Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
  • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
  • G03C7/32—Colour coupling substances
  • G03C7/3212—Couplers characterised by a group not in coupling site, e.g. ballast group, as far as the coupling rest is not specific
• • 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
  • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
  • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
  • G03C5/50—Reversal development; Contact processes
• • 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
  • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
  • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
• • 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
  • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
  • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
  • G03C7/32—Colour coupling substances

Definitions

• ABSTRACT A light-sensitive color photographic element containing nondifiusible dye-forming couplers that react with oxidized aromatic primary amine color developing agents to form nondiffusible dye images and a sufficient amount of a competing coupler to react with substantially all of the color-developing agent oxidized during negative silver development, but not enough to interfere with positive dye image formation during subsequent fogging development, is used for direct reversal image reproduction.
• a coupler-incorporated photographic element that produces nondiffusible dye images during color development is direct reversal color processed by (l contacting the element with a color developer solution in the presence of sufficient competing coupler to react with substantially all of the color-developing agent oxidized during negative silver development, but not enough to interfere with subsequent positive dye image formation and (2) contacting the element with bleach, then fix or bleach-fix to remove silver and silver halide.
• the usual color reversal photographic process for photographic elements containing incorporated color-forming couplers involves the use of a negative silver development step in which the negative silver is developed by a conventional hydroquinone-pmethylaminophenol sulfate developer or a conventional hydroquinone-l-phenyl-3-pyrazolidone developer. Negative silver development is usually followed by a stop bath and wash to rapidly stop development and prevent overdevelopment, and to remove residual developing agent.
• the remaining silver halides are then fogged either physically by a light exposure, or chemically by means of a reducing agent such as t-butylamine borane or stannous chloride, and this positive fogged silver halide is then color developed with a p-phenylenediamine developing agent to give a reversal color image.
• this procedure may take as long as 32 minutes at 24 C. up to and including the color development step and the washes required to remove the chemicals at the end of each step.
• Typical reversal processes are described in line 74, column 11 through line 36, column 12 of Carroll et al., U.S. Pat. No.
• the first developer which forms the negative silver image must be uniformly distributed throughout all layers of a multilayer color element, and negative development must stop at precisely the correct moment.
• the stop bath must therefore be uniformly applied and effective on all layers so that the cessation of development is uniform.
• the wash must remove all of the ingredients from both the development and stop bath stages so that the color development step is not interfered with.
• the reversal exposure step must expose all residual silver halide and, if done chemically, must not interfere with the color development step.
• Color development must again be uniform in all three layers to give the proper balance of speeds and curve shapes. Color development must go to completion in D-max areas, and yet in D-min areas must not give rise to unwanted color fog or stain.
• lntemal latent images or latent image traps are provided for in these inventions which give excellent results in terms of direct reversal; however, direct reversal systems are desired which do not require special silver halide emulsions and which give excellent three-color image reproductions using conventional multicolor photographic elements of camera speed (or a lower speed) with a color process requiring substantially fewer process steps than a conventional color reversal process.
• One object of our invention is to provide a novel direct color reversal system replacing the first developer, stop bath, wash, reversal exposure and color developer steps with a single processing step.
• Another object of our invention is to provide a novel photographic element for producing direct reversal image reproductions.
• Another object of our invention is to provide a novel process in which color negative and our novel color reversal films are advantageously interspliced and processed together.
• Another object is to provide a novel process system in which an image exposed color photographic film is processed either as a color negative or as a color reversal reproduction as desired.
• Our light-sensitive photographic elements for direct reversal color-processing comprise a support coated with at least one hardened hydrophilic colloid-silver halide emulsion layer containing or associated with at least one nondiffusible (in emulsion layer) dye-image-forming coupler that is capable of reacting with an oxidation product of an aromatic primary amine color-developing agent produced in a color developer solution by silver halide development to form a nondiffusible dye image (i.e., a dye image that does not wander from the site in the hydrophilic colloid layer where ,it is formed by color development) and on the same side of said support at least one hardened hydrophilic colloid layer containing a sufficient amount of at least one incorporated acceptor, scavenger or competer which reacts with oxidized aromatic primary amine color-developing agent but does not react with light exposed silver halide, e.g., a competing coupler (which chemically reacts with the oxidized color-developing agent and forms
• any soluble, diffusible, competing coupler i.e., soluble in water, aqueous alkali or in a polar organic solvent
• diffusible in hydrophilic layers or any competing coupler which is rendered noninterfering during color development by diffusing out of the photographic element or by reaction to form noncoupling compounds in aqueous, alkaline solution is used to advantage in our invention.
• Competing couplers used to advantage in our photographic elements include:
• any soluble, diffusible competing coupler which forms a colorless compound upon reaction with an oxidized colordeveloping agent, i.e., the oxidation product of an aromatic primary amine color developing agent formed by silver halide development, or
• any soluble, diffusible competing'coupler which forms a soluble, diffusible colored compound upon reacting with an oxidized color developing agent
• any soluble, diffusible or insoluble, nondiffusible competing coupler which becomes noncoupling slowly upon contact with developer solution, and which reacts with oxidized colordeveloping agent as described in (l) or when soluble, diffusible (2) above.
• diffusible we mean capable of moving freely into, through or out of the hydrophilic colloid layers of the photographic element.
• nondiffusible we mean immobile or fixed in the hydrophilic colloid layer.
• Competing couplers as in (l), (2) and'(3) above are advantageously incorporated in our photographic elements in a range of from about 0.10 g./ft. to about 5.0 g./ft. with a preferred range being from about 0.50 g.-/ft. to about 2.0 gJft. by addition to one or more of the emulsion layers as a solution or dispersion during the coating operation or applied to the outermost emulsion layer of an already coated photographic element by imbibition of a solution brought into contact with the emulsion layer or by coating a solution in a hydrophilic colloid coating composition on the emulsion layer. Application is made by dipping, rolling extruding, wiping, or any other conventional techniques.
• Insoluble, nondiffusible competing couplers are incorporated in each light-sen sitive emulsion layer of our photographic elements and, is desired, they are also incorporated in interlayers.
• the amount of competing coupler advantageously incorporated in our photographic elements depends upon a number of factors, including the photographic element and the particular competing coupler.
• the amount of competing coupler that is incorporated in a photographic element is generally more than the stoichiometric amount for the silver halide present and ranges up to about 30 times the stoichiometric amount, depending upon the rate at which the competing coupler decomposes and/or diffuses out of the silver halide emulsion layers into the developer solution.
• our photographic elements contain a blue-sensitive hydrophilic colloid silver halide emulsion layer containing a nondiffusible yellow-dye-forming coupler that couples with an oxidized aromatic primary amine to form a nondiffusible yellow image, a green-sensitized hydrophilic colloid silver halide emulsion layer containing a magenta-dye-forming coupler that couples with an oxidized aromatic primary amine color developing agent to form a nondiffusible magenta dye and a red-sensitized hydrophilic colloid silver halide emulsion layer containing a cyan-dye-forming coupler that couples with an oxidized aromatic primary amine color developing agent to form a nondiffusible cyan dye or, alternately, dispersions of each of the three differently sensitized hydrophilic colloid silver halide emulsions each containing the appropriate dyeforming coupler are dispersed in one light-sensitive layer.
• the differently sensitized layers in our multilayer elements are advantageously arranged on the supports in any of the orders conventionally used in color photographic elements and advantageously include any of the interlayers, filter layers, U.V. absorbing layers, antihalation layers, etc., found in color photographic elements.
• Our competers for oxidized color developers are advantageously added to one or more layers of any of the prior art photographic color elements.
• any of the prior art color photographic elements including commercial elements
• Another embodiment of our invention is a direct reversal color process for a color photographic element containing at least one hydrophilic colloid-silver halide emulsion layer containing a nondiffusible dye-image-forming coupler, the silver halide containing a latent image of an original light image, said process comprising the steps:
• Competers for oxidized color-developing agents for our direct reversal color process are advantageously incorporated in the photographicelement when manufactured (any time prior to image exposure) or applied to the element before or after light image exposure and prior to the development step as a prebath or applied to the element during the development step.
• an aqueous solution containing 1 mole per liter of sulfite ions is a competer for oxidized color developing agent used to advantage in a prebath in our process.
• Preferred competers are any soluble diffusible competing couplers which react with oxidized color developing agent to form a colorless compound (diffusible or nondiffusible) or form a soluble diffusiblecolored compound.
• Competing couplers are used to advantage in the concentration range of from about 6, grams per liter to about 500 grams per liter in an aqueous prebath having a pH in the range of from about 6 to about 13, in an aqueous prebath comprising an aqueous solution containing all the components of a developing solution except the developing agent and containing our competing coupler in the concentration range from about 6 g./l. about 500 g./1., or the competing coupler is used in the complete developer solution in the concentration range of from about 6 g./l. to about 500 g./l., and at a pH range of from about 8.0 to about 13.0.
• the competing coupler is advantageously used in processing solutions as well as in the photographic element, provided sufficient competing coupler is present in our photographic element to prevent the formation of any nondiffusible negative dye image during the development step and is either rendered inactive or is removed by diffusion out of the photographic element during this part of the development, so that positive silver development will now take place with the formation of positive image dye from the reaction of the incorporated coupler. It is advantageous to recirculate our developer solution through an ion exchange column so that residual or excess soluble and diffusible competing coupler of our invention is removed, thus preventing seasoning effects due to this residue or excess. Alternatively, a soluble complexing agent is used in our developer solution to render inactive or nondiffusible any residue or excess of our soluble and diffusible competing couplers (in the developer solution).
• Photographic elements for use in our invention are any color photographic element containing a nondiffusible colored or uncolored color-forming coupler that forms a nondiffusible dye on reaction with oxidized aromatic primary amine color-developing agents, such as those described in Froehlich 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; Graham, U.S. Pat. No. 3,046,129; Martinez, U.S. Pat. No. 2,284,877 and Wolf et al., U.S. Pat. application Ser. No. 634,104, filed Apr. 27, 1967 and now U.S. Pat. No. 3,516,831.
• any of the photographic silver halide emulsions e.g., silver bromide, silver bromoiodide, silver chloride, silver chlorobromide, silver bromochloroiodide, etc.
• Coarse grain or fine grain silver halide emulsions prepared by wellknown procedures are used.
• Silver halide grains having concentric shells that vary as to silver halide, such as are described by Porter et al., U.S. Pat. No. 3,206,313, U.S. Pat. No. 3,317,322 and British Pat. No. 1,027,146 are used advantageously.
• the emulsions used in the photographic element of our 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. 1,574,944, issued Mar. 2, 1926; Sheppard et al., U.S. Pat. No. 1,623,499, issued Apr. 5, 1927; and Sheppard et al., U.S. Pat. No. 2,410,689, issued Nov. 5, 1946.
• the emulsions can also be treated with salts of the noble metals, such as ruthenium, rhodium, palladium, iridium and platinum, as described in Smith et al., U.S. Pat. No. 2,448,060, issued Aug. 31, 1948 and as described in Trivelli et al., U.S. Pat. Nos. 2,566,245 and 2,566,263, both issued Aug. 28, 1951.
• the noble metals such as ruthenium, rhodium, palladium, iridium and platinum
• the emulsions can also be spectrally sensitized with cyanine and merocyanine dyes, such as those described in Brooker U.S. Pat. Nos. 1,846,301 and 1,846,302, both issued Feb. 23, 1932; and 1,942,854, issued Jan. 9, 1934; White U.S. Pat. No. 1,990,507, issued Feb. 12, 1935; Brooker and White U.S. Pat. Nos. 2,112,140, issued Mar. 22, 1938; 2,165,338, issued July 11, 1939; 2,493,747, issued Jan. 10, 1950; and 2,739,964, issued Mar. 27, 1956; Brooker et al. U.S. Pat. No. 2,493,748, issued Jan. 10, 1950; Sprague U.S. Pat.
• the emulsions may also contain speed-increasing compounds of the quaternary ammonium type of Carroll U.S. Pat. No. 2,271,623, issued Feb. 3, 1942; Carroll et al. U.S. Pat. No. 2,288,226, issued June 30, 1942; and Carroll et al. U.S. "Pat. No. 2,334,864, issued Nov. 23, 1943; and the polyethylene glycol type of Carroll et al. U.S. Pat. No. 2,708,162, issued May 10, 1955.
• the emulsions can also be chemically sensitized with gold salts as described in Waller et a1.
• Suitable compounds are potassium chloroaurite, potassium aurithiocyanate, potassium chloroaurate, auric trichloride and 2-aurosulfobenzo-thiazole methochloride.
• Hydrophilic colloids used to advantage include gelatin, colloidal albumin, a cellulose derivative, or a synthetic resin, for instance, a polyvinyl compound.
• Some colloids which may be used are polyvinyl alcohol or a hydrolyzed polyvinyl acetate as described in Lowe, U.S. Pat. No. 2,286,215, issued June 16, 1942; a far hydrolyzed cellulose ester, such as cellulose acetate hydrolyzed to an acetyl content of 19-26 percent as described in Lowe et al. U.S. Pat. No. 2,327,808, issued Aug. 24, 1943; a water-soluble ethanolamine cellulose acetate as described by Yutzy U.S. Pat. No.
• cyano-acetyl groups such as the vinyl alcoholvinyl cyano-acetate copolymer as described in Unruh et al. U.S. Pat. No. 2,808,331, issued Oct. 1, 1957; 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 -lllingsworth et al. U.S. Pat. No. 2,852,382, issued Sept. 16, 1958.
• hydrophilic colloids described above are used in various layers of our photographic elements and are advantageously hardened sufficiently to withstand photographic processing temperatures up to about 93 C. without the coated layer reticulating, frilling, blistering, transferring, etc., with hardening agents, such as, aziridine hardeners, isoxazolium salt hardeners, epoxy hardeners, vinyl sulfone hardeners, mucochloric acid, formaldehyde hardeners, etc.
• hardening agents such as, aziridine hardeners, isoxazolium salt hardeners, epoxy hardeners, vinyl sulfone hardeners, mucochloric acid, formaldehyde hardeners, etc.
• the aziridine hardeners used to advantage include 1,3-bis(l-aziridinylsulfonyl)-propane, 1-( l-aziridinyl carbonyl)-3-( l-aziridinyl-sulfonyl)-benzene and others described in Bumess U.S. Pat. No. 2,964,404 issued Dec.
• hardeners for hydrophilic colloids in our photo graphic elements include hardening compounds having two vinylsulfonylalkyl groups linked to a single linking heteroatom (e.g., nitrogen atom, or oxygen atom) or radical, including hardeners such as, bis(4-vinylsulfonylbutyl)ether, bis-(2- vinylsulfonylethyl)ether, bis(vinylsulfonylmethyl)ether, N,N- bis(2-vinylsulfonylethyl)-n-propylamine, N,N-bis(2-vinylslfonylethyl)-N-ethyl-N-propylammonium tetrafluoroborate, and bis( 1-vinylsulfonylethyl)ether, etc., and other compounds of the formula:
• m is an integer of from 1 to 4
• 2" is a heteroatom (e.g., nitrogen or oxygen) and R is hydrogen, or lower alkyl groups (e.g., methyl, ethyl, isopropyl, etc., which can in turn be further substituted), and hardening compounds having two or more vinylsulfonylalkyl groups (i.e., lower alkyl from one to four carbon atoms) attached to a plurality of tertiary or quaternary nitrogen atoms and/or a plurality of ether oxygen atoms including typical compounds, such as:
• N,N'-bis(2-vinylsulfonylethyl)piperazine 2.
• N,N-bis(2-vinylsulfonylethyl)piperazinebis( methoperchlorate) 3.
• 1,2-bis( vinylsulfonylmethoxy)ethane 6.
• Bis(2-vinylsulfonylethyl)ether 6-Oxa-3,9-dithiaundecane-l,1l-diol is prepared by the reaction of two molar proportions of sodium 2-hydroxyethylmercaptide with 1 mole of bis(2-chloroethyl)ether in methanol, followed by evaporation of the solvent.
• the disulfide is oxidized to the disulfone by hydrogen peroxide according to the method of H. S. Schultz et al., J. Org. Chem, 28, 1140, (1963).
• the resulting diol is converted to 2,2'-bis(2-chloroethylsulfonyl)ethyl ether by adding two molar proportions of thionyl chloride to a refluxingsolution of the diol in acetonitrile containing a catalytic amount of N,N- dimethylformamide.
• removal of the solvent and recrystallization from ethanol-acetone gives a high yield of a colorless chloride having a melting point of 707l C.
• Bis(4-vinylsulfonylbutyl)ether Following the procedure of bis(2-vinylsulfonylethyl)ether and starting with bis(4-chlorobutyl)ether, a colorless intermediate chloride is prepared having a melting point of 66-68 C. Dehydrohalogenation, as in bis(2-vinylsulfonylethyl)ether, carbon decolorization in methanol solution and evaporation of the methanol under reduced pressure yields a pale yellow oily product of n[ 1.5023.
• the light-sensitive layers of our photographic elements are advantageously coated on a wide variety of photographic emulsion supports.
• Typical supports used to advantage include cellulose nitrate film, cellulose acetate film, polyacetal film, polystyrene film, poly(ethylene-terephthalate) film, polyethylene film and related films of resinous materials as well as paper, glass and others.
• any of the known nondiffusible dye-image-forming couplers known in the art that form nondiffusible dye images are advantageously used in our elements, including the openchain active methylene couplers, the S-pyrazolone couplers, the phenolic couplers and the naphtholic couplers described on pages 7 through 18 in Wolf et al. forementioned, US. Pat. Application Ser. No. 634,104, incorporated 'herein by reference.
• Soluble, diffusible competing couplers used to advantage according to our invention are represented by the formula:
• Coup. represents a photographic coupling moiety (e.g., an open-chain ketomethylene coupler, a S-pyrazolone coupler, a pyrazolinobenzimidazole coupler, a 1H- pyrazolo[3,2-cl-s-triazole coupler, a phenolic coupler, a naphtholiccoupler, an 8-hydroxyquinoline coupler, a hydroxyisonicotinic acid, an ester of a hydroxyisonicotinic acid, an amide of a hydroxyisonicotinic acid, a hydroxybenzoic acid, an ester of a hydroxybenzoic acid, an amide of a hydroxybenzoic acid, an isoxazolone coupler, an indazolone coupler, etc.)', L represents a member, e.g., an alkyl group, an aryl group, a heterocyclic group, an acyloxy group, a heterocycloxy group, an an
• Couplers include those described by Formulas I, ll, III, IV, V, VI, VII, VIII IX and X.
• Soluble, diffusible couplers which form colorless compounds upon coupling with oxidized color developing agents include those described by Formulas l and II.
• R represents an alkyl group (substituted or not) (e.g., methyl, ethyl, sulfoethyl, carboxyethyl, aminoethyl, hydroxyethyl, propyl, butyl, sulfobutyl, amyl, sulfoamyl, hexyl, cyclohexyl, etc.), an aromatic group (substituted or not) (such as, a phenyl group, e.g., phenyl, tolyl, chlorophenyl, sulfophenyl, carboxyphenyl, aminophenyl, carbamylphenyl, etc.), a hetero-cyclic group (substituted or not) (e.g., a benzofuranyl group, a furanyl group, a thiazolyl group, an oxazolyl group, an imidazolyl group, a quinoly
• an amino group e.g., amino, dialkylamino, alkylamino, anilino, etc.
• R represents an alkyl group (substituted or not) or an aromatic group (substituted or not) or a heterocyclic group (substituted or not) each as already defined for R
• X represents a cyano group, a carbamyl group (substituted or not), etc., such that at least one of the groups R, R,, and X is substituted with a solubilizing group, especially a sulfo group or a carboxy group.
• soluble, diffusible competing couplers that react with oxidized color developing agents to form colorless compounds are any of the substituted 5- pyrazolone solubilized competing couplers of the formula:
• R and R are as described previously and R, represents a group such as an alkyl group, preferably lower alkyl having one to six carbon atoms, a carbamyl group (substituted or not) (e.g., an alkyl carbamyl group such as ethylcarbamyl, sulfoethylcarbamyl, butylcarbamyl, sulfobutylcarbamyl, etc.), an arylcarbamyl group such as a phenylcarbamyl group (e.g., phenylcarbamyl, sulfophenylearbamyl, tolylcarbamyl, etc.), an amino group (substituted or not with one or two alkyl groups and/or one or two aryl groups) (e.g., N- methylamino, N,N-dimethylamino, N-methylanilino, N-ethyl sulfoan
• Soluble, diffusible competing couplers forming soluble dyes used to advantage according to our invention include those having Formulas III, IV, V and VI described herein below:
• R and X are as described previously and where Y is fluoro, hydrogen, the thiocyano group, an acyloxy group [such as an alkoyloxy group (substituted or not) (e.g., acetoxy, butyryloxy, hexanoyloxy, sulfobutyryloxy, chlorobutyryloxy, etc.), an aroyloxy group (substituted or not) (e.g., a benzoyloxy group, such as, benzoyloxy, methylbenzoyloxy, chlorobenzoyloxy, sulfobenzoyloxy, carboxybenzoyloxy, aminobenzoyloxy, carbamylbenzoyloxy, etc.)] and a cycloxy group [e.g., an aryloxy group (e.g., a phenoxy group, such as, phenoxy, 4-sulfophenoxy, 3-methoxyphenoxy, 4-carboxyphen
• R and R are as described previously and Y represents halogen (e.g., Cl, F, etc.), hydrogen, the thiocyano group, an acyloxy group and an arylazo group as defined for Y previously, an aryloxy group as defined previously for Y, an alkoxy group as defined previously for Y, an arylthio group as defined previously for Y and an alkylthio group as defined previously for Y, so that R and/or R, is substituted with a solubilizing group and if desired YY is also substituted with a solubilizing group (e.g., sulfo, carboxy, etc.). Also included are couplers of the following formulas:
• lower alkyl group having from one to six carbon atoms e.g., methyl, ethyl, sulfoethyl, carboxyethyl, hydroxyethyl, aminoethyl, carbamylethyl, butyl, sulfobutyl, hexyl, sulfohexyl, cyclohexyl, etc.
• an aryl group e.g., a phenyl group, such as, phenyl, 4-sulfophenyl, tolyl, methoxyphenyl, 4-carboxyphenyl, 2-chlorophenyl, aminophenyl, methoxyphenyl, carbamylphenyl, etc.), a naphthyl group (e.g., naphthyl, 4-sulfonaphthyl, 4-carboxynaphthyl, etc.)], a heterocyclic group having from five to six
• an amino group e.g., amino, alkylamino, acylamino, arylamino, heterocyclicamino, etc.
• a substituted carbonamido group e.g., an alkylcarbonamido group (e.g., methylcarbonamido, ethylcarbonamido, sulfobutylcarbonamido, benzylcarbonamido, etc.), an arylcarbonamido group (e.g., phenylcarbonamido, 4-su1- fophenylcarbonamido, tolylcarbonamido, aminophenylcarbonamido, etc.), a heterocycliccarbonamido group (e.g., a pyridylcarbonamido group, a thiazolylcarbonamido group, etc.)], a substituted sulfonamido group [e.g., an alkylcarbonamido group (e.g., methylcarbona
• a heterocycliccarbamyl group in which the heterocyclic group has from five to six atoms in the ring e.g., pyridylcarbamyl, thiazolylcarbamyl, oxazolylcarbamyl, etc.), etc.
• a sulfo group e.g., a halogen (e.g., chlorine, bromine, fluorine), an alkoxy group (e.g., methoxy, ethoxy, hexoxy, etc.), carboxy, hydroxy, an aryloxy group [e.g., a phenoxy group (e.g., phenoxy, tolyloxy, chlorophenoxy, fluorophenoxy, 4-hydroxyphenoxy, carboxyphenoxy, sulfophenoxy, aminophenoxy, etc.), a naphthoxy group (e;g., a-naphthoxy, sulfo anaphthoxy, carboxy a-nap
• Y represents the groups previously defined for Y and also includes a cyclic imido group (e.g., a maleimido group, a succinimido group, a l,2-dicarboximido group, a phthalimido group, etc.); Y and Y are also substituted with a solubilizing group; Z represents a member, such as,
• R12 58 3 l 1 R10 R9 wherein R represents a group such as hydroxyl, an alkoxy group (e.g., methoxy, ethoxy, propoxy, dodecyloxy, benzyloxy, etc.), an amino group (e.g., amino, N-rnethylamino, N- ethylamino, N-methylanilino, N-butylamino, etc.); n
• R represents an integer of from 1 to 2;
• R represents hydrogen or a halogen atom (e.g., Cl, Br, I or F);
• R represents hydroxyl or an acyloxy group (e.g., acetyloxy, butyryloxy, lauroyloxy,
• Z represents nitrogen or CR
• R represents hydrogen or a halogen atom (e.g., Cl, Br, l or F); R represents hydroxyl or an acyloxy group (e.g., acetyloxy, butyryloxy, lauroyloxy, etc.); and R represents hydrogen or halogen (e.g., Cl, Br, I or F).
• Representative competing couplers of Formula 111 include the following:
• a-pivaloylacet-4-sulfoanilide a-pivaloylacet-2-sulfoanilide a-pivaloylacet-Z,4-dicarboxyanilide a-benzoyl-a-thiocyanoacet-4-sulfoanilide a-acetoxy-a-(4-sulfobenzoyl)acet-4-sulfoanilide a-benzoyloxy-a-(4-sulfobenzoyl )acet-4-sulfoanilide a-phenoxyacetoacet-4-sulfoanilide a-methoxyacetoacet-4-sulfoanilide 4-(w-benzoylacetamino)benzene sulfonic acid
• Representative competing couplers of Formula IV include the following:
• Decomposable competing couplers which are advantageously incorporated in a photographic element, and which decompose or are rendered inactive slowly, upon contact with developing solution, include those having the following formula:
• Couplers of Formula Vlll when contacted with strongly alkaline solutions, slowly decompose into R COOH and Y CH X,.
• Preferred compounds of Formula Vlll include:
• R and R each represent the same or a difi'erent member, e.g., hydrogen, an alkyl group (e.g., methyl, ethyl, propyl, butyl, sulfoethyl, carboxyethyl, hydroxyethyl, sulfobutyl, amyl, sulfoamyl, hexyl, etc.), an aryl group [e.g., a phenyl group (e.g., phenyl, tolyl, chlorophenyl, sulfophenyl, carboxyphenyl, aminophenyl, carbamylphenyl, etc.), a napthyl group (e.g., a-naphthyl, B-naphthyl, etc.), a heterocyclic group having from five to six atoms in the ring (e.g., a pyridyl group, a
• R represents an alkyl group (e.g., methyl, ethyl, butyl, hexyl, etc.), an aryl group [e.g., a phenyl group (e.g., phenyl, tolyl, chlorophenyl, sulfophenyl, aminophenyl, carboxyphenyl, etc.), a naphthyl group (e.g., a-naphthyl, B- naphthyl, etc.)], a heterocyclic group in which the heterocyclic group has from five to six atoms in the heterocyclic ring, e.g., pyridyl, quinolyl, triazolyl, benzotriazolyl, etc.), R represents a radical of a diazotizable amine, such as, an aryl amine [(e.g., aryl amine [(e.g., aryl amine [(e.g.,
• Competing couplers of Formula [X are advantageously prepared by ring closure of a compound having the formula:
• R groups are advantageously substituted for the hydrogen on the free base by reacting the free base with the appropriate reagent; for example, a halogen atom is introduced by treating with the desired halogen in acetic acid; a sulfo group is introduced by treating with oleum; a phenylthio group is advantageously introduced by condensing with the appropriate RSCl where R is as defined previously in the presence of a base and an inert solvent; a substituted sulfonyloxy group is advantageously introduced by reaction of the 7-bromo derivative with the silver salt of the alkyl or aryl sulfonic acid; an acyloxy group is advantageously introduced at the 7-position by reacting the 7-bromo derivative with the appropriate organic acid (or alkali metal salt thereof); a phenoxy group is advantageously introduced by reaction of the 7-bromo derivative with sodium phenolate; the thiocyano group is advantageously introduced by treating the free base with the product of the reaction of an alkal
• a benzotriazol-2-yl group is advantageously substituted on the 7-position of the coupler by preparing the 7-(2-nitrophenylazo) derivative and heating this in aqueous ethanol containing sodium hydroxide while zinc dust is added. Refluxing is continued until the solution turns colorless, after which the excess zinc is removed by filtration and the reaction mixture is advantageously acidified with hydrochloric acid to form the coupler. Still other substitutents are advantageously introduced by known methods.
• couplers of Formula X are made from the free base of couplers of Formula lX by heating with the appropriate aldehyde in dry benzene.
• Belgian Pat. No. 724,427, issued May 27, 1969 describes couplers of Formulas IX and X.
• the compounds of Formula XI are advantageously made by reacting the appropriate heterocyclic substituted hydrazine with in the presence of a base, e.g., pyridine, and compounds of Formula XII are advantageously made by reacting the appropriate heterocyclic substituted hydrazine with in an inert solvent.
• a base e.g., pyridine
• compounds of Formula XII are advantageously made by reacting the appropriate heterocyclic substituted hydrazine with in an inert solvent.
• Typical soluble, diffusible competing couplers of Formulas lX and X are as follows:
• N,N-diethyl-3-(Z-hydroxyethyl)-p-phenylenediamine 2HCl Useful antifoggants are selected from those well known in the prior art and representative compounds are:
• K PO K HPO. KH Pm, Na CO NaHCO an alkali metal salt of boric acid, etc.
• organic buffers such as described in Bard et al., US. Pat. No. 3,305,364 and etc.
• Useful silver halide solvents include:
• Useful antioxidants include:
• hydroxylamine sulfate 2. diethylhydroxyylamine 3. sodium sulfite 4. dextrose 5. p-hydroxyphenyl glycine 6. ascorbic acid 7. oxytetronic acids 8. dihydroxyacetone
• Other useful compounds which are advantageously added to our developer include thallium nitrate and tetramethylammonium chloride.
• Solutions containing our soluble and diffusible competing couplers and all the components of a color developer solution, excepting the developing agent, are used advantageously as a prebath from which is imbibed our soluble and diffusible competing couplers. Solutions having this composition and containing both color developing agent and soluble difiusible competing couplers are used advantageously to apply said competing coupler to the photographic element and also carry out negative silver development as described hereinunder. Solutions having the above composition, but lacking our soluble, diffusible competing coupler are used advantageously to carry out negative silver and positive image dye development using photographic elements in which said competing couplers have been imbibed or precoated.
• anion exchange resins include those sold under the trademarks,'e.g.:'
• l. AMBERLITE IRA 400, 401 or 410 Rohm & Haas Co. trademark for insoluble,ccross-linked polymers used as anionic exchange resins
• lONAC A-550 permutit Co. trademark for quaternary amine polystyrenes used as anionic exchange resins
• S-l A Permutit Co. trademark for anionic exchange resins
• DUOLlTE A-40, A42, A-ll, A-l02 (Diamond Alkali Co.
• R R R and R are the same or different alkyl groups having from one to 20 carbon atoms with at least one of those alkyl groups having from 12 to 20 carbon atoms and x is an anion, e.g., Cl, Br, H POf, p-toluene sulfonate, etc., in a concentration at or near the solubility limit.
• anion e.g., Cl, Br, H POf, p-toluene sulfonate, etc.
• Typical examples include N,N-dimethyl-N-B-hydroxyethylN-' stearamidopropylammonium bromide, methyl-tri-N- dodecylammonium-p-toluene sulfonate, etc.
• the negative silver development had been carried out in a separate step before being brought into contact with a p-phenylenediamine color developing agent, and the positive image was produced in the presence of a relatively low concentration of a competing coupler.
• the prior art discloses the production of a negative color image in the presence of a color developer and a competing coupler.
• negative development is carried out by a p-phenylenediamine color developing agent in the presence of a sufiicient amount of our competing coupler such that the oxidized color developer produces no image dyes, but rather, reacts with our competing coupler.
• Our invention is preferably used for the production of a direct positive image in any incorporated coupler (i.e., that form nondiffusible dyes on color development) color photographic elements by processing the element in a single color development step by the use of our competing couplers.
• Typical process cycles include the following:
• Process Cycle 4 is not strictly a direct reversal process, and the element being processes is removed from the negative developer when the negative image is developed, but it does use our invention and, therefore, does offer obvious advantages over reversal processes of the prior art.
• coupler color photographic elements in process cycles 1 and 2 and obtain a negative image, but in processes 3 4 and 5, they will give a positive dye image.
• Prehardening can be used only with process cycles 3, 4 and 5 while forehardening can be used for all process cycles.
• Advantageous prehardener solutions have been described in Baden et al., U.S. Pat. No. 3,294,536; Allen et al., U.S. Pat. No. 3,232,761; Re. No. 26,60l and Bard et al., U.S. Pat. No. 3,451,817. These are common dialdehyde (e.g... succinaldehyde) formaldehyde hardeners.
• the hardener is advantageously followed by a common scavenger or a neutralizer bath, such as described in Blackmer et al., U.S. Pat. No. 3,168,400 and which describes agents that react with the excess aldehyde before development.
• a useful agent for example, is hydroxylamine.
• a blue light-absorbing filter layer such as Carey-Lea, colloidal silver dispersed in gelatin and a blue-sensitive gelatinosilver bromoiodide emulsion layer containing a nondiffusible openchain ketomethylene yellow-dye-forming coupler of the type shown in columns 17 and 18 of U.S. Pat. No. 3,046,129 are lightexposed to a test object and processed at 51.6 C. as follows:
• Prehardener 45 Neutralizer l5" Prehath 2' Developer 10", 30", l, 2, 3'or 4' Stop 30" Wash 30 Bleach l Wash 2' Stabilizer 30"
• the prehardener is a conventional aqueous succinaldehydeformaldehyde prehardener solution and the neutralizer is an aqueous solution of hydroxylamine.
• the prebath is an aqueous solution consisting of 320 g./l. of H-Acid, i.e., S-amino-lnaphthol-3,6-disulfonic acid and 1 l4 g./l. of Na CO adjusted to a pH of 8.0 at 26.7 C.
• the developer is an aqueous solution as follows:
• diaminopropanol tetraacctie acid water softener
• the stop bath is an acidic aqueous solution which advantageously contains sulfite ions, the bleach a conventional potassium ferricyanide-postassium bromide aqueous solution, the fix a conventional sodium thiosulfate aqueous fixing solution and the stabilizer an aqueous formalin solution.
• a good direct reversal image is produced at the 2-, 3- and 4-minute development times, each development time giving substantially identical results. Color reversal images are obtained with one minute of development, however the dye densities and contrast are lower then desired. Colors from the test object and a neutral scale are properly reproduced at the intended speed for this product.
• Example 1 is repeated at 30 C. and 82,2 C, and gives good direct reversal image reproductions with development times of 8 minutes and 60 seconds, respectively.
• EXAMPLE 3 Examples 1 and 2 are repeated, but with extended development times. Good direct reversal image reproductions are obtained that are substantially identical with those obtained at the minimum satisfactory development time. There is no image degradation. This demonstrates that there is a minimum development time, but no maximum development time.
• EXAMPLE 4 Examples 1, 2, and 3 are repeated, but with a developer pH of 10.0. Useful direct reversal image reproductions obtained using the appropriate development times (i.e. 8 min, at 30 C., 2 min. at 51.6 C. and 60 sec. at 822 C.) indicated in the previous examples.
• EXAMPLE 5 Examples 1, 2 and 3 are repeated, but with a developer pH of 13.0. Useful direct reversal image reproductions are obtained using the appropriate development times, indicated in the previous examples.
• EXAMPLE 6 Examples 1, 2 and 3 are repeated, but with g./l. of developing agent. Good direct reversal image reproductions are obtained using the appropriate development times indicated in the previous examples.
• EXAMPLE 7 Examples 1, 2 and 3 are repeated but with 100 g./l. of developing agent. Good direct reversal image reproductions are obtained using the appropriate development times indicated in the previous examples.
• Examples 6 and 7 demonstrate that our system has low sensitivity to developing agent concentration once the minimum threshold development time and developing agent concentration are established.
• EXAMPLE 8 Examples 1, 2, 3, 6 and 7 are repeated, but using in one prebath 115 g./l. of 2,6-dihydroxyisonicotinic acid and in another prebath 155 g./l. of 3,5-dihydroxybenzoic acid in place of H-Acid. Useful reversal image reproductions are ob tained using the appropriate development times indicated in the previous examples.
• EXAMPLE 10 Samples of 8 different 3-color coupler incorporated reversal color films having the general layer arrangements described for the film in Example 1 and using cyan-dye-image-forming couplers of the type shown in columns l5, l6 and 17 of U.S. Pat. No. 3,046,129 or of the type shown in column 3 of U.S. Pat. No. 2,895,826 using S-pyrazalone magenta-dye-imageforming couplers of the type shown in column 17 of U.S. Pat. No. 3,046,129 and column 4 of U.S. Pat. No. 3,342,597, and using open-chain ketomethylene yellow-dye-image-forming couplers of the type shown in columns 17 and 18 of U.S. Pat.
• EXAMPLE 1 1 EXAMPLE 12 Examples 1, 2, 3, 6, 7 and 9 through 1 l are repeated, but substituting in place of the prebath, a solution having the composition:
• Diaminopropanol tetraacctic acid 5.0 g. Na,SO; 7.5 g. Na PO,-l2H,O 36.0 g. Kl (0.1 percent solution) 24.0 cc.
• B-amino-l-naphthol-3,6-disulfonic acid 320.0 g.
• the developer containing the soluble coupler is used for negative development. Good direct reversal color images are obtained with 30 seconds color development at 822 C.
• This process has the advantage of using almost identical solutions for negative and reversal development, and having fewer stops than conventional reversal processes. It also uses our invention to achieve reversal, but because there is not only a minimum but a maximum limit on negative development time, it is a less preferred embodiment of our invention.
• EXAMPLE 14 A three-color photographic element having a transparent poly(ethylene terephthalate) film support coated on one side in succession a gelatin red-sensitized silver bromoiodide emulsion layer containing an incorporated nondiffusible phenolic cyan-dye-image-forming coupler of the type shown in columns 15, 16 and 17 of Graham et al., U.S. Pat. No. 3,046,129, a gelatin green-sensitized silver bromoiodide emulsion layer containing an incorporated nondifi'usible S-pyrazolone magenta-dye-image-forming coupler of the type shown in column 17 of U.S. Pat. No.
• a gelatin layer containing a bleachable blue light-absorbing filter and a gelatin bluesensitive silver bromoiodide emulsion layer containing an incorporated nondiffusible open-chain ketomethylene yellowdye-image-forming coupler of the type shown in columns 17 and 18 of U.S. Pat. No. 3,046,129 is prepared.
• the gelatin in each of the coupler-containing layers is forehardened with a vinyl sulfone hardener, such as those described in Belgian Pat. No. 686,440 on page 2, line 1 through page 9, using an amount of hardener that is about 1.5 percent by weight of gelatin.
• EXAMPLE Example 14 is repeated, but instead of applying to the outermost light-sensitive layer of the commercial photographic element 2 g./ft. of 8-amino-1-naphtho1-3,6-disulfonic acid (in solution), application is made to other pieces of the commercial photographic element solutions of the following competing couplers:
• a-methyl-a-pivalylacet-Z,4-dicarboxyanilide a-methyl-a-pivalylacet-4-su1foanilide benzoyl-a-methylacet-4-sulfoanilide 3,4-dimethyl-l-(4-sulfophenyl)-5-pyrazolone benzolyacet-4-sulfoanilide 3-methyll 4sulfophenyl)-5 -pyrazolone 2-amino-5-naphthol-7-sulfonic acid 8-aminol -naphthol-3 ,6-disulfonic acid 4,6-dichloro-5-methyl-2-(4-sulfobenazmido)phenol 2,6-dihydroxyisonicotinic acid 3,5-dihydroxybenzoic acid a-chloro-a-pivalylacet-4-sulfoanilide benozyl-a-chloroacet-4
• EXAMPLE 16 A photographic element is made by coating on one side of a transparent film support a hardened gelatin red-sensitized silver bromoiodide emulsion layer containing a solution of our competing coupler 8-amino-l-n aphthol-3,fi-disulfonic acid and an incorporated nondiffusible phenolic cyan-dye-imageforming coupler of the type shown in columns l5, l6 and 17 of U.S. Pat. No.
• 3,046,129 a hardened gelatin layer containing a bleachable blue light-absorbing filter and a hardened gelatin blue-sensitive silver bromoiodide emulsion layer containing a solution of 8-amino-l-naphthol-3,6-disulfonic acid and an incorporated nondiffusible open-chain ketomethylene yellow-dye-imageforming coupler of the type shown in columns 17 and 18 of U.S. Pat. No. 3,046,129 so that there is a total of 1.5 g. of 8- amino-1-naphthol-3,6-disulfonic acid per square foot of the coated element.
• the gelatin in each of the layers of this element is forehardened as describe in Example 14.
• Example 16 is repeated for each of the competing couplers used in Example 15. The results are similar to those obtained in Example 16.
• EXAMPLE 18 To the outermost coating of a three-color photographic element having a paper support coated on one side in succession with a hardened gelatin blue sensitive silver chlorobromide emulsion layer containing an incorporated nondilfusible open chain ketomethylene yellow-dye-image-forming coupler, a hardened gelatin green-sensitized silver chlorobromide emulsion layer containing an incorporated nondiffusible 5- pyrazolone magenta-dye-forming coupler, and a hardened gelatin red-sensitized silver chlorobromide emulsion layer containing an incorporated nondiffusible phenolic cyan-dyeimage-forming coupler [i.e., a photographic element of the type described in Example 2 (column 7, line 55 through line 28 in column 8) of Van Campen, U.S.
• a hardened gelatin blue sensitive silver chlorobromide emulsion layer containing an incorporated nondilfusible open chain ketom
• results from this process are similar to the results obtained by the conventional and substantially longer process used for processing conventional photographic element (not containing the competing coupler solution overcoat) which require the steps first developer, harden or stop, wash, reversal exposing, color developer, stop bath, wash, bleach, fix, wash and dry.
• Example 18 is repeated using applications of other soluble, diffusible competing couplers of our invention (including those specific competing couplers used in Example 15) over the color photographic ,element. Coating rates in the range of from about 0.1 g./ft. to about 5.0 g./ft.” are advantageously used.
• EXAMPLE 19 A photographic element is made like the three-color element described in Example 18, excepting that a solution of 8- amino-1-naphthol-3,6-disulfonic acid is added to each of the coating compositions before they are coated on the paper support so that each square foot of the resulting photographic element contains a total of 2.0 g. of our competing coupler.
• a piece of this element and the overcoated element of our invention prepared in Example 18 are light image exposed and then developed in the developer solution described in Example I for 2 or 4 minutes, given an acid stop, wash, bleach, fix, wash, and dry. Good direct reversal color reproductions are obtained in each of our processed elements.
• Photographic elements are made in which the differently sensitized silver halide emulsion layers containing the appropriate incorporated nondiffusible dye-image-forming couplers described in Example 14 are coated on a film support with different layer arrangements then used in Example 14 an in Example 18.
• the support is coated in succession with the blue-sensitive layer, the red-sensitized layer and the green-sensitized layer.
• the support is coated in succession with the red-sensitized layer, the blue-sensitive layer and the green-sensitized layer.
• element C the support is coated in succession with the green-sensitized layer, the redsensitized layer and the blue-sensitive layer.
• Elements element D the support is coated in succession with the green-sensitized layer, the blue-sensitive layer and the red-sensitized layer.
• Elements A, B, C and D of our invention are made by applying to the outermost light sensitive layer of elements A, B, C and D, respectively, a solution of 8-amino-l-naphthol-3,6 -disulfonic acid. Each of the elements are given identical light image exposures.
• Elements A, B, C and D processed using four minutes of the developer of Example 1, acid stop, wash, bleach, fix, wash and dry.
• elements A, B, C and D are processed by the longer, conventional process using negative developer, stop, wash, re-exposure flash, color developer, acid stop, wash, bleach, fix, wash and dry.
• a comparison of the processed elements shows that A is similar to A; B is similar to B; C is similar to C, and D is similar to D.
• the preferred arrangement of the light-sensitive layers are those of the elements described in Examples 14 and 18; however, elements like A, B, C and D are advantageously used for special purposes.
• Elements A, B, C and D have 2 g. of competing coupler/ftF.
• Example 14 is repeated, by using a photographic element in which instead of having a single layer of each of the differently sensitized emulsion layers, there are two red-sensitized emulsion layers, two green-sensitized emulsion layers and two bluesensitive emulsion layers. To one piece of this element is applied a solution of 8-amino-l-naphthol-3,6-disulfonic acid as described in Example 14. Good direct reversal color image reproductions are obtained in this example, just as in Example 14.
• EXAMPLE 22 An incorporated coupler masked color negative film such as is described in U.S. Pat. No. 3,046,129, column 25, line 67 through line 16, column 26, is treated as in Example 1, using a 4-minute development time and a useful masked direct positive image is obtained. This shows the wide versatility of our invention. This film is now useful as a masked reversal intermediate film for printing purposes.
• EXAMPLE 23 Examples 1 and 14 are repeated, using the appropriate development times (as indicated in Examples, 1, 2, 3, 6, 7, 9 and 14), but using a continuous processing machines and a continuous strand of 35 mm. film.
• the developer solutions are continuously recirculated through a column containing an anionic exchange resin. Good direct reversal images are obtained and there is no degradation in image quality produced during this example.
• the unused soluble competing coupler is recovered from the resin by using standard recovery procedures well known in the chemical industry.
• Example 23 is repeated, but instead of recirculating the developer, a suitable complexing agent such as N ,N-dimethyl- N-B-hydroxyethyl-N-y-stearamidopropyl-ammonium dihydrogen phosphate is added to the developer solution in a a concentration of 5 g./l. Again, good direct color reversals are obtained and no image degradation is observed because our competing coupler is mutually complexed and rendered inactive in our system.
• a suitable complexing agent such as N ,N-dimethyl- N-B-hydroxyethyl-N-y-stearamidopropyl-ammonium dihydrogen phosphate is added to the developer solution in a a concentration of 5 g./l.
• EXAMPLE 25 A processing machine is charged with chemicals for the processing of a three-color negative film as described in Example 22. Negatives are processed using the conventional developing systems. intercut with the film are samples of a color reversal film as described in Example 14 above. Direct reversal images are produced from this film. During the processing, the developer solution is continually circulated through an ion exchange column to remove out soluble competing coupler that leaches from the film into the developer solution. This shows the versatility of our process.
• Example 25 is repeated with another film coating containing a diffusible competing coupler which decomposes slowly upon contact with the developer. It is added as a dispersion to the coating composition used to coat the light-sensitive images. Since the decomposition products from the decomposition of the competing coupler are photographically nonreacting, direct color reversal is obtained and other films may be intercut during continuous processing with no need for an ion exchange treatment of the developer.
• a diffusible competing coupler which decomposes slowly upon contact with the developer. It is added as a dispersion to the coating composition used to coat the light-sensitive images. Since the decomposition products from the decomposition of the competing coupler are photographically nonreacting, direct color reversal is obtained and other films may be intercut during continuous processing with no need for an ion exchange treatment of the developer.
• EXAMPLE 27 The previous examples are rerun, varying the developer components as hereinabove described, and the well-known addenda, such as antifoggants, accelerators, inhibitors, buffers and etc., are found to be beneficial in processes wherein our invention is also used. This indicates that substitutents in commercial color developers are suitable so long as a sufficient quantity of one of our competing couplers is present to prevent dye formation during negative development, but not enough to interfere with reversal image dye formation.
• addenda such as antifoggants, accelerators, inhibitors, buffers and etc.
• EXAMPLE 28 A continuous drum processing machine is built using the principles described in Burner et al., U.S. Pat. No. 3,093,052 and Edens et al. British Pat. Nos. 1,057,585 and 1,064,914 in which a continuous fresh supply of each processing solution in sequence is applied to the moving photographic element as a film by a series of rotating drums, so that each processing solution is applied to the element by a different drum.
• a continuous stand of 35 mm. film (described in Example 14) is processed on this machine to direct color reversal image reproductions and no seasoning effect due to a buildup of our soluble and diffusible completing coupler is observed. There is no need for the ion exchange resin or the complexing agent due to the high turnover of developer solution in this processing machine.
• EXAMPLE 29 The preceding examples are repeated, using the appropriate development times (indicated in the previous examples) and in the developer formula of Example 1, 20 mL/l. of benzyl alcohol.
• the benzyl alcohol performs as a development accelerator as described in the prior art, giving good direct color reversal image reproductions with increased contrast, speed and D-max.
• EXAMPLE 30 The preceding examples are repeated, adding to the developer 10 mg./l. of l-phenyl--mercaptotetrazole. It acts as an antifoggant, lowering speed and fog.
• Examples 29 and 30 are repeated with a variety of addenda used in color photographic processes for both black-and-white and color developer solutions. The results are predictable and similar to the prior art. This shows that our system responds well to well-known photographic processing solution constituents.
• EXAMPLE 31 A multilayer three-color photographic element containing incorporated color-forming couplers of the type described in Example 1 is exposed to an original light image and then given direct color reversal processing of our invention at 23.9 C. as follows:
• the blix (a bleach-fix bath) is a conventional, aqueous sodium ferric ethylenediamine tetraacetate, sodium thiosulfate blix.
• the stabilizer is an aqueous formalin solution.
• EXAMPLE 32 A piece of the multilayer color photographic element used in Example 1 is contacted with a solution containing our competing coupler 8-amino-1-naphthol-3,6-disulfonic acid so that each square foot of the element imbibes a total of 2 g. of our competing coupler. This element is exposed to an original light images and then given direct reversal color processing according to our invention at 23.9 C. as follows:
• Example 33 A multilayer color photographic element of the type described in Example 1 containing incorporated color-forming couplers in which the gelatin emulsion layers are hardened with mucochloric acid and formaldehyde sufficiently to withstand 51.6 C. processing is given light image exposure and direct color reversal processed as described in Example 31, but using the solutions at 51.6 C. to give good direct color reversal image reproductions similar to those obtained in Example 31.
• aziridin hardeners such as those described in Burness, U.S. pat. No. 2,964,404 (in column 1, line 57 through column 3, line 26); in Allen et al., U.S. Pat. No. 2,950,197 (in column 1, line 50 through column 6, line 25) etc.; isoxazolium hardeners such as those described in Van Campen et al., US Pat. No. 3,316,095 (in column 1, line 31 through column 3, line 64); in Burness et al., U.S. Pat. No.
• EXAMPLE 34 A piece of the multilayer color photographic element containing our competing coupler prepared in Example 32 is prepared with gelatin hardened as described in Example 33, exposed to an original light image, then given direct reversal color-processing according to our invention at 51.7 C. as follows:
• Example 1 Color developer from Example 1 blix from Example 31 until silver and silver halide is removed Wash 2' Stabilizer from Example 31 30" to produce a good color positive reproduction of the original light image.
• EXAMPLE 35 On a transport support is coated on side A, a gelatin greensensitized silver bromoiodide camera speed emulsion layer containing an incorporated nondiffusible magenta-imageforming coupler of the type shown in column 17 of U.S. Pat, No. 3,046,129 and about 1 g. of our competer 8-amino-lnaphthol-3,6-disulfonic acid per square feet and coated on side B, an identical gelatin green-sensitized silver bromoiodide camera speed emulsion, but containing an incorporated nondiffusible yellowimage-forming coupler of the type shown in columns 17 and 18 of U.S. Pat. No. 3,046,129 and containing no competing coupler.
• the gelatin in the element is hardened as in Example 14. The element is exposed to a light image and processed as described in Example 34 to produce on side A a good positive magenta dye image and on side B a good negative yellow image mask.
• EXAMPLE 36 A photographic element is made like the element described in Example 35, excepting that the competing coupler in side A of Example 35 element is placed in side B, and side A contains no competing coupler. After image exposure and processing as described in Example 35, side A contains a good negative magenta dye reproduction and side B contains a good positive yellow-colored mask.
• EXAMPLE 37 A color photographic element comprising a cellulose acetate film support coated with a gelatin layer containing a dispersion of blue-sensitized packets, green-sensitized packets and red-sensitized packets is made.
• the blue-sensitive packets include gelatin, a resin, a blue-sensitive silver bromoiodide emulsion and a nondiffusible yellow-dye-forming open chain ketomethylene coupler;
• the green-sensitized packets include gelatin, a resin, a green-sensitized silver bromoiodide emulsion and a nondiffusible magenta-dye-forming S-pyrazolone coupler, and the red-sensitized packets include gelatin, a
• EXAMPLE 38 The light-sensitive layer of the photographic element made in Example 37 is contacted with an aqueous solution of our competing coupler 8-amino-l-naphthol-3,6-disulfonic acid so that about 2 g. of our competing coupler are imbibed per square foot. This element is exposed to a light image and processed as described in Example 31, but without the prebath. Useful direct color reversal image reproductions are obtained of the light image.
• Example 14 is repeated but instead of applying to the multilayer color photographic element a solution of the single competing coupler S-amino-l-naphthol- 3,6-disulfonic acid, a solution of 8-amino-l-naphthol-3,6-disulfonic acid and 2,6- dihydroxyisonicotinic acid is applied so that each square foot of the element imbibes l g. of each competing coupler. Good direct color reversal image reproductions are obtained.
• Example 1 is repeated but with a prebath that contains instead of 320 g./l. of S-amino-l-naphthol-3,6-disulfonic acid, 160 g./l. of 8-amino-l-naphth0l-3,6-disulfonic acid and 160 g./l. of 2,6dihydroxyisonicotinic acid.
• a development time of 4 minutes is used. Good direct color reversal image reproductions are obtained.
• EXAMPLE 4l Example 1 is repeated at 93 C., using N,N-diethyl-3-(B- hydroxyethyl)-p-phenylenediamine 2HCl as the developing agent instead of 4-amino-3-methyl-N-ethyl-N-B-hydroxyethylaniline sulfate. Good direct reversal image reproductions are obtained with a development time of 60 seconds.
• Photographic elements are made as described in Examples l4, l5 and 18 and solutions of competing couplers are applied as described in Examples l4, l5 and 18, respectively.
• the elements are then slit, light exposed to a test object and processed according to our invention as described in Example I, but using no prehardener step, no neutralizer step and no prebath step, and using N,N-diethyl-3-(Bhydroxyethyl)-pphenylenediamine 2HCl as the developing agent, instead of 4- amino-3-methyl-N-ethyl-N-B-hydroxyethylaniline sulfate in the developer solution (of Example 1) and processing at 93 C., instead of 51.6 C. 'Good direct reversal color image reproductions are obtained with 60 seconds development.
• a panchromatically sensitized hardened gelatin silver bromoiodide emulsion is prepared and intimately blended with a dispersion of a mixture of l) a nondiffusible phenolic cyan-dye-image-forming coupler (of the type shown in columns l5, l6 and 17 of Graham et al., US. Pat. No. 3,046,l29), (2) a nondiffusible S-pyrazolone magenta-dye image-forming coupler (of the type shown in column 17 of U.S. Pat. No. 3,046,129), and (3) a nondiffusible open-chain ketomethylene yellow-dye-image-forming coupler (of the type shown in columns 17 and 18 of US.
• a nondiffusible phenolic cyan-dye-image-forming coupler of the type shown in columns l5, l6 and 17 of Graham et al., US. Pat. No. 3,046,l29
• Pati'No. 3,046,129 in a hardened gelatin.
• the weight ratio of the three couplers is adjusted to give upon direct reversal processing approximately a neutral image.
• the resulting emulsion is coated on a poly(ethylene-terephthalate) film support. After drying, the emulsion coating is overcoated with a solution of the competing coupler 8-amino-l-naphthol-3,6-disulfonic acid such that two grams of our competing coupler are present in every square foot of the coatings.
• the resulting element is sensitometrically exposed to a light image and processed as described in Example 1, except that no prehardener, no neutralizer and no prebathare used. Useful direct reversal neutral image reproductions are obtained of the original light image.
• EXAMPLE 44 Examples l and 14 are repeated seven times, once each for each of seven different developing agents in the developing solution, i.e., using in place of 4-amino-3-methyl-N-ethyl-N-B- hydroxyethylaniline sulfate in the developer solution an equimolar amount of p-aminoN,N-di-ethylaniline HCl, 4- amino-3-methyl-N,N-diethylaniline HCl 4-amino-N-ethyl-N- B-hydroxyethylaniline H 50 4-amino-N-butyl-N-w-sulfobutylaniline, 4-amino-3-methyl-N-fi-( methane sulfonamido)ethylaniline 3/2 H SO H O, 4-amino-3-B-(methane sulfonamido)ethyl-N,N-diethylaniline HCl and
• Example 24 is repeated twice, using in the developing solution in place of N,N-dimethyl-N-B-hydroxyethyl-N-'ystearamidopropyl ammonium dihydrogen phosphate, an equimolar amount of N-n-octadecyl-N,N,N-tributyl ammonium bromide in one repeat, and methyl-tri-N-dodecylammonium-p-toluene sulfonate in the second repeat. In each repeat, the results are essentially the same as obtained in Example 24.
• development is used to replace the conventional process steps of 1) first development (2) stop bath (3) wash and (4) reversal color development.
• Our process advantageously uses a single developing agent while conventional processes use from two to three different developing agents.
• Our development step goes to completion, so there is no upper limit on the development time, while the prior art has an upper limit, as well as a lower limit, on not only one development step but two development steps that must be controlled precisely.
• Our process is less sensitive to temperature variations that the prior art because our development step goes to completion and the process does not-depend upon stopping a first development step at the proper stage of development as well as stopping the reversal development step at the proper stage of development.
• Our process is distinguished from prior art processes by using an aromatic primary amine color developer to develop a negative silver image as well as a positive silver image and a positive dye image in our photographic element.
• Substantially all of the oxidized aromatic primary amine color developing agent that is formed during development of light-exposed areas of a latent image in our element reacts with a competing coupler that is present in the emulsion layers so there is no nondiffusible negative dye image formed in the element, while during the subsequent fogging development of the unexposed areas of the silver halide (advantageously in the same developer solution), there is notenough competing coupler present to interfere with the formation of a positive dye image along with the positive silver image.
• the competing coupler is advantageously incorporated in the appropriate hydrophilic colloid layer or layers during manufacture of the color photographic element that contains nondiffusible color-forming couplers that form the nondiffusible image dyes, or the photographic element is advantageously made without the competing coupler which is then imbibed into the element as the last stage of manufacture or at any subsequent time desired (be fore or after light image exposure), as long as it is present in the element just prior to the development step.
• the appropriate amount of a diffusible, competing coupler is advantageously imbibed into the emulsion layers of any commercial or other prior art color photographic element (containing incorporated couplers that form nondiffusible dye images) as indicated and then advantageously processed by our process to give good, direct reversal color reproductions.
• a light-sensitive photographic element for direct reversal color processing comprising a support coated with at least one light-sensitive hardened hydrophilic colloid silver halide emulsion layer containing at least one nondiffusible dye-image-forming coupler that is capable of reacting with an oxidation product of an aromatic primary amine color developing agent produced in a color developer solution by silver halide development to form a nondiffusible dye image and on the same side of said support at least one hardened hydrophilic colloid layer containing at least one competing coupler that is capable of reacting with said oxidation product of said color developing agent to form a reaction product selected from the class of a diffusible reaction product and a colorless reaction product, said competing coupler, instead of said dye-image-forming coupler, reacts with said oxidation product of said color developing agent, so that when said element is light image exposed to produce a latent image and then contacted with said color developer solution, there is a sufficient amount of said competing coupler present in said element to react with substantially all
• a light-sensitive photographic element of claim 1 in which the side of said support opposite the side containing said competing coupler is coated with at least one hydrophilic colloid silver halide emulsion layer containing a nondiffusible dye-image-forming coupler that forms a nondifiusible dye image.
• a light-sensitive photographic element for direct reversal color processing comprising a support coated on one side with a hardened hydrophilic colloid red-sensitized silver halide emulsion layer containing a nondiffusible cyandye-image-forming coupler that is capable of reacting with an oxidation product of an aromatic primary amine color developing agent produced in a color developer solution by silver halide development to form a nondiffusible cyan dye image, a hardened hydrophilic colloid green-sensitized silver halide emulsion layer containing a nondiffusible magenta-dyeimage-forming coupler that is capable of reacting with said oxidation product of said color developing agent to form a nondifiusible magenta dye image, and a hardened hydrophilic colloid blue-sensitive silver halide emulsion layer containing a nondiffusible yellow-dye-image-forming coupler that is capable of reacting with said oxidation product of
• a light-sensitive photographic element for direct reversal color processing comprising a support coated on one side with a hardened hydrophilic colloid red-sensitized silver halide emulsion layer containing a nondiffusible cyandye-image-forming coupler that is capable of reacting with an oxidation product of an aromatic primary amine colordeveloping agent produced in a color developer solution by silver halide development to form a nondiffusible cyan dye image, a hardened hydrophilic colloid green-sensitized silver halide emulsion layer containing a nondiffusible magenta-dyeimage-forming coupler that is capable of reacting with said oxidation product of said color-developing agent to form a nondiffusible magenta dye image, and a hardened hydrophilic colloid blue-sensitive silver halide emulsion layer containing a nondiffusible yellow-dye-image forming coupler that is capable of reacting with said oxidation
• a light-sensitive photographic element for direct reversal color processing comprising a support coated on one side with a hardened hydrophilic colloid red-sensitized silver halide emulsion layer containing a nondiffusible cyandye-image-forming coupler that is capable of reacting with an oxidation product of an aromatic primary amine colordeveloping agent produced in a color developer solution by silver halide development to form a nondiffusible cyan dye image, a hardened hydrophilic colloid green-sensitized silver halide emulsion layer containing a nondifi'usible magenta-dyeimage-forming coupler that is capable of reacting with said oxidation product of said color developing agent to form a nondiffusible magenta dye image, and a hardened hydrophilic colloid blue-sensitive silver halide emulsion layer containing a nondiffusible yellow-dye-image-forming coupler that is capable of reacting with said oxidation
• Coup. represents a photographic coupling moiety
• L represents a member selected from the class consisting of an alkyl group, an aryl group, a heterocyclic group, an acyloxy group, an aryloxy group, a heterocycloxy group, an alkoxy group, an alkylthio group, an arylthio group, hydrogen, thiocyano, chlorine, bromine, fluorine and sulfoattached to a carbon atom at an active site of said coupling moiety;
• Sol. represents a solubilizing group; Sol.
• said competing coupler present in said element in sufficient amount to react with substantially all of said oxidation product of said color-developing agent produced during development of the light exposed areas in said latent images, but not enough of said competing coupler present in said element during subsequent fogging development of unexposed areas of silver halide to interfere with the reaction of said oxidation product of said color-developing agent formed during said fogging development with said colorforming coupler to produce a positive dye image.
• a light-sensitive photographic element for direct reversal color processing comprising a support coated on one side with a hardened hydrophilic colloid red-sensitized silver halide emulsion layer containing a nondifiusible cyandye-image-forming coupler that is capable of reacting with an oxidation product of an aromatic primary amine colordeveloping agent produced in a color developer solution by silver halide development to form a nondiffusible cyan dye image, a hardened hydrophilic colloid green-sensitized silver halide emulsion layer containing a nondiffusible magenta-dyeimage-forming coupler that is capable of reacting with said oxidation product of said color-developing agent to form a nondifiusible magenta dye image, and a hardened hydrophilic colloid blue-sensitive silver halide emulsion layer containing a nondiffusible yellow-dye-image-forming coupler that is capable of reacting with said
• R represents a group selected from the class consisting of an alkyl group, an aromatic group and a heterocyclic group
• R represents an alkyl group
• X represents a group selected from the class consisting of a cyano group and a carbamyl group such that at least one of the groups R, R,, and X is substituted with'a sulfo group or a carboxy group
• R represents a group selected from the class consisting of an alkyl group, a carbamyl group, an amino group and an amido group, such that at least one of the groups R, R, and R, is substituted with a sulfo group or a carboxy group;
• Y represents a member selected from the class consisting of hydrogen, fluorine, thiocyano, an acyloxy group, a cyclooxy group, an alkoxy group, an alkthio group and an arylthio group, so that at least one of the groups R and X are substituted with a sulfo group or a carboxy group;
• R and R are as defined previously; and Y represents a member selected from the class consisting of hydrogen,
• R R R R R and R each represents a member selected from the class consisting of hydrogen, an alkyl group, an aryl group, a heterocyclic group, an amino group, a carbonamido group, a sulfonamido group, a sulfamyl group, a carbamyl group, sulfo, a halogen atom and an alkoxy group;
• Y represents a member selected from the class consisting of hydrogen, thiocyano, an acyloxy group, a heterocycloxy group, an alkoxy group, an alkthio group and an arylthio group;
• Y represents a member selected from the class represented by Y and a cyclic imido group; so that at least one of the groups R R R and R in
• R and R each represents a member selected from the class consisting of hydrogen, an alkyl group, an aryl group, a heterocyclic group, an amino group, and an acylamido group such that at least one of R and R contains a solubilizing group;
• R represents a member selected from the class consisting of hydrogen, a halogen atom, the sulfo group, the carboxy group, an acyloxy group, a sulfonyloxy group, an R,,,O group, an R S group, an R..
• R represents a group selected from the class consisting of an alkyl group, an aryl group and a heterocyclic group having from five to six atoms in the heterocyclic ring;
• R represents a radical of a diazotizable amine;
• R represents a group selected from the class consisting of an alkyl group and an aryl group;
• R represents a group selected from the class consisting of an alkyl group and an aryl group, said competing coupler instead of said dye-forming couplers reacting with said oxidation product of said developing agent so that when said element is light image exposed to produce a latent image and then contacted with a color developer solution, there is a sufficient amount of said competing coupler present in said element to react with substantially all of said oxidation product of said color-developing agent produced during development of the light-exposed areas in said latent images, but not enough of said competing coupler present in said element during subsequent fogging development of unexposed areas of silver halide to interfere
• a light-sensitive photographic element for direct reversal color processing comprising a support coated on one side with a hardened hydrophilic colloid red sensitized silver halide emulsion layer containing a nondifiusible cyandye-image-forming coupler that is capable of reacting with an oxidation product of an aromatic primary amine color developing agent produced in a color developer solution by silver halide development to form a nondiffusible cyan dye image, a hardened hydrophilic colloid green-sensitized silver halide emulsion layer containing a nondiffusible magenta-dyeimage-forming coupler that is capable of reacting with said oxidation product of said color developing agent to form a nondiffusible magenta dye image and a hardened hydrophilic colloid blue-sensitive silver halide emulsion layer containing a nondifiusible yellow-dye-image-forming coupler that is capable of reacting with said oxidation product of said colordevelop
• R R R R R and R each represent a member selected from the class consisting of hydrogen, an alkyl group, an aryl group, a heterocyclic group, an amino group, a carbonamido group, a sulfonarnido group, a sulfamyl group, a carbamyl group, sulfo, a halogen atom and an alkoxy group;
• Y represents a member selected from the class consisting of hydrogen, thiocyano, an acyloxy group, a heterocycloxy group, an alkoxy group, an alkthio group and an arylthio group;
• Y represents a member selected from the class represented by Y and a cyclic imido group; so that at least one of the groups R R R and R in formula V is sub-v stituted with a solubilizing group and so that at least one of R R R R R and R in formula
• a light-sensitive photographic element for direct reversal color processing comprising a support coated on one side with a hardened hydrophilic colloid red-sensitized silver halide emulsion layer containing a nondiffusible cyandye-image-forming coupler that is capable of reacting with an oxidation product of an aromatic primary amine colordeveloping agent produced in a color developer solution by silver halide development to form a nondiffusible cyan dye image, a hardened h; drophilic colloid green-sensitized silver halide emulsion layer containing a nondiffusible magenta-dyeimage-forming coupler that is capable of reacting with said oxidation product of said color developing agent to form a nondifi'usible magenta dye image, and a hardened hydrophilic colloid blue-sensitive silver halide emulsion layer containing a nondiffusible yellow-dye-image-forming coupler that is capable of reacting with
• R represents a member selected from the class consisting of hydroxyl, an alkoxy group, and an amino group
• n represents an integer of from 1 to 2
• R represents a member selected from the class consisting of hydrogen and a halogen atom
• R represents a member selected from the class consisting of hydroxyl and an acyloxy group
• R represents a member selected from the class consisting of hydrogen and a halogen atom; R.
• said competing coupler present in said element in sufficient amount to react with substantially all of said oxidation product of said colordeveloping agent produced during development of the light exposed areas in said latent images, but not enough of said competing coupler present in said element during subsequent fogging development of unexposed areas of silver halide to interfere with the reaction of said oxidation product of said color-developing agent formed during said fogging development with said color-forming coupler to produce a positive dye image.
• a light-sensitive photographic element for direct reversal color processing comprising a support coated on one side with a hardened hydrophilic colloid red-sensitized silver halide emulsion layer containing a nondifiusible cyandye-image-forming coupler that is capable of reacting with an oxidation product of an aromatic primary aminev color developing agent produced in a color developer solution by silver halide development to form a nonditfusible cyan dye image, a hardened hydrophilic colloid green-sensitized silver halide emulsion layer containing a nondiffusible magenta-dyeimage-forming coupler that is capable of reacting with said oxidation product of said color developing agent to form a nondiffusible magenta dye image, and a hardened hydrophilic colloid blue-sensitive silver halide emulsion layer containing a nondiffusible yellow-dye-image-fonning coupler that is capable of reacting with said
• a-methyl-a-pivalylacet-Z,4-dicarboxyanilide a-methyl-a-pivalylacet-4-sulfoanilide benzoyl-a-methylacet-4-sulfoanilide 3,4-dimethyll 4-sulfophenyl )-5-pyrazolone benzoylacet-4-sulfoanilide 3-methyll 4-sulfophenyl )-5 -pyrazolone 2-amino-5-naphthol-7-sulfonic acid 8-aminol -naphthol-3 ,fi-disulfonic acid 4,6-dichloro-5-methyl-2-(4-sulfobenzamido)phenol 2,o-dihydroxyisonicotinic acid 3,5-dihydroxybenzoic acid a-chloro-a-pivalylacet-4-sulfoanilide, benzoyl-a-chloroacet-4-sulf
• said competing coupler present in said element in sufficient amount to react with substantially all of said oxidation product of said color-developing agent produced during development of the light exposed areas in said latent images, but not enough of said competing coupler presen, in said element during subsequent fogging development of unexposed areas of silver halide to interfere with the reaction of said oxidation product of said color-developing agent formed during said fogging development with said color-forming coupler to produce a positive dye image.
• a photographic element of claim 12 in which the said hydrophilic colloid silver halide emulsions are gelatin silver bromoiodide emulsions and in which said red-sensitized layer, said green-sensitized layer and said blue-sensitive layer are arranged in that order on said support' 14.
• a photographic element of claim 12 in which the said hydrophilic colloid silver halide emulsions are gelatin silver chlorobromide emulsions and in which said blue-sensitive layer, said green-sensitized layer and said red-sensitized layer are arranged in that order on said support.
• a light-sensitive photographic element for direct reversal color processing comprising a support coated in succession on one side with a hardened gelatin red-sensitized silver bromoiodide emulsion layer containing a nondiffusible phenolic cyan-dye-image-forming coupler that is capable of reacting with an oxidation product of an aromatic primary amine color-developing agent produced in a color developer solution by silver halide development to form a nondiffusible cyan dye image, a hardened gelatin green-sensitized silver bromoiodide emulsion layer containing a nondiffusible S-pyrazolone magenta-dye-image-forming coupler that is capable of reacting with said oxidation product of said color-developing agent to form a nondiffusible magenta dye image, and a hardened gelatin blue-sensitive silver bromoiodide emulsion layer containing a nondiffusible open chain ketomethylene yellow-dye-
• a light-sensitive photographic element for direct reversal color processing comprising a support coated in succession on one side with a hardened gelatin red-sensitized silver bromoiodide emulsion layer containing a nondiffusible phenolic cyan-dye-image-forming coupler that is capable of reacting with an oxidation product of an aromatic primary amine color-developing agent produced in a color developer solution by silver halide development to form a nondiffusible cyan dye image, a hardened gelatin green-sensitized silver bromoiodide emulsion layer containing a nondiffusible 5-pyrazolone magenta-dye-image-forming coupler that is capable of reacting with said oxidation product of said color-developing agent to form a nondiffusible magenta dye image and a hardened gelatin blue-sensitive silver bromoiodide emulsion layer containing a nondiffusible open chain ketomethylene yellow-dye-image-
• a light-sensitive photographic element for direct reversal color processing comprising a support coated in succession on one side with a hardened gelatin red-sensitized silver bromoiodide emulsion layer containing a nondiffusible phenolic cyan-dye-image-forming coupler that is capable of reacting with an oxidation product of an aromatic primary amine color developing agent produced in a color developer solution by silver halide development to form a nondiffusible cyan dye image, a hardened gelatin green-sensitized silver bromoiodide emulsion layer containing a nondiffusible S-pyrazolone magenta-dye-image-forming coupler that is capable of reacting with said oxidation product of said color-developing agent to form a nondiffusible magenta dye image, and a hardened gelatin blue-sensitive silver bromoiodide emulsion layer containing a nondiffusible open chain ketomethylene yellow-dye-image-
• a light-sensitive photographic element for direct reversal color processing comprising a support coated in succession on one side with a hardened gelatin red-senble of reacting with an oxidation product of an aromatic primary amine color developing agent produced in a color developer solution by silver halide development to form a nondiffusible cyan dye image, a hardened gelatin green-sensitized silver bromoiodide emulsion layer containing a nondiffusible S-pyrazolone magenta-dye-image-forming coupler that is capable of reacting with said oxidation product of said color-developing agent to form a nondiffusible magenta dye image, and a hardened gelatin blue-sensitive silver bromoiodide emulsion layer containing a nondiffusible open chain ketomethylene yellow-dye-image-forming coupler that is capable of reacting with said oxidation product of said color-developing agent to form a nondiffusible yellow dye image and on the same side of
• a light-sensitive photographic element for direct reversal color processing comprising a support coated in succession on one side with a hardened gelatin red-sensitized silver bromoiodide emulsion layer containing a nondiffusible phenolic cyan-dye-image-forming coupler that is capable of reacting with an oxidation product of an aromatic primary amine color-developing agent produced in a color developer solution by silver halide development to form a nondiffusible cyan dye image, a hardened gelatin green-sensitized silver bromoiodide emulsion layer containing a nondiffusible S-pyrazolone magenta-dyeimage-forming coupler that is capable of reacting with said oxidation product of said color-developing agent to form a nondiffusible magenta dye image and a hardened gelatin blue-sensitive silver bromoiodide emulsion layer containing a nondiffusible open chain ketomethylene yellow-dye-image-

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• 1970
  • 1970-07-06 US US52721A patent/US3647452A/en not_active Expired - Lifetime
• 1971
  • 1971-06-14 CA CA115,522A patent/CA944996A/en not_active Expired
  • 1971-07-05 GB GB3138971A patent/GB1359006A/en not_active Expired
  • 1971-07-06 BE BE769582A patent/BE769582A/xx unknown
  • 1971-07-06 DE DE2133659A patent/DE2133659C3/de not_active Expired
  • 1971-07-06 FR FR7124653A patent/FR2100303A5/fr not_active Expired

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