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
  • G03C1/00—Photosensitive materials
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
  • G03C1/30—Hardeners
• • 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
  • G03C7/3225—Combination of couplers of different kinds, e.g. yellow and magenta couplers in a same layer or in different layers of the photographic material
• • 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
  • G03C7/42—Bleach-fixing or agents therefor ; Desilvering 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
  • G03C7/32—Colour coupling substances

Definitions

• This invention is related to color photography, color photographic elements that contain incorporated colorforming couplers and shortened photographic processes that produce photographic reproductions of improved color quality in these elements.
• Multicolor, multilayer photographic elements are well known in the art of color photography. Usually these elements have three selectively sensitized emulsion layers coated on one side of a single support. For example, the outermost layer is generally blue-sensitive. The next layer is generally green-sensitized and the layer adjacent to the support is generally red-sensitized. Between the bluesensitive and the green-sensitized layer a bleachable yellow colored filter layer is often used for absorbing blue radiation that may be transmitted through the blue-sensitive layer.
• the multilayer coatings can also have other interlayers for specialized purposes. Such multilayer ma-' terials have been previously described in the prior art, such as, Maunes et al. US. Pat. 2,252,798, issued Aug. 19, 1941.
• the sensitive layers are also known.
• the blue-sensitive layer, the greensensitized layer and the red-sensitized layer are used to produce the yellow dye image, magenta dye image and the cyan dye image, respectively.
• Open-chain ketomethylene, pyrazolone and phenolic (and naphtholic) couplers are usually used for forming the yellow, magenta and cyan dye images, respectively.
• the couplersv are incorporated in the appropriately sensitized layer of the photographic elements.
• Multicolor photographic elements are also known in which the blue-sensitive silver halide emulsion and the yellow dye-forming coupler are contained in a blue-sensitive yellow dye-forming packet, a green-sensitized silver halide emulsion and magenta dye-forming couplers are contained in a green-sensitized magenta dye-forming packet and a red-sensitized silver halide emulsion and cyan dye-forming coupler are contained in a red-sensitized cyan dye producing packet and these three different packets are dispersed in a single light-sensitive layer.
• the color developing bath is generally followed by consecutive baths comprising a fix, a bleach, and a second fix with an intervening wash step between each of the indicated baths.
• the fix bath is "ice employed to remove the undeveloped silver halide from the developed emulsion layer while the bleach bath is employed to oxidize the metallic silver formed by development of the latent image in the silver halide.
• the second fix is normally employed to remove the silver halide formed by the previous bleaching step so that the emulsion layer or layers are cleared of residual silver and silver halide. This leaves essentially a colored image of cyan, magenta and yellow dye densities as formed at the time of development by coupling of the incorporated couplers with oxidation products of a primary aromatic amino developing agent contained in the color developing bath.
• Coupler incorporated multicolor photographic elements are desired which will produce the desired yellow and magenta dye densities with a shortened color process in which it is not necessary to use a separate bleach step when a blix step is used.
• Another object is to provide a novel color photographic element which is substantially free of aldehyde hardening agents and hardening agents which release aldehydes, the said element containing incorporated color-forming couplers which do not form uncolored forms of the yellow dye and uncolored forms of the magenta dye during color development so that this element will produce color reproductions with the desired yellow dye density and desired magenta dye sensity even when processed in our novel color process which requires only the color developing step and a blix step with wash following the blix.
• our element comprises a photographic element having coated thereon a hydrophilic colloid containing a first silver halide emulsion sensitive to one region of the visible spectrum and contiguous to said first silver halide emulsion a nondifiusible ketomethylene open-chain yellow dye-forming coupler that reacts with oxidized primary aromatic amine color developing agent to form a yellow dye and substantially no uncolored form of said yellow dye which is not converted to the yellow dye by a blix solution following color development, and a second silver halide emulsion sensitive to a second region of the visible spectrum and contiguous to said second silver halide emulsion a nondiffusible 5-pyrazolone coupler (preferably aldehyde reactive) which reacts with oxidized primary aromatic amine color developing agent to form a magenta dye, said photographic element being substantially free of aldehyde hard
• the photographic element of our invention contains in addition to a first and a second silver halide emulsion described above, a third silver halide emulsion sensitive to a third region of the visible spectrum and contiguous to said third silver halide emulsion a nondifiusible phenolic or naphtholic coupler which reacts with primary aromatic amine color developing agents to form a cyan dye.
• the photographic element comprises a support coated in succession with a red-sensitive silver halide emulsion layer containing a phenolic or naphtholic coupler, a green-sensitized silver halide emulsion containing a 5-pyrazolone coupler (preferably aldehyde reactive) and a blue-sensitive silver halide emulsion layer containing the ketomethylene open-chain yellow dye-forming coupler.
• a bleachable yellow colored blue light-absorbing filter layer is advantageously placed between the green-sensitized layer and the top blue-sensitive layer.
• the light-sensitized layers are placed on the support in different orders than described above.
• the three differently sensitized silver halide emulsions containing the appropriate dye-forming couplers are dispersed as packets in a single light-sensitive layer.
• the blue-sensitive silver halide emulsion containing the yellow dye-forming coupler is incorporated in yellow image-forming packets
• the red-sensitized silver halide emulsion containing the cyan dye-forming coupler is contained in cyan dye image-forming packets.
• Our photographic elements are advantageously processed after exposure, by development in an aqueous alkaline solution in the presence of a primary aromatic amine color developing agent, followed by a blix comprising a silver halide solvent and an oxidizing agent for silver.
• a water wash is sometimes advantageously used between the development and blix steps.
• the developed and blixed photographic material is then advantageously washed and dried or washed and given a stabilizing bath treatment before drying.
• Our process, as described above produces excellent dye images with substantially no uncolored form of yellow dye and substantially no uncolored form of magenta dye being present in the processed photographic material.
• Our photographic materials provide a valuable technical advance since they are substantially free of uncolored forms of yellow dye and substantially free of uncolored forms of magenta dye when they leave the blix solution and they do not need to have a separate bleach following the blix in order to obtain the desired yellow and magenta dye densities.
• Prior art photographic materials require a separate bleach and separate fix, or a separate bleach following the blix solution in order to obtain the desired magenta and yellow dye densities.
• Our photographic materials can be processed, if desired, by using a bleach following the blix or by using a separate bleach and a separate fix in place of the blix solution, however, such processes are longer and it is generally desired to use the shortest process possible that is required to obtain the desired photographic quality.
• the light-sensitive layers of our photographic elements are advantageously coated on a wide variety of photographic emulsion supports.
• Typical supports used to ad- 4 vantage include cellulose nitrate film, cellulose acetate film, polyacetal film, polystyrene film, polyterephthalate film, polyethylene film and related films of resinous materials as well as paper, glass and others.
• 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. 2,286,215, issued June 16, 1942; a far hydrolyzed cellulose ester, such as cellulose acetate hydrolyzed to an acetyl content of 19-26% as described in Lowe et al. U.S. Pat. 2,327,808, issued Aug. 24, 1943; a water-soluble ethanolamine cellulose acetate as described by Yutzy U.S.
• cyano-acetyl groups such as the vinyl alcohol-vinyl cyano-acetate copolymer as described in Unruth et al. U.S. Pat. 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 Illingsworth et al. U.S. Pat. 2,852,382, issued Sept. 16, 1958.
• hydrophilic colloids described above are used in various layers of our photographic elements are advantageously hardened with hardening agents, such as, aziridine hardeners, isoxazolium salt hardeners, epoxy hardeners and vinyl surfone hardeners.
• hardening agents such as, aziridine hardeners, isoxazolium salt hardeners, epoxy hardeners and vinyl surfone hardeners.
• any of the photographic silver halide emulsions e.g., silver bromide, silver bromoiodide, silver chloride, silver chlorobromide, silver bromochloroiodide, etc., used in photography can be used to advantage in our photographic materials.
• 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. 1,574,944, issued Mar. 2, 1926; Sheppard et al. U.S. Pat. 1,623,499, issued Apr. 5, 1927; and Sheppard et al. U.S. Pat. 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. 2,448,060, issued Aug. 31, 1948, and as described in Trivelli et al. U.S. Pats. 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 optically sensitized with cyanine and merocyanine dyes, such as those described in Brooker U.S. Pats. 1,846,301, and 1,846,302, both issued Feb. 23, 1932; and 1,942,854, issued Jan. 9, 1934; White U.S. Pat. 1,990,507, issued Feb. 12, 1935; Brooker and White U.S. Pats. 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. 2,493,748, issued Jan. 10, 1950; Sprague U.S. Pats.
• the emulsions may also contain speed-increasing compounds of the quaternary ammonium type of Carroll U.S. Pat. 2,271,623, issued Feb. 3, 1942; Carroll et al. U.S. Pat. 2,288,226, issued June 30, 1942; and Carroll et al. U.S. Pat. 2,334,864, issued Nov. 23, 1943; and the polyethylene glycol type of Carroll et al. U.S. Pat. 2,708,162, issued May 10, 1955.
• the emulsions can also be chemically sensitized with gold salts as described in Waller et al. US. Pat. 2,399,083, issued Apr. 23, 1946, or stabilized with gold salts as described in Damschroder US. Pat. 2,597,856, issued May 27, 1952; and Yutzy et al., US. 2.597,9l5, issued May 27, 1942.
• Suitable compounds are potassium chloroaurite, potassium aurithiocyanate, potassium chloroaurate, auric trichloride and 2-aurosulf0benzothiazole methochloride.
• any nondiffusible ketomethylene open-chain yellow dyeforming coupler that reacts with primary aromatic amine color developing agent to form a yellow dye and substantially no uncolored form of said yellow dye that will not be converted to the yellow colored form of the dye by our blix solution is advantageously used in our photographic materials.
• These couplers include all of the well known nondiifusing open-chain ketomethylene yellow dyeforming couplers that have a coupling-off group substituted on the active carbon atom.
• the parent couplers from which these couplers are derived include the cyanoacetyl couplers, the acylacetyl couplers such as, the acylacetanilide couplers (e.g., the alkoylacetanilide couplers, the aroylacetanilide couplers, the pivalylacetanilide couplers, etc.), the acrylacetamide couplers (e.g., the alkoylacetamide couplers, the aroylacetamide couplers, the pivalylacetarnide couplers, etc.), etc.
• Certain of the parent couplers having two hydrogen atoms on the active carbon atom are used to advantage.
• R represents an alkyl group (substituted or not), an aromatic group (substituted or not), a heterocyclic group (substituted or not), etc.
• X represents the cyano group, a carbamyl group (substituted or not), etc.
• Solubilizing groups are advantageously used on ballasted couplers. A large variety of ballasting groups are well known in the coupler art.
• Y in Formula I, is a coupling 01f group, such as, the chlorine atom, the fluorine atom, the thiocyano group, an acyloxy group [e.g., an alkoyloxy group (substituted or not), an aroyloxy group (substituted or not), a heterocycloyloxy group (substituted or not), etc., in which the acyloxy groups are substituted with a wide variety of wellknown groups and also a group in which R and X are as described previously], and a cyclooxy group [e.g., an aryloxy group (e.g., a phenoxy group, a naphthoxy group, a heterocycloxy group (e.g., a pyridinyloxy group, a tetrahydropyranyloxy group, a tetrahydroquinolyloxy group, etc.)], an alkoxy group, an alkthio group and an arylthi
• R and/or R groups are advantageously substituted with any of the well-known substitu- (27 2-(4"-tert-amyl-3 '-phenoxybenzoylamino) -3- methyl-l-phenol (28) 2- (4"-ter-t-amyl-3'-phenoxybenzoylarnino)-6- methyl-l-phenol (29) 2- (4-.tert-amyl-3 '-phenoxybenzoylamino -3,6-
• the couplers are advantageously dispersed in high-boiling crystalloidal compounds by methods well known in the art such as are described in Ielley and Vittum U.S. Pat. 2,322,027
• the couplers are advantageously dispersed in low solvent dispersions such as are described in Fierke U.S. Pat. 2,801,171, or the couplers are advantageously dispersed in natural resin-type solvents as described in Martinez U.S. Pat. 2,284,879, or the couplers are dissolved in a monomeric solution which is then polymerized in the presence of gelatin to produce dispersions of the coupler in the polymer as described in U.S. Pat. 2,825,382.
• Fischer-type couplers are advantageously added to the hydrophilic colloid solution.
• the hydrophilic colloids 'used in our photographic elements are advantageously hardened by aziridine hardeners, isoxazolium salt hardeners, epoxide hardeners, and vinyl sulfone hardeners.
• the aziridin hardeners used to advantage include 1,3-bis(1-aziridinylsulfonyl) propane, 1 (1 aziridinylcarbonyl) 3 (1- aziridinylsulfonyl) benzene and others described in Burness U.S. Pat. 2,964,404, issued Dec.
• oxazolium hardeners used to advantage include 2,5- dimethylisoxazolium perchlorate, 2 ethyl 5 phenylisoxazolium 3 sulfonate, 2 methyl 5 p tolylisoxazolium 3' sulfonate and others described in Van Campen and Graham U.S. Pat. 3,316,095, issued Apr.
• the vinylsul-fones used to advantage as hardeners for hydrophilic colloids in our photographic 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(vinylsulfonylrnethyDether, N,N bis(2 vinylsulfOnylethyD- n propylamine, N,N bis(2 vinyls'ulfonylethyl) N- ethyl N propylammonium tetrafluoroborate, and bis(lvinylsulfonylethyDether, etc., and other compounds of the formula:
• Z 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 1 to 4 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:
• BIS(2-VINYLSULFONYLETHY L) ETHER 6-oxa-3,9-dithiaundecane-l,ll-diol is prepared by the reaction of two molar proportions of sodium Z-hydroxyethylmercaptide with one molar proportion of bis(2-chlorethyl)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 refluxing solution 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.
• Dehydrohalogenation is effected in tetrahydrofuran solution at about -5 C. with two molar proportions of triethylamine. After 24 hours, the solvent is removed and the product recrystallized from methanol giving colorless crystals having a melting point of 47.5-48.5 C.
• N,N-BIS(2-VINYLSULFONYLETHYL) -NPROPYL AMINE The dropwise addition of a tetrahydrofuran solution of n-propylamine to two molar proportions of divinyl sulfone dissolved in tetrahydrofuran at a temperature maintained at 0-10 C., yielded after two hours stirring at room temperature and evaporation of the solvent at reduced pressure, a pale tan product of 11 1.4917.
• bis vinylsulfones exhibiting good hardening include N,N bis(2 vinylsulfonylethyl)-N-ethyl-N-propyl ammonium tetrafiuoroborate, and bis(l-vinylsulfonylethy1)ether.
• Our photographic elements are advantageously processed by color development followed by a blix bath (with or Without an intervening wash), washing and drying.
• the washed photographic elements are given a stabilizer treatment before drying.
• Developer solutions used to advantage are aqueous alkaline solutions of primary aromatic amine color developing agents, preferably containing benzyl alcohol.
• Any of the well-known primary aromatic amine color-forming silver halide developing agents such as, the phenylene diamines, e.g., diethyl-p-phenylene diamine hydrochloride, monomethyl-p-phenylene diamine hydrochloride, dimethyl-p-phenylene diamine hydrochloride, 2-amino-5-diethylaminotoluene hydrochloride, 2 amino (N-ethyl-N- laurylamino toluene, N-ethyl-N,N- (B-methanesulfonamidoethyl) 3 methyl-4-aminoaniline sulfate, ethyl-N-ethyl N (,B-methylsulfonamidoethyl)-4-aminoaniline, 4- [N-eth
• any of the silver halide sovlents used in blix solutions are used advantageously in our blix baths including watersoluble thiosulfates (e.g., potassium thiosulfate, sodium thiosulfate, ammonium thiosulfate, etc.), a water-soluble thiocyanate (e.g., sodium thiocyanate, potassium thiocyanate, ammonium thiocyanate, etc.), water-soluble organic diol fixing agents containing sulfur or oxygen atoms, or atoms of both species interspersed along the carbon chain (e.g., 3-thia-1,5-pentanediol, 3,6-dithia-1,8-octanediol, 3,6,9-trithia-1,1l-undecanediol, 3,6,9,12-tetrathia-l, 14-tetradecanediol, 9-oxa-3,6,9,12,15-
• any of the silver halide oxidizing agents used in blix solutions are used advantageously in our blix baths including water-soluble ferricyanides (e.g., sodium ferricyanide, potassium ferricyanide, ammonium ferricyanide, etc.), water-soluble quinones (e.g., quinone, sulfophenylquinone, chloroquinone, methoxyquinone, 2,5-dimethoxyquinone, methylquinone, etc.), a simple water-soluble ferric salt (e.g., ferric chloride, ferric nitrate, ferric sulfate, ferric thiocyanate, ferric oxolate, etc.), a simple water-soluble cupric salt (e.g., cupric chloride, cupric nitrate, cupric sulfate, etc.), a simple watersoluble cobaltic salt (e.g., cobaltic chloride, cobaltic ammonium nitrate, etc.) and
• R', R R R and R each represent a substituted hydrocarbon residue and an unsubstituted hydrocarbon residue, and R represents hydrogen, an unsubstituted hydrocarbon residue and a substituted hydrocarbon residue
• the polyvalent cation is selected from the class of ferric ion, cobaltic ion and cupric ions.
• organic acids are ethylene diamine tetraacetic acid, nitrilotriacetic acid, malonic acid, ethyl malonic acid, tartaric acid, malic acid, fumaric acid, diglycolic acid, ethyliminodipropionic acid, ethylene dithioglycolic acid, dithioglycolic acid, etc.
• any of the addenda commonly used in blix solutions are used to advantage in our blixes including alkali metal bromide, ammonium bromide, alkali metal iodides, ammonium iodide, hydrazine, hydroxylamine salts, amines, mercapto derivatives of S-membered heterocyclic rings such as mercaptotn'azole, a formamidine sulfinic acid, etc.
• Any aqueous acidic stabilizer solution used in color processing is advantageously used in our process including stabilizer solutions containing citric acid.
• Coating 1 contains a dispersion of the yellow dye-forming coupler, a-pivalyl-2- chloro ['y-(2,4 di tert-amylphenoxy)butyramido] acetanilide in dibutylphthalate at a coupler to coupler solvent ratio of 1:1.
• Coating 2 contains a dispersion of the yellow dye-forming coupler, a-pivalyl-u-[4-(4-benzyloxyphenylsulfonyl)phenoxy]2-chloro 5 ['y(2,4 di tertamylphenoxy)butyramido]acetanilide in coupler solvent dibutylphthalate at a coupler to coupler solvent ratio :1.
• a sample of each of the two coatings are sentimetrically exposed to a step Wedge, color developed in a conventional color developing solution containing benzyl alcohol, sodium sulfite, the color developing agent N-ethyl- B methanesulfonamidoethyl 3 methyl-4-aminoaniline sulfate and alkali to give a pH of about 10, fixed for 2 minutes at 85 F. in a fixing bath having the composition:
• Processed Coating 1 contains only a barely visible amount of yellow dye whereas the image in Coating 2 is brightly yellow.
• the lack of visible yellow dye in Coating 1 is due to the generation during color development of a colorless form of yellow dye from the yellow coupler which is outside of our invention.
• the coupler used in Coating 2 is a coupler of our invention. Another set of samples of each of the two coatings are sensitometrically exposed and color developed as described above and subsequently bleached for 2 minutes at 85 F. in a solution having the composition:
• Coatings 1 and 2 which were bleached and fixed subsequent to color development contained excellent yellow dye images. These tests indicate that the colorless form of the yellow dye formed by color development in Coating 1 requires a strong oxidizing treatment (bleach) for its conversion to the visible yellow dye.
• Coating 2 of our invention contains the yellow dye image at its maximum density after color development and the treatment of this sample in the bleach serves only the purpose of oxidizing the image silver.
• a multilayer photographic element comprising a polyethylene coated paper support coated in succession with a blue-sensitive gelatino silver chlorobromide emulsion containing the yellow dye-forming coupler, a-pivalyla-[4-(4-benzyloxyphenylsulfonyl)phenoxy] 2 chloro-5- ['y-(2,4 di-tert-amylphenoxy)butyramido]acetanilide in dibutyl phthalate at a coupler to coupler solvent ratio of 10:1, a gel interlayer, a green-sensitized gelatino silver chlorobromide emulsion containing the magenta dyeforming coupler, l-(2,4-dimethyl 6 chlorophenyl)-3- [3 ⁇ oz (m-pentadecylphenoxy)butyramido ⁇ benzamido]- S-pyrazolone in tricresyl phosphate at a coupler to coupler
• PROCESS A 5-solution process (bleach and fix), temperature: F.
• the stabilizer bath used in Processes A and B is a conventional aqueous citric acid stabilizer having a pH of 3.5.
• Densitometric readings are made of the yellow, magenta, cyan dye images of the samples processed according to Process A and Process B. Sensitometric curves are plotted from these density data correlating the yellow dye density with the log of the exposure, the magenta dye density with the log of the exposure and the cyan dye density with the log of the exposure. A comparison of these curves shows that:
• the density of the magenta dye image in the sample given Process B (blix) is about 20% lower in the shoulder than the density of the magenta image dye in the sample given Process A (separate bleach and separate fix). This illustrates that the colorless form of the magenta dye formed in the green-sensitive layer (outside our invention) is not converted to the magenta dye by the relatively low oxidizing potential of the blix solution.
• EXAMPLE 3 A multilayer photographic element is made like that described in Example 2 excepting that gelatin used contained no formaldehyde.
• a sensitometrically exposed sample of this photographic element is blix-processed by Process B described in Example 2.
• a second sensitometric sample of the same coating is similarly processed except that after the blix bath it is treated in a separate ferricyanide bleach bath having the composition described in Example 1.
• the magenta dye desnsities in these two samples are determined and the curves correlating magenta dye density with the log exposure plotted as a graph for each sample. These graphs are essentially the same showing that the green-sensitive layer made according to our invention does not generate any uncolored magenta dye.
• EXAMPLE 4 On sensitometrically exposed sample of a multilayer photographic element, similar to that described in Example 2. (i.e., containing formaldehyde as the hardener) was blix-processed by Process B described in Example 2. A second sensitometrically exposed sample of the same coating is similarly processed except that after the blix bath, it is treated in a separate bleach of the composition as described in Example 1. The magenta dye densities of the images developed in the two processed samples were determined and plotted as the characteristic curves correlating magenta dye density vs. log exposure.
• a comparison of the characteristic curves shows that in the presence of formalin, the pyrazolone coupler generates a dye density that is about 27% low at a density of .48 and about 24% low at a density of 1.7 and that a separate bleach bath with an oxidation potential higher than that of the preceding blix bath is required to convert the uncolored form of the magenta dye to visible magenta dye.
• a multilayer photographic element is made having coated over a polyethylene coated support in succession a blue-sensitive gelatino silver chlorobromide emulsion containing the yellow dye-forming coupler, outside our invention, a pivalyl 2 chloro-S-[' -(2,4-di-tert-amylphenoxy)butyramindo] acetanilide in dibutyl phthalate at a coupler to coupler solvent ratio 2: 1, a gel interlayer, a green-sensitized gelatino silver chlorobromide emulsion containing the magenta dye-forming coupler 1-(2,4-dimethyl 6 chlorophenyl) 3 [3- ⁇ a-(m-pentadecylphenoxy)butyramido ⁇ benzamido] 5 pyrazolone in tricresyl phosphate at a coupler to coupler solvent ratio of 1:1, a gel interlayer, a red-sensitized gelatino silver chlor
• EXAMPLE 6 Two samples of multilayer photographic element similar to that illustrated in Example 5 but wherein the first layer coated over the paper support has the following 16 composition: a blue-sensitive gelatino silver chlorobromide emulsion containing the yellow coupler, a-pivalyl- [4 (4 benzoyloxyphenylsulfonyl)phenoxy] -2- chloro 5 ['y (2,4-di-tert-amylphenoxy)butyramido] acetanilide in dibutyl phthalate at a coupler to coupler solvent ratio of 10:1 are sensitometrically exposed and processed by the procedure described in Example 2 but leaving out the stabilizing step.
• a blue-sensitive gelatino silver chlorobromide emulsion containing the yellow coupler a-pivalyl- [4 (4 benzoyloxyphenylsulfonyl)phenoxy] -2- chloro 5 ['y (2,4-di-tert-amylphenoxy)
• the characteristic curves of the dye images are plotted from density readings made of the images in the processed photographic elements. A comparison of the graphs made shows that the characterisitc curves of the yellow and magenta dye images in both coatings are alike and at their maximum densities.
• the use of one of our yellow couplers and hardening agents in our multicolor element according to our invention prevents the formation of uncolored yellow dye in the blue-sensitive layer and prevents the formation of uncolored magenta dye in the green-sensitized layer of the color photographic element of our invention.
• the absence of the uncolored dyes in our photgraphic elements makes it unnecessary to treat the color developed photographic element in either separate bleach and separate fix solutions or in an additional bleach solution subsequently to the blix.
• Our photographic elements make it possible to get the desired magenta and yellow dye densities by using only a two-step process that is color development followed by a blix while color elements outside of our invention require a four-step process comprising color development, stop fix, bleach, and fixing with two intervening washes in order to get the desired yellow and magenta dye densities.
• a stabilizer step is used ad vantageously in the preferred process to improve the stability of the developed dye images over relatively long periods of time. Similar results are obtained with our photographic elements when they are given Process B of our invention but with a water wash in between the color development step and the blix step.
• Example 6 is repeated using gelatin hardened with other vinylsulfones having two vinylsulfonyl alkyl groups linked to a single linking heteroatom such as,
• Example '6 is repeated using gelatin hardened with hardening agents, such as,
• N,N'-bis 2-vinylsulfonylethyl) piperazine-bis (methoperchlorate) N ,N'-bis (2-vinylsulfonylethyl) -N,N-dimethyl-2.-butene- 1,4-diamine bis (metho-p-toluene sulfonate) and the corresponding bis (methofluorborate) N,N'-bis 2-vinylsulfonylethyl) -N,N'- dimethylethylene bis(metho-p-toluenesulfonate) 1 ,2-bis (vinyl sulfonylmethoxy) ethane,
• Example 6 is repeated using in our photographic element as the yellow dye-forming coupler, the magenta dyeforming coupler and the cyan dye-forming coupler, the respective couplers listed below:
• Yellow dye-forming couplers Magenta dye-forming couplers (1) 1- 2,4'-dichlorophenyl -3- 3 (2",4"'-di-tert-amylphenoxyacetamido benzamido] -5-pyrazolone (2) l- 2,4-dimethyl-6-chlorophenyl -3- 3- ⁇ a-m-pentade cylphenoxyl butyramido ⁇ -b enzamido] -5-pyrazolone (3 1- 2,4,6-trichlorophenyl) -3- (4-nitroanilino )-4- stearoyloxy-S -pyrazolone (4) l- (2,4,6-trichlorophenyl) -3- ⁇ 3 [a- 2,4-di-tert-amylphenoxy) acetamido] benzamindo ⁇ -4-acetoxy-5-pyrazolone (5) 1- (2,4,6-trichlorophenyl -3- [3
• Example 6 is repeated but using a blix in which 45 grams of sodium cobaltic ethylendiamine tetraacetic acid is used in place of sodium ferric ethylendiamine tetraacetic acid. Results are obtained that are similar to those obtained in Example 6.
• Example 6 is repeated but using a blix solution in which an equivalent amount of sodium cupric ethylenediamine tetraacetic acid is substituted for sodium ferric ethylenediamine tetraacetic acid. Results obtained are similar to those given by Example 6.
• Example 6 is repeated but using a blix in which sodium ferric ethylenediamine tetraacetic acid is replaced with an equivalent amount of sodium cupric nitrilo triacetic acid and the ethylenediamine tetraacetic acid tetrasodium salt is substituted by an equivalent amount of nitrilo triacetic acid trisodium salt. Results are obtained that are similar to those from Example 6.
• Example 6 is repeated using in place of the blix solution used in Example 6 a blix having the following composition:
• pH is adjusted to 5.5.
• Example 6 is repeated using in place of the blix solution used in Example 6 a blix having the following composition:
• Example 6 is repeated using in place of the blix solution used in Example 6 a blix adjusted to pH of 8 (prepared just prior to use), comprising:
• Potassium ferricyanide 50 Sodium thiosulfate 200 Water to 1 liter.
• Example 6 is repeated using in place of the blix solution used in Example 6 a blix adjusted to a pH of 7, comprising:
• Example 15 is repeated using in place of the blix solution used in Example 15 a blix adjusted to a pH of about 1.5, comprising:
• 3,6-dithia-1,8-octanediol is prepared as follows: To a cold solution of 46 g. of sodium in one liter of methanol is added 150 g. of Z-mercapto methanol. To the cooled reaction mixture there is added with stirring 99 g. of 1,2- dichloroethane. After the reaction mixture is allowed to remain at room temperature overnight, 500 ml. of methanol is removed at reduced pressure. The residue is mixed with 500 ml. of water and the whole extracted with chloreform. The chloroform extract is dried over anhydrous magnesium sulfate, filtered and the chloroform removed at reduced pressure leaving the product.
• 3,6,9-trithia-1,1l-undecanediol is prepared to advantage by reacting one mole of bis(2-chloroethyl)sulfide with 2 moles of 2-hydr0xyethanediol sodium salt in ethanol. Isolation and purification of the product are accomplished by methods well known in the art.
• the bis(2-chloroethyl)sulfide is advantageously made by treating one mole of 3-thia-l,5-pentadiol (available commercially) with 2 moles of thionyl chloride in a suitable inert anhydrous organic solvent.
• 3,6,9,12-tetrathia-1,l4-tetradecanediol is prepared to advantage by reacting one mole of l,2-dichloro-3,6-dithiaoctane With 2, moles of Z-hydroxyethanoldiol sodium salt in ethanol. Isolation and potfication of the product are accomplished by methods well known in the art.
• the 1,8- dichloro-3,6-dithiaoctane is advantageously prepared by treating one mole of 3,6-dithia-l,8-octanediol with 2 moles of thionyl chloride in a suitable inert anhydrous organic solvent.
• 9-oxa-3,6,9,12,15-tetrathia-l,l7-heptadecanediol is advantageously prepared by reacting one mole of 1,1l-dichloro-3,9-dithia-6-oxaundecane with 2 moles of 2-hydroxyethandiol sodium salt in methanol. Isolation and purification of the product are accomplished by methods well known in the art.
• the 1,11-dichloro-3,9-dithia-6- oxaundecane is prepared advantageously by reacting one mole of bis(2-ch1oroethyl)ether (available commercially) with 2 moles of 2-hydroxyethanethiosodium salt to form one mole of 3,9-dithia-6-oxa-1,1l-undecanediol which is treated with 2 moles of thionyl chloride in a suitable inert anhydrous organic solvent.
• 3,6,9,12,21,30,33,36,39 nonaoxa-15,18,24,27-tetrathia- 1,41-hentetradecanediol is advantageously prepared by reacting 9 oxa 3,6,12,15 tetrathi'a-1,17-heptanediol described previously with 2 moles of ethylene oxide and subsequently reacting one molar equivalent of the compound formed with 6 molar equivalents of ethylene oxide in a suitable inert anhydrous organic solvent.
• a color process for a latent image-exposed lightsensitive color photographic element comprising a support having coated thereon hydrophilic colloid containing a first silver halide emulsion sensitive to one region of the visible spectrum and contiguous to said first silver halide emulsion a nonditfusible ketomethylene open-chain yellow dye-forming coupler that reacts with oxidized primary aromatic amine color developing agent to form a yellow dye and substantially no residual uncolored form of said yellow dye, and a second silver halide emulsion sensitive to a second region of the visible spectrum and contiguous to said second silver halide emulsion a nonditfusible S-pyrazolone which reacts with oxidized primary aromatic amine color developing agent to form a ma: genta dye, said photographic element being substantially free of aldehyde hardening agents and substantially free of aldehyde-releasing hardening agents, said process comprising the steps:
• a color process for a latent image-exposed lightsensitive color photographic element comprising a support having coated thereon hydrophilic colloid containing a first silver halide emulsion sensitive to one region of the visible spectrum and contiguous to said first silver halide emulsion a nonditfusible ketomethylene open-chain yellow dye-forming coupler that reacts with oxidized primary aromatic amine color developing agent to form a yellow dye and substantially no residual uncolored form of said yellow dye, a second silver halide emulsion sensitive to a second region of the visible spectrum and contiguous to said second silver halide emulsion a nondiffusible S-pyrazolone which reacts with oxidized primary aromatic amine color developing agent to form a magenta dye, and a third silver halide emulsion sensitive.
• the silver halide solvent in the blix solution is selected from the class consisting of a water-soluble thiosulfate, a. water-soluble thiocyanate, a water-soluble organic diol fixing agent, a watersoluble sulfur-containing dibasic acid, a water-soluble salt of a sulfur-containing organic dibasic acid, and an imidazolidinthione and in which the oxidizing agent for silver is selected from the class consisting of a water-soluble ferricyanide, a water-soluble quinone, a simple watersoluble ferric salt, a simple water-soluble cupric salt, a simple water-soluble cobaltic salt and complex salts of an alkali metal and polyvalent cation with an organic acid having one of the formulas:
• X represents a member selected from the class consisting of a hydrocarbon residue, oxygen, sulfur and an :NR group; R R R R and R each represent a hydrocarbon residue and R represents a member selected from the class consisting of hydrogen and a hydrocarbon residue, and wherein the polyvalent cation is selected from the class consisting of ferric ion, cobaltic ion and cupric ions.
• the silver halide solvent in the blix solution is selected from the class consisting of a water-soluble thiosulfate, a water-soluble thiocyanate, a water-soluble organic diol fixing agent, a watersoluble sulfur-containing dibasic acid, a Water-soluble salt of a sulfur-containing organic dibasic acid, and an imidazolidinthione and in which the oxidizing agent for silver is selected from the class consisting of a water-soluble ferricyanide, a water-soluble quinone, a simple watersoluble ferric salt, a simple water-soluble cupric salt, a simple water-soluble cobaltic salt and complex salts of an alkali metal and polyvalent cation with an organic acid selected from the class consisting of ethylene diamine tetraacetic acid, nitrilotriacetic acid, malonic acid, ethyl malonic acid, tartaric acid, malic acid, fumaric acid, diglycolic acid, eth
• the blix solution comprises a water-soluble thiosulfate and sodium ferric ethylene diamine tetraacetic acid.
• the blix solution comprises a water-soluble thiocyanate and sodium ferric ethylene diamine tetraacetic acid.
• the silver halide solvent in the blix solution is a mixture of ammonium thiocyanate and 3,6-dithia-1,8-octanediol, and the oxidizing agent for silver is sodium ferric ethylene diamine tetraacetic acid.
• a color process for a latent image exposed lightsensitive color photographic element comprising -a support having coated thereon a blue-sensitive gelatino silver halide emulsion containing a nondilfusion yellow dyeforming coupler that reacts with oxidized primary aromatic amine color developing agent to form a yellow dye and substantially no residual uncolored form of said yellow dye, said coupler having the formula:
• R represents a group selected from the class consisting of an alkyl group, an aromatic group, and a heterocyclic group
• X represents a group selected from the class consisting of the cyano group and a carbamyl group
• Y represents a coupling oif group selected from the class consisting of the chlorine atom, the fluorine atom, the thiocyano group, an acyloxy group, a cyclooxy group, an alkoxy group, an alkthio group and an arylthio group
• R represents a group selected from the class consisting of an alkyl group, a carbamyl group, an amino group, and an amido group
• Y represents a coupling 01f group selected from the class consisting of the thiocyano group, an acyloxy group, an aryloxy group, an alkoxy group, an alkthio group, an arylthio group, the chlorine atom, the fluorine atom and the sulfone group; and a red-sensitized gelatino silver halide emulsion containing a cyan dye-forming coupler, said photographic element being substantially free of aldehyde hardening agents and substantially free of aldehyde-releasing hardening agents, said process comprising the steps:
• magenta dye-formin g coupler is selected from the class consisting of 1- 2',4'-dichlorophenyl -3- 3"- (2"',4"'-di-tert-amylphenoxyacetamido benzamido] -5-pyrazolone,
• the cyan dye-forming coupler is selected from the class consisting of 2- a- (4-tert-butylphenoxy) propionylamino] phenol,
• a light-sensitive color photographic element comprising a support having coated thereon hydrophilic colloid containing a first silver halide emulsion sensitive to one region of the visible spectrum and contiguous to said first silver halide emulsion a nondifiusible ketomethylene open-chain yellow dye-forming coupler that reacts with oxidized primary aromatic amine color developing agent to form a yelow dye and substantially no residual uncolored form of said yellow dye, a second silver halide emulsion sensitive to a second region of the visible spectrum and contiguous to said second silver halide emulsion a nondiifusible S-pyrazolone which reacts with oxidized primary aromatic amine color developing agent to form a magenta dye, and a third silver halide emulsion sensitive to a third region of the visible spectrum and contiguous to the said third silver halide emulsion a nondiffusible coupler which reacts with oxidized primary aromatic amine color developing agent to form a cyan dye
• a light-sensitive color photographic element comprising a support having coated thereon a blue-sensitive gelatino silver halide emulsion containing a nondiffusible yellow dye-forming coupler that reacts with oxidized primary aromatic amine color developing agent to form a yellow dye and substantially no residual uncolored form of said yellow dye, said coupler having the formula:
• R represents a group selected from the class consisting of an alkyl group, an aromatic group, and a heterocyclic group
• X represents a group selected from the class consisting of the cyano group and a carbamyl group
• Y represents a coupling-01f group selected from the class consisting of the chlorine atom, the fluorine atom, the thiocyano group, an acyloxy group, a cyclooxy group, an alkoxy group, an alkthio group and an arylthio group
• R represents as described previously; R represents a group selected from the class consisting of an alkyl group, a carbamyl group, an amino group and an amido group; Y represents a coupling-off group selected from the class consisting of the thiocyano group, an acyloxy group, an aryloxy group, an alkoxy group, an alkthio group, an arylthio group, the chlorine atom, the fluorine atom and the sulfone group; and a red-sensitized gelatino silver halide emulsion containing a cyan dye-forming coupler, which photographic element is substantially free of alde- 25 26 hyde hardening agents, substantially free of aldehyde- 1-(2,4,6-trichlorophenyl)-3-[3-(2,4-di-tert-amylphenreleasing hardening agents and can be color developed oxyacetamido)benzamido]-4-thiocyano-S-pyrazolone

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• 1968
  • 1968-06-11 US US736010A patent/US3582322A/en not_active Expired - Lifetime
• 1969
  • 1969-06-04 DE DE1928554A patent/DE1928554B2/de active Pending
  • 1969-06-06 GB GB28646/69A patent/GB1268550A/en not_active Expired
  • 1969-06-10 FR FR6919113A patent/FR2010661A1/fr not_active Withdrawn
  • 1969-06-10 BR BR209615/69A patent/BR6909615D0/pt unknown
  • 1969-06-10 SE SE08229/69A patent/SE359171B/xx unknown
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  • 1969-06-11 CH CH893469A patent/CH501949A/fr not_active IP Right Cessation
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