US3854945A - Shifted indophenol dye developers - Google Patents

Shifted indophenol dye developers Download PDF

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US3854945A
US3854945A US00227113A US22711372A US3854945A US 3854945 A US3854945 A US 3854945A US 00227113 A US00227113 A US 00227113A US 22711372 A US22711372 A US 22711372A US 3854945 A US3854945 A US 3854945A
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layer
silver halide
dye
photographic
image
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W Bush
D Reardon
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Eastman Kodak Co
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Eastman Kodak Co
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Priority to US00227113A priority patent/US3854945A/en
Priority to FR7243944A priority patent/FR2172088B1/fr
Priority to CA160,779A priority patent/CA996938A/en
Priority to GB751573A priority patent/GB1422061A/en
Priority to DE19732307738 priority patent/DE2307738C3/de
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/44—Oxygen and nitrogen or sulfur and nitrogen atoms
    • C07D231/52—Oxygen atom in position 3 and nitrogen atom in position 5, or vice versa
    • 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
    • G03C8/18—Dye developers

Definitions

  • ABSTRACT Dye developers and processes for making said dye developers are disclosed, along with photographic compositions and photographic elements containing said dye developers wherein the dye developer comprises a silver halide developing moiety connected to an indophenol moiety.
  • the light-absorption characteristics of dye developers comprising the indophenol moiety when incorporated in a photographic element can be shifted to provide for exposure of a photosensitive material without substantial absorption competition and then can be shifted by contact with an onium compound to provide a good image dye.
  • photographic elements are disclosed which contain a photosensitive composition having associated therewith a shifted indophenol dye developer;
  • This invention relates to compositions of matter, processes for preparing compositions of matter, photographic elements containing these compositions of matter and processes for forming photographic image records.
  • this invention relates to shifted dye developers wherein the dye is an indophenol moiety.
  • this invention relates to photographic elements for recording an imagewise exposure, which elements contain shifted indophenol dye developers and to photographic image records containing a dye developer wherein the dye is an onium indophenoxide.
  • this invention relates to improved image transfer film units and processes for forming image records in image transfer film units.
  • the compounds are dye developers wherein the dye is an indophenol, referred to herein as a shifted indophenol dye developer.
  • a positively charged compound which is preferably an onium com-. pound to produce an image dye having very good image characteristics including stability, density and the like.
  • this invention relates to a photographic element comprising a support and at least one layer thereon containing a photosensitive, image-recordng material having associated therewith a dye developer of the general formula:
  • D-(SID) wherein D-is an aromatic group which is a silver halide developer and (SID) is an indophenol dye moiety.
  • this invention relates-to an image transfer film unit comprising a photosensitive element containing a blue-sensitive silver halide emulsion layer having associated therewith a yellow-forming indophenol dye developer, a green-sensitive silver halide emulsion layer having associated therewith a magenta-forming indophenol dye developer, and a redsensitive silver halide emulsion having associated therewith a cyan-forming indophenol dye developer.
  • this invention relates to a photographic film unit comprising:
  • a photosensitive element comprising a support having thereon a layer containing a silver halide composition having associated therewith a dye developer having the formula:
  • D-(SID) wherein D-is a silver halide developing group, either in the oxidized or unoxidized state, (SID) is an indophenol moiety, and M is an onium group.
  • this invention relates to image transfer elements comprising the combination of a shifted indophenol dye developer and an incorporated auxiliary silver halide developer which is a reducing agent.
  • FIG. 1 shows a representative .absorption shift which is obtained with a yellow indophenol based on an open-chain ketomethylene coupler (line Y), a magenta indophenol based on a pyrazolone color coupler (line M), and a cyan indophenol based on a phenolic color coupler (line C), wherein the absorption characteristics of the indophenols as incorporated in the photographic element are shown, respectively, as lines SY, SM and SC and the absorption characteristics after contact with an onium compound are shown as lines Y, M and C. Further details of the absorption shift are described in Bush et al, U.S. Ser. No. 169,706 filed Aug. 6, 1971, now U.S. Pat. No. 3,791,827, which is incorporated herein by reference.
  • FIGS. 2 and 3 show representative absorption characteristics of the dye developers of Examples 2 (Com pound I) and 8 (Compound IV).
  • FIGS. 4-6 a preferred film unit is described which is based on the shifted indophenol dye developers.
  • the shifted dye developers of this invention are generally those which comprise a silver halide developing agent moiety linked to an indophenol dye moiety.
  • the shifted dye developers can be represented by the formula:
  • D-(SID) wherein D-is a moiety of a silver halide developing agent including those having hydrolyzable groups thereon, and preferably is a disubstituted aromatic group such as a naphthalene or, more preferably, a phenylene group wherein the disubstituted groups are hydroxy groups, primary amino groups or alkylamino 2,369,489 by Porter et a1 issued Feb.
  • (SID) is a shifted indophenol dye moiety including, of course, the desired linking groups between the dye moiety and the developing agent moiety, especially where chromophore insulating groups are desired.
  • (SID) can be represented by the formula:
  • (COUP) N-Ar-OH
  • (COUP) is a color-forming coupler including the linking group to D-, suchas phenolic couplers, pyrazolone couplers, pyrazolotriazole couplers, couplers having openchain methylene groups and the like, wherein said coupler is linked to said nitrogen atom through a carbon atom at the coupling position.
  • the shifted dye developer when the above shifted dye developers are utilized in an image transfer film unit, the shifted dye developer is diffusible and will migrate to an image-receiving layer upon contact with an alkaline processing solution unless the developer group is oxidized by reaction with developable silver halide or oxidized with a redox agent; the image-receiving layer preferably has an onium compound associated therewith to provide the onium indophenoxide image dye.
  • couplers contain a coupling position which is generally known to those skilled in the art as being the position on the coupler molecule that reacts or couples with oxidized color developing agents.
  • Typical useful couplers include phenolic couplers, including a-naphthols which couple at the 4-position, open-chain ketomethylene couplers which couple at the carbon atom forming the methylene moiety (e.g.,
  • the group defined as Ar above is preferably the residue of an aromatic color developing agent such as an aminophenol, a phenyle'nediamine and the like and, of course, including the various substituents on the aromatic group which are known in the art for the respective color developing agent.
  • the aromatic compound can contain the substituents as disclosed, for example, in Bush et al, US. Ser. No. 169,706 filed Aug. 6, 1971 now US. Pat. No. 3,791,827, which is incorporated herein by reference.
  • the indophenol moiety preferably contains an insulating linkage connecting it to the developing agent moiety (D-).
  • Insulating linkages of this type sometimes referred to as achromophoric groups or bonds, are known in the art, for example, as disclosed in US. Pat. No. 3,255,001 issued June 7, 1966.
  • the insulating group does not contribute a color-producing group to the indophenol dye chromophore, but acts to prevent or. interrupt any system of conjugation or resonance extending from the azomethine groups of the indophenol moiety to the developing group, i.e., such as a hydroquinone group.
  • the insulating linkage which preferably forms a part of the indophenol moiety as defined herein can be any group which will break up the resonance system, for example, those groups listed in US. Pat. No. 3,255,001 issued June 7, 1966, and the like.
  • azomethine linkage as used herein is understood to mean the grouping:
  • (COUP) N--ArOH
  • (COUP) is a color coupler such as a pyrazolone color coupler, a pyrazolotriazole coupler, an open-chain ketomethylene color coupler, a phenolic color coupler and the like, which is connected to the nitrogen atom in the coupling position of said coupler; and Ar is as defined above.
  • nondiffusing used herein has the meaning commonly applied to the term in color photography and denotes materials which for all practical purposes do not migrate or wander through organic colloid layers, such as gelatin, comprising the sensitive elements of the invention. The same meaning is to be attached to the term immobile.
  • diffusible as applied to the colorproviding materials of this invention has the converse meaning and denotes materials having the property of diffusing effectively through the colloid layers of the sensitive elements in the presence of the nondiffusing materials.
  • Mobile has the same-meaning.
  • the shifted indophenols are reacted with onium salts at appropriate times in photographic processes to pro vide a bathochromic absorption shift, thus forming an onium indophenoxide.
  • the onium indophenoxides can generally be represented by the formula:
  • D-(COUP) N-Ar 'M wherein D-, (SID), (COUP) and Ar are as defined above, and M is an onium group including sulfonium, phosphonium and, preferably, quaternary ammonium groups.
  • the developer group can be in the oxidized or unoxidized state.
  • the onium salts used to form the onium indophenoxides are generally quaternary ammonium salts, quaternary phosphonium salts, tertiary sulfonium salts and the like, and are generally used in concentrations necessary to form an onium indophenoxide with all of the indophenol present in the photographic element.
  • the onium compound is immobile or ballasted and present in an image layer, it is generally utilized in concentrations of about 25 mg. to about 1,000 mg. per square foot, and preferably about 50 to about 500 mg. per square foot, depending, of course, on the ratio of onium atoms to molecular weight of the compound employed.
  • typical useful concentrations range from 0.01% by weight to about by weight of the onium compound to provide complete reaction, again depending on the concentration of the dye in the photographic element and the ratio of onium groups to molecular weight of the oniumcompound.
  • color image transfer systems are prepared by using an appropriate shifted indophenol dye in each of three differently sensitized emulsion layers of a photographic element.
  • One layer of the element comprises a blue-sensitive silver halide emulsion which has associated therewith a shifted yellow indophenol dye developer.
  • Typical shifted yellow dye developers have the formula:
  • D-and Ar are as defined above and (KMC) is an open-chain ketomethylene color coupler connected to said nitrogen atom at its coupling position.
  • KMC ketomethylene color coupler connected to said nitrogen atom at its coupling position.
  • a typical Another layer of the element comprises a greensensitive silver halide emulsion having associated therewith a shifted magenta indophenol dye developer.
  • Typical shifted magenta dye developers have the formula:
  • D-and Ar are as defined above and PYZ is a pyrazolone or pyrazolotriazole color coupler
  • the shifted indophenol dye developers can be prepared by several techniques.
  • oxichromic developers are prepared as described in Lestina and Bush, U.S. Ser. No. 206,949 entitled Oxichromic Compounds, Stabilized Oxichromic Compounds and Processes for Preparing Same filed Dec. 10, 1971, and the oxichromic developers are then chromogenically oxidized by aerial oxidation, electrochemical oxidation and the like to provide indophenol-dye developers.
  • the indophenol dye devel opers are prepared by l) reacting a masked silver halide developing compound with a color coupler by a condensation reaction, 2) reacting the condensation product with an aminophenol and 3) then removing the masking groups from the moiety which was the silver halide developing compound.
  • the aminophenol can be reacted with the color coupler before condensation with the masked silver halide developing compound.
  • the color coupler can be reacted with an oxidized aminophenol to form the dye or, in certain embodiments, the couplers when halogenated on the active methylene group can be reacted with unoxidized 'aminophenols as disclosed in U.S. Ser. Nos. 206,924 by Machiele or 206,927, now abandoned, by Reardon, both filed Dec. 10, 1971.
  • dye developers comprising dye moieties containing an azomethine linkage, such as indophenol dyes
  • indophenol dyes can be prepared by condensation reactions with masked developers when precautions are taken to use mild hydrolysis conditions wherein the pH is maintained between pH of about 7 to about 10 and the masking groups are groups which will readily hydrolyze under these conditions such as, for example, masking groups forming carbonates, oxalates, trifluoroacetates and thelike with the silver halide developing moiety.
  • masking groups such as acetoxy groups are used on the silver halide developing moiety, hydrolysis of the masking group is generally accompanied by substantial destruction of the indophenol.
  • the hydrolysis reaction is preferably carried out with a mild hydrolyzing agent such as weak alkali, methylamine, thiourea, zinc and acetic acid and the like.
  • a mild hydrolyzing agent such as weak alkali, methylamine, thiourea, zinc and acetic acid and the like.
  • the hydrolysis procedure is dependent on the groups on the dye moiety and the specific group to be removed.
  • the above hydrolyzing agents can generally be used to achieve removal of carbonate, oxalate, trifluoroacetate groups and the like.
  • the masking groups are attached to a developing moiety which is preferably a polyhydroxybenzene compound such as hydroquinone', and the masking groups are carbonate-containing masking groups such as carboalkoxy groups, carbobenzoxy groups and the like which can contain from 2-20 carbon atoms.
  • a developing moiety which is preferably a polyhydroxybenzene compound such as hydroquinone'
  • the masking groups are carbonate-containing masking groups such as carboalkoxy groups, carbobenzoxy groups and the like which can contain from 2-20 carbon atoms.
  • the shifted indophenol dye developers are especially useful in image transfer systems since they can be incorporated in the silver halide image-recording layer without substantial detrimental adsorption of light in any of the recording layers, i.e.-, the yellow, green and red recording layers, During development, the indophenol dye developers are insolubilized in those areas where silver halide developmentoccurs and the unreacted indophenol dye developer is free to diffuse or migrate to a receiver layer such as a mordant layer.
  • the indophenol dye developer can be contacted with an onium compound to convert the indophenol moiety to anonium indophenoxide which will provide a desired shift in color adsorption providing highly useful dyes for color systems.
  • a photosensitive element comprising a support having thereon a silver halide emulsion layer having associated therewith an indophenol dye developer
  • a container means for discharging an alkaline processing composition within said unit is a rupturable container which is positioned during processing of said film unit so that a compressive force applied to the container by pressure-applying members will effect a discharge of the containers contents into the film unit.
  • the dye image-receiving layer of the film unit can be located on a separate support adapted to be superposed on the photosensitive element after exposure thereof.
  • Such image-receiving elements are disclosed, for example, in U.S. Pat. No. 3,362,819.
  • the rupturable container is usually positioned during processing of said film unit so that a compressive force applied to the container by pressure-applying members in a camera will effect a discharge of the containers contents between the image-receiving element and the outermost layer of the photosensitive element.
  • the dye image-receiving layer can also be located integral with the photosensitive element between the support and the lowermost photosensitive silver halide emulsion layer.
  • integral receiver-negative photosensitive elements are disclosed, for example, in U.S. Pat. No. 3,415,644 and are useful in camera apparatus of the type disclosed in Belgian pat. Nos. 718,553 and 718,554.
  • the processing composition for such integral elements wherein the receiver is permanently laminated to the negative contains opacifying agents such as titanium dioxide or carbon black.
  • Barrier layers such as those described in subsequent paragraphsmay be usedto advantage in such integral elements between the various emulsion and dye-developer layers.
  • the shifted indophenol dye developers are used in an integral image transfer system wherein the image-receiving layer is separated from the image-recording layers, i.e., photosensitive layers containing silver halide emulsions, by a processing composition and dye developerpermeable opaque layer.
  • the image-recording silver halide emulsions have associated therewith respectively a dye image-providing material which is a dye developer.
  • the processing composition is uniformly applied to the image-recording layers on the side opposite the opaque layer, which can be accomplished by inserting an alkaline composition between the imagerecording layers and a cover sheet.
  • the processing composition permeates the image-recording layers, rendering the dye developer nondiffusible in the developed areas, and initiates diffusion in the nondeveloped areas wherein the dye developer can diffuse through the opaque layer to the image-receiving layer and upon treatment with an onium compound will provide the desired image dye. Since the element cannot be exposed through the opaque layer, it must, of course, be exposed from the opposite side.
  • the-present shifted indophenol developers permit exposure through the required side and still obtain effective contact with the silver halide emulsion to render the dye developer nondiffusing in the developed areas, thus avoiding severe color contamination; since the shifted indophenol dye developers can be incorporated in the emulsion layer or positioned between the emulsion layer and the exposure source without substantial competitive light absorption, a high-speed photographic system with this format based on negative emulsions and diffusible dye image-providing substances can now be made.
  • image transfer elements of this type are made with a support having an image-receiving layer thereon and in sequence an opaque layer and at least one imagerecording layer with a cover sheet superposed on the image-recording layer to permit uniform application of a processing liquid to the side of the image-recording layer opposite the opaque layer.
  • the cover sheet can remain laminated with the support having said layers coated thereon.
  • the color film assembly of the present invention may contain various silver halide emulsion layers disposed in the usual order, i.e., the blue-sensitive silver halide emulsion layer first with respect to the exposure side, followed by the green-sensitive and red-sensitive silver halide emulsion layers.
  • a yellow dye layer of a Carey Lea silver layer may be present between the blue-sensitive and green-sensitive silver halide emulsion layer for absorbing or filtering blue radiation that may be transmitted through the blue-sensitive layer.
  • the selectively sensitized silver'halide emulsion layers may be disposed in a different order, e.g., the red-sensitive layer first with respect to the exposure side, followed by the green-sensitive and blue-sensitive layers, since many of the dye developers of this invention which are in association with the sensitive layers do not absorb substantial radiation in the visible region of the radiation spectrum.
  • Our novel indophenol dye developers may be employed for all colors or in combination with suitable ad- 3,415,645, 46, and the like.
  • the shifted dye developers having theformul D-(SID) as defined above, are useful in photographic systems and especially in image transfer systems.
  • the shifted dye developers of this type are generally diffusible in an alkaline medium.
  • the shifted dye developer is associated with a silver halide emulsion wherein the silver halide emulsion is exposed and then treated with an alkaline processing solution which permeates the layers containing the silver halide emulsion and the shifted dye developer to develop the exposed silver halide.
  • the shifted dye developer is rendered relatively nondiffusing compared with the remainder of the shifted dye developer which can diffuse imagewise to an image-receiving layer wherein it can be mordanted.
  • an onium salt which is preferably carried out near or in the image-receiving layer, the onium indophenoxide image dye is formed.
  • the developing group D in the above dye developers is generally responsible for changes in diffusibility of the shifted dye developer and, upon oxidation by reaction with exposed silver halide or an auxiliary developer, it is preferably oxidized to a relatively immobile form.
  • the group dedeveloper, and a red-sensitive emulsion has associated therewith a shifted cyan indophenol developer.
  • the shifted indophenol dye developers referred to above can be incorporated in the photographic elements in sufficient quantities to provide the desired image dye density after processing as known in the art for dye image-providing materials.
  • concentrations will vary, of course, depending on the type of compound employed, the film unit structure and the like.
  • indophenols' when indophenols' are formed in the process, they are preferably contacted with onium compounds to form onium indophenoxides.
  • the onium compounds can either be soluble compounds which can be added by contacting the indophenol with a solution of the onium compound or can be high-molecularweight compounds which are relatively insoluble in water and can be placed in at least one layer of the photographic element, such as in the mordant layer where the indophenol produces the onium indophenoxide image dye.
  • especially useful dye images have been obtained through the combination of indophenols and quaternary ammonium compounds.
  • quaternary ammonium compounds are organic compounds containing a nitrogen atom having a net positive charge. Generally, they can be considered as derivatives of ammonium compounds wherein the four wherein each R is an organic radical; Y is an anion, e.g., hydroxy, bromide, chloride, toluenesulfonate, etc.; and Z represents the atoms necessary to complete a heterocyclic ring.
  • onium compounds include tertiary sulfonium and quaternary phosphonium compounds which are represented by the formulae:
  • each R is an organic radical, e.g., alkyl, aralkyl, aryl, etc., groups; and X is an anion, e.g., hydroxy, bromide, chloride, toleuenesulfonate, etc.
  • tertiary sulfonium and quaternary phosphonium compounds mention may be made of lauryldimethylsulfonium p-toluenesulfonate, nonyldimethylsulfonium p-toluenesulfonate and octyldimethylsulfonium p-toluenesulfonate, butyldimethylsulfonium bromide, triethylsulfonium bromide, tetraethylphosphonium bromide, dimethylsulfonium p-toluenesulfonate, dodecyldimethylsulfonium p-toluenesulfonate, decyldimethyisulfonium p-toluenesulfonate and ethylene-bis-oxymethyltriethylphosphonium bromide.
  • the 0nium compounds may be used as the hydroxide or as the salt.
  • the anion may be a derivative of any acid.
  • the anion is iodide, such iodide may have deleterious effects on the emulsion and suitable precautions should be taken if it is to be in contact with the emulsion before development is complete.
  • the onium compounds employed are bromides.
  • Useful heterocyclic quaternary ammonium compounds which form the methylene bases diffusible in alkaline solution have the general formulas: l-'y-phenylpropyl-2-picolinium bromide 2,4-dimethyll -phenethylpyridinium bromide 2,6-dimethyll -phenethylpyridinium bromide 5-ethyl-2-methyll-phenethylpyridinium bromide 2-ethyll -phenethylpyridinium bromide l-[3-(N-pyridinium bromide)propyl1-2-picolinium p-toluenesulfonate pts 5 oz-picoline-B-naphthoylmethyl bromide l-B-phenylcarbamoyloxyethyl-2-picolinium bromide 1-methyl-2-picolinium p-toluenesulfonate 1-phenethy
  • Typical useful mordants of this type are vinylpyridinium compounds of the type disclosed in U.S. Pat. No. 2,484,430 issued Nov. 10, 1949; polymers containing quaternary ammonium groups such as disclosed in U.S. Ser. Nos. 734,873 by Cohen et al filed June 6, 1968, now U.S. Pat. No. 3,625,694, 100,487 by Cohen et a1 filed Dec. 21, 1970, now U.S. Pat. No. 3,758,445, 100,491 by Cohen et a1 filed Dec. 21, 1979, now U.S. Pat. No. 3,709,690, 709,793 by Cohen et a1 filed Mar. 1, 1968, now U.S. Pat. No. 3,639,357, and U.S. Pat. Nos. 3,488,706 by Cohen et al issued Jan. 6, 1970, and 3,557,006 by Cohen et a1 issued Jan. 19, 1970; and the like.
  • the mordant is an onium coacervate mordant such as disclosed in Bush, U.S. Pat. No 3,271,147 issued Sept. 6, 1966.
  • FIGS. 4-6 a preferred film unit of the invention is described with the various elements magnified for purposes of illustration only wherein like numbers appearing in the various figures refer to like components.
  • rupturable container 1 1 is positioned transverse a leading edge of the photosensitive laminate and is held in place by binding means 30, which can be a pressure-sensitive tape or the like-which encloses that edge of the laminate.
  • binding means 30 can be a pressure-sensitive tape or the like-which encloses that edge of the laminate.
  • the other edges of the photosensitive laminate are sealed together, either directly or with a spacer member, to prevent leakage of processing solution during and after photographic processing when rupturable container 1 l is broken open by pressure-applying members 36 to discharge its contents into the photosensitive laminate.
  • film unit 10 comprises rupturable container l 1 containing, prior to passing between pressureapplying members 36, an alkaline processing composition 12 containing an opacifying agent and a photosensitive laminate comprising top transparent sheet 25 coated with polymeric acid layer 24 and polymeric timing layer 23 and a photosensitive element comprising a transparent support layer 15 coated with an image receiving layer 16 associated with an 'onium compound, an opaque reflecting layer 17, a red-sensitive silver halide emulsion layer 18 associated with a cyan dye imageproviding material, barrier interlayer 19, a greensensitive silver halide emulsion layer 20 associated with a magenta dye image-providing material, barrier interlayer 21, and a blue-sensitive silver halide emulsion layer 22 associated with a yellow dye image-providing material.
  • Exposure of the film unit takes place through the top transparent sheet 25 which is preferably an actinic radiation transmissive flexible sheet material.
  • film unit 10 has been passed between pressure-applying members 36 such as would be found in a camera, thus causing rupturable container 1 l to collapse and discharge the alkaline processing composition 12 containing an opacifying agent between the polymeric timing layer 23 and the blue sensitive silver halide emulsion layer 22.
  • rupturable container 1 l to collapse and discharge the alkaline processing composition 12 containing an opacifying agent between the polymeric timing layer 23 and the blue sensitive silver halide emulsion layer 22.
  • a positive, right-reading image may be viewed through transparent support 15.
  • the structural integrity of the photosensitive laminate can be maintained, at least in part, by the adhesive characteristics between the 'various layers of the laminate. However, the adhesion exhibited at the interface between the polymeric timing layer 23 of top transparent sheet 25 and underlying layer 22 is less than the adhesion at the remaining interfaces of the laminate in order to facilitate distribution of processing composition 12 between these two layers.
  • the film unit of our invention may be constructed by assembling the various parts in an atmosphere maintained at a pressure lower than atmospheric pressure and by sealing the transparent sheet to the photosensitive element along their edges in order to prevent the admission of air between them.
  • the exclusion of air between the transparent sheet and the photosensitive element is desirable in order to prevent air bubbles from being entrained in the processing composition which would form discontinuities in the positive image. Details of this method of assembly and other methods for assuring a uniform distribution of processing composition between two sheets are described in Belgian Pat. No. 711,897.
  • the film unit of our invention can-also contain a liquid trap at the opposite end from which processing composition is introduced in order to trap any excess processing composition and keep it from being expelled from the film unit.
  • the liquid trap may also function to let air escape, if any is present.
  • Such liquid traps are disclosed, for example, in Belgian Pat. No. 71 1,899.
  • the film unit of our invention may also be processed in the manner described in Belgian Pat No. 711,898- wherein two sets of pressure rollers are used in order to expel any air between the transparent sheet and the photosensitive element and also to facilitate an even distribution of processing composition between said sheet and element.
  • the transparent sheet in our film unit may also be fluted along the length of the side edges, similar to the technique described in Belgian Pat. No. 711,898, in order to assist in distributing the processing composition evenly between the transparent sheet and the photosensitive element.
  • this may be accomplished by incorporating into the film unit a desiccating layer to absorb water or by providing access to the atmosphere in order to let the water evaporate, e.g., by employing a water-permeable transparent sheet or a water-permeable film support for the photosensitive element or by allowing water to evaporate through the liquid traps in the film unit as described above, etc.
  • Rupturable container 1 1 can be of the type disclosed in U.S. Pat. Nos. 2,543,181, 2,634,886, 2,653,732, 2,723,051, 3,056,492,. 3,056,491 and 3,152,515.
  • such containers comprise a rectangular sheet of fluidand air-impervious material folded longitudinally upon itself to form two walls which are sealed to one another along their longitudinal and end margins to form a cavity in which processing composition 12 containing an opacifying agent is contained (see FIG. 5).
  • the longitudinal marginal seal 35 is made weaker than the end margin seals so as to become unsealed in response to the hydraulic pressure generated within the fluid contents 12 of the container by the application of a compressive force to the outside walls of the container.
  • container 1 1 is fixedly positioned and extends transverse a leading edge of the photosensitive laminate so that a compressive force applied to said container will effect a unidirectional discharge of the containers contents between the polymeric timing layer 23 of top transparent sheet 25 and underlying layer 22.
  • the weak longitudinal marginal seal 35 is directed toward the interface between layers 22 and 23 to facilitate this operation.
  • the unit In the performance of a multicolor diffusion transfer process employing film unit 10, the unit is exposed to radiation incident on the photosensitive laminates upper surface through transparent sheet 25, as illustratedin FIG. 5. Subsequent to exposure, the film unit 10 is processed by passing it between pressure-applying members 36 in order to apply compressive pressure to frangible container l l and to effect rupture of longitudinal seal 35 and distribution of alkaline processing composition 12 containing an opacifying agent between layers 23 and 24.0f film unit 10.
  • the alkaline processing composition permeates the silver halide emulsion layers 22, and 18 to'initiate imagewise development of the silver halide.
  • Diffusible yellow, ma genta and cyan dye image-providing materials are formed from material associated with the silver halide emulsions in layers 22, 20 and 18 as a function of the imagewise exposure of their-associated emulsions. At least part of the imagewise distributions of mobile yellow-, magentaand cyan-forming materials transfer, by diffusion, to the image-receiving layer 16 to provide a positive dye image therein, preferably upon contact with an onium compound. This positive, right-reading image can then be viewed through transparent support layer 15 on' the opaque reflecting layer 17 background. Since the receiving layer does not have to be stripped away from the negative portion of the film unit, the composite structure can be maintained intact subsequent to said processing.
  • shifted dye developers permit exposure through the required side and still retain effective contact with the silver halide emulsion to render the-dye image-providing material nondiffusing in the developed areas, thus avoiding severe color contamination.
  • the shifted dye developers can generally be incorporated in the emulsion layer or positioned between the emulsion layer and the exposure source without substantial competitive light absorption, so that a high-speed photographic system with this format based on negative emulsions and diffusible dye image-providing substances can now be made.
  • each silver halide emulsion layer containing a dye imageproviding material or having the dye image-providing material present in a contiguous layer may be separated from the other silver halide emulsion layers in the negative portion of the film unit by materials in addition to those described above, including gelatin, calcium alginate, or any of those disclosed in U.S. Pat. No. 3,384,483, polymeric materials such as polyvinylamides as disclosed in U.S. Pat. No. 3,421,892, or any of those disclosed in French Pat. No. 2,028,236 or U.S. Pat. Nos. 2,992,104, 3,043,692, 3,044,873, 3,061,428, 3,069,263, 3,069,264, 3,121,011 and 3,427,158.
  • the silver halide emulsion layers in the invention comprise photosensitive silver halide dispersed in gelatin and are about 0.6 to 6 microns in thickness; the dye image-providing materials are dispersed in an aqueous alkaline solutionpermeable polymeric binder, such as gelatin, as a separate layer about 1 to 7 microns in thickness; and the alkaline solution-permeable polymeric interlayers, e.g., gelatin, are about 1 to 5 microns in thickness.
  • these thicknesses are approximate only and can be modified according to the product desired.
  • hydrophilic materials include both naturally occurring substances such as proteins, cellulose derivatives, polysaccharides such as dextran, gum arabic'and the like; and synthetic polymeric substances such as water-soluble polyvinyl compounds like poly(vinylpyrrolidone) acrylamide poly-- mers and the like.
  • the photographic emulsion layers and other layers of a photographic element employed in the practice of this invention can also contain, alone or in combination with hydrophilic, water-permeable colloids, other synthetic polymeric compounds such as dispersed vinyl compounds such as in latex form, and particularly those which increase the dimensional stability of the photographic materials.
  • Suitable synthetic polymers include those described, for example, in U.S. Pat. Nos. 3,142,568 by Nottorf issued July 28, 1964, 3,193,386 by White issued July 6, 1965, 3,062,674 by Houck et al issued Nov. 6, I962, 3,220,844 by Houck et al issued Nov. 30, 1965, 3,287,289 by Ream et al issued Nov.
  • any material can be employed as the image-receiving layer in this invention as long as the desired function of mordanting or otherwise fixing the dye images will be obtained.
  • the particular material chosen will, of
  • the photographic elements of this invention contain an imagereceiving layer which comprises a polyvinylpyridine mordant.
  • the dyes formed with the polyvinylpyridine mordant appear to be distinguished from those formed with an onium mordant in that they can be removed from the mordant layer by repeated washings.
  • a pl-l-lowering layer in the film unit of the invention will usually increase the stability of the transferred image.
  • the pH-lowering layer will effect a reduction in the pH of the image layer from about 13 and 14 to at least 1 1 and preferably 5-8 within a short time after imbibition.
  • polymeric acids as disclosed in US. Pat. No. 3,362,819 may be employed. Such polymeric acids reduce the pH of the film unit after development to terminate development and substantially reduce further dye transfer and thus stabilize the dye image.
  • Such polymeric acids comprise polymers containing acid groups, such as carboxylic acid and sulfonic acid groups, which are capable of forming salts with alkali metals,.such as sodium or potassium, or with organic bases, particularly quaternary ammonium bases, such as tetramethyl ammonium hydroxide.
  • the polymers can also contain potentially acid-yielding groups such as anhydrides or lactones or other groups which are capable of reacting with bases to capture and retain them.
  • the most useful polymeric acids contain free carboxyl groups, being insoluble in water in the free acid form and which form watersoluble sodium and/or potassium salts.
  • polymeric acids include dibasic acid half-ester derivatives of cellulose, which derivatives contain free carboxyl groups, e.g., cellulose acetate hydrogen phthalate, cellulose acetate hydrogen glutarate, cellulose acetate hydrogen succinate, ethyl cellulose hydrogen succinate, ethyl cellulose acetate hydrogen succinate, cellulose acetate succinate hydrogen phthalate; ether and ester derivatives of cellulose modified with sulfoanhydrides, e.g., with ortho-sulfobenzoic anhydride; polystyrene sulfonic acid; carboxymethyl cellulose; polyvinyl hydrogen phthalate; polyvinyl acetate hydrogen phthalate; polyacrylic acid, acetals of polyvinyl alcohol with carboxy or sulfo-substituted aldehydes, e.g., mor p-benzaldehyde sulfonic acid or carboxylic acid; partial esters -of
  • solid monomeric acid materials could also be used such as palmitic acid, oxalic acid, sebacic acid, hydrocinnamic acid, metanilic acid, paratoluenesulfonic acid and benzenedisulfonic acid.
  • Other suitable'materials are disclosed in US. Pat. Nos. 3,422,075 and 2,635,048.
  • the pH-loweri'ng layer is usually about 0.3 to about mils in thickness and can be located in the receiver portion of the film unit between the support and the image-receiving layer, on the cover sheet, or it can be located anywhere within the film unit as long as the desired function is obtained.
  • An inert timing or spacer layer coated over the pH- lowering layer may also be used to time" or control the pH reduction of the film unit as a function of the rate at which the alkali diffuses through the inert spacer layer.
  • This timing layer can also be used effectively to isolate oxidizing materials in a layer adjacent the image-receiving layer wherein oxidant will be released after alkali breakdown of the timing layer. Examples of such timing layers include gelatin, polyvinyl alcohol or any of those disclosed in US. Pat. No. 3,455,686.
  • the timing layer is also effective in evening out the various reaction rates over a wide range of temperatures, e.g., premature pH reduction is prevented when imbibition is effected at temperatures above room temperature, for example, at 95 to 100 F.
  • the timing layer is usually about O.l to about 0.7 mil in thickness. Especially good results are obtained when the timing layer comprises a hydrolyzable polymer or a mixture of such polymers which are slowly hydrolyzed by the processing composition.
  • hydrolyzable polymers include polyvinly acetate, polyamides, cellulose esters, etc.
  • the alkaline processing composition employed in this invention is the conventional aqueous solution of an alkaline material, e.g., sodium hydroxide, sodium carbonate or an amine such as diethylamine, preferably possessing a pH in excess of 12, and preferably containing an auxiliary developing'agent.
  • the solution also preferably contains a viscosity-increasing compound such as a high-molecular-weight polymer, e.g., a watersoluble ether inert to alkaline solutions such'as hydroxyethyl cellulose or alkali metal salts of carboxymethyl cellulose such as sodium carboxymethyl cellulose.
  • a viscosity-increasing compound such as a high-molecular-weight polymer, e.g., a watersoluble ether inert to alkaline solutions such'as hydroxyethyl cellulose or alkali metal salts of carboxymethyl cellulose such as sodium carboxymethyl cellulose.
  • concentration of viscosity-increasing compound of about 1 to about 5% by weight of the processing solution is preferred which will impart thereto a viscosity of about cps. to about 200,000 cps.
  • an adhesive may be added to the processing composition to increase further the adhesion of the transparent sheet to the photosensitive element after processing.
  • the alkaline processing composition employed in this invention can also contain an auxiliary or accelerating developing agent which does not contain the structure D-(SlD) as defined above.
  • auxiliary developing agents reducing agents
  • a plurality of auxiliary or accelerating developing agents such as those. disclosed in US. Pat. No. 3,039,869 can also be employed.
  • Such auxiliary or accelerating developing agents can be' employed in the liquid processing composition or may be contained, at least in part, in any layer or layers of the film unit such as the silver halide emulsion layers, the dye imageproviding material layers, interlayers, image-receiving layer, etc., and are preferably coated in the layers of the photosensitive element.
  • the alkaline processing composition employed in this invention can also contain a desensitizing agent such as methylene blue, nitro-substituted heterocyclic compounds, 4,4'-bipyridinium salts, etc., to insure that the photosensitive element is not further exposed after it is removed from the camera for processing.
  • a desensitizing agent such as methylene blue, nitro-substituted heterocyclic compounds, 4,4'-bipyridinium salts, etc.
  • alkaline processing composition used in this invention can be employed in a rupturable container, as described previously, to facilitate conveniently the introduction of processing composition into the film unit between the transparent sheet and the photosensitive element
  • other means of discharging processing composition within the film unit could also be employed, e.g., interjecting processing solution with communicating members similar to hypodermic syringes which are attached either to a camera or camera cartridge, as described in Harvey, US. Pat. No. 3,352,674 issued November 14, 1967.
  • opacifying agent can be employed in the processing composition in certain embodiments of our invention.
  • opacifying agents include carbon black, barium sulfate, zinc oxide, barium stearate, silver flake, silicates, alumina, zirconium oxide, zirconium acetyl acetate, sodium zirconium sulfate, kaolin, mica, titanium dioxide, organic dyes such as the nigrosines, or mixtures thereof in widely varying amounts depending upon the degree of opacity desired.
  • the concentration of opacifying agent should be sufficient to prevent further exposure of the film units silver halide emulsion or emulsions by ambient actinic radiation transversing through the top transparent sheet subsequent to distribution of the processing solution between the top transparent sheet and the underlying layer adjacent thereto.
  • carbon black or titanium dioxide will generally provide sufficient opacity when they are present in the processing solution in an amount of from about 5 to 40% by weight.
  • processing may take place out of the camera in the presence of actinic radiation in view of the fact that the silver halide emulsion or emulsions of the laminate are appropriately protected by incident radiation, at one major surface by the opaque processing composition and at the remaining major surface by the alkaline solution-permeable opaque layer.
  • Opaque binding tapes can also be used to prevent edge leakage of actinic radiation incident on the silver halide emulsion.
  • a pH-sensitive opacifying dye such as a phthalein dye.
  • a pH-sensitive opacifying dye such as a phthalein dye.
  • Such dyes are light-absorbing or colored at the pH at which image formation is effected and colorless or not lightabsorbi'ng at a lower pH.
  • Other details concerning these opacifying dyes are described in French Pat. No. 2,026,927.
  • the alkaline solutiompermeable, sus bstantially opaque, light-reflective layer' in the photographic film unit of our invention can generally comprise any opacifier dispersed in a binder as long as it has the desired properties. Particularly desirable are white lightrefelective layers since they would be esthetically pleasing backgrounds on which to view a transferred desired for reflection'of incident radiation.
  • Suitable opacifying agents include titanium dioxide, barium sulfate;-zinc oxide, barium stearate, silver flake, silicates, alumina, zirconium oxide, airconium acetyl acetate, sodium zirconium sulfate, kaolin, mica, or mixtures thereof in widely varying amounts depending upon the degree of opacity desired.
  • the opacifying agents may be dispersed in any binder such as an alkaline solutionpermeable polymeric matrix such as, for example, gelatin, polyvinyl alcohoLand the like. Brightening agents such as the stilbenes, coumarins, triazines and oxazoles can also be added to the light-reflective layer, if desired.
  • dark-colored opacifying agents may be added to it, e.g., carbon black, nigrosine dyes, etc.
  • Another technique to increase the opacifying capaicty of the light-reflective layer is to employ a separate opaque layer underneath it comprising, e.g., carbon black, nigrosine dyes, etc., dispersed in an alkaline solution-permeable polymeric matrix such as, for example,- gelatin, polyvinyl alcohol, and the like.
  • Such an opaque layer would generally have a density of at least 4 and preferably greater than 7 and would be substantially opaque to actinic radiation.
  • the opaque layer may also be combined with a developer scavenger layer if one is present.
  • the light-reflective and opaque layers are generally 1 to 6 mils in thickness, although they can be varied depending upon the opacifying agent employed, the degree of opacity desired,
  • transparent sheets When transparent sheets are used in film assemblies of this invention, they can be any transparent material as long as it does not deleteriously affect the photographic properties of the film unit and is dimensionally stable.
  • Typical actinic radiation-transmissive flexible sheet materials include cellulose nitrate film, cellulose acetate film, poly(vinyl acetal) film, polystyrene film, poly(ethyleneterephthalate) film, poly-carbonate film, poly-a-olefins such as polyethylene and polypropylene film, and related films or resinous materials, as well as glass.
  • the transparent sheet is usually about 2 to 6 mils in thickness and may contain an ultraviolet absorber for exposure control if desired. in addition, an adhesive tion may be present on the transparent sheet in order I to increase its adhesion to the photosensitive element after processing.
  • transparent supports Whentransparent supports are used in film assemblies of this invention, they can be any of the materials mentioned above for the transparent sheet. If desired, an ultraviolet-absorbing material can be employed in the support to prevent the dye images from fading due to ultraviolet light.
  • the photosensitive substances used in this invention are preferably silver halide compositions and can comprise silver chloride, silver bromide, silver bromoiodide, silver chlorobromoiodide and the like, or mixtures thereof.
  • the emulsions may be coarseor finegrain and can be prepared by any of the well-known procedures, e.g., single-jet emulsions, double-jet emulsions, such asLippmann emulsions, ammoniacal emulsions, thiocyanate or thioether ripened emulsions such as those described in U.S. Pat. No. 2,222,264 by Nietz et al, 3,320,069 by Illingsworth, and 3,271,157 by Mc- Bride.
  • Surfaceimage emulsions can be used or internal-image emulsions can be used such as those described in U.S. Pat. Nos. 2,592,250 by Davey et al,
  • the emulsions may be regular-grain emulsions such as the type described in Klein and Moisar, J. Phot, Sci., Vol. 12, No. 5, Sept./Oct., 1964, pp. 242251..lf desired, mixtures or surface-and internal-image emulsions can be used as described in Luckey et al, U.S. Pat. No. 2,996,382.
  • Negative-type emulsions are generally preferred, but direct-positive emulsions can be used if desired.
  • Typical direct-positive emulsions include those described in U.S. Pat. Nos. 2,184,013 by Leermakers, 2,541,472 by Kendall et al, 3,367,778 by Berriman, 3,501,307 by 111- ingsworth et a1 issued March 17, 1970, 2,563,785 by Ives, 2,456,953 by Knott et a1 and 2,861,885 by Land, British Pat. No. 723,019 by Schouwenaars, and U.S. Ser. Nos. 123,005 by Evans filed Mar. 10, 1971, now U.S.
  • a positive image record is obtain-in an imagereceiving layer by mordanting the diffusible imageproviding material which is not immobilized or remains diffusible in the photosensitive portion of the film unit.
  • the photosensitive element contains an image record which provides a useful image product.
  • the mobile or diffusible materials can be washed out after exposure to produce a negative image record.
  • the silver halide emulsion can be selected to produce a positive image record in the photosensitive portion of the film element.
  • EXAMPLE 2 This example demonstrates in a nonimage-forming format the property of a shifted dye developoer of undergoing a spectral-absorption change upon contact with a mordant such as an organic onium compound.
  • a supported single-layer gelatinous coating containing 250 mg. of gelatin and mg. of Compound I per square foot of coating, is dried and spectrophotometrically evaluated.
  • the spectrophotometric absorption profile of Compound I contained in the soprepared coating is represented by Curve A in FIG. 2.
  • a comparison of Curves A and B in FIG. 2 shows the compounds initial low absorption and its desirable final high absorption of blue light.
  • EXAMPLE-3 potassium hydroxide hydroxyethyl cellulose water to l liter Upon separation of the gelatin coating from the receiver, the latter contains a uniformly distributed dense yellow dye. The receiver is washed for 3 minutes without appreciable change in the appearance of the yellow dye.
  • a sample of the above-described coating is exposed through a graduated-density test object and processed in the presence of a viscous developing solution whose composition is shown below, while in contact for 30 seconds with a receiver containing the mordant of Example 3. Upon separation of the coating sample from the receiver, the latter contains a well-defined positive yellow umage of the photographed test object.
  • EXAMPLE 5 Developing Solution sodium hydroxide g. l-phenyl-4-methyl-4-hydroxymethyl-3- 0.75 g. Eyrazo'lidone ydroxyethyl cellulose g. water to 1 liter EXAMPLE 5
  • the latter contains a dense yellow dye in the area which, during the transfer cycle, has been opposite the unexposed section of the emulsion coating. The rceiver is washedfor 3 minutes without appreciable change in the appearance of the yellow dye.
  • the receiver contains yellow dye in both areas of contact.
  • the auxiliary developing agent is desirable to provide immobilizing reactions to obtain good image discrimination.
  • EXAMPLE 6 ocoocnn CH2COOH I I 0 c 0 0 can "NHCOCaFl A solution (6-1) in dry tetrahydrofuran is treated with a mixture of thionyl chloride and N,N-dimethylformamide in dry benzene and heated for 30 minutes. The solvent is removed under reduced pressure to give the acid chloride, m.p. 5053 C. The acid chloride is dissolved in dry dioxane and added to a mixture of (62) and quinoline in dry dioxane. After standing at room temperature, the solid is collected and recrystallized from acetonitrile to give Intermediate 6-A, m.p. l98-200 C.
  • Compound 6 is incorporated in a gelatin layer coated on a support and is found to transfer a cyan dye to a quaternary mordant when contacted with an alkaline processing solution with a pH of 14. The dye remains cyan when the pH is then adjusted to about 7.
  • the shifted dye developers of this invention can be prepared as illustrated in the following example by further reacting the oxichromic compounds of Lestina and Bush, U.S. Ser. No. 206,949, entitled Oxichromic Compounds, Stabilized Oxichromic Compounds and Processes for Preparing Same filed Dec. 10, 1971, and incorporated herein by reference, now abandoned and refiled as US. Ser. No. 426,177.
  • EXAMPLE 8 The oxichromic compound 4-(3,5-dichloro-4- hydroxyanilino)-2-[5-(2,5- dihydroxyphenyl)pentanoylamido]-5-(4-pentoxybenzamido)phenol (1.449, 2.11 X 10 moles), prepared according to Lestina and Bush, US. Ser. No. 206,949, Example 2, is dissolved in 300 ml. of a mixture of 80% by volume acetonitrile and 20% by volume N,N-dimethylformamide and the solution is made 0.1 molar with sodium perchlorate.
  • the solution is oxidized by controlled potential electrolysis in a twocompartment cell using a potentiostat for control and platinum electrodes at a potential of +0.55 v. until the current has decayed to 10% of its original value.
  • the progress of the reaction is monitored by occasionally recording a current-voltage curve. After 375.1 coulombs (2.05 electrons/molecule have passed, the first oxidation wave (E of the lecuo dye has diminished to approximately 5% of its original height, whereas the B.
  • a coating containing a silver halide emulsion is prepared by coating on a cellulose acetate support the following layers:
  • the nonsilver coating is evaluated on a spectrophotometer and gives Amzu at 590 nm. with a Dmax of second wave (E has retained its original height.
  • the compound has the formula:
  • the coatings containing the silver halide emulsion are given a stepped exposure and processed for 60 seconds with the processing composition above while in contact with the mordanted receiver sheet above.
  • EXAMPLE 10 The oxichromic compound 4-(3,5-dichloro-4- hydroxyanilino)-3- ⁇ 3-[5-(2,5- dihydroxyphenyl )pentanoylamido]phenylcarbamoyl ⁇ l-phenyl-2-pyraioline-5-one, prepared according to Example l-C of Stern and Machiele, U.S. Ser. No. 206,926 filed Dec. 10, 1971, and incorporated herein by reference, is subjected to hydrogenolysis to remove the masking groups on the developing moiety according to Example l-F of Stern and Machiele, U.S. Ser. No. 206,926, and then subjected to-aerial oxidation to produce the shifted dye believed to have the formula:
  • the shifted indophenol dye developers can be incorporated into the multicolor photosensitive element of a film transfer unit as disclosed in US. Pat. No. 2,983,606, Belgian Pat. Nos. 757,959 and 757,960 granted Apr. 23, i971, or Lestina and Bush, US. Ser. No. 206,836 filed Dec. 10, 197i entitled Oxichromic Compounds, now abandoned and refiled as U.S. Ser. No. 308,869, all of which are incorporated herein by reference.
  • Compound V is ineorporated in association with a green-sensitive silver halide emulsion, Compound IV is incorporated in association with the redsensitive silver halide emulsion and Compound I is incorporated in association with the blue-sensitive silver halide emulsion layer.
  • Compounds I, IV and V can be coated in the respective silver halide emulsion layers, on the exposure side of the silver halide emulsion layers, or under the emulsion layer with respect to exposure; however, the first two locations are preferred.
  • An auxiliary developer and preferably a reducing agent, such as l-phenyl-3-pyrazolidone, are incorporated in the photographic element in association with the respective shifted dye developers.
  • the image-receiving layer contains a dye mordant which is preferably an 'onium compound.
  • Suitable onium mordants are in coacervate of N-n-hexadecyl- N-morpholinium ethosulfate and 'methyl-tri-ndodecylammonium p-toluenesulfonate, the mordan t N-n-octadecyltributylammonium bromide, and the like.
  • Aphotographic element comprising a support and at least one layer thereon containing a photographic silver halide having associated therewith a dye developer which is diffusible in an alkaline processing medium and has the general formula:
  • D-(SlD) wherein D- is an aromatic nucleus polysubstituted with hydroxy groups, amino groups or alkylamino groups to provide a group which is capable of developing silver halide, and (SlD) is an indophenol dye moiety.
  • a photographic element according to claim 1 which comprises at least one layer containing an onium. salt in water-permeable association with said dy'e developer.
  • D comprises an aromatic nucleus which contains at least two substituents thereon from the class of hydroxy groups, primary amino groups or alkylamino groups.
  • a photographic element according to claim 1 wherein said element comprises at least two separate layers containing a silver halide emulsion, each having aseparate dye developer of saidformula associated therewith.
  • a photographic element wherein said element comprises a blue-sensitive silver .halide emulsion layer having associated therewith a yellow-forming indophenol. dye developer, a greensensitive silver halide emulsion layer having associated therewith a magenta-forming indophenol dye developer, and a red-sensitive silver halide emulsion layer having associated therewith a cyan-forming indophenol dye developer.
  • D-(SlD) and said element contains an image-receiving layer.
  • a photographic element according to claim 1 wherein said dye developer has the formula:
  • D- is an aromatic nucleus polysubstituted with hydroxy groups, primary amino groups or alkylamino groups to provide a group which is capable of developing silver halide
  • Ar is a phenylene group
  • (PYZ) is a pyrazolone coupler radical or a pyrazolotriazole coupler connected at its coupling position to said nitrogen atom.
  • a photographic element according to claim 1 wherein said dye developer has the formula:
  • D- is an aromatic nucleus polysubstituted with hydroxy groups, primary amino groups or alkylarnino groups to provide a group which is capable of developing silver halide
  • Ar is a phenylene group
  • (KMC) is an open-chain ketomethylene coupler radical connected at its coupling position to said nitrogen atom.
  • a photographic element according to claim 1 wherein said dye developer has the formula:
  • D- is an aromatic nucleus polysubstituted with hydroxy groups, primary amino groups or alkylamino groups to provide a group which is capable of developing silver halide
  • Ar is a phenylene group
  • (PhC) is a phenolic coupler radical connected at its coupling position to said nitrogen atom.
  • a photographic film unit comprising:
  • a photosensitive element comprising a support having thereon a layer containing a silver halide composition having associated therewith a dye developer which is diffusible in an alkaline processing medium and has the formula:
  • D-(SID) wherein D- is an aromatic nucleus polysubstituted with hydroxy groups, primary amino groups or alkylamino groups to provide a groupwhich is capable of developing silver halide, and (SID) is an indophenol dye moiy;
  • a film unit according to claim 14 containing an onium salt in liquid-permeable association with said dye developer and which is sequestered from said dye developer until contact with said liquid processing composition 17.
  • said photosensitive element comprises a support having thereon:
  • a red-sensitive silver halide emulsion layer having associated therewith a cyan-forming dye developer
  • a blue-sensitive silver halide emulsion layer having associated therewith a yellow-forming dye developer.
  • a film unit according to claim 14 wherein said discharging means comprises a rupturable container and is so positioned during processing of said film unit that a compressive force applied to said container by pressure-applying members will effect a discharge of the containers contents between said dye imagereceiving layer and the layer most remote from the support of said photosensitive element.
  • a film unit according to claim 14 wherein said discharging means comprises a rupturable container and is so positioned during processing of said film unit that a compressive force applied to said container by LII pressure-applying members will effect a discharge of the containers contents between the layer most remote from the support of said photosensitive element and a cover sheet superposed on said photosensitive element.
  • a photographic film unit according to claim 14 wherein said dye developer has the formula:
  • a photographic film unit according to claim 14 wherein said dye developer has the formula:
  • a process for producing a photographic transfer image comprising:
  • a. imagewise-exposing a photosensitive element comprising a support having thereon a layer containing a silver halide composition having associated therewith a dye developer which is diffusible in an alkaline processing medium and has the formula:
  • D-(SID) wherein D- is an aromatic nucleus polysubstituted with hydroxy groups, amino groups or alkylamino groups to provide a group which is capable of developing silver halide, and (SID) is an indophenol dye moiety;
  • D- is an aromatic nucleus polysubstituted with hydroxy groups, amino groups or alkylamino groups to provide a group which is capable of developing silver halide
  • SID is an indophenol dye moiety
  • M is an onium group.
  • D- is an aromatic nucleus polysubstituted with hydroxy groups, amino groups or alkylamino groups to provide a group which is capable of developing silver halide
  • (COUP) is a photographic color coupler
  • Ar is an arylene group containing from about 6 to about 20 carbon atoms
  • M is an onium group.
  • (COUP) is an open-chain ketomethylene color coupler group connected at its coupling position to said nitrogen atom.
  • (COUP) is a pyrazolone or pyrazolotriazole color coupler group connected at its coupling position to said nitrogen atom.
  • (COUP) is a phenolic color coupler connected at its coupling position to said nitrogen atom.
  • a photographic product according to claim 30 which contains 1) an onium indophenoxide of said formula wherein (SID) comprises a phenolic color coupler, 2) an onium indophenoxide of said formula wherein (811)) comprises an open-chain ketomethylene color coupler and 3) an 'onium indophenoxide of said formula wherein (SlD) comprises a pyrazolone or pyrazolotriazole color coupler.

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GB751573A GB1422061A (en) 1972-02-17 1973-02-15 Dye developers for photographic silver halide material
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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4009030A (en) * 1974-11-05 1977-02-22 Eastman Kodak Company Timing layer for color transfer assemblages comprising a mixture of cellulose acetate and maleic anhydride copolymer
US4199355A (en) * 1975-06-24 1980-04-22 Eastman Kodak Company Positive-working immobile photographic compounds and photographic elements containing same
US4199354A (en) * 1973-01-26 1980-04-22 Eastman Kodak Company Positive-working immobile photographic compounds and photographic elements containing same
US4235957A (en) * 1979-01-25 1980-11-25 Eastman Kodak Company Thermal silver-dye bleach element and process
US4278598A (en) * 1974-12-20 1981-07-14 Eastman Kodak Company Positive-working immobile intramolecular nucleophilic displacement compounds and photographic elements containing same
US4329411A (en) * 1974-12-30 1982-05-11 Polaroid Corporation Multicolor diffusion transfer products
US4975361A (en) * 1987-12-22 1990-12-04 Fuji Photo Film Co., Ltd. Color photographic light-sensitive material
US20030165955A1 (en) * 2002-01-22 2003-09-04 Suich Daniel J. Fluorogenic dyes
US20060128033A1 (en) * 2003-01-21 2006-06-15 Chiron Corporation Fluorogenic dyes

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3239336A (en) * 1962-04-26 1966-03-08 Polaroid Corp Photographic processes
US3255001A (en) * 1955-02-03 1966-06-07 Polaroid Corp Photographic products, processes and compositions utilizing insulated azo dye developers
US3537850A (en) * 1966-12-02 1970-11-03 Polaroid Corp Color transfer image-forming process utilizing coupler-developers whose oxidation products can couple intermolecularly
US3698897A (en) * 1971-07-06 1972-10-17 Eastman Kodak Co Diffusion transfer processes and film units comprising compounds which are cleavable upon oxidation in alkali media to produce diffusible dyes or dye precursors
US3725062A (en) * 1971-07-06 1973-04-03 Eastman Kodak Co Color diffusion processes utilizing hydroquinones which provide dye image materials upon oxidation in alkaline conditions
US3728113A (en) * 1971-07-06 1973-04-17 Eastman Kodak Co Selective transfer system and compounds for employment therein
US3765886A (en) * 1971-08-06 1973-10-16 Eastman Kodak Co Image transfer systems with {40 onium indophenoxide image dyes
US3791827A (en) * 1971-08-06 1974-02-12 Eastman Kodak Co {40 onium indophenoxides

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3255001A (en) * 1955-02-03 1966-06-07 Polaroid Corp Photographic products, processes and compositions utilizing insulated azo dye developers
US3239336A (en) * 1962-04-26 1966-03-08 Polaroid Corp Photographic processes
US3537850A (en) * 1966-12-02 1970-11-03 Polaroid Corp Color transfer image-forming process utilizing coupler-developers whose oxidation products can couple intermolecularly
US3698897A (en) * 1971-07-06 1972-10-17 Eastman Kodak Co Diffusion transfer processes and film units comprising compounds which are cleavable upon oxidation in alkali media to produce diffusible dyes or dye precursors
US3725062A (en) * 1971-07-06 1973-04-03 Eastman Kodak Co Color diffusion processes utilizing hydroquinones which provide dye image materials upon oxidation in alkaline conditions
US3728113A (en) * 1971-07-06 1973-04-17 Eastman Kodak Co Selective transfer system and compounds for employment therein
US3765886A (en) * 1971-08-06 1973-10-16 Eastman Kodak Co Image transfer systems with {40 onium indophenoxide image dyes
US3791827A (en) * 1971-08-06 1974-02-12 Eastman Kodak Co {40 onium indophenoxides

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4199354A (en) * 1973-01-26 1980-04-22 Eastman Kodak Company Positive-working immobile photographic compounds and photographic elements containing same
US4009030A (en) * 1974-11-05 1977-02-22 Eastman Kodak Company Timing layer for color transfer assemblages comprising a mixture of cellulose acetate and maleic anhydride copolymer
US4278598A (en) * 1974-12-20 1981-07-14 Eastman Kodak Company Positive-working immobile intramolecular nucleophilic displacement compounds and photographic elements containing same
US4329411A (en) * 1974-12-30 1982-05-11 Polaroid Corporation Multicolor diffusion transfer products
US4199355A (en) * 1975-06-24 1980-04-22 Eastman Kodak Company Positive-working immobile photographic compounds and photographic elements containing same
US4235957A (en) * 1979-01-25 1980-11-25 Eastman Kodak Company Thermal silver-dye bleach element and process
US4975361A (en) * 1987-12-22 1990-12-04 Fuji Photo Film Co., Ltd. Color photographic light-sensitive material
US20030165955A1 (en) * 2002-01-22 2003-09-04 Suich Daniel J. Fluorogenic dyes
US7026166B2 (en) * 2002-01-22 2006-04-11 Chiron Corporation Fluorogenic dyes
US20060128033A1 (en) * 2003-01-21 2006-06-15 Chiron Corporation Fluorogenic dyes
US7704756B2 (en) 2003-01-21 2010-04-27 Novartis Vaccines And Diagnostics, Inc. Fluorogenic dyes

Also Published As

Publication number Publication date
DE2307738B2 (de) 1976-01-22
GB1422061A (en) 1976-01-21
BE792600A (fr) 1973-06-12
FR2172088B1 (en)) 1977-10-14
CA996938A (en) 1976-09-14
FR2172088A1 (en)) 1973-09-28
DE2307738A1 (de) 1973-08-30

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