US3617272A - Multicolor dye developer systems - Google Patents

Multicolor dye developer systems Download PDF

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US3617272A
US3617272A US797283A US3617272DA US3617272A US 3617272 A US3617272 A US 3617272A US 797283 A US797283 A US 797283A US 3617272D A US3617272D A US 3617272DA US 3617272 A US3617272 A US 3617272A
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dye
silver halide
stratum
forming units
permeable
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Paul H Stewart
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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
    • G03C8/08—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of organic compounds
    • G03C8/10—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of organic compounds of dyes or their precursors
    • G03C8/12—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of organic compounds of dyes or their precursors characterised by the releasing mechanism
    • G03C8/14—Oxidation of the chromogenic substances
    • G03C8/16—Oxidation of the chromogenic substances initially diffusible in alkaline environment

Definitions

  • the present invention relates to the art of photography, and more particularly, to multicolor dye diffusion transfer systems utilizing dye developers.
  • Photographic elements containing such dye developers generally comprise a plurality of photosensitive silver halide emulsions wherein each of the emulsions is selectively sensitized to a different region of the spectrum.
  • a dye developer is positioned contiguous to the silver halide in each of such emulsions, the dye developer more generally beingsubstantially complimentary in color to the color of light recorded in the contiguous silver halide.
  • Such a photoelement is processed with an alkaline composition.
  • the latent image is developed in the negative image areas with the dye developers, this development immobilizing the dye developers in such negative image areas.
  • the dye developers in the unexposed areas diffuse to the surface imagewise and are transferred to a reception layer or receiving sheet to form a positive multicolor image.
  • Such color diffusion transfer processes are disclosed in U.S. Pats. Nos. 2,983,606, 3,253,915, British Pat. 804,971, and French Pat. 1,313,767, as well as elsewhere in the literature.
  • each dye developer should develop only contiguous silver halide, to wit, the cyan dye developer should develop only the red-sensitive silver halide emulsion layer, the magenta dye developer should develop only the green-sensitive silver halide emulsion layer, and the yellow dye developer should develop only the blue-sensitive silver-halide emulsion layer in a conventional three-color system.
  • each dye'developer has been found to develop to an undesirable extent each silver halide emulsion layer. The result of this effect is to produce color contaminationand'desaturation of colors in the transfer printspred in particular being a color of relatively poor quality.
  • Conventional interlayers or barrier layers between each of the color-formingunits of such materials as gelatin have been utilized, such layers, however,'only beingeffective to a limited degree-in improving the interimage characteristics in multicolor dye developer diffusion transfer systems.
  • photographic elements comprising a support having coated thereon (l at least two dye image-forming units composed of a light-sensitive silver halide emulsion and a dye developer contiguous to silver halide of the emulsion, and (2) an alkali-permeable and water-insoluble stratum or barrier, layer of a polyvalent metal salt of a film-forming, alkali- -permeable, water-soluble polymeric carboxylic acid positioned between at least two of the dye image-forming units, such stratum being less permeable to dye developers in aqueous alkaline solution than the polymeric carboxylic acid used to prepare the salt stratum.
  • Such photographic elements are described in Becker U.S. Pat. No. 3,384,483, issued Mar. 25, 1 968.
  • processing of such photographic elements is carried out in the presence of a material that is chelating or sequestering agent for the polyvalentmetal moiety of the salt stratum, the chelating function of said material being destroyed imagewisein just exposed areas as a function of development.
  • the material thus increases permeability of the barrier layer in just the unexposed areas.
  • the chelating materials employed in this invention can be initiallyprese'nt int'he llght sensitive photographic element, in the processing composition or in the dye developer image receiving element.
  • the catechol is an auxiliary developer, as shown in my copending U.S. Pat. application Ser. No. 676,603, filed Oct. 19, 1967, and now abandoned. This invention results in color'prints havinghighcolor saturation and low colorcontamination.
  • catechol can be used in the practice of this invention which chelates the polyvalentmetal moiety of the salt stratum barrier layer and which is a silver halide developing agent.
  • the catechols are preferably colorless and soluble in the alkaline processing solution.
  • catechol is used generically herein to include l,2-dihydroxybenzencs, which can contain additional hydroxyl groups, such as a 1,2,3-trihydroxybenzene, a 1,2,4-trihydroxybenzene or a 1,2,3,4,Stetrahydroxybenzene.
  • Suitable catechols include those having thestructural formula:
  • R R R and R can be hydrogen, an alkyl radical, preferably of about I to 8 carbon atoms (e.g., methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, etc.,), an aryl radical (e.g., phenyl, tolyl, naphthyl, etc.), hydroxyl, aryloxy such as phenoxy, halogen such as chlorine or bromine, carboxy or R and R or R and R when taken together with the carbon atoms to which they are attached, represent the atoms to complete a eycloalkyl group containing from 4 to 6 carbon atoms (e.g., eyclohexyl, cyelopentyl, etc.) which can contain an endomethylene group (e.g., methanocyclohexyl, methanocyclopentyl, etc.). Salts and esters of these
  • a preferred class of catechols having the aforesaid structural formula are those in which R,, R R and R, are either hydrogen or an alkyl radical of from 1 to 8 carbon atoms.
  • Suitable catechols include:
  • the amount of chelating material utilized in the invention can be widely varied, the amount varying with such variables as the number and type of barrier layers of polyvalent metalpoly earboxylic acid salt in the photographic element, the amount of polyvalent ion present in the system, the particular chelating material, the processing time, the particular positioning of the material in the system, the use of
  • chelating material should be used to increase permeability in just unexposed areas.
  • typical useful concentration ranges are about I to I50 mg. of cateehol per square foot when utilized in the light-sensitive element, about 50 to 200 mg. of cateehol per square foot when utilized in the dye developer image receiving sheet or layer, and about 0.1 to percent by weight of the alkaline processing composition when utilized therein. Good results are obtained when a cateehol is the only chelating or sequestering agent present during processing.
  • the chelating material can be coated in combination with other constituents in the present photographic elements and image receiving sheets, or it can be coated in separate layers.
  • the chelating material can be coated in an organic hydrophilic colloid as an aqueous coating melt.
  • the chelating material can be dissolved in a high-boiling (e.g., greater than l75 C.) solvent and dispersed in finely divided droplets in a hydrophilic colloid and the resulting dispersion coated.
  • the salt strata or barrier layers utilized in the subject dye developer diffusion transfer system can be prepared with a variety of polyvalent metal salts and polymeric carboxylic acids.
  • the subject salt strata can be formed on the element by coating a solution, on a water-permeable substrate, containing the polyvalent metal in water-soluble form on a polymeric carboxylic acid layer previously coated on the element to form a thin layer of a water-insoluble salt.
  • the polyvalent metal in water-soluble form can be coated directly on silver halide emulsion layers if the vehicle for the silver halide is a polymeric carboxylic acid that forms a water-insoluble salt with the polyvalent metal moiety.
  • lnterlayers of water-permeable materials can be utilized on either side of the subject water-insoluble salt strata.
  • Such salt strata are preferably utilized between the magenta and cyan dye image-forming units to particularly improve red purity and saturation of the transferred dye developer images.
  • the subject salt strata can be utilized between the yellow and the magenta dye image-forming units as well as between both the magenta and the cyan dye image-forming units to improve color purity and saturation of the transfer dye developer images.
  • a wide variety of film-forming, alkali-permeable, watersoluble polymeric compositions containing free carboxylic acid groups, and including water-soluble salts thereof, can be utilized to form the subject salt strata with polyvalent metal moieties.
  • such polymers typically contain about 5 percent to 60 percent by weight of polymer of free carboxylic acid groups (i.e., available for reaction with the subject polyvalent metal moieties in aqueous alkaline solutions) or the equivalent weight of water-soluble salts thereof.
  • suitable acid polymers include:
  • carboxylic acid group-containing polysaccharides and derivatives thereof such as alginic acid, pectic acid, tragacanthic acid, carboxymethyl cellulose, and the like, and
  • succinoylatcd polyvinyl alcohol include succinoylatcd polyvinyl alcohol, maleic acid-styrene polymers, alkylacrylate-acrylic acid polymers, formaldehydesalicylic acid polymers, acidic polyesters, acid polyamides and the like.
  • Polyvalent metal moieties are utilized to form the present salts as such moieties can be used to cross-link carboxylic acid moieties of the polymeric carboxylic acid to form the present strata which have the proper degree of alkali permeability and water-insolubility to serve as barrier layers to prevent color contamination and interdevelopment between dye imageforming units.
  • a wide variety of polyvalent metal moieties can be utilized in preparing the subject salt strata. Suitable polyvalent metals with which suitable salt strata of the invention can be prepared include alkaline earth metals, such as calcium, barium and strontium, and the like polyvalent metals that form alkali-permeable, water-insoluble salts with the above-described polymeric materials containing carboxylic acid groups.
  • the amount of polymeric salt utilized in the subject salt strata can be widely varied, the amount varying with the effect desired and the nature of the polyvalent metal and the polymeric carboxylic acid. More generally, the amount or coverage of the polyvalent metalpolymeric carboxylic acid salt stratum utilized is that which is substantially equivalent in permeability to dye developers in aqueous alkaline solution to the calcium alginate formed when a stratum consisting essentially of sodium alginate is reacted with calcium chloride coated thereover at a coverage of about 5 to mg. per square foot.
  • Typical alkali-permeable water-insoluble salts comprising the barrier layers of the light-sensitive photographic elements used in the invention include:
  • Dye developers are well known in the photographic art. Such compounds function both as a silver halide developing agent and as a dye in photographic difiusion transfer system's.
  • Dye developers are characterized as being relatively nondiffusible in colloid layers such as the hydrophilic organic colloids used in photographic emulsions at neutral pH, but diffusible in the photographic elements in the presence of alkali ne processingsolutions.
  • dye developers are substantially insoluble in water, which property usually necessitates the use of organic solvents to incorporate the dye developers into the organic colloid layers of the photoelements.
  • the dye developers are particularly characterized as containing both a chromophoric ordye moiety and at least one moiety having a silver halide developing agent function.
  • Particularly useful dye developers are those wherein the chromophoric moiety is an azo or anthraquinone d'ye moiety and the silver halide developing moiety is a benzenoid moiety such as a hydroquinonyl moiety.
  • M is an aromatic or heterocyclic ring or ring system such as a benzene, napthalate, tetralin, anthracene, anthraquinone, pyrazole, quinoline, ,etc., ring which can be substittuted with such groups as hydroxyl, amine, keto, nitro, alk
  • D represents a silver halide developing agent moiety imparting the developing agent function to the dye developer such as a hydroquinonyl group which can be substituted with amino, alkylamino, alkyl, hydroxyl, alkoxyl or halogen groups.
  • Typical useful dye developers are described in columns 9l3,of US. Pat, No 3,146,102, as well as elsewhere in the patent literature, including: Australian 220,279; German 1,036,640; British 804,971 and 804,973-; Belgian 554,935; French 1,168,292; and Canadian 557,021 and 579,038.
  • the dye developers are preferably incorporated in hydrophilic organic colloidal vehicles or carriers comprising the layers of the photographic element dissolved in high-boiling or crystalloidal solvents and dispersed in finely divided droplets.
  • high-boiling or substantially water-immiscible organic liquids having boiling points above about 175 C. are utilized.
  • the high-boiling solvent can be used alone in dissolving the dye developer and in forming the dispersion or it can be mixed with a low-boiling organic solvent e.g., boiling at least 25 C. below the boiling point of the higher boiling solvent), or a water-soluble organic solvent, as an auxiliary solvent to facilitate solution of the dye developer.
  • a preferred range of proportions of high-boiling solvent to auxiliary is 1/0 to l/ 10 on a weight basis.
  • auxiliary solvents can be readily removed from the high-boiling solvent, for example, by air-drying a chilled, noodled dispersion or by continuous water washing.
  • highboiling solvents and auxiliary solvents utilized for incorporating dye developers are described in French Pat. No. 1,313,765.
  • the dye developers can also be incorporated into vehicles soluble in organic solvents which are also solvents for the dye developer. Likewise, other incorporating techniques for the dye developer such as ball-milling can be utilized.
  • the photographic elements of the. invention desirably contain auxiliary developing agents, in addition to catechols, such as colorless substantially water-insoluble hydroquinone derivatives, e.g., those disclosed in French Pat. No. 1,313,086.
  • Such auxiliary developing agents can be incorporated in the silver halide emulsion layers, in overcoat layers, in inter-layers or in other layers of the element.
  • the silver halide emulsions utilized in preparing the photographic elements of the invention are more generally the conventional negative-type developing-out emulsions, positive transfer images resulting from such emulsions.
  • the silver halide emulsions utilized in preparing the photographic elements of the invention are more generally the conventional negative-type developing-out emulsions, positive transfer images resulting from such emulsions.
  • reversal emulsions such as solarized emulsions and emulsions that form latent images predominantly internal to the silver halide grains as described in US. Pat. No. 2,592,250, can also be used, negative transfer images resulting from such emulsions.
  • Typical suitable silver halides include silver chloride, silver bromide, silver bromoiodide, silver chloroiodide, silver chlorobromoiodide, etc.
  • Useful'sensitizers are those in Kennard Ser. No. 337,792, filed Jan. 15, 1964. Mixtures of more than one of such silver halides can also be utilized.
  • hydrophilic organic colloids can be utilized as the vehicle or carrier.
  • gelatin as the hydrophilic colloid or carrier material although such material as polyvinyl alcohol and its water-soluble derivatives and copolymers, water-soluble copolymers such as polyacrylamide, imidizedpolyacrylamide, etc., or polymerized vinyl compounds such as those disclosed in US. Pat. Nos. 3,142,568, 3,193,386, 3,062,674 and 3,220,844, and including the water-insoluble polymers of alkyl acrylates and methacrylates, acrylic acid, sulfoalkyl acrylates or methacrylates and the like.
  • the dye developers are disposed integral with the element and contiguous to silver halide of each of the light-sensitive silver halide emulsion layers. Such dye developers can be incorporated directly in the light-sensitive silver halide emulsion layers or in separate layers contiguous to the layers containing the silver halide.
  • the present photographic elements contain at least two dye image-forming units, each unit comprising a light-sensitive silver halide emulsion and a dye developer contiguous to silver halide in the unit. Each dye image-forming unit is preferably spectrally sensitized to record light that is substantially-complementary to the color of the dye developer in the unit.
  • Typical supports include cellulose nitrate film, cellulose acetate film, polyvinyl acetal film, polystyrene film, polyethylene terephthalate film, polyethylene film, polypropylene film, paper, polyethylenecoated paper, glass;
  • a wide variety of receiving sheets can be utilized to receive the dye developer images from the present light-sensitive photographic elements.
  • the sequestering agents used in the invention can be positioned in any of the layers of the receiving sheet.
  • Typical reception layers for dye developer receiving sheets which are, or include, mordants for dye developers, are such material as linear polyamides, proteins such as gelatin, polyvinyl pyrrolidones, poly-4-vinyl pyridine, polyvinyl alcohol, polyvinyl salicylal, partially hydrolyzed polyvinyl acetate, methyl cellulose, regenerated cellulose, carboxymethyl cellulose and hydroxyethyl cellulose, or mixtures of such.
  • reception layers can be coated on a suitable support of the type described above for the light-sensitive elements of the invention and including transparent as well as opaque supports.
  • receiving sheets that release acidic material such as that derived from an acidic polymer or other acidic compound at a controlled rate are as described in US. Pat. No. 2,584,030 are particularly useful.
  • acidic materials are typically positioned in layers on the receiving sheet below the dye developer reception layer, there suitably being a spacer layer between the acid layer and the mordanting layer to control the release of acidic material.
  • Such acidic materials serve to neutralize residual portions of the alkaline activator on the receiving sheet.
  • nondiffusible cationic or basic dye-mordanting compounds can be used in liquid permeable reception layers including amines such as polymeric amines, quaternary ammonium compounds, quaternary phosphonium compounds and tertiary sulfonium compounds.
  • amines such as polymeric amines, quaternary ammonium compounds, quaternary phosphonium compounds and tertiary sulfonium compounds.
  • Such mordants are nondiffusible in the alkaline processing composition and contain at least one hydrophobic ballast group.
  • the receiving sheet can be prepared by superficially hardening with a nondifiusing hardener and a surfactant.
  • a dye developer image receiving layer on a receiving sheet containing poly-4- vinyl pyridine mordant in polyvinyl alcohol can be efficaciously treated with an oxyguar gum hardener solution containing a surfactant such as soidum cetyl sulfate or sodium N- methyl-N-oleoyl taurate.
  • integral reception layers for dye developer images can also be utilized.
  • Such integral reception layers can be coated beneath the emulsion and dye developer layers near the support.
  • a stripping layer coated over the integral reception layer can be used to facilitate the removal of the overcoated layers after the diffusion of the dye developer images to the reception layer.
  • the processing compositions or activators used to initiate development of the exposed light-sensitive elements of the invention are strongly alkaline.
  • Such processing compositions generally have a pH of at least about 12 or contain a least 0.01 N hydroxyl ion.
  • Alkali metal hydroxides such as sodium hydroxide, and potassium hydroxide, are advantageously used in the composition for imparting such high alkalinity.
  • volatile amines such as diethyl amine can also be used, such amines having the advantage of being volatilized from the prints to leave no residue of alkali.
  • Such processing compositions are generally aqueous liquids or solutions, and when utilized in rupturable pods for in-camera processing, generally contain thickening agents such as hydroxyethyl cellulose, particularly as described in U.S. Pat. No. 3,266,894, or carboxymethyl cellulose.
  • thickening agents such as hydroxyethyl cellulose, particularly as described in U.S. Pat. No. 3,266,894, or carboxymethyl cellulose.
  • Onium compounds such as are disclosed in U.S. Pat. No. 3,146,102 are preferably utilized in the alkaline processing composition.
  • the described sequestering agents can also be utilized in the alkaline processing compositions used in the processes of the invention.
  • Camera apparatus of the type useful for exposing and processing the sensitive elements of the invention have been described, for example, in U.S. Pat. No. 2,435,717.
  • the processing of the subject photographic elements can also be effected outside of camera apparatus by imbibing either the receiving element or the negative element or both in the alkaline processing composition, and thereafter sandwiching together the two elements to allow the dye developer images to diffuse to the receiving element.
  • the positioning of the dye image-forming units of the photographic elements of the invention can be varied. ln three-color systems, it is preferred to utilize the cyan dye image-forming unit most proximate to the support, the yellow dye-forming unit furthest from the support, the yellow dye image-fonning units. lt is also preferred to utilize the dye developers in the respective dye image-forming units in a separate underlying layer contiguous to the silver halide emulsion layer. Likewise, it is preferred to utilize in each dye image-forming unit a dye developer that is substantially complementary in color to the color of light recorded by the silver halide in the unit.
  • Cyan Dye Developer Layer A coating of the cyan dye developer, 5,8-dihydroxy-l ,4-bis[ B-hydroquinonyl-a-methyl)ethylaminoI-anthraquinone, dissolved in N-n-butylacetanilide, dispersed in gelatin and coated on the support.
  • Red-sensitive Emulsion Layer A coating of a developing-out negative gelatino-silver bromoiodide emulsion sensitized to red light coated at a coverage of about 180 mg. of silver per square foot.
  • Sodium Alginate Layer A coating of sodium alginate at a coverage of about 30 mg. per square foot is applied over the gelatin layer.
  • magenta Dye Developer Layer A coating of the magenta dye developer, 4-isopropoxy-2-l p- (B-hydroquinonylethyl)-phenylazo]-1-naphthol, dissolved in N-n-butylacetanilide, dispersed in gelatin and containing about 2 mg. 4'-methylphenyl-hydroquinone and about 15 mg. of calcium chloride per square foot is coated over layer 4. the calcium chloride reacts with the sodium alginate in layer 4 to form a calcium alginate salt barrier layer between the two layers.
  • Green-Sensitive Emulsion Layer A coating of a developing-out negative geIatino-silver bromoiodide emulsion sensitized to green light is then coated at a coverage of about 1 10 mg. of silver per square foot.
  • lnterlayer A gelatin layer is coated containing about 5 mg. per square foot 4-methylphenylhydro quinone.
  • Sodium alginate is coated at about 15 mg. per square foot.
  • Yellow Dye Developer Layer A coating of the yellow dye developer, l-phenyI-S-N-n-hexylcarboxamide-4-[p-(2, 5'-dihydroxyphenethyl)-phenylazo]- S-pyrazolone, dissolved in ditetrahydrofurfuryl adipate, dispersed in gelatin and containing about 2 mg. of 4'- methylphcnylhdeydroquinone and about 10 mg. of calcium chloride per square foot. The calcium chloride reacts with the sodium alginate in the adjacent layer to form a calcium alginate salt barrier between the two layers.
  • Blue-Sensitive Emulsion Layer A developing-out negative gelatino-silver bromoiodide emulsion that is inherently sensitive to blue light is coated at a coverage of about 70 mg. of silver per square foot, the emulsion also containing about 25 mg. 4'-methylphenyl-hydroquinone per square foot.
  • the photographic element described above is the control.
  • Another element, element 2 is prepared exactly the same as element 1, the control, except, except that element 2 also contains 20 mg. per square foot 4-phenylcatechol in layer no. 3.
  • Another element, element 3, is exactly the same as element 1, the control, except that element 3 also contains 30 mg. per square foot 4-phenylcatechol in layer no. 7.
  • the photographic elements obtained are each exposed through a 0.3 density increment color step wedge in an intensity scale sensitometer one-fiftieth inches to a 500 watt positive lamp using a blue colored filter that absorbs some red light to convert the tungsten exposure to daylight color balance, and processed with a processing solution disposed in a processing pod and having a composition like that described by Land in example 7 of U.S. Pat. No.
  • the exposed film is processed at a gap of 0.004 inch (corresponding to the thickness of the activator layer) for a period of 60 seconds in contact with a color receiving sheet.
  • the receiving sheet is a cellulose acetate butyrate subbed paper support carrying in the following order:
  • magenta drop-off is a measure of the amount of density of the magenta dye developer image resulting from the magenta developer developing in the red-sensitive emulsion layer. It is determined by substracting the magenta density in the red scale from the magenta Dmax. The magenta density in the red scale is measured at a point 0.8 log E greater exposure than the log E value of a 0.6 density in the neutral scale. Yellow drop-off is a measure of the-amount of desaturation of the.
  • yellow dye developer image resulting from the yellow dye developer developing in'the green sensitive emulsion layer It is determined by subtracting the yellow density in the green scale from yellow Dmax. Yellow density in the green scale is measured at a point 0.8 log E slower than the log E value of a 0.6 density in the neutral scale. Table A shows the increased cyan dye developer image saturation, without undesirable increases in magenta and yellow drop off, due to the use of a catechol in accordance with the invention.
  • a photographic element, element 4 is prepared exactly the same as element 1 of example 1, with the following exceptions:
  • Layer 7 contains 140 mg. of gelatin and mg. of 4'- methylphenylhydroquinone per square foot;
  • Layer 8 (sodium alginate) is omitted
  • Layer 9 contains no calcium chloride or 4'-methylphenylhydroquinone
  • Layer 10 contains 12 mg. of 4-methylphenylhydroquinone.
  • Element 4 is a control.
  • Element 5 is prepared in the same manner except that layer 1 also contains mg. of 4-phenylcatechol per square foot. The elements are exposed and processed exactly the same as in example I. The results are shown in table B.
  • a photographic element comprising a support having coated thereon at least two dye image-forming units with an alkali-permeable, water-insoluble salt ,stratum positioned between at least two of said dye image-forming units, said dye image-forming units comprising a silver halide emulsion layer and a dye developer contiguous to silver halide of said emul sion, and said salt stratum comprising an alkali-permeable, water-insoluble salt of a polyvalent metal and a film-forming, alkali-permeable, water-soluble polymer having free carboxylic acid groups, said salt stratum being less permeable to dye developers comprising said dye image-forming units in aqueous alkaline solution than said water-soluble polymer used to prepare said salt stratum, the improvement which comprises having coated on the salt stratum side of the photographic element a material that is a chelating agent for said polyvalent metal, the chelating function of said material being destroyed imagewise in just exposed area as a function of development.
  • a photographic element comprising a support having coated thereon at least two dye image-forming units with an alkali-permeable, water-insoluble salt stratum positioned between at least two of said dye image-forming units, said dye image-fanning units comprising a silver halide emulsion layer and a dye developer contiguous to silver halide of said emulsion, and said salt stratum comprising an alkali-permeable, water-insoluble salt of an alkaline earth metal and a film-forming, alkali-permeable, water-soluble polymer having free carboxylic acid groups, said salt stratum being less permeable to dye developers comprising said dye image-forming units in aqueous alkaline solution than said water-soluble polymer used to prepare said salt stratum, the improvement which comprises having coated on the salt stratum side of the photographic element a catechol which develops silver halide and is a chelating agent for said polyvalent metal.
  • R R,, R and R are each selected from the group consisting of hydrogen, hydroxyl, halogen, carboxy, aryloxy, alkyl, aryl and, R, and R, and R when taken together with the carbon atoms to which they are attached, represent the atoms to complete a cycloalkyl group.
  • a photographic element as defined by claim 4 wherein the catechol is 4-phenylcatechol.
  • a photographic element comprising superposed on a photographic support three dye image-forming units in layers capable of recording red, green and blue light respectively, the dye image-forming unit recording blue light being furthest from the support and the dye image-fonning unit recording red light being most proximate to the support, and an alkali permeable, waterinsoluble stratum of calcium alginate positioned between each of the said image-forming units, said dye image-forming units comprising a gelatino-silver halide emulsion layer and an underlying contiguous layer containing a dye developer substantially complementary in color to the color of light recorded in the contiguous silver halide emulsion layer, and a catechol which develops silver halide and is a chelating agent for calcium ions being positioned between said support and said stratum of calcium alginate, said catechol being present in an amount sufficient to increase the permeability of said stratum in just the unexposed areas.
  • a photographic element comprising superposed on a photographic support three dye image-forming units in layers capable of recording red, green and blue light respectively, the dye image-fonning unit recording blue light being furthest from the support and the dye image-forming unit recording red light being most proximate to the support, and an alkaliperrneable, water-insoluble stratum of calcium alginate positioned between the said image-forming units recording red and green light, said dye image-forming units comprising a gelatino-silver halide emulsion layer and an underlying contiguous layer containing a dye developer substantially complementary in color to the color of light recorded in the contiguous silver halide emulsion layer, and a catechol which develops silver halide and is a chelating agent for calcium ions being positioned between said support and said stratum of calcium alginate, said catechol being present in an amount sufficient to increase the permeability of said stratum in just the unexposed areas.
  • an imagewise exposed photographic element comprising a support having coated thereon at least two dye image-forming units with an alkali-permeable, waterinsoluble salt stratum positioned between at least two of said dye image-fonning units, said dye image-forming units comprising a silver halide emulsion layer and a dye developer contiguous to silver halide of said emulsion, and said salt stratum comprising an alkali-permeable, water-insoluble salt of a polyvalent metal and a film-forming alkali-permeable, watersoluble polymer having free carboxylic aid groups, said salt stratum being less permeable to dye developers comprising said dye image-forming units in aqueous alkaline solution than said water-soluble polymer used to prepare said salt stratum, which comprises treating the photographic element with an alkaline processing liquid, developing latent images in the regions of exposure of the silver halide emulsion layers and thereby immobilizing dye developers in said regions of exposure, dye developers in undeveloped regions diffusing imagewise in
  • an imagewise exposed photographic element comprising a support having coated thereon at least two dye image-forming units with an alkali-permeable, waterinsoluble salt stratum positioned between at least two of said dye image-forming units, said dye image-forming units comprising a silver halide emulsion layer and a dye developer contiguous to silver halide of said emulsion, and said salt stratum comprising an alkali-permeable, water-insoluble salt of an alkaline earth metal and a film-forming alkali-permeable, watersoluble polymer having free carboxylic acid groups, said salt stratum being less permeable to dye developers comprising said dye image-forming units in aqueous alkaline solution than said water-soluble polymer used to prepare said salt stratum, which comprises treating the photographic element with an alkaline processing liquid, developing latent images in the regions of exposure of the silver halide emulsion layers and thereby immobilizing dye developers in said regions of exposure, dye developers in undeveloped regions diffusing imagewise
  • R R R and R are each selected from the group consisting of hydrogen, hydroxyl, halogen, carboxy, aryloxy, alkyl, aryl and, R and R or R and R when taken together with the carbon atoms to which they are attached, represent the atoms to complete a cycloalkyl group.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
US797283A 1969-02-06 1969-02-06 Multicolor dye developer systems Expired - Lifetime US3617272A (en)

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JP (1) JPS494330B1 (enrdf_load_stackoverflow)
BE (1) BE745489A (enrdf_load_stackoverflow)
CA (1) CA934207A (enrdf_load_stackoverflow)
CH (1) CH526797A (enrdf_load_stackoverflow)
DE (1) DE2005281C3 (enrdf_load_stackoverflow)
FR (1) FR2033882A5 (enrdf_load_stackoverflow)
GB (1) GB1292359A (enrdf_load_stackoverflow)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4365072A (en) * 1981-10-22 1982-12-21 Polaroid Corporation Biphenyl aldehydes
US4417064A (en) * 1981-01-05 1983-11-22 Polaroid Corporation Biphenyl compounds and method of preparing same

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62185647U (enrdf_load_stackoverflow) * 1986-05-19 1987-11-26
GB2299991B (en) * 1995-04-20 1998-09-09 Ag Technology Corp Glass substrate for magnetic disk

Citations (4)

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Publication number Priority date Publication date Assignee Title
US3196015A (en) * 1962-01-31 1965-07-20 Polaroid Corp Diffusion transfer process
US3262781A (en) * 1962-07-05 1966-07-26 Polaroid Corp Photographic products
US3345163A (en) * 1956-02-13 1967-10-03 Polaroid Corp Photographic diffusion transfer color processes
US3477849A (en) * 1964-03-23 1969-11-11 Eastman Kodak Co Multi-color dye developer systems

Patent Citations (4)

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Publication number Priority date Publication date Assignee Title
US3345163A (en) * 1956-02-13 1967-10-03 Polaroid Corp Photographic diffusion transfer color processes
US3196015A (en) * 1962-01-31 1965-07-20 Polaroid Corp Diffusion transfer process
US3262781A (en) * 1962-07-05 1966-07-26 Polaroid Corp Photographic products
US3477849A (en) * 1964-03-23 1969-11-11 Eastman Kodak Co Multi-color dye developer systems

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Martell, A. E. and Calvin, M., Chemistry of the Metal Chelate Compounds, Third Printing (1956); Prentice-Hall, Englewood Cliffs, N. J., Pages 134 138 and 556. *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4417064A (en) * 1981-01-05 1983-11-22 Polaroid Corporation Biphenyl compounds and method of preparing same
US4365072A (en) * 1981-10-22 1982-12-21 Polaroid Corporation Biphenyl aldehydes

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JPS494330B1 (enrdf_load_stackoverflow) 1974-01-31
BE745489A (fr) 1970-07-16
DE2005281A1 (de) 1970-08-27
DE2005281C3 (de) 1974-02-14
GB1292359A (en) 1972-10-11
CH526797A (fr) 1972-08-15
DE2005281B2 (de) 1973-07-19
CA934207A (en) 1973-09-25
FR2033882A5 (enrdf_load_stackoverflow) 1970-12-04

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