US3816125A - Photographic products and processes - Google Patents

Photographic products and processes Download PDF

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US3816125A
US3816125A US00263539A US26353972A US3816125A US 3816125 A US3816125 A US 3816125A US 00263539 A US00263539 A US 00263539A US 26353972 A US26353972 A US 26353972A US 3816125 A US3816125 A US 3816125A
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layer
silver halide
polymeric
onium salt
dye
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J Demember
H Haas
J Reid
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Polaroid Corp
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Polaroid Corp
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Priority to US00263539A priority Critical patent/US3816125A/en
Priority to GB2761973A priority patent/GB1438187A/en
Priority to NLAANVRAGE7308143,A priority patent/NL179237C/xx
Priority to JP6677473A priority patent/JPS5311378B2/ja
Priority to CA174,205A priority patent/CA1026982A/en
Priority to DE2330621A priority patent/DE2330621C2/de
Priority to FR7322007A priority patent/FR2189775B1/fr
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
    • G03C8/02—Photosensitive materials characterised by the image-forming section

Definitions

  • ABSTRACT The present invention is directed to photography and particularly to diffusion transfer color processes wherein the color separation and highlights are significantly enhanced by carrying out said process in the presence of an onium salt of a polymeric anion.
  • a photosensitive element containing a dye developer that is, a dye which is a silver halide developing agent, and a silver halide emulsion may be exposed and wetted by a liquid processing composition, for example, by immersion, coating, spraying, flowing, etc., in the dark, and the exposed photosensitive element is superposed prior to, during, or after wetting, on a sheetlike support element which may be utilized as an image-receiving element.
  • the liquid processing composition is applied to the photosensitive element in a substantially uniform layer as the photosensitive element is brought into superposed relationship with the image-receiving layer.
  • the liquid processing composition positioned intermediate the photosensitive element and the image-receiving layer, permeates the emulsion to initiate development of the latent image contained therein.
  • the dye developer is immobilized or precipitated in exposed areas as a consequence of the development of the latent image. This immobilization is apparently, at least in part, due to a change in the solubility characteristics of the dye developer upon oxidation and especially as regards its solubility in alkaline solutions. It may also be due in part to a tanning effect on the emulsion by oxidized developing agent, and in part to a localized exhaustion of alkali as a result of development.
  • the dye developer In unexposed and partially exposed areas of the emulsion, the dye developer is unreacted and diffusible and thus provides an imagewise distribution of unoxidized dye developer dissolved in the liquid processing composition, as a function of the point-to-point degree of exposure of the silver halide emulsion. At least part of this imagewise distribution of unoxidized dye developer is transferred, by imbibition, to a superposed image-receiving layer or element, said transfer substantially excluding oxidized dye developer.
  • the image-receiving element receives a depthwise diffusion, from the developer emulsion, of unoxidized dye developer without appreciably disturbing the imagewise distribution thereof to provide the reversed or positive color image of the developed image.
  • the imagereceiving element may contain agents adapted to mordant or otherwise fix the diffused, unoxidized dye developer. If the color of the transferred dye developer is affected by changes in the pH of the image-receiving element, this pH may be adjusted in accordance with well-known techniques to provide a pH affording the desired color.
  • the desired positive image is revealed by stripping theimage-receiving layer from the photosensitive element at the end of a suitable imbibition period.
  • the dye developers are compounds which contain, in the same molecule, both the chromophoric system of a dye and also a silver halide developing function.
  • a silver halide developing function is meant a grouping adapted to develop exposed silver halide.
  • a preferred silver halide development function is a hydroquinonyl group.
  • Other suitable developing functions include ortho-dihydroxyphenyl and orthoand para-amino substituted hydroxyphenyl groups.
  • the development function includes a benzenoid developing function, that is, an aromatic developing group which fonns quinonoid or quinone substances when oxidized.
  • Multicolor images may be obtained using color image-forming components such as, for example, the previously mentioned dye developers, in diffusion transfer processes by several techniques.
  • One such technique contemplates obtaining multicolor transfer images utilizing dye developers by employment of an integral multilayer photosensitive element, such as is disclosed in the aforementioned U.S. Pat. No. 2,983,606, and particularly with reference to FIG. 9 of the patents drawing, wherein at least two selectively sensitized photosensitive strata, superposed on a single support, are processed, simultaneously and without separation, with a single, common image-receiving layer.
  • a suitable arrangement of this type comprises a support carrying a red-sensitive silver halide emulsion stratum, a green-sensitive silver halide emulsion stratum and a blue-sensitive silver halide emulsion stratum, said emulsions having associated therewith, respectively, for example, a cyan dye developer, a magenta dye developer and a yellow dye developer.
  • the dye developer may be utilized in the silver halide emulsion layer, for example, in the form of particles, or it may be employed as a layer behind the appropriate silver halide emulsion strata.
  • Each set of silver halide emulsion and associated dye developer strata are disclosed to be optionally separated from other sets by suitable interlayers, for example, by a layer of gelatin or polyvinyl alcohol.
  • suitable interlayers for example, by a layer of gelatin or polyvinyl alcohol.
  • a yellow dye developer of the appropriate spectral characteristics and present in a state capable of functioning as a yellow filter may be employed. In such instances, a separate yellow filter may be omitted.
  • imagereceiving elements particularly adapted for employment in diffusion transfer processes of the type disclosed in aforementioned U.S. Pat. No. 2,983,606, wherein the image-receiving elements are separated from contact with a superposed photosensitive element, subsequent to substantial transfer image formation, preferably comprise a support layer possessing on one surface thereof, in sequence, a polymeric layer which is acidic in character and an image-receiving layer adapted to provide a visible image upon transfer to said layer of diffusible dye image-forming substance, and most preferably include an inert timing or spacer layer intermediate the acidic polymeric layer and the image-receiving layer.
  • the acid polymeric layer may comprise polymers which contain acid groups, such as carboxylic acid and sulfonic acid groups, which are capable of forming salts with alkali metals, such as sodium potassium etc., or with organic bases, particularly quaternary ammonium bases, such as tetramethyl ammonium hydroxide, or 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 acid polymer contains free carboxyl groups and the transfer processing composition employed contains a large concentration of sodium and/or potassium ions.
  • the acid polymers stated to be most useful are characterized by containing free carboxyl groups, being insoluble in water in the free acid form, and by forming water-soluble sodium and/or potassium salts.
  • 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 hydrogen succinate hydrogen phthalate; ether and ester derivates 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., o-, m-, or pbenzaldehyde sulf
  • the acidic polymer layer is disclosed to contain at least sufficient acid groups to effect a reduction in the pH of the image layer from a pH of about 13 to 14 to a pH of at least 1 l or lower at the end of the imbibition period, and preferably to a pH of about 5 to 8 within a short time after imbibition.
  • the pH of the processing composition preferably is of the order of at least 13. to 14.
  • the pH of the image layer is kept at a level of pH 12 to 14 until the dye image has been formed after which the pH is reduced very rapidly to at least about pH 1 1, and preferably about 9 to 10.
  • Unoxidized dye developers containing hydroquinonyl developing radicals diffuse from the negative to the positive as the sodium or other alkali salt. The diffusion rate of such dye image-forming components thus is at least partly a function of the alkali concentration, and it is necessary that the pH of the image layer remain on the order of 12 to 14 until transfer of the necessary quantity of dye has been accomplished.
  • the subsequent pl-l reduction in addition to its desirable effect upon image light stability, serves a highly valuable photographic function by substantially terminating further dye transfer.
  • the processing technique thus effectively minimizes changes in color balance as a result of longer imbibition times in multicolor transfer processes using multilayer negatives.
  • the acid component is disclosed to be so distributed in the acidic polymer layer that the rate of its availability to the alkali is controllable, e.g., as a function of the rate of swelling of the polymer layer which rate intum has a direct relationship to the diffusion rate of the alkali ions.
  • the desired distribution of the acid material in the acid polymer layer may be effected, for example, by
  • the layer'containing the acid component may contain a water-soluble polymer, preferably a cellulose ester, which acts to control or modulate the rate at which the alkali salt of the acid is formed.
  • a water-soluble polymer preferably a cellulose ester
  • cellulose esters contemplated for use mention is made of cellulose acetate, cellulose acetate butyrate, etc.
  • the particular polymers and combinations of polymers employed in any given embodiment are, of course, selected so as to have adequate wet and dry strength and when necessary or desirable, suitable subcoats may be employed to help the various polymeric layers adhere to each other during storage and use.
  • the acid polymeric layer may be disposed within the photosensitive element of the film unit intermediate that elements support and next adjacent photosensitive silver halide emulsion layer and associated dye image-providing material, with the optional presence of a spacer or timing layer intermediate the acid layer and next adjacent silver halide emulsion layer.
  • the inert spacer layer of the last-mentioned U.S. Patents acts to time control the pH reduction by the polymeric acid layer. This timing is disclosed, to be a function of the rate at which the alkali diffuses through the inert spacer layer. It was stated to have been found that the pH does not drop until the alkali has passed through the spaced layer, i.e., the pH is not reduced to any significant extent by the mere diffusion into the interlayer, but the pH drops quite rapidly once the alkali diffuses through the spacer layer.
  • the aforementioned rate at which the cations of the alkaline processing composition, i.e., alkali ions, are available for capture in the polymeric acid layer should be decreased with increasing transfer processing temperatures in order to provide diffusion transfer color processes relatively independent of positive transfer image variations over an extended range of ambient temperatures.
  • the last mentioned inert spacer layer was disclosed to provide an effective traverse of the inert spacer layer by alkali having temperature depressed diffusion rates and to result in maintenance of the transfer processing environments high pH for such an extended time interval as to facilitate formation of transfer image stain and its resultant degradation of the positive transfer images color definition.
  • acetals of polyvinyl were stated to generally comprise saturated aliphatic hydrocarbon chains of a molecular weight of at least 1,000, preferably of about 1,000 to 50,000, possessing a degree of acetalation within about to 30 percent, 10 to 30 percent, to 80 percent, and 10 to 40 percent, of the polyvinyl alcohols theoretical polymeric hydroxyl groups, respectively, and including mixed acetals where desired.
  • a mixture of the polymers is to be employed, for example, a mixture of hydroxypropyl methyl cellulose and partial polyvinyl butyral.
  • solution dyeable polymers such as nylon as, for example, N- methoxymethyl polyhexamethylene adipamide; partially hydrolyzed polyvinyl acetate; polyvinyl alcohol with or without plasticizers; cellulose acetate with filler as, for example, one-half cellulose acetate and one-half oleic acid; gelatin; and other materials of a similar nature.
  • Preferred materials comprise polyvinyl alcohol or gelatin containing a dye mordant such as poly-4- vinylpyridine, as disclosed in U.S. Pat. No. 3,148,061, issued Sept. 8, 1964.
  • the liquid processing composition referred to for effecting multicolor diffusion transfer processes comprises .at least an aqueous solution of an alkaline material, for example, diethylamine, sodium hydroxide or sodium carbonate and the like, and preferably includes a viscosity-increasing compound constituting a filmforming material of the type which, when the composition is spread and dried, forms a relatively firm and relatively stable film.
  • the preferred film-forming materials disclosed comprise high molecular weight polymers such as polymeric, water-soluble ethers which are inert to an alkaline solution such as, for example, a hydroxyethyl cellulose or sodium carboxymethyl cellulose.
  • film-forming materials or thickening agents whose ability to increase viscosity is substantially unaffected if left in solution for a long period of time are also disclosed to becapable of utilization.
  • the film-forming material is preferably contained in the processing composition in such suitable quantities as to impart to the composition a viscosity in excess of cps. at a temperature of approximately 24 C. and preferably in the order of 100,000 cps. to 200,000 cps. at that temperature.
  • an image-receiving layer of the type disclosed in that patent need not be separated from its superposed contact with the photosensitive element, subsequent to transfer image formation, if the imagereceiving element is transparent and a processing composition containing a substance rendering the dried processing composition layer opaque is spread between the image-receiving layer and the silver halide emulsion or emulsions.
  • U.S. Pat. No. 3,415,644 also discloses a composite photosensitive structure, particularly adapted for reflection type photographic diffusion transfer color process employment, which comprises a plurality of essential layers including, in sequence, a dimensionally stable opaque layer; one or more silver halide emulsion layers having associated therewith dye image-providing material for providing an imagewise distribution of a dye which is soluble and diffusible, in alkali, at a first pH, as a function of the point-to-point degree of its associated silver halide emulsions exposure to incident actinic radiation; a polymeric layer adapted to receive solubilized dye image-providing material difiusing thereto; a polymeric layer containing sufficient acidifying capacity to effect reduction of a processing composition from the first pH to a second pH at which the dye image-providing material is substantially nondiffusible; and a dimensionally stable transparent layer, may be exposed to incident actinic radiation and processed by interposing, intermediate the silver halide emul
  • the transfer dye image is viewed, as a reflection image, through the dimensionally stable transparent layer against the background provided by the opacifying agent, distributed as a component of the processing composition, intermediate the reception layer and next adjacent silver halide emulsion layer.
  • the thus-formed opacifying stratum effectively masks residual dye image-providing material retained in association with the silver halide emulsion layer subsequent to processing. Additional film units of this general type are also set forth in US. Pat. Nos. 3,573,043; 3,576,625; 3,615,421; and 3,586,501.
  • U.S. Pat. No. 3,173,786 disclosed and claims color diffusion transfer processes wherein increased density is achieved in the positive image and is primarily the result of increased transfer of the dye developer from unexposed areas of the negative.
  • This increased density is achieved by carrying out the development process in the presence of an onium compound and is believed to be due at least in part to the ability of the onium compounds to increase the solubility of the dye developers, thus effecting control, especially in exposed areas, of the diffusibility of the dye developers.
  • the disposition of the onium compounds in the film unit is limited to some degree. For example, care must be taken in disposing the onium compound in the film unit prior to exposure to prevent the onium compound from desensitizing the emulsion.
  • the present invention is directed to improved photographic products and processes, particularly color diffusion transfer processes, wherein the development of the exposed film unit is carried out in the presence of an onium salt of a polymeric anion.
  • the polymeric nature of the compound permits it to be disposed at various locations in the film unit in a form that renders the onium compound unavailable with respect to interaction with other elements of the film unit.
  • the cation becomes readily available by cation exchange upon contact of the film unit with the alkali of the processing composition when said processing composition is applied to the film unit subsequent to exposure.
  • FIGURE is a cross-sectional view of the film unit of the present invention.
  • the present invention is directed to products suitable for use in photographic processes, particularly color diffusion transfer processes.
  • the film unit of the present invention in its preferred embodiment, comprises at least a first silver halide emulsion layer having associated therewith color image-providing materials and an onium salt of a polymeric anion.
  • an onium salt of a polymeric anion can be disposed in the film unit, either in a separate layer on in another layer in the film unit, which will provide the onium compound at the desired time, that is, during the development of the exposed photosensitive element, but which will be maintained in a photographically inactive or nonreactive state until the processing composition is applied to the film unit, thus insuring the desired degree of stability and sensitivity of the film unit.
  • the onium salt of the polymeric anion be disposed in the photosensitive element and preferably is employed as an overcoat over the photosensitive element or is disposed in the silver halide emulsion.
  • the advantages of processing a photographic silver halide emulsion film unit in the presence of an onium compound to achieve the well-known properties of emulsion speed, accelerated development and enhanced color isolation by virtue of the insolubilizing of oxidized dye developer without the necessity of adding the onium compound with the processing composition.
  • the onium compound is applied to the film unit as a component of the processing composition, efficient use is not made of the entire quantity of onium compound provided.
  • a portion of the onium compound will remain on the surface of the film unit; in the case of diffusion transfer processing, a portion will migrate into the receiving element or positive layer and a portion must penetrate various layers of the negative to contact the silver halide emulsion and the dye developers in order to carry out its function.
  • the onium compound is disposed in the film unit in or close to the location in which it is to function.
  • it since it is unavailable or photographically inactive, it can be, if desired, incorporated directly into the silver halide emulsion layer without the well-known detrimental effects normally associated with onium compounds, namely desensitizing at high relative humidity or fogging at low relative humidity.
  • loss of onium compound to other portions of the film unit is minimal and its reaction with the appropriate components in the film unit is initiated significantly earlier in the processing. Removing the onium compound from the processing com position also enhances the stability and efficacy of the processing composition by eliminating the possibility of extraneous reactions and instability resulting from the presence of the onium compound.
  • the anion selected for employment in the present invention may comprise substantially any polymeric organic acid, that is, a polymeric backbone having pendant acid groups thereon such as carboxyl groups, sulfonic acid groups, carbonic acid groups and the like.
  • the polymeric material selected as the anion will have a relatively low charge density.
  • the onium salt of a polymeric anion may be diluted with an innocuous diluent such as gelatin.
  • polyvinyl hydrogen phthalate polyvinyl acrylic acid and carboxymethyl cellulose.
  • quaternary ammonium compounds are organic compounds containing a pentavalent nitrogen atom. Generally, they can be considered as derivatives of ammonium compounds wherein the four valences usually occupied by the hydrogen atoms are occupied by organic radicals. Generally, the organic radicals are joined directly to the pentavalent nitrogen through a single or double carbon-to-nitrogen bond.
  • quaternary ammonium is intended to cover compounds wherein the pentavalent nitrogen is one of the nuclear atoms in a heterocyclic ring as well as those wherein each of the four valencesis attached to separate organic radicals, e.g., tetraalkyl quaternary ammonium compounds.
  • organic radicals e.g., tetraalkyl quaternary ammonium compounds.
  • N,N-diethyl-piperidinium and and for ex- EXAMPLE I Preparation of N-phenethyl-a-picolinium polyvinylhydrogen phthalate 109 g. (0.43 mole polymer units) of potassium polyvinyl hydrogen phthalate in 2 liters of water was mixed with 250 g. of N-phenethyl-a-picolinium bromide (0.76 mole) in 500ml. of water. The resulting solution was dialyzed with distilled water until a negative silver nitrate test was observed. This final mixture was freezedried to yield polyvinyl hydrogen phthalate with percent.
  • N-phenethyl-a-picolinium salt poly( acrylic acid) The procedure was essentially the same as that described in Example I except that the ammonium salt of poly'acrylic acid was used as anion sources instead of potassium polyvinyl hydrogen phthalate.
  • film unit 10 comprises rupturable container 11, retaining, prior to processing, aqueous alkaline solution 12, and photosensitive laminate 13 including, in order, dimensionally stable support layer 14, preferably a flexible sheet material; cyan dye developer layer 15; red-sensitive halide emulsion layer 16; interlayer l7; magenta dye developer layer 18; green-sensitive silver halide emulsion layer 19; interlayer 20; yellow dye developer layer 21; bluesensitive silver halide emulsion layer 22; auxiliary layer 23, which may contain an auxiliary silver halide developing agent; and an image-receiving element 28 including image-receiving layer 24; spacer layer 25; neutralizing layer 26; and dimensionally stable support layer 27, preferably a flexible sheet material.
  • Rupturable container 11 may be of the type shown and described in any of US. Pat. Nos. 2,543,181; 2,634,886; 2,653,732; 2,723,051; 3,056,492; 3,056,491; 3,152,515; and the like.
  • such containers will comprise a rectangular blank of fluidand air-impervious material folded longitudinally upon itself to form two walls 29 which are sealed to one another along their longitudinal and end margins to form a cavity in which processing solution 12 is retained.
  • the longitudinal marginal seal 30 is made weaker than the end 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 compressive pressure to walls 29 of the container.
  • container 11 is fixedly positioned and extends transverse a leading edge of laminae l3 and 28 whereby to effect unidirectional discharge of the containers contents 12 between imagereceiving layer 24 and the stated layer next adjacent thereto, upon application of compressive force to container 11.
  • container 11, as illustrated is positioned and extends transverse a leading edge of laminae 13 and 28 with its longitudinal marginal seal 30 directed toward the interface between image-receiving layer 28 and auxiliary layer 23.
  • the fluid contents of the container comprise an aqueous alkaline solution having a pH at which the dye developers are soluble and diffusible.
  • film unit is processed by being passed through opposed suitably gapped rolls 35 in order to apply compressive pressure to frangible container 11 and to effect rupture of longitudinal seal 30 and distribution of alkaline processing composition 12, having a pH at which the cyan, magenta and yellow dye developers are soluble and diffusible, intermediate dyeable polymeric layer 24 and auxiliary layer 23.
  • Alkaline processing solution 12 permeates emulsion layers 16, 19 and 22 to initiate development in the respective emulsions, the cyan magenta and yellow dye developers of layers 15, 18 and 21 are immobilized, as a function of the development of their respective associated silver halide emulsions, preferably substantially as a result of their conversion from the reduced form to their relatively insoluble and nondiffusible oxidized form, there providing imagewise distributions of mobile, soluble and diffusible cyan, magenta and yellow dye developer, as a function of the point-to-point degree of their associated emulsions exposure.
  • At least part of the imagewise distributions of mobile cyan, magenta and yellow dye developer transfers, by diffusion, to aqueous alkaline solution permeable polymeric layer 24 to provide a multicolor dye transfer image to that layer.
  • a sufficient portion of the ions comprising aqueous alkaline solution 12 transfers, by diffusion, through permeable polymeric layer 24, permeable spacer layer 25 and to permeable polymeric acid layer 26 whereby alkaline solution 12 decreases in pH, as a function of neutralization, to a pH at which thecyan, magenta and yellow dye developers, in the reduced form, are insolubleand nondiffusible, to provide thereby a stable multicolor dye transfer image.
  • print-receiving element 28 may be manually dissociby stripping or if film units of the described US. Pat. Nos. 3,594,194 and 3,594,165 are employed, the film unit is a permanent laminate.
  • the onium compound may be employed in a variety of locations in the film unit.
  • it may be disposed in one or more of the emulsion or dye layers or it may comprise overcoat layer 23. It is preferred that the onium compound be disposed in the emulsion layer.
  • a film unit within the scope of the present invention may be prepared, for example, by coating, in succession, on a gelatin subbed, 4 mil. opaque polyethylene terephthalate film base, the following layers:
  • ll-CHr-CH and the auxiliary developer 4-methylphenyl hydroquinone dispersed in gelatin and coated at a coverage of about 81 mgs./ft. of dye, about 15 mgs./ft. of auxiliary developer and 54 mgs./ft. of gelatin;
  • polyester film base may be coated, in succession with the following illustrative layers:
  • a rupturable container comprising an outer layer of lead foil and an inner liner or layer of polyvinyl chloride retaining an aqueous alkaline processing solution comprising:
  • CHr-N-C uHsrn may then be fixedly mounted on the leading edge of such as suitably gapped, opposed rolls, to effect rupture of the container and distribution of its contents.
  • the multicolor dye transfer image formation may be viewed through the transparent polyethylene terephthalate layer against the titanium dioxide background provided by distribution of the pigment containing processing composition between Layer 9 and the polymeric image-receiving layer.
  • tlie'liquid processing easibo r tion employed may contain an auxiliary or accelerating developing agent, such as p-methylaminophenol, 2,4- diamino-phenol, p-benzylaminophenyl, hydroquinone, toluhydroquinone, phenylhydroquinone, 4-methylphenylhydroquinone, etc. It is also contemplated to employ a plurality of auxiliaryor accelerating developing agents, such as a 3-pyrazolidone developing agent and a benzenoid developing agent, as disclosed in U.S. Pat. No. 3,039,869, issued June 19, 1962.
  • auxiliary developing agents examples include l-phenyl-3-pyrazolidone in combination with p-benzylaminophenol and l-phenyl- 3-pyrazolidone in combination with 2,5-bisethylenimino-hydroquinone.
  • auxiliary developing agents may be employed in the liquid processing composition or they may be initially incorporated, at least in part, in any one or more of the silver halide emulsion I strata, the strata containing the dye developers, the interlayers, the overcoat layer, the image-receiving layer, or in any other auxiliary layer, or layers, of the film unit.
  • the dye developer oxidized during development may be oxidized and immobilized as a result of a reaction, e.g., an energy-transfer reaction, with the oxidiation product of an oxidized auxiliary developing agent, the latter developing agent being oxidized by the development of exposure silver halide.
  • a reaction e.g., an energy-transfer reaction
  • Such a reaction of oxidized developing agent with unoxidized dye developer would regenerate the auxiliary developing agent for further reaction with the exposed silver halide.
  • the relative proportions of the agents of the diffusion transfer processing composition may be altered to suit the requirements of the operator.
  • modify the herein described developing compositions by the substitution of preservatives, alkalies, etc., other than those specifically mentioned, provided that the pH of the composition is initially at the first pH and solvent concentration required.
  • components such as restrainers, accelerators, etc.
  • concentration of various components may be varied over a wide range and when desirable adaptable components may be disposed in the photosensitive element, prior to exposure, in a separate permeable layer of the photosensitive element and/or in the photosensitive emulsion.
  • dye image-forming materials such as those disclosed in U.S. Pat. Nos. 2,647,049;
  • color diffusion transfer processes which employ color coupling techniques comprising, at least in part, reacting one or more color developing agents and one or more color formers or couplers to provide a dye transfer image to a superposed image-receiving layer and those disclosed in U.S. Pat. Nos.
  • the silver halide crystals may be prepared by reacting a water-soluble silver salt, such as silver nitrate, with at least one water-soluble halide, such as ammonium, potassium or sodium bromide, preferably together with a corresponding iodide, in an aqueous solution of a peptizing agent such as a colloidal gelatin solution; digesting the dispersion at an elevated temperature, to provide increased crystal growth; washing the resultant water-soluble salts by chilling the dispersion, noodling the set dispersion, and washing the noodles with cold water, or alternatively, employing any of the various flocc systems, or procedures, adapted to effect removal of undesired components, for example, the procedures described in U.S.
  • Optical sensitization of the emulsions silver halide crystals may be accomplished by contact of the emulsion composition with an effective concentration of the selected optical sensitizing dyes dissolved in an appropriate dispersing solvent such as methanol, ethanol, ac-
  • Additional optional additives such as coating aids, herdeners, viscosity-increasing agents, stabilizers, preservatives, and the like, for example, those set forth hereinafter, also may be incorporated in the emulsion formulation, according to the conventional procedures known in the photographic emulsion manufacturing art.
  • the photoresponsive material of the photographic emulsion will, as previously described, preferably comprise a crystal of silver, for example, one or more of the silver halides such as silver chloride, silver iodide, silver bromide, or mixed silver halides such as silver chlorobromide, silver chloroiodobromide or silver iodobromide, of varying halide ratios and varying silver concentrations.
  • the silver halides such as silver chloride, silver iodide, silver bromide, or mixed silver halides such as silver chlorobromide, silver chloroiodobromide or silver iodobromide, of varying halide ratios and varying silver concentrations.
  • the aforementioned galatin may be, in whole or in part, replaced with some other colloidal material such as albumin; casein; or zein; or resins such as a cellulose derivatives, as described in U.S. Pat. Nos. 2,322,085 and 2,327,808; polyacrylamides, as described in U.S. Pat. No. 2,541,474; vinyl polymers such as described in an extensive multiplicity of readily available U.S. and foreign patents.
  • the photosensitive component of the film unit may comprise at least two sets of selectively sensitized minute photosensitive elements arranged in the form of a photosensitive screen wherein each of the minute photosensitive elements has associated therewith, for example, an appropriate dye developer in or behind its respective silver halide emulsion portion.
  • a suitable photosensitive screen will comprise minute red-sensitized emulsion elements, minute greensensitized emulsion elements and minute bluesensitized emulsion elements arranged in side-by-side relationship in a screen pattern and having associated therewith, respectively, a cyan, a magenta and a yellow dye developer.
  • the present invention also includes the employment of a black dye image-providing material and the use of a mixture of dye image-providing material adapted to provide a black-and-white transfer image, for example, the employment of dye developers of the three subtractive colors in an appropriate mixture in which the quantities of the dyedevelopers are proportioned such that the colors combine to provide black.
  • the expression positive image has been used, this expression should not be interpreted in a restrictive sense since it is used primarily for purposes of illustration, in that it defines the image produced on the image-carrying layer as being reversed, in the positive-negative sense, with respect to the image in the photosensitive emulsion layers.
  • the expression positive image assume that the photosensitive element is exposed to actinic light through a negative transparency. in this case, the latent image in the photosensitive emulsion layers will be a positive and the dye image produced on the image-carrying layer will be a negative.
  • the expression positive image is intended to cover such an image produced on the image-carrying layer.
  • the film unit may also contain one or more subcoats or layers, which, in turn, may contain one or more additives such as plasticizers, intermediate essential layers for the purpose, for example, of improving adhesion, and that any one or more of the described layers may comprise a composite of two or more strata of the same, or different, components and which may be contiguous, or separated from, each other, for example, two or more neutralizing layers or the like, one of which may be disposed intermediate the cyan dye image-forming component retaining layer and the dimensionally stable opaque layer.
  • additives such as plasticizers, intermediate essential layers for the purpose, for example, of improving adhesion
  • any one or more of the described layers may comprise a composite of two or more strata of the same, or different, components and which may be contiguous, or separated from, each other, for example, two or more neutralizing layers or the like, one of which may be disposed intermediate the cyan dye image-forming component retaining layer and the dimensionally stable opaque layer.
  • the above tive element comprising at least one silver halide emulsion having associated therewith a dye image-providing material and an onium salt of a polymeric anion.
  • a film unit as defined in claim 1 which includes a support carrying on a surface a plurality of photosensitive silver halide emulsions, each of said emulsions having associated therewith a dye which is a silver halide developing agent and at least one of said emulsions having additionally associated therewith an onium salt of a polymeric anion.
  • a product as defined in claim 5 wherein said quaternary ammonium salt of a polymeric anion is N-phenethyl-a-picolinium polyvinyl hydrogen phthalate.
  • a product as defined in claim 5 wherein said onium salt of a polymeric anion is N-phenethyl-apicolinium carboxymethyl cellulose.
  • said onium salt of a polymeric anion is benzyl-a-picolinium polyvinyl hydrogen phthalate.
  • a product as defined in claim 5 wherein said onium salt of a polymeric anion is N-phenethyl-apicolinium polyvinyl acrylic acid.
  • a process for forming a transfer image in color which comprises exposing a photosensitive element comprising at least one silver halide emulsion having associated therewith an onium salt of a polymeric anion and a color providing material, developing said exposed photosensitive element, and transferring at least a portion of an imagewise distribution of said colorproviding material to a superposed image-receiving layer.
  • a process as defined in claim 11 which comprises exposing a photosensitive element comprising at least one silver halide emulsion, each of said silver halide emulsions having associated therewith a dye which is a silver halide developing agent and at least one of said silver halide emulsions having additionally associated therewith an onium salt of a polymeric anion, developing said exposed photosensitive element, forming in undeveloped areas of each of said silver halide emulsions as a function of development, an imagewise distribution of associated dye developer in unoxidized diffusible condition and transferring by diffusion at least a portion of said imagewise distribution of unoxidized dye developer to a superposed image-receiving layer to form said color transfer image.
  • a process as defined in claim 12 wherein said onium salt of a polymeric anion comprises a layer overlying said silver halide emulsions.
  • said photosensitive element comprises a support carrying a red-sensitive silver halide emulsion stratum, a greensensitive silver halide emulsion stratum and a bluesensitive silver halide emulsion stratum, each of said silver halide emulsions having associated therewith, respectively, a cyan dye developer, a magenta dye developer and a yellow dye developer, each of said dye developers disposed in an alkali permeable layer behind its associated silver halide emulsion.
  • a photographic product comprising a photosensitive element, said photosensitive element comprising a support carrying at least one silver halide emulsion, each of said silver halide emulsions having associated therewith a dye which is a silver halide developing agent, at least one of said silver halide emulsions additionally having associated therewith an onium salt of a polymeric anion, an image-receiving element comprising a support carrying an image-receiving layer and a rupturable container releasably holding an aqueous alkaline processing solution, said photosensitive element and said image-receiving element being capable of being superposed on each other with said rupturable container positioned therebetween so as to release said processing solution upon rupture of said container to permeate said silver halide emulsions and said imagereceiving layer.
  • a composite photographic diffusion transfer color process film unit which comprises, in combinationi a. a photosensitive laminate containing, as essential layers, a dimensionally stable transparent support carrying onv one surface, in order, a dyeable polymeric layer, a processing composition permeable opaque layer, and a photosensitive silver halide layer having associated therewith a dye imagefonning material which is processing composition diffusible, as a function of the point-to-point degree of silver halide layers exposure to actinic radiation; and having additionally associated therewith an onium salt of a polymeric anion;
  • a rupturable container retaining a processing composition including an opacifying agent positioned extending transverse a leading edge of the film unit to effect unidirectional discharge of the containers contents intermediate the dimensionally stable sheet and the photosensitive laminate.
  • a product as defined in claim 18 wherein said onium salt of a polymeric anion comprises a layer intermediate said photosensitive silver halide emulsion layer and said dyeable polymeric layer.
  • a photographic film unit as defined in claim 18 which is adapted to be processed by passing said unit between a pair of juxtaposed pressure-applying members and which includes, in combination:
  • a photosensitive laminate containing, as essential layers, at least two selectively sensitized silver halide emulsion layers each having a dye, which dye is a silver halide developing agent, of predetermined color associated therewith, at least one of said silver halide emulsion layers additionally having associated therewith an onium salt of a polymeric anion, each of said dyes soluble and diffusible, in alkali, at a first pH, an alkaline solution permeable polymeric layer dyeable by said dyes, an alkaline solution permeable opaque layer positioned intermediate said dyeable polymeric layer and the silver halide emulsion layer next adjacent thereto, a dimensionally stable alkaline solution impermeable transparent layer, and an alkaline solution permeable transparent polymeric acid layer containing sufiicient acidifying groups to effect reduction of a processing solution having said first pH to a second pH at which said dyes are nondiffusible positioned intermediate said dimensionally stable transparent layer and the essential layer next adjacent thereto;
  • a rupturable container retaining an aqueous alkaline processing solution containing an opacifying agent, having said first pl-l fixedly positioned and extending transverse said leading edge of said laminate to effect unidirectional discharge of the containers contents coextensive the surface of the laminate intermediate said laminate and said transparent sheet.
  • each of said silver halide emulsion layers has an onium salt of a polymeric anion disposed therein.
  • a product as defined in claim 26 wherein said quaternary ammonium salt of a polymeric anion is N-phenethyl-a-picolinium polyvinyl hydrogen phthalate.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US00263539A 1972-06-16 1972-06-16 Photographic products and processes Expired - Lifetime US3816125A (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
US00263539A US3816125A (en) 1972-06-16 1972-06-16 Photographic products and processes
GB2761973A GB1438187A (en) 1972-06-16 1973-06-11 Photographic silver halide products and processes
NLAANVRAGE7308143,A NL179237C (nl) 1972-06-16 1973-06-12 Fotografisch materiaal voor kleurdiffusieoverdracht.
JP6677473A JPS5311378B2 (ja) 1972-06-16 1973-06-13
CA174,205A CA1026982A (en) 1972-06-16 1973-06-15 Photographic products and processes
DE2330621A DE2330621C2 (de) 1972-06-16 1973-06-15 Photographisches Aufzeichnungsmaterial für das Farbdiffusionsübertragungsverfahren
FR7322007A FR2189775B1 (ja) 1972-06-16 1973-06-15

Applications Claiming Priority (1)

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US00263539A US3816125A (en) 1972-06-16 1972-06-16 Photographic products and processes

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US00263539A Expired - Lifetime US3816125A (en) 1972-06-16 1972-06-16 Photographic products and processes

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US (1) US3816125A (ja)
JP (1) JPS5311378B2 (ja)
CA (1) CA1026982A (ja)
DE (1) DE2330621C2 (ja)
FR (1) FR2189775B1 (ja)
GB (1) GB1438187A (ja)
NL (1) NL179237C (ja)

Cited By (4)

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Publication number Priority date Publication date Assignee Title
US4543317A (en) * 1984-12-19 1985-09-24 Polaroid Corporation Photographic system with salt of phenylmercaptoazole and quaternary radical
US4588672A (en) * 1985-08-08 1986-05-13 Polaroid Corporation Photographic system with quaternary releaser
US4677206A (en) * 1985-08-08 1987-06-30 Polaroid Corporation, Patent Dept. 2-hydroxy ethyl benzyl pyridinium compounds
US20050106484A1 (en) * 2003-11-17 2005-05-19 Gerard Gomes Image-receiving element

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Publication number Priority date Publication date Assignee Title
JPS56133735A (en) * 1980-03-25 1981-10-20 Fuji Photo Film Co Ltd Photographic element for color diffusion transfer

Citations (3)

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Publication number Priority date Publication date Assignee Title
US3173786A (en) * 1960-08-22 1965-03-16 Polaroid Corp Color diffusion transfer process, element and composition therefor
US3649265A (en) * 1970-05-06 1972-03-14 Eastman Kodak Co Diffusion transfer system comprising dye developers, a pyrazolone and an onium compound
US3698896A (en) * 1970-12-21 1972-10-17 Eastman Kodak Co Diffusion transfer film unit with improved dye image receiving layer comprising a basic polymeric mordant

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US2984039A (en) * 1958-07-03 1961-05-16 Willey Elihue Hook setting mechanism for fishing rods and poles

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3173786A (en) * 1960-08-22 1965-03-16 Polaroid Corp Color diffusion transfer process, element and composition therefor
US3649265A (en) * 1970-05-06 1972-03-14 Eastman Kodak Co Diffusion transfer system comprising dye developers, a pyrazolone and an onium compound
US3698896A (en) * 1970-12-21 1972-10-17 Eastman Kodak Co Diffusion transfer film unit with improved dye image receiving layer comprising a basic polymeric mordant

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4543317A (en) * 1984-12-19 1985-09-24 Polaroid Corporation Photographic system with salt of phenylmercaptoazole and quaternary radical
US4588672A (en) * 1985-08-08 1986-05-13 Polaroid Corporation Photographic system with quaternary releaser
EP0212748A2 (en) * 1985-08-08 1987-03-04 Polaroid Corporation Photographic product containing a compound which releases a quaternary salt in an alkaline environment, and compounds in compliance therewith
US4677206A (en) * 1985-08-08 1987-06-30 Polaroid Corporation, Patent Dept. 2-hydroxy ethyl benzyl pyridinium compounds
EP0212748A3 (en) * 1985-08-08 1988-02-10 Polaroid Corporation Photographic product containing a compound which releases a quaternary salt in an alkaline environment, and compounds in compliance therewith
US20050106484A1 (en) * 2003-11-17 2005-05-19 Gerard Gomes Image-receiving element
US6946232B2 (en) * 2003-11-17 2005-09-20 Polaroid Corporation Image-receiving element

Also Published As

Publication number Publication date
GB1438187A (en) 1976-06-03
NL179237B (nl) 1986-03-03
NL7308143A (ja) 1973-12-18
FR2189775A1 (ja) 1974-01-25
FR2189775B1 (ja) 1980-09-05
JPS4953038A (ja) 1974-05-23
DE2330621C2 (de) 1984-03-01
NL179237C (nl) 1986-08-01
JPS5311378B2 (ja) 1978-04-21
CA1026982A (en) 1978-02-28
DE2330621A1 (de) 1974-01-10

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