US3414411A - Dye bleach process - Google Patents

Dye bleach process Download PDF

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US3414411A
US3414411A US512907A US51290765A US3414411A US 3414411 A US3414411 A US 3414411A US 512907 A US512907 A US 512907A US 51290765 A US51290765 A US 51290765A US 3414411 A US3414411 A US 3414411A
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silver
dye
layer
acid
salt
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Michel Stephen
George M Reitter
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Eastman Kodak Co
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Eastman Kodak Co
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Priority to US512907A priority Critical patent/US3414411A/en
Priority to BE690848D priority patent/BE690848A/xx
Priority to DE19661547759 priority patent/DE1547759B1/de
Priority to CH1757566A priority patent/CH465401A/fr
Priority to FR86801A priority patent/FR1504238A/fr
Priority to GB55637/66A priority patent/GB1173017A/en
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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
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/28—Silver dye bleach processes; Materials therefor; Preparing or processing such materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/261—Non-bath processes, e.g. using pastes, webs, viscous compositions

Definitions

  • the silver-dye-bleaclr system involves developing a silver image in an exposed silver halide emulsion containing bleachable dye, and bleaching the dye in just those areas where the silver has been developed. All of the silver ion is removed or rendered transparent and insensitive to light, leaving a dye-image in the areas where no metallic silver was present.
  • One object of this invention is to provide improved novel dye-bleach materials and processes.
  • a further object of this invention is to provide novel dye-bleach materials and processes which allow short processing times.
  • Another object of this invention is to provide novel dye-bleach materials and processes which can be utilized by a relatively unskilled individual.
  • Another object of this invention is to provide novel dye bleach materials and processes suitable for in-camera processing.
  • It is another object of this invention to provide novel photographic dye-bleach processes which reduce the number of processing baths or steps required to produce images by the dye-bleach system.
  • dye images are produced in photographic elements comprising a support having thereon a silver halide emulsion containing the salt of an acid and a developed silver image having in association therewith a bleachable dye, or dye precursor by the method which comprises contacting the emulsion with a web having an acidic substituent which is capable of exchanging hydrogen ion with the cation of the salt of an acid which is present in the emulsion or activator to lower the pH of the emulsion to a level at which imagewise bleaching of the dye in areas of metallic silver and in the presence of a silver complexing agent may proceed.
  • the dye bleaching is preferably conducted in the presence of a catalyst.
  • a method for producing dye images in an exposed silver halide emulsion having in association therewith a bleachable dye which comprises elevating the pH of the emulsion, in the presence of a silver halide developer, to a level at which the developable silver halide is reduced to metallic silver.
  • the element is then contacted with a web having an acidic substituent which exchanges hydrogen ion with the cation of the salt of a strong acid which is present in the emulsion or activator, thereby converting the said salt to its free acid form.
  • the pH of the ice emulsion is lowered, stopping development and reducing the pH to a level at which bleaching of the dye occurs irnagewise in the presence of a silver complexing agent in areas where metallic silver is present.
  • the bleaching is preferably conducted in the presence of dye bleach catalyst.
  • a silver halide complexing agent is employed during processing to remove, or render light-insensitive, the silver ion. The use of such complexing agents permits the bleaching of the metallic silver to silver ion to be carried to completion.
  • a method of developing silver-dye-bleach elements which requires only one processing solution and is suitable for in-camera processing.
  • an exposed silver halide emulsion having in association therewith a bleachable dye or dye precursor is contacted in the presence of a silver halide developer, with an alkaline processing solution to elevate the pH to a level at which the developable silver halide is reduced to metallic silver, at least the alkaline processing solution being contained in a rupturable pod or container, e.g., a pressure rupturable container.
  • suitable means are provided for rupturing the pod and evenly distributing the contents thereof over the exposed silver halide emulsion.
  • the emulsion is contacted with a processing web having acid substituents.
  • the processing web stops development by lowering the pH of the emulsion by ion exchange with the salt of an acid present in either the emulsion or the activator solution, or both.
  • the salt of a strong acid is incorporated in the emulsion at any convenient time prior to contacting it with the acidic web, such as when the emulsion is made, or by incorporating the salt in the alkaline processing solution.
  • the ion exchange lowers the pH to a level at which bleaching of the metallic silver and the dye in the presence of a silver complexing agent may be affected.
  • a timing layer may be coated over the acidic web.
  • the rupturable pod may be affixed to the acid web or matrix and the exposed photographic element brought into contact with the pod and acidic web, the pod ruptured and the element and web contacted in overlying relationship with the contents of the pod evenly distributed between the web and the element.
  • the timing layer serves to allow development to take place prior to reducing the pH by ion exchange between the acidic web and salt of a strong acid present in the alkaline processing solution or element.
  • an integral three-part photographic element comprising as part 1, a light-sensitive material including a support having coated thereon at least one light-sensitive silver halide emulsion having in association therewith a bleachable dye.
  • the light-sensitive element may contain a plurality of emulsions containing or having in contiguous colloid layers, different bleachable dyes to provide multicolor images.
  • Part 2 comprises a rupturable pod containing an alkaline processing solution to raise the pH of the emul-, sion to a level at which, reduction of developable silver halide to metallic silver takes place when a silver halide developer is present.
  • Part 3 of the photographic element comprises an acidic web which is capable of exchanging the hydrogen ion with the salt of a strong acid which is introduced into the emulsion at any convenient time prior to contacting the emulsion with the Web, the salt of a strong acid may be incorporated in the emulsion when it is made, or it may be added to the alkaline processing solution.
  • the element of this invention may be assembled in various arrangements.
  • the rupturable container is :aflixed to the processing web.
  • the rupturable container may be attached to the light-sensitive element.
  • parts 1 and 3 may be in the roll form, with part 2 being affixed to either part, preferably, part 3.
  • a light-sensitive element labeled part 1
  • a support 1 overcoated with a blue-sensitive emulsion 2 which contains bleachable yellow dye, a green-sensitive emulsion 3 which contains a bleachable magenta dye and a red-sensitive emulsion 4 which contains a bleachable cyan dye.
  • each of these emulsions may consist of two emulsions having different speeds and double coated to provide a wider latitude for the element.
  • each emulsion layer a hydrophilic colloid interlayer which may contain various addenda, such as ballasted quinones (i.e., to prevent interlayer diffusion of reduced dye bleach catalyst), removable filter dyes, etc.
  • the drawing further shows an acidic processing, web, labeled part 3, comprising a support 5 having coated thereon a hydrophilic colloid layer identified in the figure as gelatin containing acid containing free acid 6, and overcoated with a timing layer 7 identified in the figure as gelatin timing layer.
  • a rupturable pod labeled part 2 is composed of a film 8 which may be ruptured by suitable means.
  • the rupturable pod shown contains an alkaline processing material 9.
  • the light-sensitive emulsions employed in the elements and processes of this invention comprise any of the useful silver halide light-sensitive salts such as silver chloride, silver bromide, silver iodide, and mixed halide salts such as silver chlorobromide.
  • the emulsions may be conventional surface sensitive emulsions, direct positive emulsions or internally sensitive emulsions.
  • the emulsions used in this invention, as well as the photosensitive elements thereof, may be used to record light and other radiation, such as infrared, X-ray, etc.
  • alkalipermeable binders may be used for the silver halide, such as gelatin, polyvinyl alcohol, water-soluble cellulose derivatives and other binders of the type referred to in column 13 of US. Patent No. 3,039,873.
  • the emulsions may contain chemical sensitizers, spectral sensitizers, stabilizers, speed increasing compounds, gelatin plasticizers, and hardeners, examples of which are referred to in columns 10-12 of US. Patent 3,039,873.
  • bleachable dyes preferably non-difiusible dyes, of the type well known in the art.
  • bleachable dyes includes compounds which are dye precursors, i.e., compounds which become colored during processing of the photographic material.
  • non-difiusible refers to bleachable dyes which in themselves are nondiifusible in the emulsion, or dyes which are rendered nondiffusible by the use of a suitable mordant, such as those described in US. Patent No. 2,882,156.
  • the elements of this invention may have a single emulsion coating for monochrome dye images formed from either one or a mixture of dyes, which dye images are either colored or neutral (e.g., black and White) images.
  • Typical useful neutral dyes for such materials are the azo dyes described in British Patent 999,996.
  • the elements of the invention may have a plurality of coatings each containing a different bleachable dye for providing multi-color images.
  • Especially useful arrangements are those in which at least three light-sensitive emulsion layers are provided which are respectively sensitized to blue, green and red radiation, and containing, respectively, non-diffusible yellow, magenta and cyan dyes.
  • the emulsions used in this invention may contain the bleachable dyes.
  • a support has coated thereon, in the following order, layers containing, respectively, blue-sensitive silver halide; bleachable yellow dye; greensensitive silver halide; bleachable magenta dye; red-sensitive silver halide; and, bleachable cyan dye.
  • the reference to bleachable dyes being in association with a particular layer means that the bleachable dye is in that layer or in an alkali-permeable layer contiguous to such layer.
  • Development of the exposed photographic emulsion is effected, in the presence of a silver halide developer, by elevating the pH of the emulsion with an alkaline processing solution.
  • the pH of the emulsion is raised to about 9.0 or above.
  • alkaline solutions can be employed, such as sodium or potassium hydroxide.
  • Development rate controllers such as potassium bromide, may be used.
  • Other agents found in conventional developers, such as spreading agents (saponin), antifoggants and stabilizers may be included in the alkaline processing solution.
  • Conventional photographic developers are operable in the invention. These developers may be incorporated in emulsions in accordance with prior art procedures, or may be added to the alkaline processing solution referred to herein also as activator solution. In certain instances, it is possible to incorporate in the emulsion one molecule which contains both the developing function and the bleachable dye function. Such molecules are non-diffusible and the dye portion of the molecule must be bleachable.
  • a suitable silver halide complexing agent is employed.
  • the term complexing agent refers to compounds which either (1) dissolve and remove from the emulsion layer silver ion, or (2) stabilizing compounds which react with the silver ion to render itinsensitive to light and transparent.
  • the complexing agents are incorporated in the activator solution or, in some instances, in the acidic processing web, or in both.
  • Typical useful complexing agents are dimethylolthiourea, trimethylolthiourea, cyclic thione, 1-(5-hydroxyethyl)imidazolidene-Z-thione, etc.
  • the salt of a strong acid Prior to contacting the developed silver halide emulsion with the acidic processing web in accordance withthe invention, the salt of a strong acid is introduced into the emulsion.
  • the salt of an acid can be incorporated in the emulsion during the making thereof, or it may be incorporated in the alkaline processing solution, or in both.
  • the salt of the strong acid reacts with the acidic processing web to reduce the pH of the emulsion at the proper time during processing; An ion exchange occurs between the acidic processing web and the salt of a strong acid,the strong acid salt losing its cation to the acidic function in the web, and thereby effectively lowering the pH of the emulsion to facilitate bleaching of the dye by the metallic silver in the presence of a silvercomplexing agent.
  • Useful salts of strong acids in this invention are those which, in their free acid form, are capable of reducing the pH of the emulsion low enough to enable bleaching. Generally ,this is at a pH level of less than about 3, and preferably is less than about 2.0. Especially useful acids arethose which have an ionization constant greater than about l0 The salts of acids employed should be free from exerting deleterious effects on the photographic elements, such as fogging the emulsion, and they must not bleach the dyes in areas Where metallic silver is not present.
  • Especially useful salts arethe ammonium (e.g., unsubstituted and substituted), alkali metal and alkaline earth chlorides, bromides, nitrates, sulfates, sulfonates, phosphates, phosphonates, and the like.
  • Other useful acid salts include tetraalkyl ammonium chlorides, such as tetramethyl or tetrabutyl ammonium chloride, sodium chloride, sodium meta-t-but-yl-benzene sulfonate sodium salt suflicient to effectively lower the pH of the emulsion to a level at which bleaching of the dye takes place.
  • concentrations range from 0.5 to 2.0 moles of acid salt per liter of developer or activator.
  • concentration of the acid salt depends on the strength of the acid.
  • suflicient concentration of the acid, in the form of its salt to reduce the pH to less than about 3.0 and preferably less than 2.0 or 1.5, When the ion exchange takes place.
  • the function of the acidic web employed in accordance with this invention is to stop development and activate bleaching.
  • the acid web allows one-solution dye-bleach processing.
  • the web itself may comprise any suitable support, such as paper, a polyolefin such as polyethylene or polypropylene; polycarbonate; or a cellulose ester such as cellulose acetate butyrate.
  • a suitable subbing coating to adhere the acid to the web.
  • the web itself may be a self-supporting acidic polymer, such as a cross-linked polystyrene having free acidic groups, such as sulfonic acid groups.
  • Cation exchange membranes are also useful such as those described in Nature, volume 165, p. 568 (1950).
  • the acidic processing web may comprise a suitable support, such as a film base of the type referred to above having a hydrophilic coating thereon containing a free acid which is capable of exchanging hydrogen ion with the cation of a strong acid salt present in the emulsion.
  • a suitable support such as a film base of the type referred to above having a hydrophilic coating thereon containing a free acid which is capable of exchanging hydrogen ion with the cation of a strong acid salt present in the emulsion.
  • acids are suitable for this purpose, including strongly acidic polymers, ballasted sulfonic acids and ballasted phosphonic acids, such as dodecanesulfonic acid and hexadecanephosphonic acid.
  • ballasted refers to acids having limited mobility or complete immobility in aqueous media.
  • the ballasted sulfonic acids including high molecular weight monomeric acids such as an alpha-sulfostearic acid.
  • Polymeric cation ion exchange resins may also be employed, such as phenol sulfonic acid condensed with formaldehyde or para-formaldehyde or polystyrene sulfonic acids.
  • the acids may be adhered to the web in any convenient manner, preferably by incorporating the acid in an alkali permeable layer, such as a hydrophilic colloid, e.g., gelatin, polyvinyl alcohol and other colloids of the type referred to in column 13 of US Patent 3,039,873.
  • the processing web of the invention must contain suflicient free acid substituent to exchange hydrogen ion with the salt of a strong acid in the emulsion, and thereby reduce the pH of the emulsion to a level where bleaching of dye takes place.
  • suflicient free acid substituent to exchange hydrogen ion with the salt of a strong acid in the emulsion, and thereby reduce the pH of the emulsion to a level where bleaching of dye takes place.
  • silver halide complexing agents may be included in the acidic processing web, for example, by including the complexing agent with the free acid in an alkali permeable layer.
  • the acidic processing web contains a colloid overcoating which serves as a timing layer.
  • the purpose of this overcoating is to allow development of exposed silver halide to progress to completion prior to the exchange of hydrogen ion with the cation of the acid salt present in the emulsion.
  • Gelatin, polyvinyl alcohol, and polyvinyl alcoholpolyvinyl acetate mixtures are the preferred colloidal timing substances, some examples of which are referred to in column 13 of US. Patent 3,039,873.
  • the timing layer is coated at a concentration of at least 500 mg./ square foot, or about 0.5 mil in thickness.
  • the concentration (or thickness) of the timing layer depends on several variables, such as strength of developer and pH, and thus may be varied considerably.
  • the light-sensitive emulsions employed in the process and elements of this invention may be coated on a wide variety of supports, including film bases such as polyethylene, terephthalate, cellulose acetate butyrate, polycarbonate, polyolefins (e.g., polyethylene and polypropylene) and the like.
  • film bases such as polyethylene, terephthalate, cellulose acetate butyrate, polycarbonate, polyolefins (e.g., polyethylene and polypropylene) and the like.
  • the photographic product obtained may be used, for example, as a transparency.
  • the emulsions may be coated on an opaque support such as paper, polyolefin coated paper such as polyethylene or polypropylene coated paper which may be pigmented, with TiO for example, and electron bombarded to promote emulsion adhesion.
  • a color photographic print may be obtained.
  • the emulsions coated on such supports are exposed to an original, it is necessary to employ a suitable optical system
  • the bleaching of the image dye is conducted in the presence of a suitable catalyst, such as a phenazine, a quinoxaline or an anthraquinone.
  • a suitable catalyst such as a phenazine, a quinoxaline or an anthraquinone.
  • a suitable catalyst such as a phenazine, a quinoxaline or an anthraquinone.
  • the catalyst may be incorporated in the emulsion, the alkaline processing material, the acidic processing web, or in more than one, or all of these elements. These compounds oxidize the metallic silver to silver ion, and in so doing are reduced. The reduced catalyst then cross-oxidizes with the image dye. This cross-oxidation decolorizes (i.e., bleaches) the image dye and oxidizes the catalyst back to its original state.
  • silver bleaching agents Compounds which are useful in oxidizing excess metallic silver to silver ion and which do not interact in their reduced form with the bleachable image dyes are known as silver bleaching agents; typical examples of which are oand m-nitrobenzene sulfonic acids, ditfusible azo dyes, etc.
  • Other typical silver bleaching agents are disclosed in British Patent No. 533,190. These agents may be incorporated in the emulsion, the alkaline processing material, the acidic processing web, or in more than one, or in all, of these elements.
  • the coating was then squeegeed in contact with the dye acid sheet No. 1 (structure below) for 45 seconds, the sheets were separated and a positive dye image remained on the coating. All of the silver had been removed.
  • the dye acid sheet used above is composed of a cellulose acetate film having a single layer coating thereon of the following composition:
  • EXAMPLE II A coating similar to the coating described in Example I above was prepared, except that 3,6-bis(2-hydroxyethyl)- 2,3,4,5,6,7-hexahydro-1,8-dioxy-3-diazophenanthrene was used as the incorporated black-and-white developer.
  • This coating had the following structure:
  • This coating was then soaked for 3 minutes in a solution of 50 g. of the developer, 4- ⁇ oz-[N,N bis(fl hydroxyethyl) amino] methyl ⁇ -2-methylhydroquinone dimethyl sulfate in 1 liter of water, after which time the coating was air dried.
  • the coating was then exposed through a 0.3 neutral density step tablet for 3 seconds at 18" with a No. 212 Photoenlarger Lamp and a 2B filter.
  • the exposed coating was then processed by immersion in Activator C (see below) for 40 seconds, and then squeegeed in contact with the acid sheet No. 1 of Example I for 2 minutes. A positive dye image was obtained in the matrix and the silver was removed.
  • Example III was repeated using acid sheet No. 2 having a structure as described below, in place of the acid sheet used in Example III. The results were similar to those obtained in Example III above.
  • the acid sheet No. 2 used above is composed of cellulose acetate film base having a single layer coating thereon of the following composition:
  • This coating was exposed through a .3 neutral density step tablet for 3 seconds at 18" with a No. 212 Photoenlarger Lamp and processed as follows: The exposed coating was squeegeed in-contact for 2 minutes with the acid sheet No. 1 described in Example I, with a .004" spacer, using the following viscous activator solution:
  • a positive dye image was obtained in the coating simultaneously with the removal of the silver.
  • Example V was repeated but using an acid sheet containing a timing layer (i.e., a layer which increases the diffusion time allowing development to become completed before the pH is shifted to an acid condition).
  • This acid sheet was prepared by overcoating the acid sheet of Example I with a timing compositioncontaining 570 mg./ft. of polyvinyl alcohol and 570 mg./ft. of polyvinyl acetate.
  • Example V In the developer solution the rnethylaminoethanolsulfite complex of Example V was omitted and'the NaCl was replaced with 100 g. of NaNO A positive dye image of good quality was obtained. All of the silver was removed. The results appeared substantially identical with those of Example V.
  • Example VII The silver halide coating described in Example I was exposed as in Example I and processed by squeegeeing the coating into .contact 'with fan acid sheet No. 3 (structure below) usingviscous activator E, 0.006"thick between the element and the sheet.
  • pH as mixed was 13.0.
  • a sample of the above multilayer film was used to record a picture ,using a camera of the type described in US. Patent 2,543,160, and using an exposure index of ASA 5.
  • the exposed film was then developed by squeegeeing it into contact with an acid sheet No. 3 (of Example VII) at 75 F. for 1.5 minutes using Activator F, with a .008" spacer. After activation, the film was separated from the web, the viscous activator was squeegeed from the surface of the film which contained a good quality 3-color positive dye image of the subject. All of the silver was removed simultaneously with the formation of the dye image.
  • Example VII A sample of this film was used to record a picture as described in Example VII.
  • the exposed film was then developed by squeegeeing it into contact with acid sheet No. 3 of Example VII at 75 F. for 1.5 minutes using an activator similar to Activator F of Example VIII with a .008" spacer (except that the strong acid salt, potassium chloride, was not used).
  • the film was separated from the web.
  • the viscous activator and removable overcoat were squeegeed from the surface of the film which contained a good quality three-color image of the subject. All of the silver was removed simultaneously with the formation of the dye image.
  • This system is not limited to aqueous solutions but is readily adopted to the use of webs coated with succinamide or polyethylene oxide containing the alkali and, optionally, other processing agents.
  • the web may be placed against the exposed photographic element and heated to develop a metallic silver image, thus two webs can be used to proces the photographic dye-bleach element by contacting the element first with a web containing the alkali, and then with a web containing free acid and silver halide complexing agent.
  • heat is applied to the first processing web to facilitate development.
  • the salt of an acid employed is selected from the group consisting of the ammonium, substituted ammonium, alkali metal and the alkaline earth chloride, bromides, nitrates, sulfates, sulfonates, phosphates and phosphonates
  • the processing web comprises a support having coated thereon an alkali-permeable layer containing a free acid selected '1 1 from the group consisting of a strongly acidic polymer, ballasted sulfonic acid and a ballasted phosphonic acid.
  • the method of producing dye images in a photographic element comprising a support having coated thereon a gelatin silver halide emulsion containing a developed silver image, a non-diffusible bleached dye and potassium chloride which comprises contacting said element with an acidic processing web comprising a support having coated thereon alpha-sulfostearic acid in polyvinyl alcohol, said potassium chloride and said alpha-sulfostearic acid, respectively, being present in said emulsion and said processing web in concentrations sufiicient to lower the pH of said layer to about 1.0 when said processing web is pressed against said emulsion, thereby causing exchange of the hydrogen ion of said alpha-sulfostearic acid with the cation of said potassium chloride, and bleaching said dye imagewise in the presence of a silver complexing agent at a pH of about 1.0 in the areas of said metallic silver, said bleaching being catalyzed with 2-hydroxy-3-aminophenazine.
  • the salt employed is the salt of an acid having an ionization constant greater than l 8.
  • the salt of an acid employed is selected from the group consisting of the ammonium, substituted ammonium, alkali metal and the alkaline earth chlorides, bromides, nitrates, sulfates, sulfonates, phosphates, and phosphonates, and the processing web comprises a support having coated thereon an alkalipermeable layer containing a free acid selected from the group consisting of a strongly acidic polymer, a ballasted sulfonic acid and a ballasted phosphonic acid.
  • Part 1 comprising a support having thereon an alkalipermeable layer containing light sensitive silver halide, said layer having in association therewith a bleachable dye;
  • Part 2 comprising a pressure rupturable pod containing an alkaline processing solution which, when contacted with said layer of Part 1, raises the pH thereof to a level at which silver halide is developed imagewise to metallic silver when a silver halide developer is present;
  • Part 3 comprising a web having free acid substituents
  • Parts 1 and 3 during processing being in superimposed relation with said layer facing said web, and Part 2 being positioned between Parts 1 and 3;
  • At least one of said Parts 1 and 2 containing a silver halide developer
  • At least one of said Parts 1 and 2 containing a sufficient quantity of the salt of an acid which, when converted to its free acid form, lowers the pH of said layer of Part 1 to a level at which the dye is bleached imagewise in the presence of a silver complexing agent in areas where metallic silver is present, said free acid substituents in said web being capable of converting at least a sufficient amount of said salt of an acid to its free acid form whereby the pH of said layer of Part 1 is reduced to a level at which said dye of Part 1 is bleached imagewise in the areas of the metallic silver image, at least one of Parts 2 and 3 containing a silver complexing agent, and at least one of Parts 1, 2 and 3 containing a dye bleach catalyst.
  • the photographic element of claim 10, wherein the salt employed is the salt of an acid having an ionization constant greater than l0- 12.
  • the photographic element of claim 10, wherein the salt of an acid employed is selected from the group consisting of the ammonium, substituted ammonium, alkali metal and the alkaline earth chlorides, bromides, nitrates, sulfates, sulfonates, phosphates and phosphonates, and the processing web comprises a support having coated thereon an alkali-permeable layer containing a free acid selected from the group consisting of a strongly acidic polymer, a ballasted sulfonic acid and a ballasted phosphonic acid.
  • the salt employed is the salt of an acid having an ionization constant greater than 10- 16.
  • the salt of an acid employed is selected from the group consisting of the ammonium, substituted ammonium, alkali metal and the alkaline earth chlorides, bromides, nitrates, sulfates,
  • the processing web comprises a support having coated thereon an alkali-permeable layer containing a free acid selected from the group consisting of a strongly acidic polymer, a ballasted sulfonic acid and a ballasted phosphonic acid.

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  • General Physics & Mathematics (AREA)
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US512907A 1965-12-10 1965-12-10 Dye bleach process Expired - Lifetime US3414411A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
US512907A US3414411A (en) 1965-12-10 1965-12-10 Dye bleach process
BE690848D BE690848A (fr) 1965-12-10 1966-12-07
DE19661547759 DE1547759B1 (de) 1965-12-10 1966-12-09 Silberfarbbleichverfahren
CH1757566A CH465401A (fr) 1965-12-10 1966-12-09 Procédé de photographie en couleur
FR86801A FR1504238A (fr) 1965-12-10 1966-12-09 Nouveaux produits photographiques utilisables dans le procédé par décoloration
GB55637/66A GB1173017A (en) 1965-12-10 1966-12-12 Photographic Materials and their use for Silver-Dye-Bleach Systems

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US512907A US3414411A (en) 1965-12-10 1965-12-10 Dye bleach process

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US3414411A true US3414411A (en) 1968-12-03

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BE (1) BE690848A (fr)
CH (1) CH465401A (fr)
DE (1) DE1547759B1 (fr)
FR (1) FR1504238A (fr)
GB (1) GB1173017A (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3642478A (en) * 1970-02-25 1972-02-15 Eastman Kodak Co Processes and compositions for converting zero valent metals photographic images to formazan dye images
US4125402A (en) * 1976-08-19 1978-11-14 Ciba-Geigy Ag Method of processing silver dye bleaching materials and preparations suitable for the dye and silver bleaching
US4168169A (en) * 1976-03-01 1979-09-18 Eastman Kodak Company Dry heat-activated bleaching of silver images
US4168170A (en) * 1976-03-01 1979-09-18 Eastman Kodak Company Dry heat-activated bleaching of silver images
US4235957A (en) * 1979-01-25 1980-11-25 Eastman Kodak Company Thermal silver-dye bleach element and process
US4256826A (en) * 1978-08-14 1981-03-17 Eastman Kodak Company Bleach-fix sheets
US4304847A (en) * 1978-11-13 1981-12-08 Fuji Photo Film Co., Ltd. Color image forming dye bleach process
US4480025A (en) * 1983-01-13 1984-10-30 Eastman Kodak Company Water reservoir layers in bleach-fix sheets
EP1164424A2 (fr) * 2000-06-13 2001-12-19 Eastman Kodak Company Elément photographique contenant un composé photographiquement utile à échange d'ion

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2472211B2 (fr) * 1978-08-14 1985-09-06 Eastman Kodak Co Produit photographique formateur d'image en couleurs qui comprend une feuille de blanchiment-fixage et procede de formation d'images en couleurs qui utilise une telle feuille de traitement
CH657710A5 (de) * 1983-07-20 1986-09-15 Ciba Geigy Ag Verfahren zur verarbeitung photographischer silberfarbbleichmaterialien.

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Publication number Priority date Publication date Assignee Title
BE514019A (fr) * 1952-01-08
NL297895A (fr) * 1962-09-14

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3642478A (en) * 1970-02-25 1972-02-15 Eastman Kodak Co Processes and compositions for converting zero valent metals photographic images to formazan dye images
US4168169A (en) * 1976-03-01 1979-09-18 Eastman Kodak Company Dry heat-activated bleaching of silver images
US4168170A (en) * 1976-03-01 1979-09-18 Eastman Kodak Company Dry heat-activated bleaching of silver images
US4125402A (en) * 1976-08-19 1978-11-14 Ciba-Geigy Ag Method of processing silver dye bleaching materials and preparations suitable for the dye and silver bleaching
US4256826A (en) * 1978-08-14 1981-03-17 Eastman Kodak Company Bleach-fix sheets
US4304847A (en) * 1978-11-13 1981-12-08 Fuji Photo Film Co., Ltd. Color image forming dye bleach process
US4235957A (en) * 1979-01-25 1980-11-25 Eastman Kodak Company Thermal silver-dye bleach element and process
US4480025A (en) * 1983-01-13 1984-10-30 Eastman Kodak Company Water reservoir layers in bleach-fix sheets
EP1164424A2 (fr) * 2000-06-13 2001-12-19 Eastman Kodak Company Elément photographique contenant un composé photographiquement utile à échange d'ion
EP1164424A3 (fr) * 2000-06-13 2002-08-07 Eastman Kodak Company Elément photographique contenant un composé photographiquement utile à échange d'ion

Also Published As

Publication number Publication date
BE690848A (fr) 1967-05-16
GB1173017A (en) 1969-12-03
FR1504238A (fr) 1967-12-01
DE1547759B1 (de) 1971-08-26
CH465401A (fr) 1968-11-15

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