US3664835A - Photographic product,composition and process comprising an anhydro dihydro amino reductone developing agent - Google Patents

Photographic product,composition and process comprising an anhydro dihydro amino reductone developing agent Download PDF

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US3664835A
US3664835A US863363A US3664835DA US3664835A US 3664835 A US3664835 A US 3664835A US 863363 A US863363 A US 863363A US 3664835D A US3664835D A US 3664835DA US 3664835 A US3664835 A US 3664835A
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photographic
silver halide
developing agents
employed
reductone
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Mary J Youngquist
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Eastman Kodak Co
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Eastman Kodak Co
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
    • G03C8/02—Photosensitive materials characterised by the image-forming section
    • G03C8/04—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of inorganic or organo-metallic compounds derived from photosensitive noble metals
    • G03C8/06—Silver salt diffusion transfer

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  • Photographic developing agents which are anhydro dihydro reductone silver halide developing agents such as anhydro dihydro amino reductone silver halide developing agents provide reduced stain without loss of desired sensitometric properties at reduced concentrations in a diffusion transfer system. These can be used in combination with other photographic developing agents such as aminomethyl hydroquinone developing agents, cinnamic acid developing agents, lactone developing agents or developing agent precursors, and the like. They are specially useful in a black and white silver halide diffusion transfer process.
  • This invention relates to photographic developing agents and to photographic products, processing compositions, especially developer compositions, and to processes employing such developing agents.
  • the invention relates to anhydro dihydro reductone silver halide developing agents, such as anhydro dihydro amino reductone silver halide developing agents and photographic products, processes and/ or processing compositions, especially those employed in diffusion transfer systems.
  • the invention is directed to processing compositions such as viscous processing compositions designed for diffusion transfer systems containing the described developing agents.
  • the diffusion transfer process in brief is characterized by the use of a photographic emulsion layer and an image receiver or precipitating layer contiguous to the emulsion layer. After exposure of the photographic emulsion layer, typically a processing composition, tag. a developer composition, is applied between the exposed photographic emulsion layer and the image receiver or precipitating layer.
  • the processing composition usually contains a silver halide solvent such as sodium thiosulfate which causes the unexposed silver salts usually silver halides to dissolve forming the silver complex which diffuses to the image receiver or precipitating layer where development nuclei or an image precipitating agent in that layer causes the silver to be precipitated from the silver complex imagewise.
  • Development nuclei or precipitating agents can be present in the image receiving layer before contact with the complex silver or the nuclei can be formed in situ.
  • Diffusion transfer photographic processes, elements and compositions for such processes are well known and described, for example, in U.S. Pat. 2,698,237 of Land issued Dec. 28, 1954 and U.S. Pat. 2,647,056 of Land issued July 28, 1953 as well as in U.S. Pat. 3,108,001 of Green issued "ice Oct. 22, 1963 and U.S. 3,345,166 of Land issued Oct. 3, 1967.
  • a processing composition employed in diffusion transfer processes normally contains a developing agent and is usually applied as a viscous fluid layer spread between the photographic layer and the image receiving layer.
  • the requirements for developing agents for diffusion transfer systems are very stringent and relatively few of the develiping agents which are satisfactory for general silver halide developing processes are satisfactory or sufficiently active for diffusion transfer systems.
  • One of the diffusion transfer developing agents used more successfully is a 2,4-diaminophenol, such as 2,4-diaminophenol dihydrochloride, also known as Amidol.
  • 2,4-diaminophenol dihydrochloride also known as Amidol.
  • developing agents will produce a positive image they are subject to rapid oxidation which results in unsightly and objectionable dark oxidation products 'which stains the positive print.
  • anhydro dihydro reductone silver halide developing agent with other silver halide developing agents such as pyrimidine silver halide developing agent, aminomethyl hydroquinone developing agents, cinnamic acid developing agents and coumarin developing agents or developing agent precursors are especially suitable in the practice of the invention.
  • the described anhydro dihydro reductone silver halide developing agents in a diffusion transfer system are specially advantageous over reductone developing agents in general due to their unexpected properties of providing desired sensitometric properties at concentration significantly lower than those necessary for reductone silver halide developing agents in general.
  • anhydro dihydro reductone silver halide developing agents which provide reduced stain without loss of desired sensitometric properties can be employed according to the invention. These include any anhydro dihydro reductone silver halide developing agents which provide desired developing activity and reduction of stain without adversely affecting desired maximum density, minimum density, photographic speed, gamma and other desired sensitometric properties.
  • anhydro dihydro reductone silver halide developing agents which are employed in the practice of the invention are anhydro dihydro amino reductone silver halide developing agents.
  • anhydro dihydro reductone silver halide developing agents can be employed in the practice of the invention.
  • Suitable anhydro dihydro reductone silver halide developing agents include, for example, compounds of the formula:
  • R and R are each hydrogen, alkyl, especially alkyl containing 1 to 5 carbon atoms such as methyl, ethyl, propyl and pentyl, or atoms completing a heterocyclic nucleus, as denoted by the broken line in Structure 1, containing a nitrogen atom, preferably containing 5 to 6 carbon atoms in the nucleus, including, for example, the second nitrogen or an oxygen atom, e.g. morpholino, piperazino, pyrrolidino, piperidino and the like.
  • Suitable anhydro dihydro reductone silver halide developing agents include:
  • the described anhydro dihydro reductone silver halide developing agents are typically prepared from the corresponding anhydro hexose reductone compounds which in turn are typically prepared from corresponding amino hexose reductones.
  • a typical method of preparing the described amino hexose reductones and anhydro amino hexose reductones. is set out in US. Pat. 2,936,308 of Hodge issued May 10, 1960.
  • Such compounds are typically prepared from sugars especially D-glucose although other reducing sugars such as D-galactose, D-fructose, L- sorbose or the like can be used.
  • a typical method of preparing the starting amino hexose reductones comprises heating in a reaction medium substantially free of water, a hexose reducing sugar and an aliphatic or cyclic secondary amine in the presence of an acidic reductone forming catalytic agent such as phosphoric acid, boric acid, acetic acid, succinic acid or the like. The removal of 3 mols of water results during the formation of the amino hexose reductone.
  • the described anhydro amino hexose reductone can be prepared by heating the hydrochloride salts of the amino hexose reductones further in the presence of strong acids such as sulfuric acid, acetic anhydride, zinc chloride and the like to remove another mol of water.
  • the described dihydro anhydro hexose reductone compounds can be prepared from the described anhydro amino reductones by hydrogenation in the presence of a suitable catalyst such as Raney nickel.
  • a suitable catalyst such as Raney nickel.
  • the prep aration of anhydro dihydro piperidino hexose reductone is typical of the preparation of the class of compounds employed in the practice of the invention.
  • One mol of anhydrous D-glucose and 1.3 mols of piperidine are stirred together in absolute ethanol under nitrogen for about 15 minutes.
  • the resulting mixture is then heated on a stream and stirred until the solution becomes homogeneous.
  • a solution of glacial acetic acid in absolute ethanol is added dropwise to the solution.
  • the resulting solution is stirred and refluxed under nitrogen for about 12. hours.
  • the resulting piperidino hexose reductone is dehydrated with a butanol solution of anhydrous hydrogen chloride to form the intermediate anhydro piperidino hexose reductone.
  • This product is then hydrogenated in ethanol over a suitable catalyst such as Raney nickel to form the desired anhydro dihydro piperidino hexose reductone.
  • the resulting product can be purified if desired such as by recrystallization from a suitable solvent e.g. ethanol.
  • anhydro dihydro reductone silver halide developing agents can be employed in the form of an acid salt such as a hydrochloride, sulfate or the like salt.
  • An anhydro dihydro reductone silver halide developing agent as employed herein includes such compounds either in salt or in their nonsalt form.
  • the described anhydro dihydro reductone silver halide developing agents can be employed in the practice of the invention in a range of physical locations in a diffusion transfer photographic system. They can be employed in one or more layers of a photographic element and/or in a processing compoistion if desired. The optimum location will depend upon the desired image, processing con dition and the like.
  • the described anhydro dihydro reductone silver halide developing agents can be employed in a processing composition, such as an aqueous alkaline developer solution or they can be incorporated into one or more layers of a photographic element, such as a photographic silver halide emulsion layer, a layer between the support and the silver halide emulsion layer, and/or an overcoat layer.
  • Suitable diffusion transfer systems processes, processing compositions and elements therefor which can be employed in the practice of the invention are described for example in US. Pat. 2,352,014 of Rott issued June 20, 1944; US. 2,452,181 of Land issued Feb. 27, 1951; and US. 3,337,342 of Green issued Aug. 27, 1967. They can be used in so-called high speed diffusion transfer processes and compositions therefor as described, for example, in US. Pat. 3,326,683 of Land et al. issued June 20, 1967; or in other types of diffusion transfer systems processes and compositions therefor such as described in US. Pat. 2,857,274 of Land et al. issued Oct. 21, 1958; US. 3,020,155 of Yackel issued Feb. 6, 1962; US.
  • one embodiment of the invention comprises in a photo graphic product comprising in combination (a) a photographic element comprising a photographic silver halide, (b) a processing compoistion containing a silver halide solvent, and (c) an image receiving layer, the improvement comprising an anhydro dihydro reductone silver halide developing agent.
  • the described anhydro dihydro reductone silver halide developing agent can be employed, as described, in any suitable physical location such as in the photographic element, in the processing composition and/ or in the image receiving layer or a layer contiguous thereto.
  • the developing agents described can be employed for developing an image in a wide range of photographic emulsions. They can be employed in such emulsions if desired. They photographic emulsions employed in the practice of the invention can be X-ray or other nonspectrally sensitized emulsions or they can contain spectral sensitizing dyes such as described in US. 2,526,632 of Brooker et al. issued Oct. 24, 1950 and US. 2,503,776 of Sprague issued Apr. 11, 1960. Spectral sensitizers which can be used include e.g. cyanines, merocyanines, complex (trinuclear) cyanines, complex(trinuclear)mereocyanines, styryls and hernicyanines.
  • photographic silver salts can be used in the practice of the invention. These include photographic silver halides such as silver bromide, silver chloride, as well as mixed halides such as silver bromoiodide, silver chloroiodide and the like.
  • the photosensitive layers and/ or image receiving layers which are employed in the practice of the invention can be coated on a wide variety of supports.
  • Suitable supports include for example those generally employed for photographic elements, such as cellulose nitrate film, cellulose ester film, poly(vinyl acetal) film, polysyrene film, poly (ethylene terephthalate) film and related films or resinous materials, as Well as papers such as paper supports coated with resinous materials, e.g. paper coated with alpha-olefin polymers particularly polymers of alpha-olefins containing 2 to 4 carbon atoms as exemplified by polyethylene, polypropylene, ethylenebutene copolymers or the like; as well as glass, metal and the like.
  • the supports or layers coated on them, typically paper supports can contain fluorescent brightening agent, such as stilbenes, benzothiazoles, benzoxazoles and coumarins.
  • the photographic elements and image receiver layers employed in the practice of the invention typically contain binding materials suitable for photographic purposes. These include natural and synthetic binding materials generally employed for this purpose, e.g. gelatin, colloidal albumin, water-soluble vinyl polymers, cellulose derivatives, acrylamide polymers, polyvinyl pyrrolidone and the like. Mixtures of binding agents can also be used.
  • the binding agents for an emulsion layer of a photographic element as described can also contain other dispersed polymerized vinyl compounds. Such compounds are described for example in U.S. 3,142,568 of Nottorf issued July 28, 1964; U.S. 3,193,383 of White issued July 6, 1965 U.S. 3,062,674 of Houck, Smith and Yudelson issued Nov. 6, 1962; and U.S.
  • Photographic emulsions employed in the practice of the invention can also contain speed increasing compounds such as quaternary ammonium compounds, polyethylene glycols or thioethers. Frequently, useful effects can be obtained by adding the described speed increasing compounds to the processing solutions instead of, or in addition to the photographic emulsions.
  • speed increasing compounds such as quaternary ammonium compounds, polyethylene glycols or thioethers.
  • Photographic silver halide emulsions employed in the practice of the invention can be chemically sensitized using any of the Well-known techniques in emulsion making, e.g. by digesting with naturally active gelatin or various sulfur, selenium, tellurium and/or noble metal sensitizers and/or reduction sensitizers. Combinations of sensitizers can be employed such as described in U.S. 3,297,446 of Dunn issued J an. 10, 1967 and U.S. 3,408,196 of McVeigh issued Oct. 29, 1968.
  • the described developing agents employed in the practice of the invention can be employed in combination with addenda known in the art to be useful in processing photographic elements, especially those employed in photographic diifusion transfer systems.
  • Suitable addenda include hardeners, e.g. those set out in British 974,317; buffers which maintain desired developing activity and/ or pH level; coating aids; plasticizers; and stabilizing agents, such as sodium sulfite.
  • the described developing agents employed in the practice of the invention can be used in colloid transfer processes and elements. They can also be used in photographic elements and/or in processing composition intended for use in monobath processing such as described in U.S. 2,875,048 of Haist et al. issued Feb. 24, 1959, and British 1,063,844 of Beavers et al. published Mar. 30, 1967. They can also be used in so-called web type processing such as described in U.S. 3,179,517 of Tregillus et al. issued Apr. 20, 1965.
  • the described developing agents employed in the practice of the invention can also be used to advantage in multilayer, single element diffusion transfer systems which utilize undeveloped silver halide in nonimage areas of a negative to form a positive by physical development of this silver onto a nuclei containing, contiguous, image receiving layer after which the upper layer is removed by scrubbing, washing, stripping or other suitable method.
  • Processes of this type are described, for instance, in U.S. 3,020,155 of Yackel et al. issued Feb. 6, 1962.
  • the developing agents employed in the practice of the invention can be employed if desired in photographic elements designed for stabilization type processing. For instance, they can be incorporated in one or more layers of a photographic element which is exposed, and then processed by contact with an alkaline development activator, and followed by stabilization with a suitable stabilizer, and such as with a thiocyanate or thiosulfate stabilizer, e.g. by contact with a thiocyanate or thiosulfate solution containing ammonium thiocyanate or sodium thiosulfate. They can be incorporated in the alkaline activator if desired. Such processes are described, for example, in U.S. 3,326,684 of Nishio et al.
  • the developing agents employed according to the invention can also be present in one or more layers of a photographic element designed for recording color images.
  • these compounds can be employed in one or more layers of a photographic element containing a photographic layer sensitive to the blue region of the spectrum, a photographic layer sensitive to the green region of the spectrum, and a photographic layer sensitive to the red region of the spectrum. Layers sensitive to the blue, green and red regions of the spectrum can contain any suitable sensitizing dyes.
  • Photographic elements designed for recording color images in which the developing agents of the invention can be used are described, for example, in Mees The Theory of the Photographic Process, 3rd ed., 1966, pp. 382396.
  • the developing agents employed in the practice of the invention can be employed in an element containing development nuclei or silver precipitating nuclei, e.g. an image receiver. As described, they can also be employed in photographic elements and/or processing compositions designed for use with an image receiver.
  • Development nuclei or silver precipitating agents which can be employed in diffusion transfer systems as described can be physical development nuclei or chemical precipitants including, for example, (a) heavy metals in colloidal form and salts of these metals; (b) salts of amines which form silver salts and/ or (c) nondilfusing polymeric materials with functional groups capable of combining with silver amines.
  • Suitable development nuclei and/0r silver image precipitating agents within the described classes include metals sulfides, selenides, polysulfides, polyselenides, thiourea and its derivates, stannous halides, silver, gold, platinum, palladium, and mercury, colloidal sulfur, aminoguanidine sulfate, aminoguanidine carbonate, arsenous oxide, sodium stannite, hydrazines, xanthates, and similar agents disclosed, for example, in U.S. Pat. 3,020,155 of Yackel issued Feb. 2, 1962.
  • a nondiffusing polymeric silver precipitant or development nuclei such as polyvinylmercaptoacetate can also be employed.
  • a wide range of concentrations of development nuclei or silver precipitating agents can be employed.
  • a concentration of the development nuclei or silver precipitant in the image receiving layer must be at least suflicient to insure the development of a positive image and suflicient removal of undeveloped silver salt from the light-sensitive layer to be processed.
  • concentration of the developing agent as described is about 320 mg. per square foot of the layer containing the precipitants or development nuclei.
  • the developing agents employed in the practice of the invention can be employed in combination with any silver halide developing agent.
  • the developing agents employed in the practice of the invention can be employed in such combinations as auxiliary developing agents or as the main component of the developing combination.
  • Suitable silver halide developing agents which can be employed in combination with the described pyrimidine developing agents include, for example, polyhydroxybenzenes such as hydroquinone developing agents, e.-g.
  • hydroquinone alkyl substituted hydroquinones as exemplified by tertiary butyl hydroquinone, methyl hydroquinone and 2,5-dimethylhydroquinone; catechol and pyrogallol; aminomethyl hydroquinone; chloro substituted hydroquinone such as chlorohydroquinone or dichlorohydroquinone; alkoxy substituted hydroquinone such as methoxyhydroquinone or ethoxyhydroquinone; amino phenol developing agents, such as 2,4- diaminophenols and methylaminophenols; pyrimidine developing agents; ascorbic acid developing agents such as ascorbic acid, ascorbic acid ketals, and ascorbic acid such as those described in U.S.
  • the developing agents employed in the practice of the invention can be used in combination, for example, with the following compounds:
  • One or more of the described combination of compounds can be in a photographic element and/or processing composition, e.g. a developer composition employed in the practice of the invention.
  • a photographic element can contain a 3-pyrazolidone developing agent and/or a 2,4- diaminophenol developing agent and/or polyhydroxybenzene developing agents and/or other described addenda and be developed employing a processing composition containing a developing agent of the invention, i.e. an anhydro dihydro reductone developing agent.
  • the developing agents employed in the practice of the invention can be employed in a photographic silver salt emulsion designed for diffusion transfer processing and/ or in a processing composition designed for such processing.
  • a typical processing composition employed in dilfusion transfer systems is described, for example, in U.S. Pat. 3,120,795 of Land et al. issued Feb. 11, 1964.
  • Another embodiment of the invention is in a liquid photographic processing composition
  • a liquid photographic processing composition comprising (A) a silver halide solvent and (B) a silver halide developing agent, the improvement wherein said developing agent is an anhydro dihydro amino reductone silver halide developing agent.
  • composition is typically employed in a combination of (a) a photographic element comprising a photographic silver salt layer, (b) a viscous processing composition comprising:
  • an image receiving layer comprising development nuclei, especially palladium development nuclei, dispersed in a polymeric binder.
  • a processing composition employed in the practice of the invention is typically a viscous processing composition.
  • a wide range of suitable viscosity can be employed. The viscosity is usually about 20 to about 100,000 centipoise.
  • Various thickening agents are suitable in the described processing compositions and processes of the invention. Any of those commonly employed in diffusion transfer photographic systems can be employed as well as those employed in viscous monobaths. These include those described in U.S. Pat. 3,120,795 of Land et al. issued Feb. 11, 1964, such as hydroxyethylcellulose and carboxymethylcellulose.
  • Suitable viscous monobaths in which the described anhydro dihydro reductions silver halide developing agents can be employed are described, for example, in the Monobath Manual by Grant M. Haist (1966), and U.S. Pat. 3,392,019 of ⁇ Barnes et al. issued July 9, 1968.
  • silver halide solvents can be employed in the practice of the invention.
  • the silver halide solvent is sodium thiosulfate, however various organic silver halide complexing agents such as those described in Haist et al. Photographic Science and Engineering, vol. 5, page 198 (1961) and described in French Pat. 1,312,687, issued Nov. 12, 1962 and Belgian Pat. 606,559 of Ulrich et al. issued July 26, 1960 and similar agents can also be used.
  • Another embodiment of the invention comprises in a photographic diffusion transfer process comprising developing a latent image in a photographic silver salt layer and precipitating an image in an image receiver layer, the improvement comprising developing said latent image with an anhydro dihydro reductone silver halide developing agent.
  • a photographic diffusion transfer process according to this invention is typically a black and white silver salt ditfusion transfer system.
  • the described process is carried out at a pH which activates the described anhydro dihydro reductone silver halide developing agent.
  • the activating pH is usually about 10 to about 14 with good results being obtained when the pH is above about 12.
  • the pH of the system is lowered to less than about 8, e.g. between 8 and 2, the developing activity stops.
  • the optimum pH for any particular diffusion transfer system will be influenced by the particular photographic element, the desired image, various addenda employed in the processing composition, emulsion and image receiver, processing conditions and the like. Any development activator can be employed which provides the desired pH.
  • Typical development activators which can be employed are alkaline metal hydroxide such as sodium hydroxide, potassium hydroxide or lithium hydroxide as Well as organic development activators such as amines, e.g. 2-aminoethanol, Z-methylaminoethanol, Z-dimethylaminoethanol, Z-ethylaminoethanol, Z-diethylaminoethanol, 2,2-diiminodiethano1, S-diethylamino-2-pentanol, and the like.
  • alkaline metal hydroxide such as sodium hydroxide, potassium hydroxide or lithium hydroxide
  • organic development activators such as amines, e.g. 2-aminoethanol, Z-methylaminoethanol, Z-dimethylaminoethanol, Z-ethylaminoethanol, Z-diethylaminoethanol, 2,2-diiminodiethano1, S-diethylamino-2-pentanol, and the like.
  • a photographic process according to the invention accordingly can comprise the steps of exposing a photographic element comprising a photographic silver salt layer to form a latent image therein, developing the resulting latent image with a processing composition as described at a pH of about 12 to about '14 comprising an anhydro dihydro reductone silver halide developing agent, contacting undeveloped silver salts in the photographic silver salt layer with a silver halide solvent to form an imagewise distribution of a silver complex in the unexposed areas of the photographic silver salt layer, transferring at least part of the silver complex to an image receiver layer contiguous to the photographic silver complex in the presence of development nuclei, to form a visible image in the receiver layer.
  • Processing conditions, time of development and the like can vary depending on several factors such as the desired image, the particular components of the described photographic element, processing, composition and image receiver. Typical processing is carried out under normal atmospheric conditions and is completed within about 60 seconds, e.g. within about seconds. Processing temperatures are typically about 20 C. to about 30 C. but elevated temperatures can be employed if desired such as temperatures up to about 50 C.
  • the described photographic element, receiving element and/or processing composition can also contain toning agents.
  • Typical toning agents which can be employed include, for example, polyvalent inorganic salts as described in US. Pat. 2,698,236 of Land issued Dec. 28, 1954; silica as described in U.S. Pat. 2,698,237 or Land issued Dec. 28, 1954; and heterocyclic mercaptans such as mercaptoazoles, e.g. mercaptodiazoles, mercaptotriazoles, and mercaptotetrazoles.
  • concentrations of developing agents used in the practice of the invention can vary over wide ranges depending on the particular photographic and physical variables present in the system. For example, the location of the developing agent in the system, and the photographic element, processing composition, the desired image, processing conditions and the like. Suitable concentrations also depend on the particular addendum present in the photographic element to be processed and/ or in the processing compositions. Typically when a developing agent according to the invention is employed in a photographic element, it is employed in the concentration of about 0.01 to about 5 mol of developing agents per mol of silver present in the photographic element. When a developing agent as described is employed in a processing composition, the total concentration of developing agents in the system is typically about 0.01 to about 10, preferably 1 to about 5% by Weight of the total developer composition.
  • Suitable anti foggants include organic antifoggants, such as benzotriazole, benzimidazole, Z-mercaptobenzimidazole, nitroindazole, and mercaptotetrazole antifoggants.
  • the developer compositions of the invention can contain inorganic antifoggants such as potassium bromide, potassium iodide and/or sodium bromide.
  • the concentration of antifoggant in either the processing composition or photographic ele- Especially good results can be obtained in the practice of the invention when the described anhydro dihydro reductone silver halide developing agents are employed in combination with other silver halide developing agents such as hydroxycinnamic acid silver halide developing agents and/or lactone silver halide developing agent precursors and/or pyrimidine silver halide developing agents and/ or aminomethyl polyhydroxybenzene silver halide developing agents.
  • One or more of these developing agents according to the practice of the invention are suitable in a range of physical locations in the described diffusion transfer system.
  • One or more can be employed in one or more layers of a photographic element and/ or processing composition and/or in an image receiver employed therewith.
  • one or more of the described developing agents can be employed in the processing composition such as an aqueous alkaline developer solution and one or more can be incorporated in a layer of a photographic element such as in a silver salt emulsion layer, an overcoat layer, a layer between the emulsion layer and the support and/or some other layer contiguous to the silver salt to be developed.
  • the described developing agents can be employed in such combinations as auxiliary developing agents or one or more can be used as the main components of the developing combination or developing precursor combination.
  • pyrimidine silver halide developing agents can be employed in combination with the described anhydro dihydro reductone silver halide developing agents according to the practice of the invention.
  • Suitable pyrimidine silver halide developing agents include, for example:
  • the described pyrimidine silver halide developing agents are typically in the form of an acid salt such as a hydrochloride, chloride, sulfate or the like.
  • a pyrimidine silver halide developing agent as emloyed herein includes such compounds either in salt form or in their nonsalt form.
  • cinnamic acid silver halide developing agents can also be employed in combination with the described anhydro dihydro reductone silver halide developing agents in the practice of the invention.
  • Suitable cinnamic acid silver halide developing agents include for example:
  • cinnamic acid silver halide developing agents are derived from corresponding hydroxycoumarin and/or aminocoumarln developing agent precursors.
  • Suitable aminocoumarin and/or hydroxycoumarin developing agent precursors which can be employed in the practice of the invention include for example:
  • EXAMPLE 1 This illustrates an anhydro dihydro reductone silver halide developing agent in a dilfu'sion transfer system according to the invention.
  • a processing composition is prepared by mixing the following components:
  • Hydroxyethyl cellulose (sold under the tradename Natrasol 2501-1 by Hercules Powder Company, U.S.A.) 25.0
  • the resulting processing solution is a viscous liquid.
  • a photographic element is prepared by coating a gelatin solution containing the silver halide developing agent, Z-methyl-S-morpholinornethyl hydroquinone on electron bombarded polyethylene coated paper at 240 mg. of gelatin per square foot at 50 mg. of developing agent per square foot. Over this layer is coated a coarse grained silver bromoiodide gelatino emulsion containing 5 mole percent iodide and a concentration of 125 mg. of silver per square foot and 320 mg. of gelatin per square foot.
  • An image receiver is prepared by coating a Water resistant paper support wtih palladium development nuclei dispersed in a polymeric binder.
  • the described photographic element is sensitometrically exposed.
  • the processing composition as described is then squeezed between the photographic element and the image receiver and the resulting so-called sandwich is pressed together by running it between two rollers. After 20 seconds the so-called sandwich is pulled apart and the resulting image on the image receiver is observed for oxidation stain.
  • the relative speed of the control image on the image receiver is assigned the value of and has a maximum density of 1.15.
  • the image on the image receiver employing the described anhydro dihydro piperidino hexose reductone in the processing composition has a relative speed of 100 and a maximum density of 1.55. This illustrates that the described reductone silver halide developing agent provides increased maximum density without undesired loss of photographic speed.
  • the image on the image receiver in both cases contains no stain.
  • EXAMPLE 2 This is a comparative example.
  • a processing composition is prepared by mixing the following components:
  • the resulting processing solution is a viscous liquid.
  • -A photographic element is prepared by coating a gelatino coarse grained silver bromoiodide photographic emulsion on a film support.
  • An image receiver is prepared by coating a Water resistant paper support with palladium development nuclei dispersed in a polymeric binder. The photographic element is sensitometrically exposed.
  • the processing composition, as described, is then squeezed between the photographic element and the image receiver and the resulting so-called sandwich is pressed together by running it between two rollers. After 30 seconds the so-called sandwich is peeled apart and the resulting image on the image receiver is observed for oxidation stain.
  • the positive image is produced which has heavy yellow or orange stain.
  • the developing agent such as a 2,4-diaminophenol developing agent causes undesired oxidation stain as compared to the described developing agents employed in the practice of the invention.
  • Example 2 The procedure set out in Example 2 is repeated with the exception that hydroquinone is employed in place of the described 2,4-diaminophenol developing agent.
  • Example 2 The procedure set out in Example 2 is repeated with the exception that tertiary butyl hydroquinone is employed in place of the described 2,4-diaminophenol developing agent.
  • the resulting positive image contains heavy yellow or orange stain.
  • Example 1 The procedure set out in Example 1 is repeated with the exception that piperidino hexose reductone is employed as a developing agent in place of the described anhydro dihydro piperidino hexose reductone and also at a concentration of 20.0 grams per liter of processing solution.
  • the resulting positive image has a relative speed of 80 compared to the described control at a maximum density of 1.55.
  • Example 6-12 The procedure set out in Example 1 is repeated with the exception that the following anhydro dihydro reductone silver halide developing agents are employed in place of the described anhydro dihydro piperidino hexose reductone. In each instance, similar results are obtained as set out in Example 1.
  • the concentration of the developing agent is about 320 milligrams per square foot of the layer containing the precipitants or development nuclei or the concentration can be about 2 grams to about 50 grams per liter of processing solution, e.g. 5 grams to grams per liter of processing solution.
  • the supports or layers coated on them employed in the practice of the invention can contain acids, e.g. polymeric acids as described in U.S. Pat. 2,584,030 of Land issued Jan. 29, 1952, and U.S. Pat. 3,415,644 of Land issued Dec. 10, 1968.
  • antioxidants in a photographic element employed in the practice of the invention. This is typically in a layer containing a developing agent, as described.
  • Typical antioxidants suitable for this purpose are sodium formaldehyde bisulfite and those described in U.S. Pat. 3,212,895 of Barbier et al. issued Oct. 19, 19 65, and U.S. Pat. 3,418,132 of Kitze issued Dec. 24, 1968.
  • R and R are each hydrogen, alkyl containing 1 to 5 carbon atoms, or, taken together, are atoms selected from the group consisting of carbon, hydrogen, oxygen and nitrogen atoms completing a 4 to 6 member heterocyclic nucleus.
  • anhydro dihydro amino reductone silver halide developing agent is anhydro dihydro piperidino hexose reductone, anhydro dihydro morpholino hexose reductone, or anhydrodihydro pyrimidino hexose reductione.
  • a photographic product as in claim 1 comprising an auxiliary silver halide developing agent.
  • a photographic product as in claim 1 comprising a hydroxy cinnamic acid silver halide developing agent.
  • a photographic product as in claim 1 comprising a lactone silver halide developing agent precursor.
  • a photographic product as in claim 1 comprising a 3-pyrazolidone silver halide developing agent.
  • a photographic product comprising in combination (a) a photographic element comprising a photographic silver salt, (b) a processing composition containing a silver halide solvent, and ,(c) an image receiving layer, said product containing a silver halide developing agent, the improvement wherein said developing agent is an anhydro dihydro amino reductone silver halide developing agent of the formula:
  • R and R are each hydrogen, alkyl containing 1 to 5 carbon atoms, or, taken together, are atoms selected from the group consisting of carbon, hydrogen, oxygen 15 and nitrogen atoms completing a 4 to 6 member heterocyclic nucleus.
  • a liquid photographic processing composition as in claim 11 wherein said silver halide developing agent is anhydro dihydro piperidino hexose reductone, anhydro dihydro morpholino hexose reduction, or anhydro dihydro pyrimidino hexose reductone.
  • a liquid photographic processing composition as in claim 11 which is a monobath.
  • a liquid photographic processing composition as in claim 11 which is a viscous solution.
  • a liquid photographic processing composition comprising (a) a silver halide solvent and (b) a silver halide developing agent, the improvement wherein said developing agent is an anhydro dihydro amino reductone silver halide developing agent of the formula:
  • R and R are each hydrogen, alkyl containing 1 to 5 carbon atoms, or, taken together, are atoms selected from the group consisting of carbon, hydrogen, oxygen and nitrogen atoms completing a 4 to 6 member heterocyclic nucleus.
  • said silver halide developing agent is anhydro dihydro piperidino hexone reductone, anhydro dihydro morpholino hexose reductone, or anhydro dihydro pyrimidino hexose reductone.
  • a photographic diffusion transfer process comprising developing a latent image in a photographic silver salt layer and precipitating an image in an image receiver layer, the improvement comprising developing said latent image with an anhydro dihydro amino reductone silver H CH;
  • R and R are each hydrogen, alkyl containing 1 to 5 carbon atoms, or, taken together, are atoms completing a morpholino, piperazino, pyrrolidino, piperidino, dimethylmorpholino, methyl piperidino or pyrimidino heterocyclic nucleus, contacting undeveloped silver salts in the photographic silver salt layer with a silver halide solvent to form an imagewise distribution of a silver complex in the unexposed areas of the photographic silver salt layer, transferring at least part of the silver complex to an image receiver layer contiguous to the photographic silver salt complex in the presence of development nuclei, to form a visible image in the receiver layer.
  • a photographic process as in claim 20 wherein said anhydro dihydro amino reductone silver halide developing agent is anhydro dihydro piperidino hexose reductone, anhydro dihydro morpholino hexose reductone, or anhydro dihydro pyrimidino hexose reductone.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
US863363A 1969-10-02 1969-10-02 Photographic product,composition and process comprising an anhydro dihydro amino reductone developing agent Expired - Lifetime US3664835A (en)

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AT (1) AT298239B (enrdf_load_stackoverflow)
AU (1) AU1188370A (enrdf_load_stackoverflow)
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CA (1) CA933021A (enrdf_load_stackoverflow)
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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3816137A (en) * 1970-12-02 1974-06-11 Eastman Kodak Co Amino hydroxy cycloalkenone silver halide developing agents
US3816136A (en) * 1972-07-17 1974-06-11 Eastman Kodak Co Photographic element and process of developing
DE2622950A1 (de) * 1976-05-21 1977-12-01 Agfa Gevaert Ag Fotografische farbentwicklerzusammensetzung
DE2700938A1 (de) * 1977-01-12 1978-07-13 Agfa Gevaert Ag Photographische farbentwicklerzusammensetzung
US4154611A (en) * 1978-02-27 1979-05-15 Polaroid Corporation Bicyclic reductone developing agents
US4365085A (en) * 1978-02-27 1982-12-21 Polaroid Corporation Bicyclic reductone developing agents
US5342741A (en) * 1992-07-10 1994-08-30 Fuji Photo Film Co., Ltd. Method of processing silver halide photographic material and composition for processing
US5427905A (en) * 1994-07-13 1995-06-27 Polaroid Corporation Thermally processable image-recording material including reductone developing agent
CN114524771A (zh) * 2020-11-23 2022-05-24 江苏八巨药业有限公司 一种6-羟基-2,4,5-三氨基嘧啶硫酸盐的制备方法

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3816137A (en) * 1970-12-02 1974-06-11 Eastman Kodak Co Amino hydroxy cycloalkenone silver halide developing agents
US3816136A (en) * 1972-07-17 1974-06-11 Eastman Kodak Co Photographic element and process of developing
DE2622950A1 (de) * 1976-05-21 1977-12-01 Agfa Gevaert Ag Fotografische farbentwicklerzusammensetzung
US4155764A (en) * 1976-05-21 1979-05-22 Agfa-Gevaert, A.G. Photographic color developer composition
DE2700938A1 (de) * 1977-01-12 1978-07-13 Agfa Gevaert Ag Photographische farbentwicklerzusammensetzung
US4154611A (en) * 1978-02-27 1979-05-15 Polaroid Corporation Bicyclic reductone developing agents
US4365085A (en) * 1978-02-27 1982-12-21 Polaroid Corporation Bicyclic reductone developing agents
US5342741A (en) * 1992-07-10 1994-08-30 Fuji Photo Film Co., Ltd. Method of processing silver halide photographic material and composition for processing
US5427905A (en) * 1994-07-13 1995-06-27 Polaroid Corporation Thermally processable image-recording material including reductone developing agent
EP0692732A1 (en) 1994-07-13 1996-01-17 Polaroid Corporation Thermally processable image-recording material including reductone developing agent
CN114524771A (zh) * 2020-11-23 2022-05-24 江苏八巨药业有限公司 一种6-羟基-2,4,5-三氨基嘧啶硫酸盐的制备方法

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BR7017030D0 (pt) 1973-01-18
AT298239B (de) 1972-04-25
DE2009078A1 (de) 1971-04-08
NL7014477A (enrdf_load_stackoverflow) 1971-04-06
CA933021A (en) 1973-09-04
BE749935A (fr) 1970-10-16
AU1188370A (en) 1971-09-02
FR2065795A5 (enrdf_load_stackoverflow) 1971-08-06

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