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Publication numberUS3617291 A
Publication typeGrant
Publication dateNov 2, 1971
Filing dateOct 10, 1967
Priority dateOct 10, 1967
Also published asDE1800420A1, DE1800420B2, DE1800420C3
Publication numberUS 3617291 A, US 3617291A, US-A-3617291, US3617291 A, US3617291A
InventorsGeorge W Sawdey
Original AssigneeEastman Kodak Co
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Two-equivalent couplers for photography
US 3617291 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

United States Patent Rochester, N.Y.

App]. No Filed Patented Assignee TWO-EQUIVALENT COUPLERS FOR PHOTOGRAPHY 10 Claims, No Drawings US. Cl 96/100, 96/82, 96/565, 96/74, 96/29 Int. Cl G03c 1/40 Field of Search 96/100, 50

References Cited UNITED STATES PATENTS 1/1966 Barret al 96/100X 3,311,476 3/1967 Loria 3,369,895 2/1968 Loriaetal.

ABSTRACT: Two-equivalent development inhibitor releasing couplers derived from four-equivalent couplers by replacing a single hydrogen atom on the carbon atom in the reactive coupling position with a benzotriazolyl radical are valuable couplers for use in photographic materials and processes. The immediate couplers including the 2,6biscoupler benzol 1,2- d:4,5-d]bistriazoles absorb ultraviolet light, fluoresce and have good stability to exposure to light, heat, humidity and aldehyde hardening agents, and couple actively to produce good dyes having excellent stability to heat and light,

TWO-EQUIVALENT COUPLlElRS FOR PHOTOGRAPHY This invention relates to photography and particularly to a new class of two-equivalent dye-forming couplers and their use in color photography.

The formation of colored photographic images by the coupling of oxidized aromatic primary amino developing agents with color forming or coupling compounds is well known. In these processes the subtractive process of color formation is ordinarily used and the image dyes are intended to be cyan, magenta and yellow, the colors that are complementary to the primary colors. Usually phenol or naphthol couplers are used to form the cyan dye image, pyrazolone couplers are used to form the magenta dye image, and couplers containing a methylene group having one or two carbonyl groups attached to it are used to form the yellow dye image.

In these color developing processes the color-forming coupler may be either in the developer solution or incorporated in the light-sensitive photographic emulsion layer so that during development it is available in the emulsion layer to react with the color developing agent that is oxidized by silver image development. Diffusible-type couplers are used in color developer solutions. Fischer-type couplers and hydrophobic couplers are incorporated in photographic emulsion layers. When the dye image formed is to be used in situ, couplers are selected which form nondiffusing dyes. The dye image used for image transfer processes should be diffusible but capable of being mordanted or fixed in the receiving sheet. For this purpose a coupler is selected which will produce this type of dye.

Conventional color-forming couplers are four-equivalent, that is, they require the development of four molecules of exposed silver halide in order to supply one molecule of oxidized color developing agent that is free to couple and form one molecule of dye. Two-equivalent couplers require the development of only two molecules of exposed silver halide to bring about the formation of one molecule of dye. Twoequivalent couplers are very desirable for color photography, since only one-half the usual amount of silver halide is needed and the light-sensitive coatings can thus be made thinner. Development inhibitor releasing two-equivalent couplers have been described in Whitmore et al., US. Pat. No. 3, l48,062, issued Sept. 8, 1964. For certain purposes, it is desired to have development inhibitor releasing two-equivalent couplers which absorb ultraviolet radiation and which fluoresce. The couplers of US. Pat. No. 3,148,062 do not absorb ultraviolet light nor do they fluoresce. It is therefore an object of my invention to provide a novel class of development inhibitor releasing two-equivalent dye-forming couplers which absorb ultraviolet radiation and fluoresce in the blue region of the visible spectrum.

Another object of my invention is to provide novel development inhibitor releasing two-equivalent couplers which not only absorb ultraviolet radiation and fluoresce in the blue region of the visible spectrum but which have exceptional resistance to the formation of stain from the effects of light, heat, humidity, and aldehyde hardening agents.

Still another object of my invention is to provide a novel class of two-equivalent couplers which not only absorb ultraviolet radiation, fluoresce in the blue region of the visible spectrum and have exceptional resistance to the formation of stain from the effects of heat, light, humidity, and aldehyde hardening agents but which also produce dyes which have excellent stability to exposure to light and heat.

It is another object of my invention to provide photographic emulsions and photographic elements which contain my novel color-forming two-equivalent couplers. Still other objects of my invention will become apparent from the following specification and claims.

These and still other objects of my invention are accomplished according to my invention by the synthesis and use of my novel development inhibitor releasing two-equivalent couplers which have a benzotriazolyl radical including a benzo[1,2-Bd:4,5-d'] bistriazolyl radical substituted on the carbon in the coupling position. The dye-forming coupler moiety of may coupler is advantageously derived from any of the four-equivalent dyeforming couplers well known in the art including the magenta-forming cyanoacetyl coumarone couplers, the S-pyrazolone couplers, etc., the cyan-forming phenolic and naphtholic couplers, and the open-chain yellowforming acylacetonitrile couplers (e.g., alkoylacetonitriles, the aroylacetonitriles, the heterocycloyl acetonitriles, etc.), and the open-chain ketomethylene couplers such as the acylacetyl couplers (e.g., the acylacetanilides, the acylacetamides, etc.). The acylacetanilide couplers include the alkoylacetanilide couplers, the aroylacetanilide couplers, the pivalylacetanilide couplers, etc. The acylacetamide couplers include the alkoylacctamide couplers, the aroylacetamide couplers, the pivalylacetamide couplers, etc.

My novel couplers are characterized by absorbing ul traviolet light, fluorescing in the blue region of the visible spectrum, having good stability to the effects oflight, heat, hu midity and aldehyde hardening agents as well as producing upon color development, dyes having good stability to exposure to light and heat.

The novel two-equivalent couplers of my invention are advantageously described by the following formulas:

A wherein A and A represent any of the dye-forming coupler moieties derived from prior art four-equivalent couplers linked in their coupling position by a single bond to the benzotriazolyl radical; R and R each represent the same or different member such as hydrogen, halogen (chlorine, bromine, iodine, fluorine), the nitro group, amino, an amido radical (e.g., 2,4-di-t-amylphenoxy acetamido, 2,4-diamylphenoxy butyramido, phenylacetamido, etc.), hydroxyl, an alkoxy radical having from one to four carbon atoms, e.g., methoxy, chloromethoxy, ethoxy, carboxyethoxy, aminoethoxy, butoxy, etc., an alkyl radical having from one to four carbon atoms, e.g., ethyl, methyl, butyl, chloromethyl, trifluoromethyl, omega iodobutyl, 2-nitroethyl, Z-carboxyethyl, Z-aminobutyl, etc. and one of R and R, can represent a phenylazo radical (e.g., phenylazo, methylphenylazo, ethoxyphenylazo, chlorophenylazo, sulfophenylazo, carboxyphenylazo, hydroxyphenylazo, etc.); R and R each represent the same or different member such as hydrogen, halogen (chlorine, bromine, iodine, fluorine), nitro, amino, an amido radical (e.g., 2,4-di-t-amylphenoxy acetamido, 2,4-diamylphenoxy butyramido, phenylacetamido, etc.), hydroxyl, an alkoxy radical having from one to 18 carbon atoms (e.g., methoxy, cyclohexylmethoxy, phenylmethoxy, naphthylmethoxy, tribromomethoxy, Z-aminoethoxy, 3-hydroxypropoxy, 4-sulfobutoxy, ethoxy, cyclopentylethoxy, butoxy, dodecyloxy, octadecyloxy, chloromethoxy, nitroethoxy, carboxyethoxy, aminobutoxy, etc.) and an alkyl radical having from one to 18 carbon atoms, e.g., methyl, trifluoromethyl, trichloromethyl, ethyl, nitroethyl, aminoethyl, 2-hydroxyethyl, Z-carboxyethyl, 4-carboxybutyl, 2-sulfoethyl, 2- amidoethyl, N-methylacetamidobutyl, sulfonamidoethyl, phenethyl, cyclohexylethyl, cyclopentylethyl, butyl, dodecyl, octadecyl, etc. and one of R and R, can represent a phenylazo radical (e.g., phenylazo, methylphenylazo, octadecylphenylazo, sulfobutylphenylazo, butoxyphenylazo, chlorophenylazo, etc.) and any two adjacent substituents represented by R R R and R can be the nonmetallic atoms necessary to form a 5- to 6-membered ring, such as, a carbocyclic ring (e.g cyclohexanc, cyclopentane, norbornane, benzene, toluene, etc.) or a heterocyclic ring (e.g., morpholine, pyridine, quinoline, piperidine, triazole, etc.

The preferred yellow dye-forming open-chain couplers of formulas I and ll include couplers in which A and A are represented by the formula:

in which R represents an alkyl group such as an acyclic alkyl group having from one to 32 carbon atoms which may be a normal alkyl radical having from one to 18 carbon atoms, e.g., methyl, propyl, hexyl, octyl, dodecyl, pentadecyl, octadecyl, etc., a secondary alkyl radical in which the secondary carbon atom is attached directly to the carbonyl radical and has attached to it two alkyl radicals each of which may have from one to 18 carbon atoms, as defined above, provided that the R group does not have more than a total of 32 carbon atoms, and includes such groups as l-methylheptadecyl, l-butylheptadecyl, l-decylheptadecyl, l-dodeeylheptadecyl, l-pentadecylhexadecyl, etc.; a tertiary alkyl radical in which the tertiary carbon atom is preferably attached directly to the carbonyl radical and has attached to it three alkyl radicals each of which may have from one to 18 carbon atoms as defined above, provided that the R group does not have more than a total of 32 carbon atoms and in which one or two of these alkyl radicals attached to the tertiary carbon may themselves be secondary or tertiary alkyl radicals having from one to 18 carbon atoms, and includes such groups as apivalyl, l,ldimethylpropyl, l,l-dibutylheptadecyl, l-butyll -pentadecylheptadecyl, l,l -di-isobutylheptadecyl, l,l-di-tert-butylheptadecyl, etc., a tertiary alkyl radical in which one, two or three of the alkyl groups defined above that are attached to the tertiary carbon atom are replaced by alkoxy radicals having from one to 18 carbon atoms such as methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, octoxy, nonoxy, decoxy, dodecoxy, tridecoxy, tetradecoxy, pentadecoxy, hexadecoxy, octadecoxy, etc., or alkoxyalkyl radicals having from one to 18 carbon atoms in which the alkoxy and alkyl radicals are among those defined above such as methoxymethyl, ethoxymethyl, propoxymethyl, butoxymethyl, hexoxymethyl, decoxymethyl, pentadecoxymethyl, methoxypropyl, methoxyhexyl, methoxyoctyl, methoxydecyl, methoxydodecyl, methoxypentadecyl, nonoxynonyl, etc., and include such groups as l-methoxy-lbutylhexoxy, l,l-dioctoxyhexadecyl, l-decosyl -octoxyhexadecyl, l-methoxyethyl-l-butoxyethylhexadecyl, etc., or R represents a cycloalkyl group, such as, a cyclohexyl radical, a cyclohexyl radical substituted with an alkyl radical, an alkoxy radical, an alkoxy-alkyl radical, each having from one to 18 carbon atoms as described above, for example, l-methylcyclohexyl, l-ethylcyclohexyl, l-propylcyclohexyl, l-octylcyclohexyl, l-dodecyclohexyl, l-pentadecylcyclohexyl, l-octadecylcyclohexyl, 2-methylcyclohexyl, 3-ethylcyclohexyl, 4- octycyclohexyl, etc., lmethoxycyclohexyl, l-ethoxycyclohexyl, l-propoxycyclohexyl, l-nonoxycyclohexyl, l-octadecoxycyclohexyl, 2-butoxycyclohexyl, etc., l-methoxymethylcyclohexyl l-propoxymethylcyclohexyl, l-decoxymethylcyclohexyi, l-pentoxymethylcyclohexyl, l-methoxydecylcyclohexyl, l-nonoxynonylcyclohexyl, 2-nonoxynonylcyclohexyl, 3-nonoxydecylcyclohexyl, etc., or a cyclohexyl radical substituted with an aryl group such as l-phenylcyclohexyl, l-tolylcyclohexyl, etc., or R represents a bicycloalkyl radical such as a terpenyl radical, e.g., 7,7- dimethylnorbomyl, a 2-alkyl-7,7-dimethylnorbornyl, a Z-alkoxy-7,7-dimethylnorbornyl, a 2-alkoxyalkyl-7,7-dimethylnorbornyl, preferably although not necessarily attached to the carbonyl group through the bridgehead carbon, and in which the etc., alkoxy, and alkoxyalkyl substituents each have from one to 18 carbon atoms as defined above, such as 2-methyl- 7,7-dimethylnorbornyl, 2-octyl-7,7-dimethylnorbornyl, 2-octadecyl-7,7-dimethylnorbornyl, etc., 2-ethoxy-7,7-dimethylnorbornyl, 2-nonoxy-7,7-dimethylnorbornyl, 2-octadecoxy- 7,7-dimethylnorbornyl, etc., 2-methoxybutyl-7,7-dimethylnorbornyl, 2-octoxydecyl-7,7-dimethylnorbomyl, etc., a 2- aryl-7,7-dimethylnorbomyl such as 2-phenyl-7,7-dimethylnorbornyl, 2-tolyl-7,7-dimethylnorbornyl, etc., or R represents an aryl radical, such as a phenyl radical, e.g., phenyl, and alkphenyl radical in which the alkyl radical has from one to l8 carbon atoms, e.g., 3-methylphenyl, Z-butylphenyl, 4-octylphenyl, 2-dodecylphenyl, 3-octadecylphenyl, etc., an alkoxyphenyl radical in which the alkyl group has from one to l8 carbon atoms, e.g., 2-methoxyphenyl, 2-propoxyphenyl, 2- hexoxyphenyl, 2-nonoxyphenyl, 2decoxyphenyl, 2-octadecoxyphenyl, etc., a halophenyl such as 2-chlorophenyl, 2,4,6-tribromophcnyl, 2,4,6-trifluorophenyl, etc., a 2 -halo-5- alkamidophenyl radical, e.g., 2-chloro-5-[a-(2,4-di-tertamylphenoxy)acetamido]phenyl, 2-chloro-5-l-(2,4-di-tert= amylphenoxy)butyramido1phenyl, 2-chloro-5-[a-(2,4-di-tertamylphenoxy)amylamido1phenyl, 2-chloro-5-[y-(2,4-di-tertamylphenoxy)butyramidolphenyl, 2-chloro-5-(4-methylphenylsulfonamido)phenyl, 2-fluoro-5-(N-hexylamido)phenyl, etc., a 2-methoxy-5-alkamidophenyl radical, e.g., 2-methoxy- 5-(2,4-di-tert-amylphenoxy)acetamidophenyl, 2-methoxy-5-[ a-(2,4-di-ter1-amylphenoxy)butryamidolphenyl, etc., a 4-alkamidophenyl radical, e.g., 4-(2,4-di-tert-amylphenoxy)acetamidophenyl, 4-['y-(2,4-di-tert-amylphenoxy)butyramidoIphenyl, etc., a 4-methoxyphenyl radical, e.g., 4-[N- ('y-phenyipropyl)-N-(p-tolyl)-carbamylmethoxyl-phenylpropyl)-N(p-tolyl)-carbamylmethoxy]phenyl, 4-[N-(y-phenylhexyl)-N-(p-tolye) -phenylhexyl)-N'(p-tolyl) carbamylmethoxylphenyl, etc., a 4-sulfamylphenyl radical, e.g., 4-[N-( -phenylpropyl)-N-(p-tolyl)sulfamyH-phenylpropyl)-N-(ptolyl)sulfamyl]phenyl, 4-[phenylethyl)-N-(p-tolyl)sulfamyl] phenyl, etc., a 2-chloro-S-sulfonamidophenyl radical, e.g., 2- chloro-S-(p-toluenesulfonamido)phcnyl, 2-chloro-5- (bcnzenesulfonamido)phenyl, etc., a 3,5-dicarboxyphenyl radical, esters of 3,5-dicarboxyphenyl radicals, e.g., 3,5- dimethoxycarbonylphenyl, 3,5-dihexoxycarbonylphenyl, 3,5- didodecoxycarbonylphcnyl, 3,S-dipentadecoxycarbonylphenyl, 3,5-dioctadecoxycarbonylphenyl, etc., a 2-phenoxy-5-carbamylphenyl radical, e.g., 2-(2,4-di-tert-amylphcnoxy)-5- (3,5-dicarbomcthoxyphenylcarbamyl) phenyl, 2-(2,4-di-tertamylphenoxy)-5-(N-morpholinocarbonyl)phcnyl, etc., a 3,5- dicarbamylphenyl radical, etc., or R represents a heterocyclic radical containing a heterocyclic ring with five to six atoms in the ring, typical examples including a bcnzofuranyl radical, a furanyl radical, a thiazolyl radical, a benzothiazolyl radical, a naphthothiazolyl radical, an oxazolyl radical, a bcnzoxazolyl radical, an imidazolyl radical, a benzimidazolyl radical, a quinolinyl radical, etc., and any of the alkyl, aryl and heterocyclic radicals described for R contain substituent groups such as halogen (chlorine, bromine, iodine, fluorine), nitro, hydroxyl, carboxyl, carboxyl esters (e.g,, carbethoxy, carbophenoxy, etc.), an amino group (e.g., amino, dimethylamino, N- methylanilino, etc.), amido (e.g., acetamido, butyramido, ethylsulfonamido, benzamido, etc), It is the integer l or 2; R represents hydrogen or a lower alkyl group, e.g., methyl, ethyl, etc., R represents an alkyl group having from one to l8 carbon atoms (as defined above for R an aryl radical such as a phenyl radical, e.g., phenyl, alkoxyphenyl in which the alkyl radical may have from one to l8 carbon atoms (as defined above for R halophenyl radicals such as 2-chlorophcnyl, 2,4-dichlorophenyl, 2,4,6trichlorophenyl, the corresponding bromoand corresponding fluorophenyl radicals, etc., a 2- halo-S-alkamidophenyl radical, e.g., 2-chloro-S-[a-(2,4-ditcrt-amylphenoxy)acetamidolphcnyl, 2-chloro-5-[oz(2,4-ditcrt-amylphenoxy)butyramido]phcnyl, 2-chloro- 5-[ a-( 2,4ditert-amylphcnoxy)amylamido]phenyl, 2-chloro5-[y-(2,4- tert-amylphenoxy)butyramido1phenyl, 2-chloro-5-(4- methylphenylsulfonamido)phenyl, 2-fluoro5-(N-hex- 7 151112188 among typical couplers illustrating my couplers of formulas l and II when A and A are represented by formulas IV and V are the following:

a-Benzotriazolyl-a-cyanoacetylcoumarone a-Benzotriazolyl-4-[a'-(2,4-di-t-amylphcnoxy) butyramido]-cyanoacctylbenzene 4-Benzotriazolyl-3-pentadecyl-l phenyl5- pyrazolonc 4-Bcnzotriazolyl-3-mcthyl-lhenylpyrazolonc d-Bcnzorriazolyl-l-(2 4,6-trichlorophcnyl)-3-[3 a- (ZAdM-amylphcnoxy )aciamido} bcnzamido]-5- pyrazolonc 4-l5-(4-Anilinophenyl-Z-bcnzotriazolyl)1-3-(4- cyanoanilino)- l 2,4,6 trichlorophcnyl)-5- pyrazolonc d-lfi'fl-Cyanocthyl)-2-bcnzotriazolyl]-3-(2,4-

dichloroanilino)-l-(2,4.6-lrichlorophenyl)-S- yrazolonc 4- {s 3-(2,d-Di-t-amylphcnoxyacclamido)- phcnylcarhamyl]2 bcnzutriazolyl}-3-(3- nitroanilinoyl-(2,4,6-trichlorophenyl)-S pyraznloue 4514-Butylphcnoxy-a-propionamidol-2- benzothiazolyl}-l-(2,4,6-trichlorophcnyl)-3-(4- nitroanilino)-5-pyra1olone 4-(5-Mcthoxy-Z-hcnzotriazolyl)-3-pentadecyl-lphcnyl-S-pyruzolone 4-(4-Carhoxy-2-bcnzolriazolyl)-l-(2,4,6-

trichlorophcnyl)-3-penladccyl-$-pyrazolonc 4-(6-Chloro-S-phcnoxy-2-bcnzotriazolyl)-3- octadecylamino-l-phcnyl 5-pyrazolonc 4-[5-(Phenylmclhyloxyphenylsulfonyl-Z- benzotriazolyl)l-li-phenylcarbamyl-l-(3-quinoly|)- 5-pyrazolone 4-[5-(d-carboxyphcnoxy) 2benzotriazolyl]'l-(2 chloro-4 6-dimethylphcnyl-3-(4-sulfo6- cntadecyl henoxy-Zbutyramido)-5 pyrazolonc 4-15-(2-Carboxyelhyl)Q-bcnzulriazolyl))-3-(3,S- dicarboxybcnzamido-l-mclhyl'S-pyrazolonc 2,6- Bis[4(3-mcthyl l-phenyl-5-pyrazolone)] benzol I ,2-d:4,5-d' ]bistriazole 4-Benzotriazolyl-l-(2,4,6-trichlorophenyl)-3-(3- qu inolyHd-pyrazolonc lncluded among typical couplers illustrating my couplers of formulas land II in which A and A represent coupler moieties offormulas VI and VII are the following:

36 4-(Z-Bcnzotriaznlyl)-2-l8-(2,4-

diamylphcnoxybutyl)ld-hydroxynaphthamide 37 A-(Z-Benzotriazolyl)-lhydroxy-N-mclhyl-N-(B- sulfocthyl)Z-naphthamidc, sodium salt 39 4-(2-Benzotriazolyl)-N-(2-benzimidazolyl)-lhydroxy-Z-naphthamidc 40 4-(Z-Bcnzoiriazolyl)-l-hydroxy-2- naphthomorpholidc 42 I-Hydroxy-4-(5-methylsulfonyl-2-benzolriazolyl)-2- naphthamide 42 l-Hydroxy-4- S-la-(S- pentadecylphcnoxy)butyramido]f-4-bcnzo\riazolyl 2-(3,5-dicarboxy-N-cthyl)-naphthanilidc 43 l-Hydroxy-4-(6-nitro-2-benzolriazolyl)-N-[ 8-(2,4di-

t-amylphenoxy)bulyl]-2-na hlhamide 44 l-Hydroxy-4-(S-phcnoxy-2-benzolriazolyl)-2'- mclhoxy-Z-naphthanilirle 4S l-Hydroxy-4-(S-(4-nilrophenyl)-2-benzutriazolyl]-N- (B- hcnylcthyl)maphthamidc 46 l-Hydrnxy-4J5-(4-acetamidophenyU-2- benzotriazolyH-NJB-(2-acelamidophcnyl)cthyl]-2 -naphthamide 47 l-Benzotriazolyl-l-hydroxy-N- 5 b-lA-(ZA-di-tamylphenoxy)acetamido]phenyl cthyl -2- naphthamide 4B 4-l3enzotriazolyl-l-hydroxy-3-[u-(3 pentadccylphcnoxy)butyramidolf-2-naphthanilidc 49 4-Bcnzotriazolyl 2.-dimethylohenol 50 4-Bcnzotriazolyl-2,5-dichlorophenol 5| 2-Aectamido-4-bcnzotriazolyl-6-chloro-5- mclhyl hcnol 52 l-Hydroxy-4-(2 -naphthotria1.olyl)-2-methoxy-2- naphthanilidz:

5 3 4-( l -aza-6,7-naphthotriazolyl l -hydroxy-2 methoxy-Z-naphthanilide 54 2,6 I Bisl4-( l -hydroxy-2'-mcthoxy-2-naphthanilidc)l} benzo-[ l 2-d:4,5-d']bistriazole In general my couplers of formula I are prepared by contacting the corresponding four-equivalent coupler represented by AH wherein A is as defined previously, with a diazonium salt having the formula:

l l R3 R wherein R R R and R are as defined previously, in the presence of pyridine, and preferably also in the presence of a solvent such as, methanol, ethanol, etc., and a buffering agent such as sodium acetate to prepare a compound having the formula:

which is then reduced with zinc dust and sodium hydroxide in aqueous alcohol to give my coupler of formula I. It is advantageous to heat the reduction mixture between room temperature and the reflux temperature. Couplers of formula ll are advantageously made by a similar reaction series in which a diazonium salt having the formula:

NgCl NO;

NO: NO:

is used in place of a compound of formula Vlll. The coupler,

formed is then reduced so that only one of the remaining nitro groups is converted to amino by heating with sodium sulfide in methanol, then the amino group is diazotized by treating with cold nitrous acid in hydrochloric acid, the diazonium salt is then treated with a coupler A'H to produce a coupler having the formula:

COUPLER 21 i 4 -(2-Benzotriazolyl)-3-pentadecyl-l-phenyl-5-pyrazolone A quantity of 5.2 g. (0.01 mole) of l-phenyl-3-pentadecyl- 4-(2nitrophenylazo)-5-pyrazolone is added to a solution of 400 ml. of ethanol and 25 ml. of a 40 percent aqueous solution of sodium hydroxide contained in a one-liter three-neck flask fitted with a reflux condenser. After the solution is heated nearly to boiling while being stirred, 8 g. (12 equivalents) of zinc dust is added. Refluxing is continued until the solution turns colorless, at which stage the solutions temperature is reduced slightly. Stirring is continued for 1% hours. The reaction mixture is filtered for the purpose of removing excess zinc, then acidified with hydrochloric acid. The resulting precipitate is collected by filtration and recrystallized from methanol to provide coupler 21 in the form of 4 g. (82 percent) of white needles having a melting point of l06108 C.

COUPLER 36 4-( 2-Benzotriazolyl )-N- 8-( 2 ,4-diamylphenoxy)butyl l hydroxynaphthamide A quantity of 6.2 g. (0.01 mole) of 2-[6-(2,4-diamylphenoxy)bytyl]-1-hydroxy-4-(2-nitrophenylazo)naphthamide is suspended in 300 ml. of methanol containing 70 ml. of a 25 percent aqueous solution of sodium hydroxide. The reaction mixture is heated nearly to boiling under a reflux condenser, at which stage 8 g. (12 equivalents) of zinc dust is added. The color of the reaction mixture changes quickly to pale yellow. Refluxing is continued for 4 hours, after which time the excess quantity of zinc dust is recovered by filtration. After cooling the preparation, the precipitate is collected and recrystallized from methanol, suspended in diluted hydrochloric acid, and extracted with ether. After evaporation of the ether, the finally obtained solid is recrystallized from acetonitrile and provides a yield of 3 g. (51 percent) of coupler 36 in the form of white needles having a melting point of 146l47 C.

COUPLER 1 By using the procedures described for coupler 36 abenzoyl-a-( 2-nitrophenylazo)-acetanilide is suspended in methanol containing aqueous sodium hydroxide and while heating nearly to boiling under a reflux condenser, zinc dust is added. After the reaction is completed, the excess zinc dust is recovered by filtration and the coupler is precipitated from the filtrate by cooling. The coupler is extracted and recrystallized to give coupler 1 having a melting point of 2l4-2 1 6 C.

COUPLER 2 This coupler is prepared by the method described for coupler 1 using a-pivalyl-a-(Z-nitrophenylazo)acetanilide in place of a-benzoyl-a-(2-nitrophenylazo)acetanilide. The purified coupler 2 has a melting point of l6l-162 C.

COUPLER 19 This coupler is prepared by a method like that described for coupler 1 using a-(2-nitrophenylazo)-cyanoacetyl coumarone in place of a-benzoyl-a-(2-nitrophenylazo)-acetanilide. The recrystallized coupler 19 has a melting point of 220 3222 C.

COUPLER 22 This coupler is advantageously prepared by heating an aqueous methanol solution containing sodium hydroxide and 3-methyl-1-phenyl-4-(2-nitrophenylazo)'5-pyrazolone while adding zinc dust as described for the preceding couplers. After separating the excess zinc dust, extracting and recrystallizing, coupler 22 having a melting point of 154156 C. is obtained.

COUPLER 23 This coupler is obtained as described above using 3-[3-(2,4- di-amyiphenoxy acetamido)benzamido ]-4-(Z-nitrophenylazo)l-(2,4,6-trichlorophenyl)-5-pyrazolone in place of 3- ethyl-N43-hydroxyethylaminoaniline,

methyl- 1 -phenyl-4-( Z-nitrophenylazo )-5 -pyrazolone. The recrystallized coupler 23 has a melting point of -l 66 C.

The other couplers used to illustrate my invention are prepared advantageously using the methods described above in which the appropriate intermediates are used.

As mentioned previously, the 4-equivalent parent couplers used to make my couplers are well known in the art and need not be described further. The compounds of formula Vlll are prepared from the corresponding amino compounds which are either available or are prepared by methods well known in the art.

The diffusible couplers of my invention, such as couplers l, 2, 7, l5, 16, 17, 19, 22, 24, 25, 37, 38, 41, 44 and 49 through 52, are used to advantage in color developer solutions used to color develop light-sensitive elements used for color photography which do not contain a color-forming coupler. Any of the well-known primary aromatic amino color-forming silver halide developing agents such as the phenylenediamine, e.g., diethyl-p-phenylenediamine hydrochloride, monomethyl-pphenylenediamine hydrochloride, dimethyl-p-phenylenediamine hydrochloride, 2-amino-5-diethylaminotoluene hydrochloride, 2-amino-5(N-ethylNJauryl)toluene, N-ethylfl-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, Nethyl-3 methanesulfonamidoethyl-4-aminoaniline, 4-N- etc., the paminophenols and their substitution products where the amino group is unsubstituted may be used in the alkaline developer solution with my couplers. Various other materials may be included in the developer solutions depending upon the particular requirements, for example, an alkali metal sulfite, carbonate, bisulfite, bromide, iodide, etc., and the thickening agents used in viscous developer compositions such as are described in Whitmore and Mader U.S. Pat. No. 3,227,550. The following is a typical developer solution given to illustrate but not limit the invention.

2-Amino-S-diethylaminotoluene HCl 2.0 g. Sodium sulfite (anhydrous) 2.0 g. Sodium carbonate (anhydrous) 20.0 g. Potassium bromide 1.0 g. Coupler 2.0 g. Water to 1000.0 ml.

The diffusible couplers of my invention are used to advantage in emulsion layers when incorporated by the methods described by Mannes et al. U.S. Pat. No. 2,304,940, issued Dec. 15, 1940.

The other coupler examples used to illustrate my invention are nondiffusing and are used to advantage in photographic emulsion layers. Couplers 4, 6, 10, 29, 32 and 33 illustrate those that are incorporated as Fischer-type couplers. The other nondiffusing couplers are incorporated in emulsion layers by methods such as are described by Mannes et al. U.S. Pat. No. 2,304,939, issued Dec. 15, 1942, Jelley et al. U.S. Pat. No. 2,322,027, issued June 15, 1943, etc., in which highboiling organic solvents are used to dissolve the coupler, and

by methods described in Vittum et al. U.S. Pat. No. 2,801,170, and Fierke et al. U.S. Pat. No. 2,801,171, issued July 30, 1957, and Julian U.S. Pat. No. 2,949,360, issued Aug. 16, 1960, in which low-boiling or water-soluble organic solvents are used with or in place of the high-boiling solvent.

My nondiffusing coupler 4 forms diffusible dye images upon color development and is used to advantage either in image transfer elements or in emulsion layers that contain my coupler as a nonimage-forming competing coupler along with an image-forming coupler.

The other nondifl'using couplers used to illustrate my invention form nondiffusing dyes and are used to advantage in any photographic element where incorporated image-forming couplers are desired.

My couplers are used in the color development of photographic hydrophilic colloid-silver halide emulsion layers of the developing-out type either in the color developer solution or in the emulsion layer. The emulsions advantageously contain silver chloride, silver bromide, silver iodide, silver chlorobromide, silver bromoiodide, silver chloroiodide, etc., as the light-sensitive material.

Hydrophilic colloids used to advantage include gelatin, col- I loidal albumin, a cellulose derivative, or a synthetic resin, for instance, a polyvinyl compound. Some colloids which are used are polyvinyl alcohol or a hydrolyzed polyvinyl acetate as described in U.S. Pat. No. 2,286,215, of Lowe; a far hydrolyzed cellulose ester, such as cellulose acetate hydrolyzed to an acetyl content of 19-26 percent as described in U.S. Pat. No. 2,327,808 of Lowe and Clark, a water-soluble ethanolamine cellulose acetate as described in U.S. Pat. No. 2,322,085 of Yutzy; a polyacrylamide having a combined acrylamide content of 30-60 percent and a specific viscosity of 025-1 .5 on an imidized polyacrylamide oflike acrylamide content and viscosity as described in U.S. Pat. No. 2,541,474 of Lowe, Minsk and Kenyon zein as described in U.S. Pat. No. 2,563,791 of Lowe; a vinylalcohol polymer containing urethane carboxylic acid groups of the type described in U.S. Pat. No. 2,768,154 of Unruh and Smith, or containing cyanoacetyl groups, such as the vinyl alcohol-vinyl cyano-acetate copolymer as described in U.S. Pat. No. 2,808,331 of Unruh, Smith and Priest; or a polymeric material which results from polymerizing a protein or a saturated acylated protein with a monomer having a vinyl group as described in U.S. Pat. No. 2,852,382 oflllingsworth, Dann and Gates.

The emulsions used in the photographic element of my invention can be chemically sensitized by any of the accepted procedures. The emulsions can be digested with naturally active gelatin, or sulfur compounds can be added, such as those described in Sheppard U.S. Pat. No. 1,574,994; Sheppard and Punnett U.S. Pat. No. 1,623,499; and Sheppard and Brigham U.S. Pat. No. 2,410,689.

The emulsions can also be treated with salts of the noble metals, such as ruthenium, rhodium, palladium, iridium and platinum. Representative compounds are ammonium chloropalladate, potassium chloroplatinate, and sodium chloropalladite, which are used for sensitizing in amounts below that which produces any substantial fog inhibition, as described in Smith and Trivelli U.S. Pat. No. 2,448,060, and as antifoggants in higher amounts, as described in Trivelli and Smith U.S. Pat. No. 2,566,245 and 2,566,263.

The emulsions can also be chemically sensitized with gold salts as described in Waller, Collins and Dodd U.S. Pat. No. 2,399,083 or stabilized with gold salts as described in Damschroder U.S. Pat. No. 2,597,856 and Yutzy and Leermakers U.S. Pat. No. 2,597,915. Suitable compounds are potassium chloroaurite, potassium aurithiocyanate, potassium chloroaurate, auric trichloride and 2-aurosulfobenzothiazole methochloride.

The emulsions can also be chemically sensitized with reducing agents, such as stannous salts (Carroll U.S. Pat. No. 2,487,850), polyamines, such as diethylene triamine (Lowe and Jones U.S. Pat. No. 2,518,698), polyamines, such as spermine (Lowe and Allen U.S. Pat. No. 2,521,925), or bis(fiaminoethyl)sulfide and its water-soluble salts (Lowe and Jones US. Pat. No.2,52l,926).

The emulsions can also be optically sensitized with cyanine and merocyanine dyes, such as those described in Brooker U.S. Pats. Nos. 1,846,301; 1,846,302; and 1,942,854; White U.S. Pat. No. 1,990,507; Brooker and White U.S. Pats. Nos. 2,112,140; 2,165,338; 2,493,747; and 2,739,964; Brooker and Keyes U.S. Pat. No. 2,493,748; Sprague U.S. Pat. Nos. 2,503,776 and 2,519,001; Heseltine and Brooker U.S. Pat. No. 2,666,761; Heseltine U.S. Pat. No. 2,734,900; VanLare U.S. Pat. No. 2,739,149; and Kodak Limited British Pat. No. 450,958.

The emulsions may also contain speed-increasing compounds of the quaternary ammonium type of Carroll U.S. Pat. No. 2,271,623; Carroll and Allen U.S. Pat. No. 2,288,226; and Carroll and Spence U.S. Pat. No. 2,334,864; and the polyethylene glycol type of Carroll and Beach U.S. Pat. No. 2,708,162.

The above-described emulsions can be coated on a wide variety of photographic emulsion supports. Typical supports include cellulose nitrate film, cellulose acetate film, polyvinyl acetal film, polystyrene film, polyethylene terephthalate film,

polyethylene film, polypropylene film, and related films of resinous materials, as well as paper, glass and others.

Usually my emulsions are coated on photographic supports in the form of multilayer color photographic elements wherein at least three differently sensitized emulsion layers are coated over one another on the support. Usually the support is coated in succession with a red-sensitive layer, a green-sensitive layer and a blue-sensitive layer either with or without a Carey Lea filter layer between the blue-sensitive and gree-sensitive layers. The three differently color sensitized layers may be arranged in any other order over one another that is desirable; however, the Carey Lea filter layer obviously would not be put over the blue-sensitive layer. Preferably, these light-sensitive layers are arranged on the same side of the support.

Elements made for image transfer processing may use a separate reception sheet which is contacted with the light-sensitive layer during its development or the reception layer may be an integral part of the light-sensitive element. Any of the support materials mentioned previously may be used for a separate reception sheet. The reception layer comprises a hydrophilic colloid layer containing a cationic mordant, e.g., the polymers of amino guanidine derivatives of vinyl methyl ketone such as described in Minsk U.S. Pat. No. 2,882,156, granted Apr. 14, 1959. Other mordants include the 2-vinyl pyridine polymer metho-p-toluene sulfonate and similar compounds described in Sprague et a1. U.S. Pat. No. 2,484,430, granted Oct. 11, 1949, and cetyl trimethyl ammonium bromide, etc. Particularly effective mordanting compositions are described in Kneckel et al. U.S. Pat. No. 3,271,148 and Bush U.S. Pat. No. 3,271,147.

The following examples will still further illustrate my invention.

EXAMPLE 1 Two single-layer bromoiodide silver halide emulsion coatings A and B are made on a cellulose acetate film support. The silver halide emulsions are of the type described by Trivelli and Smith Photo. Journal, 79, 330 (1939). Each coating contains:

Silver 136 mgJft. Gelatin 4S0 mgJft. Coupler 78 mgJft. Tri-o-crcayl phosphate 39 m Jl't.

The coupler in Coating A is coupler A, i.e., 3-pentadecyl-1- phenyl-5-pyrazolone (outside the invention) and coating B contains my coupler 21, i.e., 4-benzotriazolyl-3-pentadecyl-lphenyl-5-pyrazolone which is derived from Coupler A. Both coatings are exposed to an intensity scale test object and processed as follows:

1. Development for 10 minutes in Developer Solution 1 Sodium hexametaphosphate 0.5 g. Sodium sulfitc 2.0 g. 4-Amino-J-methyl-N,N-diethylnniline hydrochloride 2.0 g. Sodium carbonate, monohydratc 20.0 g. Sodium bromide (50% solution) 3.46 ml. Water to 1 liter (adjust pH to 10.86)

2. Stop-Fix for 5 minutes in F-5 Sodium lhiosulfate 240 g. Sodium sulfitc 15 g. Acetic Acid (28%) 48 ml. Boric Acid 8- Potassium alum 15 3 Water to l (adjust pH to 4.25)

3. Wash for 5 minutes in H 0 4. Silver bleach for 5 minutes in 5. Wash for minutes in water 6. Fix for 5 minutes in F5 7. Wash for minutes in H 0 8. Dry

The test is repeated as described above with a developer solution 2 of the following composition:

' Bcnzyl alcohol 4 g.

Sodium hexametaphosphate 0.5 g. Sodium carbonate 2 g. Sodium hydroxide (40% solution) 0.4 ml 4-Amino-J-methyl-N-ethyl-N-a-(methanesullonamido)ethylaniline sesquisulfate hydrate 5.0 g. Sodium carbonate monohydrate 50.0 g. Sodium bromide (50% solution) 1.72 ml. Water to l liter Each coating is sensitometrically evaluated and subjected to printout and yellowing tests. The results are recorded in table I.

TABLE I D-mln. increase from exposure L1 ht Heat pr ntyellow- Gouout ing, Developpler D-max. A-max. percent percent ment Coating A A 2.42 527 40 Solution. B 21 3.03 526 7 9 Solution. A. A 527 14 36 Solution". B 21 524 3 8 Solution".

Developer. MM

Conclusion: The coupler No. 21 according to my invention yields more dye and is more stable to light and heat than its corresponding parent four-equivalent Coupler A.

EXAMPLE 2 Two single-layer coatings C and D both essentially like those in example 1 are prepared. Coating C contains Coupler B, i.e., 4-(2-benzotriazolyloxy)-2-[8-(2,4-diamylphenoxybutyl)] l -hydroxynaphthamide (outside the invention) and Coating D contains Coupler 36 i.e., 4-( 2-benzotriazolyl)-2-[8-(2,4- diamylphenoxybutyUl-l-hydroxynaphthamide. Samples of these coatings are exposed and processed as in example 1, except that instead of the test for printout and yellow they are subjected to a 2-day SANS (simulated average north skylight at 500 foot candles intensity) and a heat fading test (1 week,

l40 F., 70 percent R.H.), respectively. The results of these tests are given in table ll.

Coupler 36 according to my invention yields substantially more dye than coupler B, and the dye formed from my coupler is substantially more stable to light and heat than the dye generated from Coupler B.

EXAMPLE 3 Two single-layer coatings consisting of 78 mg./ft. of coupler and 39 mg /ft. of the coupler solvent tri-cresyl phosphate dispersed in 450 mg./ft. of gelatin are identified as E and F. Coating E contains the coupler B identified above (outside the 'invention) and coating F contains Coupler 36 according to my invention. Both coatings are overcoated with a dilute dispersion of silver bromoiodide grains and gelatin and dried. Coatings E and F are identically exposed to a test object and processed by the procedure described in example 1 except that the pH of the developing solution I is adjusted to 12.0. The examination of a micrographic cross section of each processed coating indicates that no dye is formed in the upper layer of coating F (of my invention) and that the lower half of the upper layer of exposed portions of coating E contain distinct clouds of cyan dye formed around the dispersed silver halide grains, indicating a 50 percent wandering rate for the coupler B (outside the invention).

EXAMPLE4 A processed sample of each of Coatings A and B of example 1 and coatings C and D of example 2 is viewed while being ililuminated with a fluorescent lamp. The areas of no dye density or minimum dye density in the samples containing the couplers of my invention (i.e., B and D) show a pronounced blue fluorescence; the corresponding areas in coatings A and C (outside my invention) do not fluoresce.

EXAMPLE 5 Coupler A l/ll area units Coupler 2| 33 area units Coupler C 7 area units Coupler 23 45 area units Coupler 55 58 area units Coupler D I! area units Coupler 36 area units The couplers of myinvention absorb substantially more radiation in the region of the electromagnetic spectrum between 300 and 400 m than do the corresponding couplers outside of my invention.

Cyan dyeforming couplers disclosed in Whitmore et al. US. Pat. No. 3,148,062, such as, 4(2-benzotriazolyloxy)-2- ['6-(2,4-diamylphenoxybutyl)]-l-hydroxynaphthamide which I have identified as coupler B for convenience, are not to be confused with my cyan-forming couplers, such as, my corresponding coupler 36. My coupler 36 has very markedly different properties from coupler B. For example, my coupler 36 has a melting point of l46-l47 C. compared to 222 C. for coupler B. My coupler 36 in solid form or in solution gives an intense blue fluorescence while coupler B does not fluoresce when exposed to ultraviolet radiation. Coupler 36 couples rapidly to produce a good clean cyan dye while coupler B couples more slowly and produces a somewhat greenish cyan dye. l have found that none of my coupler 36 is or can be made by the method in U.S. Pat. No. 3,148,062 described to make the coupler l have identified as coupler B. Similarly no coupler B is produced by my synthesis of coupler 36.

My couplers have the valuable property of resisting attack by aldehyde hardeners used in photographic materials and processes. Undesirable stain formation as well as loss of conventional 5-pyrazolone couplers from attack by aldehydes is avoided by use of my S-pyrazolones.

The valuable characteristics discussed above and demonstrated for representative couplers of my invention (and dyes from them) in the preceding examples can be shown for the other couplers of my invention.

As mentioned previously, when my couplers react with oxidized color developing agents to form dye, a benzotriazole compound is released that tends to inhibit photographic development in those regions where coupling has occurred. This effect is used advantageously in photography for controlling the sensitometric characteristics of the developed emulsion layer.

My couplers are used to advantages in photography, particularly in color print materials where the residual incorporated coupler left in highlight areas of processed prints, for example, will fluoresce to brighten these areas in the color print.

The invention has been described in detail with particular embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention as described hereinabove and as defined in the appended claims.

lclaim:

l. A hydrophilic colloid silver halide emulsion containing a two-equivalent dye-forming coupler consisting of one or two four-equivalent dye-forming coupler moieties directly linked in their coupling position by a single bond to a benzotriazolyl radical of the formula wherein R, is a member selected from the class consisting of a hydrogen, halo, nitro, amino, amido, hydroxyl, alkoxy having from one to four carbon atoms, alkyl having from one to four carbon atoms, the nonmetallic atoms which taken together with R, form a to 6-membered ring, and phenylazo radicals; R is a member selected from the class consisting of a hydrogen, halo, nitro, amino, amido, hydroxyl, alkoxy having from one to l8 carbon atoms, alkyl having from one to l8 carbon atoms, the nonmetallic atoms which taken together with R, form a 5- to 6-membered ring, the nonmetallic atoms which taken together with R form a 5- to 6-membered ring, and a phenylazo radical; R, is a member selected from the class consisting of a hydrogen, halo, nitro, amino, amido, hydroxyl, alkoxy having from one to 18 carbon atoms, alkyl having from one to l8 carbon atoms, the nonmetallic atoms which taken together with R, form a 5 to 6-membered ring, the nonmetallic atoms which taken together with R, form a 5- to 6-membered ring, and phenylazo radicals; and R, is a member selected from the class consisting of a hydrogen, halo, nitro, amino, amido, hydroxyl, alkoxy having from one to four carbon atoms, alkyl having from one to four carbon atoms, the nonmetallic atoms which taken together with R form a 5-to 6-membered ring, and phenylazo radical, not more than one of R, and R, and not more than one of R and R being defined as a phenylazo radical.

2. A hydrophilic colloid silver halide emulsion of claim 1 in which the two-equivalent dye-forming coupler has the formula:

wherein R, is a member selected from the class consisting of a hydrogen, halo, nitro, amino, amido, hydroxyl, alkoxy having from one to four carbon atoms, alkyl having from one to four carbon atoms, the nonmetallic atoms, which taken together with R form a 5- to 6-membered ring, and phenylazo radical; R, is a member selected from the class consisting of a hydrogen, halo, nitro, amino, amido, hydroxyl, alkoxy having from one to l8 carbon atoms, alkyl having one -l8 carbon atoms, the nonmetallic atoms which taken together with R, form a 5- to 6-membered ring, the nonmetallic atoms which taken together with R form a 5- to 6-membered ring, and phenylazo radical; R is a member selected from the class consisting of a hydrogen, halo, nitro, amino, amido, hydroxyl, alkoxy having from one to 18 carbon atoms, alkyl having onel8 carbon atoms, the nonmetallic atoms which taken together with R form a 5- to 6-membered ring, the nonmetallic atoms which taken together with R, form a 5- to 6-membered ring, and phenylazo radical; and R, is a member selected from the class consisting of a hydrogen, halo, nitro, amino, amido, hydroxyl, alkoxy having from one to four carbon atoms, alkyl having from one to four carbon atoms, the nonmetallic atoms which taken together with R fonn a 5- to 6-membered ring, and a phenylazo radical; not more than one of R, and R, and not more than one of R and R, being defined as a phenylazo radical; A and A each represent a dye-forming coupler moiety selected from the class consisting of those having the formulas wherein R, is a member selected from the class consisting of an alkyl, aryl, and heterocyclic radical; n is an integer of from one to two; R is a member selected from the class consisting of a hydrogen, and an alkyl group; R is a member selected from the class consisting of an alkyl, aryl and a heterocyclic group; R, is a member selected from the class consisting of a hydrogen, alkyl, aryl and a heterocyclic group; R is a member selected from the class consisting of a hydrogen, alkyl, aryl, heterocyclic, amino, carbonamido, carbamyl, sulfonamido and a sulfamyl radical; R,,,, R,,, R R,,,, R,, each represent a member selected from the class consisting of a hydrogen, alkyl, aryl, heterocyclic, amino, carbonamido, carbamyl, sulfonamido, sulfamyl and a halo radical; and X is defined as the nonmetallic atoms necessary to form a fused 5- to 6-membered ring.

3. An emulsion of claim 1 in which the coupler is abenzotriazolyl-a-benzoylacetanilide.

4. An emulsion of claim 1 in which the coupler is abenzotriazolyl'a-pivalylacetanilide.

5. An emulsion of claim I in which the coupler is abenzotriazolyl-a-cyanoacetylcoumarone.

6. An emulsion of claim 1 in which the coupler is 4- benzotriazolyl-2-[ 8-( 2 ,4-diamylphenoxybutyl l -h ydroxynaphthamide.

7. An emulsion of claim 1 in which the coupler is 4- ,benzothiazolyl-3-pentadecyl-l-phenyl-5-pyrazolone.

8. An emulsion of claim 1 in which the coupler is 4- benzotriazolyl-3-methyll -phenyl-5-pyrazolone.

9. An emulsion of claim 1 in which the coupler is 4- benzotriazolyll 2,4,6-trichl0rophenyl)-3-[ 3 {a-( 2,4-di-tertamylphenoxy )acetamido benzamidol-S-pyrazolone.

10. A hydrophilic colloid silver halide emulsion containing a two-equivalent dye-forming coupler having substituted on the carbon in the coupling position a benzotriazolyl radical.

lOlOOS OlJl P0405? UNITED STATES PATENT OFFICE 56g CERTIFICATE OF CORRECTION Patent No. 3,617,291 Dated November 971 Inventor-(s) George W- wdey It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 1, line 75, change "4l,2-Bd ,5-dl7" to read Column 2, line 2, replace "may" with -my-;

line 39, delete "A" (first occurrence); lines U6 and 59 replace "-t" with -g- Column 3, line 52, replace "l-clocosy" with --l-doooxy--;

line 65, after "ymethylcyclohexyl" insert a comma Column 1, line 1, replace "etc with --alkyl,-;

line 10, replace "and" with -an;

line 21, replace "2-chloro-5-1?" with --2ch1oro-5AZC lines 32-37 replace entire lines with the following (Y --phenylpropyl)-N-(p -tolyl)-carbamylmethoxl/ phenyl, l-LN-(V -phenylhexyl)-N(p-tolyl) carhamylmethox 7 phenyl etc a 4-sulfamylphenyl radical e.g. l-LN-(v -phenylpropyl-N-(p -tolyl)sulfamyl/phenyl, l-[fihenylethyl )-N-(ptolyl)sulf'amyl 7 line 7U, bef re "tert", insert -di-.

Column 5, line 7, replace "3,5dioctadecoxycarbonyl h" t '3,5-61ioctadecoxycarhonylphlolumn 6, last li ne, Coupler No l8 replace "111241 4 ,5-d7" with --Ll,2d: l,5-d

Jolumn 7 Coupler No 3 4 after "2,6-" insert replace "Bis" with -Bis-; after "-pyrazolonel/ insert 2 r Coupler No 36, after "diamylphenoxybutyl replace "d" with l-; laae l of 2 pages @1050 UNITED STATES PATENT OFFICE 569 CERTIFICATE OF CORRECTION Patent No. 3 $17,291 Dated November 2 1971 Imem:o1.'(s) W- Sawde It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 7, change 42 to l-;

Coupler No 42, after 4-" insert after "butyramid o/" delete "f"; after "benzotriazolyl" insert Coupler No H7, after "-N-" insert after insert after l-A delete "A and insert --a replace "(2, ldi-t" with {2,U-di-tafter "phenyl" insert after "ethyl" insert Coupler No 48, after "butyramidgfi' delete "f" Column 10, line 20, replace "diethyl-p" with diethyl-preplace "monomethyl-p" with -monomethyl-p line 21, replace "dimethyl-p" with "dimeth T- line 26, replace "p-" with --pline 58 after "U.S Pat No 2,80l ,171" insert both-.

Column 11, line 15, replace "vinylalcohol" with --vinyl alcohol-.

Column 13, line 16, after "N" (second occurrence) replace "a" with 5 line 53, after "subjected to a" replace "2-day" with --2l-day.

Column l l, line 32, after "A; 2l; C" insert -(i.e., l-(2,U,6- trichlorophenyl)3-[ 3: [oi-(2, i-di-t amylphenoxy) acetamido} -benzamid2/-5pyrazolone)-;

Page 2 of 3 pages UNITED STATES PATENT OFFICE 5 69 CERTIFICATE OF CORRECTION Patent No. 7, 9 1 Dated November 2, 1971 Inventor(s) George Sawdey It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 15 line 8 after "to" replace "advantages" with --advantage--.

, line 38 lines 19 22, 27, 28, 15, 46 and 71-7 4 lines 2- 4, 19, 20 and 67 l line 32 and 6, line 73 replace "tert" with --ter't.

Column 3 Column 1 Column 5 Column 1 Column 1 Column 5, line 5, replace "(2, 4di-tert-" with -(2, l di-tertlines 7 8 and 10, replace "(p-tolyl)" with -I p-tolyl)-; line 12, replace "(p-toluenesul-" with -(p -toluenesul Signed and sealed this 27th day of June 1972.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. ROBERT GOTTSCHALK Attesting Officer Commissioner of Patents Page 3 of 3 pages

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Classifications
U.S. Classification430/544, 430/957, 430/555, 430/558, 430/553, 430/557
International ClassificationC07D249/20, G03C7/305, C07D249/16, G03C7/392, C07D249/18, G03C1/815, C07D249/22
Cooperative ClassificationG03C1/8155, Y10S430/158, G03C7/30541, C07D249/16, C07D249/18, C07D249/20, G03C7/392, C07D249/22
European ClassificationC07D249/18, G03C7/305C, C07D249/22, G03C7/392, G03C1/815C, C07D249/20, C07D249/16