Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • 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
• • 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

Definitions

• a developer scavenger layer comprising an isocyanate-bisulflte addition product and a polymeric S "96/29 binder is useful for reducing background stain in a dye [58] image receiving element of a color diffusion transfer Field of Search .Q ..96/29, 56
• the above film unit containing an aromatic primary amino color developing agent, preferably in the rupturable container, and an isocyanate-bisulfite addition product in a polymeric binder which is capable of reacting with unused aromatic primary amino color developing agent to form a colorless urea reaction product.
• the developer-scavenging, isocyanate-bisulfite addition products or adducts employed in our invention have the following general formula:
• R represents an acyclic alkyl group, including a substituted acyclic alkyl group, preferably a lower acyclic alkyl group, i.e., having one to six carbon atoms in the chain such as methyl, ethyl, isopropyl, benzyl, hexyl, carbethoxymethyl, etc.; an alkenyl group such as vinyl, isopropenyl, allyl, etc., preferably having one to six carbon atoms; an alicyclic group typically having four to six carbon atoms in the ring such as cyclohexyl, cyclopentyl, cyclobutyl, etc.; or an aryl group, including a substituted aryl group, such as phenyl, tolyl, naphthyl, methoxyphenyl, biphenylyl, etc.;
• R represents a hydrogen atom or an alkyl group, including a substituted alkyl group as described above for R; and a M represents an alkali metal ion, e.g., a sodium, potassium or ammonium ion.
• the bisulfite adduct functions as a developer scavenger precursor and under the basic conditions of color development reverts to the parent isocyanate compound which in turn reacts with excess unused aromatic primary amino color developing agent to form a colorless product, thereby reducing the yellowish-brown stain which results from the diffusion of unused aromatic primary amino color developing agent into the image-receiving element. Therefore, any isocyanate bisulfite addition product which is compatible with the photosensitive and image-receiving elements can be employed in the practice of the invention provided the addition product reverts under alkaline conditions to the parent isocyanate compound which in turn will react with primary amino color developing agent to form a colorless product.
• the novel dye image-receiving element comprises a support having thereon the following layers:
• the image dyes formed in the respective blue, green and red-sensitive silver halide emulsion layers diffuse out of the photosensitive element through the viscous developer composition and into the dye image-receiving layer, e.g., into the dye image-receiving element described above, where the dyes are mordanted to form the transferred image.
• the timing layer if one is present, prevents the diffusion of color developer into the scavenger layer for the time necessary to ensure the efficient use of the aromatic primary amino color developing agent in the photosensitive element.
• auxiliary developer scavenger layer comprising the isocyanate-bisulfite adducts described herein can be located on the opaque process sheet.
• each silver halide emulsion layer in the photosensitive element there is associated with each silver halide emulsion layer in the photosensitive element a dye image-providing material comprising a nondiffusible coupler which produces a diffusible dye on reaction with oxidized aromatic primary amino color developing agent in alkaline processing composition.
• the nondiffusible couplers employed in this invention include those having formulas:
• BALL LINK f (COUP SOL) wherein l. DYE is a dye radical exhibiting selective absorption in the visible spectrum and containing an acidic solubilizing radical;
• BALL is a photographically inert organic ballasting radical of such molecular size and configuration as to render such coupler nondiffusible during development in the alkaline processing composition
• SOL is a hydrogen atom or an acidic solubilizing group when the color developing agent contains an acidic solubilizing group, and SOL is an acidic solubilizing group when the color developing agent is free of an acidic solubilizing group;
• n is an integer of l to 2 when LINK is an alkylidene radical, and n is I when LINK is an azo radical, a mercuri radical, an oxy radical, a thio radical, a dithio radical or an azoxy radical.
• the acidic solubilizing radicals attached to the diffusible dye producing couplers described above can be solubilizing radicals which when attached to the coupler or developer moieties of the dyes, render the dyes diffusible in alkaline processing compositions.
• Typical of such radicals are carboxylic, sulfonic, ionizable sulfonamide, and hydroxy-substituted groups that lend to dyes negative charges.
• ballast groups in the diffusible dyeproducing coupler compounds described above are not critical as long as they confer nondiffusibility to the coupler compounds.
• Typical ballast groups include long chain alkyl radicals linked directly or indirectly to the coupler molecules as well as aromatic radicals of the benzene and naphthalene series, etc., linked directly or indirectly to the coupler molecules by a splittable linkage, or by a removable or irremovable but otherwise nonfunctional linkage depending upon the nature of the coupler compound.
• Useful ballast groups have at least eight carbon atoms.
• Typical dye radical substituents include azo, azomethine, indoaniline, indophenol, anthraquinone and related dye radicals well known in the art that exhibit selective absorption in the visible spectrum.
• the dye radicals contain acidic solubilizing moieties.
• the cyanproducing coupler has the formula BALL--O CYANCOUP
• the yellowproducing coupler has the formula BALLOYELL- COUP wherein:
• nondiffusing used herein as applied to the couplers, 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 dyes formed from the nondiffusing couplers in 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 from which they are derived.
• Mobile has the same meaning.
• the color of the diffusible dye is determined by the color of the preformed dye moiety (DYE), the color of the reaction product of color developer oxidation product and the coupler moiety (COUP) being unimportant to the color of the diffusible image.
• the connecting radical (LINK) is split and a diffusible dye is formed with the color developing agent oxidation product and the coupling portion (COUP) of the coupler which diffuses imagewise to a reception layer. Diffusibility is imparted to the dye by an acidic solubilizing group attached to a noncoupling position of the coupling portion (COUP) of the coupler or to the color developing agent. The ballasting portion of the coupler remains immobile.
• the color of the diffusible dye is determined by the color of the reaction product of color developer oxidation product and the coupler moiety (COUP).
• Suitable fogging agents include the hydrazines disclosed in Ives U.S. Pat. No. 2,588,982 issued Mar. 11, 1952 and 2,563,785 issued Aug. 7, 1951; the hydrazides and hydrazones disclosed in Whitmore U.S. Pat. No. 3,227,552 issued Jan. 4, l966;hydrazone quaternary salts described in Lincoln and Heseltine application Ser. No. 828,064 filed Apr.
• the merocyanine dyes can contain the basic nuclei mentioned above as well as acid nuclei such as thiohydantoins, rhodanines, oxazolidenediones, thiazolidenediones, barbituric acids,. thiazolineones, and malononitrile.
• acid nuclei can be substituted with alkyl, alkylene, phenyl, carboxyalkyl, sulfoalkyl, hydroxyalkyl, alkoxyalkyl, alkylamino groups, or heterocyclic nuclei. Combinations of these dyes can be used, if desired.
• supersensitizing addenda which do not absorb visible light
• addenda which do not absorb visible light
• ascorbic acid derivatives for instance, ascorbic acid derivatives, azaindenes, cadmium salts, and organic sulfonic acids as described in Mc- Fall et al. U.S. Pat. No. 2,933,390 and Jones et al. U.S. Pat. No. 2,937,089.
• the silver halide emulsions used in this invention may contain speed increasing compounds vsuch as polyalkylene glycols, cationic surface active agents and thioethers or combinations of these as described in Piper U.S. Pat. No. 2,886,437; Dann et al. U.S. Pat. No. 3,046,134; Carroll et al. U.S. Pat. No. 2,944,900; and Goffe U.S. Pat. NO. 3,294,540.
• speed increasing compounds v such as polyalkylene glycols, cationic surface active agents and thioethers or combinations of these as described in Piper U.S. Pat. No. 2,886,437; Dann et al. U.S. Pat. No. 3,046,134; Carroll et al. U.S. Pat. No. 2,944,900; and Goffe U.S. Pat. NO. 3,294,540.
• interlayers are generally employed between the various photosensitive color-forming units to scavenge oxidized developing agent and prevent it from forming an unwanted dye in another color-forming unit.
• Such interlayers would generally comprise a hydrophilic polymer such as gelatin and an immobilizing coupler, which is capable of reacting with oxidized aromatic primary amino color developing agent to form an immobile product.
• the aromatic primary amino color developing agent employed in the abovedescribed embodiments is preferably present in the alkaline processing composition in the rupturable pod.
• the color developing agent can also be incorporated into the negative portion of the film unit as a separate layer, e.g., by employing a Schiff base derivative of an aromatic primary amino color developing agent such as that formed by reacting o-sulfobenzaldehyde and N,N- diethyl-3-methyl-4-aminoaniline.
• a Schiff base derivative of an aromatic primary amino color developing agent such as that formed by reacting o-sulfobenzaldehyde and N,N- diethyl-3-methyl-4-aminoaniline.
• Such incorporated developing agent will be activated by the alkaline processing composition.
• the incorporated developing agent can be positioned in any layer of the photosensitive element from which it can be readily made available for development upon activation with alkaline processing composition, it is generally either incorporated in the light-sensitive silver halide emulsion layers or in layers contiguous thereto.
• each silver halide emulsion layer containing a dye imageproviding material or having the dye image-providingmaterial 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.
• the silver halide emulsion layers in the invention com approximate only and can be modified according to the product desired.
• suitable 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(viny1pyrrolidone), acrylamide polymers and the like.
• the photographic emulsion layers andother 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 photo graphic materials.
• Suitable synthetic polymers include those described, for example, in Nottorf U.S. Pat. No. 3,142,568, issued July 28, 1964; White U.S. Pat. No. 3,193,386, issued July 6, 1965; Houck et a1.
• 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.
• 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 concentration of viscosity-increasing compound of about 1 to about 5 percent by weight of the processing composition is preferred which will impart thereto a viscosity of about 100 cps. to about 200,000 cps.
• an opacifying agent e.g., TiO carbon black, etc. may be added to the processing composition.
• the alkaline solution-permeable, substantially opaque, light-reflective layer employed in certain embodiments of integral photographic film units of our invention can generally comprise any opacifier dispersed in a binder as long as it has the desired properties. Particularly desirable are white light-reflective layers since they would be esthetically pleasing backgrounds on which to view a transferred dye image and would also possess the optical properties desired for reflection of incident radiation.
• Suitable opacifying agents include titanium dioxide, barium sulfate, zinc oxide, barium stearate, silver flake, silicates, alumina, zirconium oxide, zirconium 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 solution-permeable polymeric matrix such as, for example, gelatin, polyvinyl alcohol, and 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.
• the supports for the photographic elements of this invention can be any material as long as it does not deleteriously effect the photographic properties of the film unit and is dimensionally stable.
• Typical flexible sheet materials include cellulose nitrate film, cellulose acetate film, poly(vinyl acetal) film, polystyrene film, poly(ethyleneterephthalate) film, polycarbonate film, poly-a-olefins such as polyethylene and polypropylene film, and related films or resinous materials as well as glass.
• the support is usually about 2 to 6 mils. in thickness.
• dotwise coating such as would be obtained using a gravure printing technique, could also be employed.
• small dots of blue, green and red-sensitive emulsions have associated therewith, respectively, dots of yellow, magenta and cyan color-providing substances. After development, the transferred dyes would tend to fuse together into a continuous tone.
• the photographic layers employed in the practice of this invention can contain surfactants such as saponin, anionic compounds such as the alkyl aryl sulfonates described in Baldsiefen U.S. Pat. No. 2,600,831; amphoteric compounds such as those described in Ben- Ezra U.S. Pat. No. 3,133,816; and water soluble adducts of glycidol and an alkyl phenol such as those described in Olin Mathieson British Pat. No. 1,022,878.
• surfactants such as saponin, anionic compounds such as the alkyl aryl sulfonates described in Baldsiefen U.S. Pat. No. 2,600,831; amphoteric compounds such as those described in Ben- Ezra U.S. Pat. No. 3,133,816; and water soluble adducts of glycidol and an alkyl phenol such as those described in Olin Mathieson British Pat. No. 1,02
• the photographic layers used in the practice of this invention can be coated by various coating procedures including dip coating, air knife coating, curtain coating, or extrusion coating using hoppers of the type described in Beguin U.S. Pat. No. 2,681,294. If desired, two or more layers can be coated simultaneously by the procedures described in Russell US. Pat. No. 2,761,791 and Wynn British Pat. No. 837,095. This invention also can be used for silver halide layers coated by vacuum evaporation as described in British Pat No. 968,453 and Lu Valle etal. US. Pat. No. 3,219,451.
• the photographic and other hardenable layers used in the practice of this invention can be hardened by various organic or inorganic hardeners, alone or in combination, such as the aldehydes, and blocked aldehydes, ketones, carbocyclic and carbonic acid derivatives, sulfonate esters, sulfonyl halides and vinyl sulfonyl ethers, active halogen compounds, epoxy compounds, aziridines, active' olefin, isocyanates, carbodiimides, mixed function hardeners and polymeric hardeners such as oxidized polysaccharides like dialdehyde starch and oxyguargum and the like.
• various organic or inorganic hardeners such as the aldehydes, and blocked aldehydes, ketones, carbocyclic and carbonic acid derivatives, sulfonate esters, sulfonyl halides and vinyl sulfonyl ethers, active halogen compounds, epoxy compounds, azirid
• Red-sensitive internal image gelatin-silver chlorobromide emulsion (171 mg. gelatin/ft and 110 mg. silverlft cyan image transfer coupler l-hydroxy- 4- ⁇ 4-[a -(3-pentadecylphenoxy(butyramido]phenoxy ⁇ -N-ethyl-3',5-dicarboxy-2-naphthanilide (120 mg/ft and a foggingagent formyl-4-methylphenylhydrazine (0.5 g/mole of silver chlorobromide) 2.
• a scavenger interlayer comprising l-hydroxy-N- [a-(2,4-di-tert arnylphenoxy)butyl]-2-naphthamide (45 mglft tri-cresyl phosphate (23 mg/ft) and gelatin (65 mglft 3. Green-sensitive internal image silver chlorobromide emulsion (116 rng. gelatin/f9 and 100 mg.
• a scavenger and a yellow filter layer comprising 1- hydroxy-N-[a-(2,4-di-tert-amylphenoxy)butyl]-2 'naphthamide (-50 mg/ft), tri-cresyl phosphate (25 mg/ft"), yellow Carey Lea silver l5 mg/ft and gelatin (65 mglft 5.
• Two samples of the photosensitive element are exposed to a graduated-density multicolor test object.
• the following processing composition is employed in a pod and is spread between the exposed surface of the photosensitive element and each superposed dye image-receiving element by passing the transfer sandwich" between a pair of juxtaposed pressure rollers:
• a multilayer, multicolor photosensitive element is prepared according to the procedure described in Example 1 except that a blue sensitive gelatin-silver chlorobromide emulsion (126 mg gelatin/ft and mg silverlft is substituted for the silver chlorobromoiodide emulsion in layer 5 of Example 1.
• a multilayer dye image-receiving element is prepared by coating the following layers in the order recited on an opaque cellulose acetate film support:
• Example II Two samples of the photosensitive element are exposed and processed as in Example I.
• the elements are oven-tested as in Example l and then the background densities measured.
• the background density of the dye image-receiving element of the invention is 60 percent less than the background density observed with the control dye image-receiving element which does not contain the developer scavenger layer.
• Example 2 The procedure as described in Example 2 is followed with the exception that layers 1 and 2 of the dye imagereceiving layer are combined into a single 'layer.
• the background density of the dye image-receiving elements of the invention after 24 hrs. at 60C./70% R.H. is 64 percent less than the background density observed with a dye image-receiving element of the same configuration, but without the isocyanate-bisulfite adduct scavenger layer.
• a rupturable container containing an alkaline processing composition and which is adapted to be positioned during processing of said film unit so that a compressive force applied to said container by said pressure-applying members will effect a discharge of the containers contents within said film unit;
• said film unit containing an aromatic primary amino color developing agent; the improvement comprising employing a developing agent scavenger layer comprising an isocyanate-bisulfite addition product in a polymeric binder, said isocyanate-bisulfite addition product having the formula:
• M represents an alkali metal ion.
• the film unit of claim 4 which contains a timing layer between said scavenger layer and said dye imagereceiving layer.
• each-said nondiffusible coupler having the formula DYE LINK (COUP BALL) BALL LINK (COUP SOL) group consisting of a S-pyrazolone coupler radical, a pyrazolotriazole coupler radical, a phenolic coupler radical and an open-chain ketomethylene coupler radical, said COUP being substituted in the coupling position with said LINK;
• BALL is a photographically inert organic ballasting radical of such molecular size and configuration as to render said coupler nondiffusible during development in said alkaline processing composition;
• n is an integer of l to 2 when said LINK is an alkylidene radical, and n is I when said LINK is a radical selected from the group consisting of an azo radical, a mercuri radical, an oxy radical, a thio radical, a dithio radical and an azoxy radical;
• a dye image-receiving element comprising a support having thereon a dye image-receiving layer, said element being adapted to be superposed over said blue-sensitive silver halide emulsion layer after exposure of said photosensitive element;
• a rupturable container containing an alkaline processing composition and which is adapted to be positioned during processing of said film unit so that a compressive force applied to said container by said pressure'applying members will effect a discharge of the containers contents between said dye image-receiving layer and said blue-sensitive silver halide emulsion layer of said photosensitive element; said film unit containing an aromatic primaryamino color developing agent; the improvement comprising employing between said dye image-receiving layer and its said support a developing agent scavenger layer comprising an isocyanate-bisulfite addition product in a polymeric binder, said isocyanate-bisulfite addition product having the formula:
• a developing agent scavenger layer comprising an isocyanatebisulfite addition product in a polymeric binder, said isocyanate-bisulfite addition product having the formula:
• R represents an acyclic alkyl group, an alke- Posed photosensitive element and Said y image nyl group, an alicyclic group, or an aryl group; receiving y and R represents a hydrogen atom or an alkyl group; and Q p y a Compressive force to Said container to M represents an alkali metal i effect a discharge of the containers contents 5 between said outermost layer of said exposed 13.
• said treatment h t iti element d id d i i step B) is effected by ing layer.

Landscapes

• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)
• Photosensitive Polymer And Photoresist Processing (AREA)

Applications Claiming Priority (1)

Publications (1)

Family

ID=22310562

Family Applications (1)

Country Status (8)

Cited By (5)

Citations (1)

• 1971
  • 1971-01-13 US US00106281A patent/US3725063A/en not_active Expired - Lifetime
  • 1971-12-06 CA CA129,386A patent/CA982394A/en not_active Expired
• 1972
  • 1972-01-04 FR FR7200083A patent/FR2121553B1/fr not_active Expired
  • 1972-01-06 BE BE777782A patent/BE777782A/fr unknown
  • 1972-01-12 NL NL7200475A patent/NL7200475A/xx unknown
  • 1972-01-12 GB GB146272A patent/GB1376234A/en not_active Expired
  • 1972-01-13 DE DE19722201392 patent/DE2201392A1/de active Pending
  • 1972-01-13 IT IT19343/72A patent/IT946557B/it active

Patent Citations (1)

Also Published As

Similar Documents