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
  • G03C8/42—Structural details
  • G03C8/52—Bases or auxiliary layers; Substances therefor
• • 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
  • G03C8/42—Structural details
  • G03C8/44—Integral units, i.e. the image-forming section not being separated from the image-receiving section
  • G03C8/48—Integral units, i.e. the image-forming section not being separated from the image-receiving section characterised by substances used for masking the image-forming section
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
  • Y10S430/142—Dye mordant

Definitions

• U.S. Pat. No. 3,445,228 issued May 20, 1969, of Beavers et al discloses that a white pigment contained in an interlayer of a dye image-receiving element for use in the above-described process conceals the stain formed in an acid layer and functions also as a timing layer. It would be desirable to provide an image-receiving element wherein higher maximum dye densities and lower minimum dye densities are obtainable, as well as a reduction of visible stain and background densities.
• a photographic film unit according to my invention which is adapted to be processed by passing the unit between a pair of juxtaposed pressure-applying members, such as would be found in a camera designed for in-camera processing, comprising:
• a photosensitive element comprising a support having thereon at least one, and preferably three, photosensitive silver halide emulsion layers, each silver halide emulsion layer having associated therewith a dye image-providing material comprising a nondiffusible coupler capable of reacting with oxidized aromatic primary amino color developing agent to produce a diffusible dye;
• a dye image-receiving element comprising a support having thereon (l) a light-reflecting layer comprising a basic polymeric mordant and an opacifying agent and (2) a dye image-receiving layer comprising a basic polymeric mordant; and
• a rupturable container containing an alkaline processing composition and which is adapted to be positioned between said photosensitive element and said dye image-receiving element during processingof 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 film unit containing an aromatic, primary amino color developing agent, preferably in the rupturable container.
• the dye image-receiving layer of my film unit is located on a separate support which is adapted to be superposed on the photosensitive element after exposure thereof.
• the processing composition diffuses through the film unit thereby initiating imagewise development of the silver halide emulsion layers.
• Dye images formed as a result of the reaction of oxidized developer with nondiffusible couplers contained in each silver halide emulsion layer or in a layer contiguous thereto are formed as a function of the imagewise exposure of each said silver halide emulsion layer. At least a portion of the imagewise distributions of diffusible dye diffuses to the imagereceiving layer.
• a positive dye image is viewable upon separation of the image-receiving element from the negative element.
• each silver halide emulsion layer of the film assembly of my invention will have associated therewith a dye image-providing material possessing a spectral absorption range substantially complementary to the predominant sensitivity range of its associated emulsion, i.e., the blue-sensitive silver halide emulsion layer will have a yellow dye image-providing material associated therewith, the green-sensitive silver halide emulsion layer will have a magenta dye image-providing material associated therewith, and the red-sensitive silver halide emulsion layer will have a cyan dye imageproviding material associated therewith.
• the dye image-providing material associated with each silver halide emulsion layer can be contained either in the silver halide emulsion layer itself or in a layer contiguous to the silver halide emulsion layer.
• Spectral-sensitizing dyes can be used conveniently to confer additional sensitivity to the light-sensitive silver halide emulsion of the multilayer photographic elements of the invention.
• additional spectral sensitization can be obtained by treating the emulsion with a solution of a sensitizing dye in an organic solvent or the dye may be added in the form of dispersion as described in Owens et al., British Pat. No. 1,154,781 issued June ll, 1969.
• the dye can either be added to the emulsion as a final step or at some earlier stage.
• Sensitizing dyes useful in sensitizing such emulsions are described, for example, in Brooker et al., U.S. Pat. No. 2,526,632 issued Oct. 24, 1950; Sprague, U.S. Pat. No. 2,503,776 issued Apr. 11, 1950; Brooker et al., U.S. Pat. No. 2,493,748 issued Jan. 10, 1950; and Taber et al., U.S. Pat. No. 3,384,486 issued May 21, 1968.
• Spectral sensitizers which can be used include the cyanines, merocyanines, complex (trior tetranuclear) merocyanines, complex (trior tetranuclear) cyanines, holopolar cyanines, styryls, hemicyanines (e.g., enamine hemicyanines), oxonols and hemioxonols.
• Dyes of the cyanine classes can contain such basic nuclei as the thiazolines, oxazolines, pyrrolines, pyridines, oxazoles, thiazoles, selenazoles and imidazoles.
• Such nuclei can contain alkyl, alkylene, hydroxyalkyl, sulfoalkyl, carboxyalkyl, aminoalkyl and enamine groups and can be fused to carbocyclic or heterocyclic ring systems either unsubstituted or substituted with halogen, phenyl, alkyl, haloalkyl, cyano, or alkoxy groups.
• the dyes can be symmetrical or unsymmetrical and can contain alkyl, phenyl, enamine or heterocyclic substituents on the methine or polymethine chain.
• 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 substitutd with alkyl, alkylene, phenyl, carboxyalkyl, sulfoal yl, 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
• Thevarious silver halide emulsion layers of a color film assembly of the invention can be 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 or a Carey Lea silver layer can be present between the bluesensitive 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 can be disposed in a different order, e.g., the blue-sensitive layer first with respect to the exposure side, followed by the red-sensitive and green-sensitive layers.
• the silver halide emulsions used in this invention can comprise, for example, silver chloride, silver bromide, silver chlorobromide, silver bromoiodide, chlorobromoiodide or mixtures thereof.
• the emulsions can be coarse or fine grain and can be prepared by any of the well-known procedures, e.g., single jet emulsions such as those described in Trivelli and Smith, The
• Surface image emulsions can be used or internal image emulsions can be used such as those described in Davey et al. U.S. Pat. No.
• 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). Negative type emulsions may be used or direct positive emulsions may be used such as those described in Leermakers U.S. Pat. No. 2,184,013 issued Dec. 19, 1939; Kendall et al. U.S. Pat. No. 2,541,472 issued Feb. 13, 1951;
• the emulsions used with this invention may be sensitized with chemical sensitizers, such as with reducing agents; sulfur, selenium or tellurium compounds; gold, platinum or palladium compounds; or combinations of these.
• chemical sensitizers such as with reducing agents; sulfur, selenium or tellurium compounds; gold, platinum or palladium compounds; or combinations of these.
• Suitable procedures are described in Sheppard et al. U.S. Pat. No. 1,623,499 issued Apr. 5, 1927; Waller et al. U.S. Pat. No. 2,399,083 issued Apr. 23, 1946; McVeigh U.S. Pat. No. 3,297,447 issued Jan. 10, 1967; and Dunn U.S. Pat. No. 3,297,446 issued Jan. 10, 1967.
• the silver halide emulsions used with this invention may contain speed increasing compounds 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 issued May 12, 1959; Dann et al. U.S. Pat. No. 3,046,134 issued July 24, 1962; Carroll et al. U.S. Pat. No. 2,944,900 issued July 12, 1960; and Goffe U.S. Pat. No. 3,294,540 issued Dec.27, 1966.
• the silver halide emulsions used in the practice of this invention can be protected against the production of fog and can be stabilized against loss of sensitivity during keeping.
• Suitable antifoggants and stabilizers each used alone or in combination include thiazolium salts described in Brooker et a1.
• U.S. Pat. No. 2,694,716 issued Nov. 16, 1954 the azaindenes described in Piper U.S. Pat. No. 2,886,437 issued May 12, 1959; and l-leimbach et al.
• U.S. Pat. No. 2,444,605 issued July 6, 1948; the mercury salts as described in Allen et al.
• the nondiffusible couplers employed in this invention include those having the formulas:
• l DYE is a dye radical exhibiting selective absorption in the visible spectrum and containing an acidic solubilizing radical
• LINK is a connecting radical such as an azo radical, a mercuri radical, an oxy radical, an alkylidene radical, a thio radical, a dithio radical or an azoxy radical;
• COUP is a coupler radical such as a S-pyrazolone coupler radical, a pyrazolotriazole coupler radical, a phenolic coupler radical or an open-chain ketomethylene coupler radical, COUP being substituted in the coupling position with LINK;
• 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 1 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 attachedto 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 carboxylie, sulfonic, ionizable sulfonamide and hydroxy-substituted groups that lend to dyes negative charges.
• ballast groups in the diffusible dyeproducing coupler compounds described above is 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 8 carbon atoms.
• Typical dye radical substitutents 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.
• coupler radicals couple at the carbon atom in the 4- position
• the phenolic coupler radicals including anaphthols
• the open-chain ketomethylene coupler radicals couple to the carbon atom forming the methylene moiety
• BALL is a photographically inert organic ballasting radical having at least eight carbon atoms and of such molecular size and configuration as to render the coupler nondiffusible during development in an alkaline processing composition
• CYANCOUP is a phenolic coupler radical substituted in the 2-position with a fully substituted amido group and attached to the -O-moiety of the cyanproducing coupler in the coupling position;
• YELLCOUP is an open-chain ketomethylene coupler radical attached to the O moiety of the yellowproducing coupler in the coupling position.
• 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 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 connecting radical (LINK) is split and a diffusible preformed dye (DYE) is released which diffuses imagewise to a reception layer.
• An acidic solubilizing group on the preformed dye lends diffusibility to the dye molecule.
• the coupling portion of the coupler (COUP) couples with the color developing agent oxidation product to form a dye that is nondiffusible because of the attacked ballasting group (BALL) in a noncoupling position.
• 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 production of diffusible dye images is a function of the reduction of developable silver halide images which may involve direct or reversal development of the silver halide emulsions with an aromatic primary amino developing agent.
• the silver halide emulsion employed is a direct-positive silver halide emulsion, such as an internal-image emulsion or a solarizing emulsion, which is developable in unexposed areas, a positive image can be obtained in the dye image-receiving layer.
• the nondiffusible coupler can be located in the silver halide emulsion itself.
• the alkaline processing composision layers After exposure of the film unit, the alkaline processing composision layers.
• the aromatic primary amino color developing agent present in the film unit develops each of the silver halide emulsion layers in the unexposed areas (since the silver halide emulsions are direct-positive ones), thus causing the developing agent to become oxlayer to form imagewise distributions, respectively, of
• diffusible cyan,'magenta and yellow dye as a function of the imagewise exposure of each of the silver halide emulsion layers. At least a portion of the imagewise distributions of diffusible cyan, magenta and yellow dye diffuse to the image-receiving layer to provide a positive dye image upon separation of the receiver from the negative. Specific examples of such nondiffusing couplers and other details concerning this type of photographic chemistry are found in U.S. Pat. Nos. 3,227,550 and 3,227,552.
• Internal-image silver halide emulsions useful in the above-described embodiment are direct-positive emulsions that form latent images predominantly inside the silver halide grains, as distinguished from silver halide grains that form latent images predominantly on the surface thereof. Such internal-image emulsions were described by Davey et al. in U.S. Pat. No. 2,592,250 issued Apr. 8, 1952, and elsewhere in the literature. Internal-image silver halide emulsions can be defined in terms of the increased maximum density obtained when developed with intemal-type developers over that obtained when developed with surface-type developers.
• Suitable internal-image emulsions are those which, when measured according to normal photographic techniques by coating a test portion of the silver halide emulsion on a transport support, exposing to a light-intensity scale having a fixed time between 0.01 and 1 second, and developing for 3 minutes at 20 C.
• Developer A internaltype developer
• Developer B described below-(- surface-type developer).
• the maximum density in Developer A is at least 0.5 density unit greater than the maximum density in Developer B.
• the solarizing direct-positive silver halide emulsions useful in the above-described embodiment are wellknown silver halide emulsions which have been effectively fogged either chemically or by radiation to apoint which corresponds approximately to the maximum density of the reversal curve as shown by Mees, I
• Intemal-image silver halide emulsions which contain or which are processed in the presence of fogging or nucleating agents are particularly useful in the abovedescribed embodiment employing nondiffusible couplers,since the use of fogging agents is a convenient way to inject electrons into the silver halide grains.
• Suitable fogging agents include the hydrazines disclosed in Ives, U.S. Pat. Nos. 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, 1966; hydrazone quaternary salts described in Lincoln and Heseltine, U.S. Ser. No.
• the quantity of fogging agent employed can be widely varied depending upon the results desired.
• concentration of fogging agent is from about 1 to about mg. per square foot of photosensitive layer in the photosensitive element or from about 0.1 to about 2 g. per liter of developer if it is located in the developer.
• 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. 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.
• aromatic primary amino color developing agents employed in this invention are preferably pphenylenediamine developing agents.
• These developing agents are well-known to those skilled in the art and include the following compounds and salts thereof: 4- amino-N,N-diethyl-3-methyl aniline, N,N-diethyl-pphenylenediamine, N-ethyl-fl-methanesulfonamidoethyl-3-methyl-4-aminoaniline, 4-amino-N- ethyl-3-methyl-N-(B-sulfoethyUaniline, 4-amino-N- ethyl-3 -methoxy-N-(fi-sulfoethyl)aniline, 4-amino-N- ethyl-N-(fl-hydroxyethyD-aniline, 4-amino-N,N- diethyl-3-hydroxymethyl aniline, 4-amino-N-methyl-N- (B-carboxyethyl)aniline, 4-amino-N,N-bisUB-hydrox- 4-amino
• the rupturable container employed in this invention 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 fluid and 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 the processing composition is contained.
• each silver halide emulsion layer containing a dye image providing 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 U.S. Pat. Nos. 2,992,104, 3,043,692, 3,044,873, 3,061,428, 3,069,263, 3,069,264, 3,121,011and 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, and the alkaline solution-permeable polymeric interlayers, e.g., gelatin, are about 1 to 5 microns in thickness.
• the alkaline solution-permeable polymeric interlayers e.g., gelatin
• these thicknesses are approximate only and can be modified according to the product desired.
• other 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(vinylpyrrolidone), acrylamide polymers 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 Nottorf, U.S. Pat. No. 3,142,568 issued July 28, 1964; White, U.S. Pat. No. 3,193,386 issued July 6, 1965; l-louck et al., U.S. Pat. No. 3,062,674 issued Nov. 6, 1962;1-Iouck et al., U.S. Pat. No. 3,220,844 issued Nov.
• the dye image-receiving layer and the polymer in the light-reflecting layer in this invention comprises a basic polymeric mordant.
• Especially preferred basic polymeric mordants are those described and claimed in copending U.S. Ser. No.
• the basic polymeric mordants are g; and xeis an anion, a monovalem ga composed of a polymer having quaternary nitrog salt-forming radical or atom in ionic relationship with groups d at least two aromatic l i f h the positive salt-forming radical orpolymer cation such quaternary nitrogen atom, said monomer: compound as a halide, alkyl, Sulfonate, for p 1 being substantially free of carboxy groups.
• said polymer comprises at least two aromatic nuclei for Preferred basic polymeric mordants comprise units 0 each quaternary mtfogen said R y of the following formula in copolymerized relationship T above'descnbed baslclpolymenc mordants are with units of at least one other ethylenically unsatuwater'soluble P y having a Polyhydrocarbon rated monomer:
• the polymers should be L 1 I J v substantially free of carboxy groups for the presence of carboxy groups in the interpolymers interferes with ef- 3 fective dye mordanting.
• the above-described basic polymeric mordants are generally prepared by quatemizing an intermediate polymer having tertiary nitrogen atoms with an alkylating or aralky1ation agent.
• the method of preparation of the -intermediate polymer containing the. tertiary nitrogen atoms for subsequent quaternization is not critical. Any of the methods known in the art such as mass, solution, or head polymerization, as well as condensation polymerization, can be used, and the catalysts known to the art such as ultraviolet light,
• R and R can each be hydrogen atoms, lower alkyl, e.g., one to six carbon atoms such as methyl, ethyl, propyl, n-butyl, t-butyl, and the like; and R can additionally be a group containing at'least one aromatic nucleus including substituted aryl, e.g., pheny], naphthyl, tolyl, etc.; 0 can be a covalent bond, a divalent alkylene, arylene, aralkylene or arylenealkyl radical such as:
• the mordanting amount of basic polymeric mordant to be employed in a dye image-receiving layer will vary radicals including: over a wide range depending upon the amount of dye to be mordanted, the particular polymer employed, the imaging chemistry involved, etc. This amount can easily be determined by one skilled in the art.
• Typical ethylenically unsaturated monomers which where -R- is an alkylene radical typically having one can be used to form ethenic interpolymers comprising to four carbon atoms or R can be taken together with so the above-described basic polymeric mordants include Qto forma ethylene, propylene, l-butene, isobutene, 2-methylpentene, 2-methylbutene, l,l,4,4-tetramethylbu- 0 tadiene, styrene, alpha-methylstyrene; monoethylenically unsaturated esters of aliphatic acids such as vinyl acetate, isopropenyl acetate, allyl acetate, ctc.; esters of ethylenically unsaturated monoor dicarboxylic acids such as methyl acrylate, methyl methacrylate,
• monoeth lenicall unsaturated com ounds such as B' P and R5 arc lower alkyl mcludmg 0 acrylonitr ile, ally l cyanide, and dier fes such as bustituted alkyl, e.g., aralkyl, cyanomethyl, alkoxymethyl, adieu and isoprene.
• backbone and are composed of recurring units supply-' peroxides, azo compounds, e.g., azobisisobutyronitrile,
• Basic polymeric mordants included within the scope of the invention include the following:
• a pl-I-lowering layer in the dye image-receiving element employed in this invention will 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 or 14 to at least 11 and preferably -8 within a short time after imbibition.
• polymeric acids as disclosed in U.S. Pat. No. 3,362,819 may be employed. Such polymeric acids reduce the pH of the film unit after development to further terminate 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 water-soluble sodium and/or potassium salts.
• polymeric acids examples 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 sult'oanhydrides, e.g., with orthosulfobenzoic 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., 0-, mor pbenzaldehyde sulfonic acid or carboxylic acid; ethylene/maleic anhydride copolymers and their partial esters; methylvinyl ether/maleic anhydride copolymers and-their partial esters such as the butyl half-ester of medium viscosity poly-(methylvinyl ether/maleic anhydride); etc.
• solid monomeric acid materials could also be used such as palmitic acid, oxalic acid, sebacic acid, hydrocinnamic acid, metanilic acid, paratoluenesulfonic acid and bensenedisulfonic acid.
• Other suitable materials are disclosed in U.S. Pat. Nos. 3,422,075 and 2,635,048.
• the pH-lowering layer is usually about 0.3 to about 1.5 mils in thickness and is preferably located in the dye image-receiving element between the sup port and the opacifying layer.
• the light-reflecting layer employed in my invention comprises a basic polymeric mordant, such as the ones described above, and an opacifying agent.
• white opacifying agents since they would provide an esthetically pleasing background on which to view a transferred dye image and would 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. Especially good results are obtained with titanium dioxide.
• Zinc oxide in combination with titanium dioxide may also be employed to great advantageas disclosed and claimed in copending application U.S. Ser. No. 174,443 of my co-workers'Abbott, Dappen and lrani filed of even date herewith.
• Brightening agents such as the stilbenes, coumarins, triazines and oxazoles can also be added to the light-reflecting or opacifying layer, if desired. It is believed that any stain resulting from excess developing agent or oxidized developing agent is hidden in or masked by this layer.
• the basic polymeric mordant in the light-reflecting layer will function as a timing layer and will control the pH reduction of the dye image-receiving element as a function of the rate at which the alkali diffuses through the layer.
• the basic polymeric mordant can be employed in the light-reflecting layer, depending upon the results desired.
• 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 solution is preferred which will impart thereto a viscosity of about cps. to about 200,000 cps.
• alkaline processing composition used in this invention can be employed in a rupturable container, as described previously, other methods of applying processing composition could also be employed, e.g., bathing the photosensitive element in a processing I bath, interjecting processing composition with communicating members similar to hypodermic syringes which are attached either to a camera or camera cartridge,
• film units of my invention can be modified so as to'be employed in roll form, they are preferably used in cartridges similar to those described in U.S. Pat. Nos. 3,080,805, 3,161,118 and 3,161,122, said patents also illustrating typical cameras for performing color diffusion transfer processes of my invention.
• the supports for the photographic elements of this invention can be any material as long as it does not deleteriously affect the photographic properties of the film unit and is dimensionally stable.
• Typical 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, paper, metal, etc.
• the support is usually about 2 to 6 mils in thickness.
• the dye image-receiving element of my invention can be prepared by employing various leveling agents and/or coating aids such as the copolymers of dimethyl siloxane and polyoxyalkylene ether described in U.S. Pat. Nos. 3,324,058 and 3,483,240.
• the dye image- 1 receiving element according to my invention can also be overcoated with a hydrophilic colloid layer such as gelatin, gum arabic or any of those materials described in U.S. Application Ser. No. 100,486 of Abbott, filed Dec. 21, 1970.
• the dye image-receiving element of my invention can contain ultraviolet absorbing materials to protect the mordanted dye images from fading due to ultraviolet light. Such materials are described in U.S. Pat. Nos. 3,460,942; 3,069,262; 3,330,680 and 3,330,656.
• the photographic layers employed in the practice of this invention may contain surfactants such as saponin or any of the materials described in U.S. Pat. Nos. 2,600,831; 3,133,816; or 3,514,293 or British Pat. No. 1,022,878.
• the various layers, including the photographic layers, employed in the practice of this invention can contain light-absorbing materials and filter dyes such as those described in Sawdey, U.S. Pat. No. 3,253,921 issued May 31, 1966; Gaspar, U.S. Pat. No. 2,274,782 issued Mar. 3, 1942; Silberstein et al., U.S. Pat. No. 2,527,583 issued Oct. 31, 1950; and VanCampen, U.S. Pat. No.'2,956,879 issued Oct. 18, 1960.
• the sensitizing dyes and other addenda used in the practice of this invention can be added from water solutions or suitable organic solvents may be used.
• photographic layers used in the practice of this invention may 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. 2,681,294 issued June 15, 1954. 1f desired, two or more layers may be coated .simultaneously by the procedures described in Russell,
• a I control dye image-receiving element is prepared by coating the following layers in the order recited on a polyethylene-coated paper support;
• polymeric acid layer of poly(methyl vinyl ether/maleic anhydride) (825 mg./ft.'),
• a dye image-receiving element according to my invention is prepared by coating the following layers in the order recited on a polyethylene-coated paper support:
• polymeric acid layer of poly(methyl vinyl ether/maleicanhydride) (825 mg./ft.);
• benzyl-N ,N-dimethyl-N-( 3- maleimidopropyl)ammonium chloride 400 mg./ft.
• titanium dioxide 1000 mg./ft.
• a multicolor photographic element of the type described in Example 1 of Whitmore et al., U.S. Pat. No. 3,227,550 issued Jan. 4, 1966, is prepared.
• the emulsions are directpositive, gelatino, silver bromoiodide emulsions containing cyan, magenta and yellow dye-forming couplers in the red, green and blue light-recording emulsions, respectively.
• mordant layer of copoly[styrene-N-benzyl-N,N- dimethyl-N-(3-maleimidopropyl)ammonium chloride] (200 mg./ft.) and gelatin (200 mg./ft.);
• an image-receiving element similar to (B) of Example l is prepared except that mordant layer (3) contains 200 mg./ft. instead of 350 mg./ft. of the mordant compound and also contains 200 mg./ft. of gelatin. Layer (4) is also omitted.
• a photographic film unit which is adapted to be processed by passing said unit between a pair of juxtaposed pressure-applying members comprising:
• a photosensitive element comprising a support having thereon at least one photosensitive silver halide emulsion layer, each said silver halide emulsion layer having associated therewith a nondiffusible coupler capable of reacting with oxidized aromatic primary red, green and blue are then measured, both fresh and 45 amino color developing agent to produce a diffusible after 4 days at 140 F./% R.H.
• the following results dye are obtained: b. a dye image-receiving layer coated on a support 4 days at. Fresh l .l70% RJI.
• a rupturable container containing an alkaline processing composition and which is adapted to be E l 3 positioned between said photosensitive element and Xamp e said dye image-receiving layer during processing of said Dye image-receiving elements are prepared coatfllm unit SO a compressive force to said ing the following layers in the order recited on a polyethylene-coated paper support:
• polymeric acid layer of poly(methyl vinyl ether/maleic anhydride) (825 mg./ft.”
• said film unit containing an aromatic primary amino color developing agent; the improvement comprising employing a basic polymeric mordant as said dye image-receiving layer, said dye image-receiving layer being coated over a light-reflecting layer comprising a basic polymeric mordant and an opacifying agent.
• said photosensitive element comprises a support having thereon a red-sensitive silver halide emulsion layer having associated therewith a cyan dye image-providing material comprising a nondiffusible coupler capable of reacting with oxidized aromatic primary amino color developing agent to produce a diffusible cyan dye, a green-sensitive silver halide emulsion layer having associated therewith a magenta dye image-providing material comprising a nondiffusible coupler capable of reacting with oxidized aromatic primary amino color developing agent to produce a diffusible magenta dye, and a blue-sensitive silver halide emulsion layer having associated therewith a yellow dye image-providing material comprising a nondiffusible coupler capable of reacting with oxidized aromatic primary amino color polymer having at least 1/3 of the units represented by the following formula in copolymerizedrelationship with units of at least one other ethylenically unsaturated monomer.
• R and R are hydrogen atoms or lower alkyl groupsand R can additionally be a group containing at least one aromatic nucleus; Q can be a covalent bond, a
• divalent alkylene radical a divalent arylene radical, a
• divalent aralkylene radical a divalent arylenealkylene radical
• R is analkylene radical, or R can be taken together with Q to form a i and X6is a monovalent negative salt-forming radical or atom; wherein said polyr'neris substantially free of car;
• each said basic polymeric mordant is copoly[styrene- N-benzyl-N,N-dimethyl-N-(3-maleimidopropyl)animonium chloride].
• each said basic polymeric mordant comprises copoly[styrene-N-benzyl-N,N-dimethyl-N (3- maleimidopropyl)ammonium chloride].
• a photographic film unit which is adapted to be processed by passing said unit between a pair of juxtaposed pressure-applying members comprising:
• a photosensitive element comprising a support having thereon the following layers in sequence;
• I a direct-positive, green-sensitive silver halide emulsion layer containing a nondiffusible cou-, pler capable of reacting with oxidized aromatic emulsion layer containing a nondiffusible coupler capable of reacting with oxidized aromatic primary amino color developing agent to produce a diffusible yellow dye; each said nondiffusible coupler, having the formula:
• DYE is a dye radical exhibiting selective absorption in the visible spectrum and containing an acidic solubilizing group
• LINK is a connecting radical'selected from the group consisting of an azo radical, a mercuri radical, an oxy radical, an alkylidene radical, a thio radical, a dithio radical and an azoxy radical;
• COUP is a coupler radical selected from the group consisting of a 5-pyrazolone coupler radical, a pyrazolotriazole coupler radical, a
• 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;
• SOL is selected from the group consisting of a hydrogen atom and an acidic solubilizing group when said color developing agent contains an acidic solubilizing group, and SOL is an acidic solubilizing group when said color developing agent is free of an acidic solubilizing group;
• n is an integer of l to 2 when said LINK is an alkylidene radical, and n is 1 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; II. 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; 7 said film containing an aromatic primary amino color developing agent; the improvement comprising employing as said dye image-receiving element a support having thereon a polymeric acidic material layer, a light-reflecting layer comprising a basic polymeric mordant and an opacifying agent, and a dye image-receiving layer comprising a basic polymeric mordant.
• each said basic polymeric mordant comprises a polymer having at least one-third of the units represented by the following formula in copolymerized relationship with units of at least one other ethylenically unsaturated monomer:
• R and R are hydrogen atoms or lower alkyl groups and R can additionally be a group containing at least one aromatic nucleus;
• Q can be a covalent bond, a divalent alkylene radical, a divalent arylene radical, a divalent aralkylene radical, a divalent arylenealkylene radical,
• R is an alkylene radical, or R can be taken together with Q to form a group
• R R and R" can be lower alkyl or aryl groups, or R and R and the nitrogen atom to which they are attached can be taken together to represent the atoms and bonds necessary to form a quaternized nitrogencontaining heterocyclic ring which is attached to Q
• X is a monovalent negative salt-forming radical or atom
• said polymer is substantially free of carboxy groups and wherein the positive salt-forming radical of said polymer comprises at least two aryl groups for each quaternary nitrogen atom in said polymer and said opacifying agent comprises titanium dioxide.
• a photosensitive element comprising a support having thereon at least one photosensitive silver halide emulsion layer, each said silver halide emulsion layer having associated therewith a nondiffusible coupler capable of reacting with oxidized aromatic primary amino color developing agent to produce a diffusible dye;
• composition comprising an aromatic primary amino color developing agent between said exposed photosensitive element and said dye image-receiving layer;
• the improvement comprising employing a basic polymeric mordant as said dye image-receiving layer,
• said dye image-receiving layer being coated over a light-reflecting layer comprising a basic polymeric mordant and an opacifying agent.
• said photosensitive element comprises a support having thereon a redsensitive silver halide emulsion layer having associated therewith a cyan dye image-providing material comprising a nondiffusible coupler capable of reacting with oxidized aromatic primary amino color developing agent to produce a diffusible cyan dye, a green-sensitive silver halide emulsion layer having associated therewith a magenta dye image-providing material comprising a nondiffusible coupler capable of reacting with oxidized aromatic primary amino color developing agent to produce a diffusible magenta dye, and a bluesensitive silver halide emulsion layer having associated therewith a yellow dye image-providing material comprising a nondiffusible coupler capable of reacting with oxidized aromatic primary amino color developing agent to produce a diffusible yellow dye.
• each said basic polymeric mordant comprises a polymer having at least one-third of the units represented by the following formula in copolymerized relationship with units of at least one other ethylenically unsaturated monomer:
• R and R are hydrogen atoms or lower alkyl' groups and R can additionally be a group containing at least one aromatic nucleus; can be a covalent bond, a divalent alkylene radical, a divalent arylene radical, a divalent aralkylene radical, a divalent arylenealkylene radical,
• R is'an alkylene radical, or R can be taken together with Q to form a group
• R, R and R can be lower alkyl or aryl groups, or R and R and the nitrogen atom to which they are attached can be taken together to represent the atoms and bonds necessary to form a quaternized nitrogencontaining heterocyclic ring which is attached to Q
• X is a monovalent negative salt-forming radical or atom; wherein said polymer is substantially free of carboxy groups.
• each said basic polymeric mordant is copoly[styrene-N-benzyl-N,N- dimethyl-N-(3-maleimidopropyl)ammonium chloride].
• each said basic polymeric mordant comprises copoly[styrene-N- henzyl-N,N-dimethyl-N-(3-maleimidporopyl)ammonium chloride].
• a photosensitive element comprising a support having thereon: a. a direct-positive, red-sensitive silver halide emulsion layer containing a nondiffusible coupler capable of reacting with oxidized aromatic primary amino color developing agent to produce a diffusible cyan dye;
• pler capable of reacting with oxidized aromatic primary amino color developing agent to the group consisting of an azo radical, a mercuri radical, an oxy radical, an alkylidene radical, a thio radical, a dithio radical and an azoxy radical;
• COUI is a coupler radical selected from the 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; v
• 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;
• SOL is selected from the group consisting of a hydrogen atom and an acidic solubilizing group when said color developing agent contains an acidic solubilizing group, and SOL is an acidic solubilizing group when said color developing agent is free of an acidic solubilizing group;
• n is an integer of l to 2 when said LINK is an alkylidene radical, and n is 1 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;
• the improvement comprising employing as said dye image-receiving element a support having thereon a polymeric acidic material layer, a light-reflecting layer comprising a basic polymeric mordant and an opacifying agent, and a dye im age-receiving layer comprising a basic polymeric mordant.
• each said basic polymeric mordant comprises a polymer having at least one-third of the units represented by the following formula in copolymerized relationship with units of at least one other ethylenically unsaturated monomer:
• R and R are hydrogen atoms or lower alkylgroups and R can additionally be a group containing at least one aromatic nucleus;
• Q can be a covalent bond, a divalent alkylene radical, a divalent arylene radical, a divalent aralkylene radical, a divalent arylenealkylene radical,
• R is an alkylene radical, or R can be taken together with Q to form a group
• R, R and R can be lower alkyl or aryl groups, or R and R and the nitrogen atom to which they are attached can be taken together to represent the atoms and bonds necessary to form a quaternized nitrogencontaining heterocyclic ring which is attached to Q
• X is a monovalent negative salt-forming radical or atom; wherein said polymer is substantially free of carboxy groups and wherein the positive salt-forming radical of said polymer comprises at least two aryl groups for each quaternary nitrogen atom in said polymer and said opacifying agent comprises titanium dioxide.
• a reception element comprising a support having thereon:
• a light-reflecting layer comprising a basic polymeric mordant and an opacifying agent and 2.
• a dye image-receiving layer comprising a basic polymeric mordant.
• each said basic polymeric mordant comprises a polymer having at least one-third of the units represented by the following formula in copolymerized relationship with units of at least one other ethylenically unsaturated monomer:
• R and R are hydrogen atoms or lower alkyl groups and R can additionally be a group containing at least one aromatic nucleus;
• Q can be a covalent bond, a divalent alkylene radical, a divalent arylene radical, a divalent aralkylene radical, a divalent arylenealkylene radical,
• R is an alkylene radical, or R can be taken together with Q to form a group
• R, R and R can be lower alkyl or aryl groups, or R and R and the nitrogen atom to which they are attached can be taken together to represent the atoms and bonds necessary to form a quaternized nitrogencontaining heterocyclic ring which is attached to Q
• X is a monovalent negative salt-forming radical or atom; wherein said polymer is substantially free of carboxy groups.
• each said basic polymeric mordant is copoly[styrene-N- benzyl-N,N-dimethyl-N-(3-maleimidopropyl)amrnonium chloride].
• each said basic polymeric mordant is copoly[styrene-N- benzyl-N,N-dimethyl-N-(3-maleimidopropyl)ammonium chloride].

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• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Engineering & Computer Science (AREA)
• Architecture (AREA)
• Structural Engineering (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)
• Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)

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• 0
  • BE BE787862D patent/BE787862A/fr unknown
• 1971
  • 1971-08-24 US US00174506A patent/US3721556A/en not_active Expired - Lifetime
• 1972
  • 1972-06-30 CA CA146,120A patent/CA981510A/en not_active Expired
  • 1972-08-23 NL NL7211521A patent/NL7211521A/xx unknown
  • 1972-08-23 FR FR7230000A patent/FR2150444A1/fr not_active Withdrawn
  • 1972-08-24 GB GB3942872A patent/GB1397646A/en not_active Expired
  • 1972-08-24 JP JP47084155A patent/JPS4830932A/ja active Pending

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