at least one dye having one of the following formulas:
  • Z, Z Z and 2 each represents the nonmetallic atoms necessary to complete a heterocyclic nucleus containing from 5 to 6 atoms; each L represents a methine linkage; d, n, c, e and g each represents an integer of from one to two p and f each represents an integer of from one to three; m represents an integer of from one to five; R R R and R each represents an alkyl group or an aryl group; X and X each represents an acid anion; Q, Q, and each represents the non-metallic atoms required to complete a nitrogencontaining heterocyclic nucleus containing from to 6 atoms in the heterocyclic ring; D represents an enamine group selected from a 2,3,4,4a, 5,6-hexahydro-7-( l-pyrrolidinyl)-lmaphthyl group; a 2,6,7,7a-tetrahydro-5-( l-pyrrolidinyl)-3-indenyl
  • a photographic silver halide emulsion comprising light-sensitive silver halide grains having an average grain size up to about 0.1 micron; said silver halide grains being sensitized with the combination of a gold sensitizer, at a concentration of about 50 to 200 milligrams gold per mole of silver, and a sulfur sensitizer at a weight ratio of sulfur to gold of from 1:15 to 1:75; and, said silver halide being spectrally sensitized with a methine dye having one of the following formulas:

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USB360719I5 (enrdf_load_stackoverflow) * 1970-08-13 1975-01-28
US4808516A (en) * 1987-07-21 1989-02-28 Eastman Kodak Company Photographic emulsion and element
US5283165A (en) * 1992-12-23 1994-02-01 Eastman Kodak Company Pyrrolinone dyes
EP0666496A1 (en) * 1994-02-08 1995-08-09 Minnesota Mining And Manufacturing Company Photographic silver halide elements comprising infrared sensitizing dyes
US5441858A (en) * 1992-10-30 1995-08-15 Minnesota Mining And Manufacturing Company Photographic silver halide elements comprising infrared sensitizing dyes
US5460928A (en) * 1994-04-15 1995-10-24 Eastman Kodak Company Photographic element containing particular blue sensitized tabular grain emulsion
US6133445A (en) * 1997-12-17 2000-10-17 Carnegie Mellon University Rigidized trimethine cyanine dyes
US6686145B1 (en) 1997-12-17 2004-02-03 Carnegie Mellon University Rigidized trimethine cyanine dyes
US20060223076A1 (en) * 2004-09-10 2006-10-05 Anaspec, Inc. Cyanine dyes and their applications as luminescence quenching compounds
US20100285515A1 (en) * 2007-02-16 2010-11-11 The University Of Tokyo Fluorescent probe

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DE2415161C3 (de) * 1974-03-29 1981-11-12 Du Pont de Nemours (Deutschland) GmbH, 4000 Düsseldorf Verfahren zum Konservieren photographischer Materialien
JPS5830747A (ja) * 1981-08-17 1983-02-23 Konishiroku Photo Ind Co Ltd ハロゲン化銀写真乳剤

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USB360719I5 (enrdf_load_stackoverflow) * 1970-08-13 1975-01-28
US3915715A (en) * 1970-08-13 1975-10-28 Eastman Kodak Co Silver halide photographic materials containing a high weight ratio of gold to sulfur sensitizers and a sensitizing methine dye
US4808516A (en) * 1987-07-21 1989-02-28 Eastman Kodak Company Photographic emulsion and element
US5441858A (en) * 1992-10-30 1995-08-15 Minnesota Mining And Manufacturing Company Photographic silver halide elements comprising infrared sensitizing dyes
US5283165A (en) * 1992-12-23 1994-02-01 Eastman Kodak Company Pyrrolinone dyes
EP0666496A1 (en) * 1994-02-08 1995-08-09 Minnesota Mining And Manufacturing Company Photographic silver halide elements comprising infrared sensitizing dyes
US5460928A (en) * 1994-04-15 1995-10-24 Eastman Kodak Company Photographic element containing particular blue sensitized tabular grain emulsion
US6133445A (en) * 1997-12-17 2000-10-17 Carnegie Mellon University Rigidized trimethine cyanine dyes
US20030224391A1 (en) * 1997-12-17 2003-12-04 Carnegie Mellon University Rigidized trimethine cyanine dyes
US6686145B1 (en) 1997-12-17 2004-02-03 Carnegie Mellon University Rigidized trimethine cyanine dyes
US7964361B2 (en) 1997-12-17 2011-06-21 Carnegie Mellon University Rigidized trimethine cyanine dyes
US20070243527A9 (en) * 1997-12-17 2007-10-18 Carnegie Mellon University Rigidized trimethine cyanine dyes
US7408062B2 (en) 1997-12-17 2008-08-05 Carnegie Mellon University Rigidized trimethine cyanine dyes
US20060223076A1 (en) * 2004-09-10 2006-10-05 Anaspec, Inc. Cyanine dyes and their applications as luminescence quenching compounds
US20100331543A1 (en) * 2004-09-10 2010-12-30 Zhenjun Diwu Cyanine dyes and their applications as luminescence quenching compounds
US7910753B2 (en) 2004-09-10 2011-03-22 Anaspec Incorporated Cyanine dyes and their applications as luminescence quenching compounds
US8093411B2 (en) 2004-09-10 2012-01-10 Anaspec Incorporated Cyanine dyes and their applications as luminescence quenching compounds
US8426618B2 (en) 2004-09-10 2013-04-23 Anaspec Incorporated Luminescence quenching compounds
US20100285515A1 (en) * 2007-02-16 2010-11-11 The University Of Tokyo Fluorescent probe
US8507677B2 (en) 2007-02-16 2013-08-13 The University Of Tokyo Fluorescent probe

Also Published As

Publication number Publication date
GB1356978A (en) 1974-06-19
CA988773A (en) 1976-05-11
FR2104271A5 (enrdf_load_stackoverflow) 1972-04-14
AU3230471A (en) 1973-02-15
JPS515780B1 (enrdf_load_stackoverflow) 1976-02-23
DE2140323A1 (de) 1972-02-17
BE771248A (fr) 1971-12-16
AU458920B2 (en) 1975-03-13
DE2140323C3 (de) 1975-06-26
DE2140323B2 (de) 1974-11-14

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