US3615543A - Multicolor photographic element comprising an oxacyanine sensitizing dye - Google Patents

Multicolor photographic element comprising an oxacyanine sensitizing dye Download PDF

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US3615543A
US3615543A US880684A US3615543DA US3615543A US 3615543 A US3615543 A US 3615543A US 880684 A US880684 A US 880684A US 3615543D A US3615543D A US 3615543DA US 3615543 A US3615543 A US 3615543A
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dye
image
photosensitive
silver halide
layer
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Alan E Rosenoff
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Polaroid Corp
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
    • C09B23/04—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups one >CH- group, e.g. cyanines, isocyanines, pseudocyanines
    • 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

  • Photosensitivity of a blue-sensitive emulsion in a multicolor diffusion transfer photographic system may be increased by sensitizing that emulsion with a member of a class of oxacyanine dyes.
  • a photosensitive element containing the image-receiving dye developer that is, a dye which is a silver halide developing agent, and a silver halide emulsion, may be exposed to actinic radiation and wetted by a liquid development of composition, for example, by immersion, coating, spraying, flowing etc., in the dark, and the exposed photosensitive element is superposed prior to, during, the latent 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.
  • 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 diffusion, to a superposed image-receiving layer or element, said transfer substantially excluding oxidized dye developer.
  • the iamge-receiving element receives a depthwise diffusion, from the developed 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 image-receiving element may contain agents adapted to mordant or otherwise fix the diffused, unoxidized dye developer.
  • the desired positive image is revealed by stripping the image-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 forms 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 patent's 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 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.
  • a yellow filter in front of the green-sensitive emulsion and such yellow filter may be incorporated in an interlayer.
  • a yellow dye developer of the appropriate spectral characteristics and present in a state capable of functioning as a yellow filter may be employed. ln such instances, a separate yellow filter may be omitted.
  • the dye developers are dye image-forming materials which are preferably selected for their ability to provide colors that are useful in carrying out substractive color photography, that is, the previously mentioned cyan, magenta and yellow.
  • the dye developers employed may be incorporated in the respective silver halide emulsion or, in the preferred embodiment, in a separate layer behind the respective silver halide emulsion.
  • the dye developer may, for example, be in a coating or layer behind the respective silver halide emulsion and such a layer of dye developer may be applied by use of a coating solution about 0.5 to 8 percent by weight, of the respective dye developer distributed in a film-forming natural, or synthetic, polymer, for example, gelatin, polyvinyl alcohol, and the like, adapted to be permeated by the chosen diffusion transfer fluid processing composition
  • a coating solution about 0.5 to 8 percent by weight
  • the respective dye developer distributed in a film-forming natural, or synthetic, polymer, for example, gelatin, polyvinyl alcohol, and the like, adapted to be permeated by the chosen diffusion transfer fluid processing composition
  • nitrocarboxymethyl cellulose as disclosed in U.S. Pat. No. 2,992,104
  • an acylamidobenzene sulfo ester of a partial sulfobenzal of polyvinyl alcohol as disclosed in U.S. Pat. No. 3,043,692
  • polymers of N-alkyl-a,B-unsaturated carboxamides and copolymers of N-alkyl-mBcarboxamides with N-hydroxyalkyl-afi-unsaturated carboxamides as disclosed in U.S. Pat. No.
  • the preparation of the dye developer dispersion may also be obtained by dissolving the dye in an appropriate solvent, or mixture of solvents, and the resultant solution distributed in the polymeric binder, with optional subsequent removal of the solvent, or solvents, employed as, for example, by vaporization where the selected solvent, or solvents, possesses a sufficiently low boiling point or washing where the selected solvent, or solvents, possesses a sufficiently high differential solubility in the wash medium, for example, water, when measured against the solubility of the remaining composition components and/or obtained by dissolving both the polymeric binder and dye in a common solvent.
  • 3,362,819 discloses image-receiving elements, particularly adapted for employment in the preceding diffusion transfer processes, which comprise a support layer possessing on one surface thereof, in sequence, a polymeric acid layer, preferably an inert timing or spacer layer, and an imagereceiving layer adapted to provide a visible image upon transfer to said layer of diffusible dye image-forming substance.
  • the polymeric acid layer comprises 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-reacting group is, of course, nondiffusible from the acid polymer layer.
  • 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, beinginsoluble in water in the free acid form, and by forming watersoluble sodium and/or potassium salts.
  • dibasic acid halfester derivatives of cellulose modified with sulfoanhydrides e.g., with ortho-sulfobenzoic anhydride
  • polystyrene sulfonic acid carboxymethyl cellulose
  • polyvinyl hydrogen phthalate polyvinyl acetate hydrogen phthalate
  • polyacrylic acid acetals of polyvinyl alcohol with carboxy or sulfo-substituted aldehydes, e.g., M-, or p-benzaldehyde sulfonic acid or carboxylic acid
  • partial esters of ethlenelmaleic anhydride copolymers partial esters of methyl-vinyl ether/maleic anhydride copolymers, etc.
  • the acid polymer layer is disclosed to contain at least sufficient 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 11 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 action of the polymeric acid be so controlled as not to interfere with either development of the negative or image transfer of unoxidized dye developers.
  • the pH of the image layer is kept at a level of pH 12 to 14 until the positive dye image has been formed, after which the pH is reduced very rapidly to at least about pH 1 l, and preferably about pH 9 to 10, which renders unoxidized dye developer substantially nondifi'usible.
  • 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 pH reduction in addition to its desirable effect upon image light stability, serves a highly valuable photographic function by substantially terminating further dye transfer. This processing technique thus efi'ectively minimizes changes in color balance which might result from a longer than necessary imbibition time for multicolor transfer processes using multilayer negatives.
  • the acid groups are disclosed to be so distributed in the acid polymer layer that the rate of their availability to the alkali which acts controllable, e.g., as a function of the rate of swelling of the polymer the polymer which rate in turn has a direct relationship to the diffusion rate of the alkali ions.
  • the desired distribution of the acid groups in the acid polymer layer may be effected by mixing the acid polymer with a polymer free of acid groups, or lower in concentration of acid groups, and compatible therewith, or by using only the acid polymer but selecting one having a relatively lower proportion of acid groups.
  • the layer containing the polymeric acid may contain a water insoluble polymer, preferably a cellulose ester, which acts to control or modulate the rate at which the alkali salt of the polymer acid is formed.
  • a water insoluble 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 inert spacer layer of the aforementioned patent 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 spacer layer, i.e., the pH is not reduced to any significant extent by the mere diffusion into the interlayer, but thepH drops quite rapidly once the alkali difiuses through the spacer layer.
  • Other such spacer layers which are suitable for use in the image-receiving element are disclosed and claimed in U.S. Pat. No. 3,421,893.
  • solution dyeable polymers such as nylons as, for examples, N-methyoxymethyl polyhexamethylene adipamide; partially hydrolyzed polyvinyl acetate; polyvinyl alcohol with or without plasticizers; cellulose acetate with fillers as, for example, one-halt 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.
  • 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 possessing a pH in excess of i2 and most preferably, a viscosity-increasing compound constituting a film-forming 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 let in solution for a long period of time are also disclosed to be capable 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 100 cps. at a temperature of approximately 24 C. and preferably in the order of 100,000 cps. to 200,000 cps. at that temperature.
  • 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,
  • Optical sensitization of the emulsion 's silver halide crystals, toward which the instant invention is directed, 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, acetone, water, and the like; all according to the traditional procedures of the art, as described in Hammer, F. M., The Cyanine Dyes and Related Compounds.
  • an appropriate dispersing solvent such as methanol, ethanol, acetone, water, and the like
  • Additional optional additives such as coating aids, hardeners, 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 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 or silver iodobromide, of varying halide ratios and varying silver concentrations.
  • the emulsions may include the various adjuncts, or addenda, according to the techniques disclosed in the art.
  • the aforementioned gelatin 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 derivative, 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 a multiplicity of readily available U.S. Patents.
  • an image-receiving element need not be separated from superposed contact with a photosensitive element comprising a silver halide emulsion subsequent to substantial transfer image formation if the image-receiving element is transparent and a processing composition containing a substance'rendering the processing composition layer opaque is spread between the image-receiving layer and the photosensitive element.
  • an integral diffusion transfer photographic film unit particularly adapted for the production of a dye transfer image of improved stability will be constructed, for example, in accordance with aforementioned U.S. Pat. No. 3,415,644 to include a photosensitive element comprising a laminate having in sequence as essential layers, a dimensionally stable opaque support layer, a photosensitive silver halide emulsion layer having associated therewith dye image-providing material which is soluble and diffusible in alkali at a first pH, an alkaline solution penneable polymeric layer dyeable by the dye image-providing material, a polymeric acid layer containing sufi'rcient acidifying material to effect reduction subsequent to substantial transfer dye image formation of a processing solution having the first pH to a second pH at which said dye image-providing material is insoluble and nondiffusible, and a dimensionally stable transparent support layer, said dimentionally stable support layers comprising extremities of the described photographic film unit composite structure.
  • a rupturable container retaining an aqueous alkaline processing composition having the first pH and containing an opacifying agent in a quantity sufficient to mask the dye image-providing material is fixedly positioned and extends transverse the leading edge of the laminate whereby to effect unidirectional discharge of the containers contents between the alkaline solution permeable and dyeable polymeric layer and the photosensitive silver halide emulsion layer next adjacent thereto upon application of compressive force to the container.
  • an ultraviolet light absorbing composition In numerous multicolor photographic difiusion transfer systems, it is desirable to utilize, integral, with the photosensitive element thereof, in a layer more distal from the photosensitive element support layer than any of the photosensitive emulsion layers, an ultraviolet light absorbing composition. It will be appreciated that such composition will remove spectral components of incident radiation which generally stimulate response in the inherently sensitive region of photosensitive silver halide emulsions, that is, in the blue and violet portions of the spectrum.
  • the primary objects of the present invention are to provide photographic products particularly adapted for employment in photographic difiusion transfer color processes; to provide photographic products which include a photosensitive ele- 1 ment which comprises at least two selectively sensitized photosensitive strata at least one of which contains an oxacyanine sensitizing agent, said photosensitive strata being associated with dyes of predetermined color which are silver halide developing agents and are separated each from the other by a suitable interlayer; to provide photographic diffusion transfer products comprising photosensitive element of the last-identified type which additionally includes an ultraviolet absorbing material in a layer superposed on said photosensitive strata wherein said oxacyanine sensitized layer is capable of potentiating the effect of incidentradiation within the blue portion of the visible spectrum whereby color balance of the I ultimate image is unefi'ected; and to provide photographic diffusion transfer color images and processes which possess improved lamination latitude, substantial latent image stabilization, and antifoggant functionality.
  • the invention accordingly comprises the product possessing the features, properties and the relation of components and the process involving the several steps and the relation and order of one or more of such steps with respect to each of the other which are exemplified in the following detailed disclosure, and the scope of the application of which will be in dicated in the claims.
  • FIGS. 1 through 5 are reproductions of wedge spectograms of iodobromide silver halide emulsions sensitized with various materials within the context of the present invention
  • FIGS. 6 through 10 are reproductions of latent image stabilization density studies which demonstrate the latent image stabilization effect produced by a typical compound of the present invention at various levels with respect to the silver present in the system.
  • oxacyanine sensitizing dye of the formula:
  • R C C alkylene l alk ldene 1 wherein R and R are each' hydrogen or acid functional groups, such as, preferably, SO,H; CO,H; -SO,'; and CO wherein not more than one of said R and R may be hydrogen; R and R are alkyl, alkoxy, halogen, or hydrogen; and the alkylene groups denoted contain between I and [8 carbon atoms, inclusive.
  • Sensitizing materials of the present invention are incorporated into the emulsion by well-known techniques as, for example, by being distributed uniformly throughout a washed, finished emulsion in a concentration dependent on the sensitometric characteristics of the particular emulsion and the effects desired, as hereinabove denoted. Ordinarily, best results may be obtained in about a 'ratio of 1 mg. of dye per gram of silver. However, it is generally conceded that ratios between 0.05 mg. of dye to 4.0 mgs. of dye per gram of silver may be employed.
  • the dyes are added to the emulsion, in a suitable solvent as, for example, methanol, ethanol, etc., slowly and under constant stirring.
  • the sensitized emulsion may be handled, stored and coated thereafter according to conventional techniques.
  • a monochromatic photosensitive element was prepared film coating, in succession, on a gelatin subcoated cellulose triacetate folm base the following layers: 1. a layer of the yellow dye developers 4-(p-[fi-hydroquinonyl ethyl]-phenylazo)- 3-(N-n-hexylcarboxamido)-l-phenyl-S-pyrazolone dissolved in diethyl lauramide dispersed in gelatin and coated at a coverage of about 30 mgs./ft. of dye and about 40 mgs./ft. of gelatin; and 2. a blue-sensitive gelatino silver iodobromide emulsion coated at a coverage of about 90 mgs./ft. of silver and about 65 mgs./ft. of gelatin.
  • Typical diffusion transfer image-receiving elements were then fabricated by coating a cellulose nitrate subcoated baryta paper with the partial butyl ester of polyethylene-maleic anhydride copolymer prepared by refluxing for 14 hours 300 grams of high viscosity poly-(ethylene/maleic anhydride), I40 grams of N-butyl alcohol and l cc. of 85 percent phosphoric acid to provide a polymeric acid layer approximately 0.75 mil. thick. The external surface of the acid layer was then coated with a 4 percent solution of polyvinyl alcohol in water to provide a polymeric spacer layer approximately 0.30 mils. thick.
  • the external surface of the spacer layer was then coated with a 2:l mixture, by weight, of polyvinyl alcohol and poly-4- vinylpyridine at a coverage of approximately 600 mgs./ft. to provide a polymeric image-receiving layer.
  • the thus prepared image-receiving element is then baked at l80 F. for 30 minutes and allowed to cool.
  • N-benzyl-a-picolinium bromide 2.0 g.
  • FIG. 1 denotes the inherent sensitivity of the emulsion utilized. It will be appreciated that increased sensitivity is predominant in FIGS. 2, 3, 4 and 5 due to the addition of the denoted sensitizing materials within that class of materials forming the subject matter of the present invention.
  • peak sensitivity is produced between approximately 495 and 505 nanometers depending upon the particular sensitization material utilized.
  • photosensitive monochromes of the aboveidentified type were fabricated wherein the green-sensitive gelatino silver halide emulsion contained varying levels of 3- carboxymethyl-l'-ethyloxa-2'-cyanine bromide including 0.l mg., 0.5 mg., l.0 mg., and L4 mgs. per gm. of silver, respectively.
  • the fresh coatings on each of the above-denoted monochromes were uniformly exposed through a vertical step wedge.
  • the exposed materials where then placed in an accelerated aging atmosphere by being held .under approximately 52 atmospheres pressure for a week in order to simulate about one year's aging.
  • sensitizer dye per gm., of silver which appears to represent a balance between latent image regression and latensification, the former being a relative loss of latent image as a function of time while the latter is a relative gain in latent image as a function of time.
  • sensitized silver halide emulsions utilizing dye materials of the herein denoted class do not lose spectral sensitization, i.e., are not antisensitized, in the presence of dye couplers and other materials commonly utilized in diffusion transfer photographic systems.
  • dye couplers and other materials commonly utilized in diffusion transfer photographic systems.
  • at least one of the R or R denoted moities with the class of materials disclosed must be acid functional.
  • a requisite function of the dye sensitizers of the present invention is that they be nonmigratory-for were they to ditTuse, they might provide a chromatically deleterious effect to any ultimate image formed.
  • the migration propensities of the denoted sensitizers may best be controlled by choosing appropriate alkylene groups in the generic formula above.
  • the moieties denoted as R and R comprise conventional cyanine dye substituents as defined in Hamer, above, the selection of which is made by the operator
  • the liquid processing composition employed may contain an auxiliary or accelerating developing agent, such as p-methylaminophenol, 2,4-diamino-phenol, pbenzylaminophenol, hydroquinone, toluhydroquinine, phenylhydroquinone, 4'-methylpyenylhydroquinone, etc.
  • auxiliary or accelerating developing agent such as p-methylaminophenol, 2,4-diamino-phenol, pbenzylaminophenol, hydroquinone, toluhydroquinine, phenylhydroquinone, 4'-methylpyenylhydroquinone, etc.
  • auxiliary of accelerating developing agents such as a 3-pyrazolidone developing agent and a benzenoid developing agent, as disclosed in U.S. Pat. No.
  • auxiliary developing agents examples include l-phenyl-3-pyrazolidone in combination with pbenzylaminophenol and l-phenyl-3-pyrazolidone in combination with 2,5-bis-ethyleneimino 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 strata, the strata containing the dye developers, the interlayers, the overcoat layer, the image-reeeiving 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 oxidation product of an oxidized auxiliary developing agent, the latter developing agent being oxidized by the development of exposed 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.
  • dye image-forming materials such as those disclosed in U.S. Pat. Nos. 2,647,049, 2,661,293, 2,698,244, 2,698,798, and 2,802,735, wherein color diffusion transfer processes are described which employ color coupling techniques comprising, at least in part, reacting one or more color developing agents and one more color formers or couplers to provide a dye transfer image to a superposed image-receiving layer and those disclosed in U.S. Pat. No. 2,774,668, wherein color diffusion transfer processes are described which employ the imagewise differential transfer of complete dyes by the mechanisms therein described to provide a transfer dye image to a contiguous image-receiving layer.
  • a camera apparatus suitable for processing film of the type just mentioned is provided by the Polaroid Land Camera, sold by Polaroid Corporation, Cambridge, Massachusetts, or similar camera structure such, for example, as the roll film type camera forming the subject matter of U.S. Pat. No. '2,435,7 l 7 or the film pack type camera forming the subject matter of U.S. Pat. No. 2,991,702.
  • Camera apparatus of this type permits successive exposure of individual frames of the photosensitive element from the emulsion side thereof as well as individual processing of an exposed frame by bringing said exposed frame into superposed relation with a predetermined portion of the imagereceiving element while drawing these portions of the film assembly between a pair of pressure member which rupture a container associated therewith and effect the spreading of the processing liquid released by rupture of said container, between and in contact with the exposed photosensitive frame and the predetermined, registered area of the image-receiving element.
  • 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, silver halide solvents, etc., other than those specifically mentioned, provided that the pH of the composition is preferably in excess of at least 10 initially.
  • 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.
  • the support layers referred to may comprise any of the various types of conventional rigid or flexible supports, for example, glass, paper, metal, and polymeric films of both synthetic types and those derived from naturally occurring products.
  • Suitable materials include paper; aluminum; polymethacrylic acid methyl and ethyl esters; vinyl chloride polymers; polyvinyl acetal; polyamides such as nylon; polyesters such as polymeric films derived from ethylene glycol terephthalic acid; and cellulose derivatives such as cellulose acetate, triacetate, nitrate, propionate butyrate, acetate-propionate, or acetate-butyrate
  • rupturable containers is well understood in the art; see, for example, U.S. Pat. No. 2,543,181, issued Feb. 27, 1951, and U.S. Pat. No. 2,634,886, issued Apr. 14, 1953.
  • a rupturable container provides a convenient means for spreading a liquid processing composition between layers of a film unit whereby to permit the processing to be carried out within a camera apparatus
  • the practices of invention may be otherwise effected.
  • a photosensitive element after exposure in suitable apparatus and while preventing further exposure thereafter to actinic light, may be removed from such apparatus and permeated with the liquid processing composition, as by coating the composition on said photosensitive element or otherwise wetting said element with the composition, following which the permeated, exposed photosensitive element, still, without additional exposure to actinic light, is brought into contact with the image-receiving element for image formation in the manner heretofore described.
  • 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.
  • additives such as plasticizers, intermediate essential layers for the purpose, for example, of improving adhesion.
  • a photosensitive element containing a plurality of essential layers including, in sequence:
  • said blue-sensitive halide emulsion additionally including an oxacyanine dye of the formula:
  • -I alkrl lene alkyl lene R wherein R and R are hydrogen or acid-functional substituents, provided at least one of said R or R is an acid-functional substituent; and R and R are alkyl, alkoxy, halogen, or hydrogen.
  • a photographic film unit which comprises, in combination:
  • photosensitive element having a diffusion transfer imagereceiving element affixed at least one edge thereof, said photosensitive element comprising, as essential layers:
  • a yellow dye-containing layer associated with a blue-sensitive silver halide emulsion, each of said cyan, magenta and yellow dyes being silver halide developing agents and said blue-sensitive silver halide emulsion additionally including an oxacyanine dye of the formula:
  • R and R are hydrogen or acid-functional substituents, provided at least one of said R of R is an acid-functional substituent; and R and R are alkyl, alkoxy, halogen, or hydrogen;
  • said diffusion transfer image-receiving element comprising as essential layers, in sequence 1. a support layer, and
  • an alkaline processing composition permeable and dyeable layer wherein said photosensitive and said imagereceiving elements are adapted to be superposed, the support layers of each comprising the extremities of the superposed structure.
  • the element of claim 5 including a rupturable container retaining an aqueous alkaline processing composition affixed one edge of said photosensitive and said image-receiving elements and adapted upon rupture to distribute its contents intermediate said superposed photosensitive and said imagereceiving element.

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  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Indole Compounds (AREA)
US880684A 1969-11-28 1969-11-28 Multicolor photographic element comprising an oxacyanine sensitizing dye Expired - Lifetime US3615543A (en)

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US88068469A 1969-11-28 1969-11-28

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US3615543A true US3615543A (en) 1971-10-26

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Country Status (8)

Country Link
US (1) US3615543A (fr)
JP (1) JPS492617B1 (fr)
BE (1) BE758825A (fr)
CA (1) CA944207A (fr)
DE (1) DE2058545C3 (fr)
FR (1) FR2143984A5 (fr)
GB (1) GB1333415A (fr)
NL (1) NL166798C (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4974938A (fr) * 1972-10-13 1974-07-19
US20060165625A1 (en) * 2005-01-22 2006-07-27 Verrall Andrew P Water-soluble film article having salt layer, and method of making the same
US20090045535A1 (en) * 2005-05-09 2009-02-19 Yousuke Miyashita Method of producing organic particles and production apparatus usable for the same
US20090059138A1 (en) * 2006-01-23 2009-03-05 Keisuke Matsumoto Method of producing organic nanoparticles, organic nanoparticles thus obtained, inkjet ink for color filter, colored photosensitive resin composition and photosensitive resin transfer material, containing the same, and color filter, liquid crystal display device and ccd device, prepared using the same
US20090069473A1 (en) * 2005-05-09 2009-03-12 Takayuki Kusano Method of producing organic-particles-dispersion liquid
US20090071908A1 (en) * 2005-05-06 2009-03-19 Fujifilm Corporation Method of concentrating nanoparticles and method of deaggregating aggregated nanoparticles

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5293314U (fr) * 1976-01-05 1977-07-12

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2189599A (en) * 1933-01-16 1940-02-06 Eastman Kodak Co Process of preparing cyanine dyes with strong organic bases
US2213995A (en) * 1938-03-08 1940-09-10 Gen Aniline & Film Corp Photographic emulsion
DE929080C (de) * 1951-10-23 1955-08-16 Agfa Ag Fuer Photofabrikation Verfahren zur Herstellung von Betain-Cyanin-Farbstoffen und von Betain-Styryl-Farbstoffen

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4974938A (fr) * 1972-10-13 1974-07-19
US20060165625A1 (en) * 2005-01-22 2006-07-27 Verrall Andrew P Water-soluble film article having salt layer, and method of making the same
US8728449B2 (en) * 2005-01-22 2014-05-20 Monosol Llc Water-soluble film article having salt layer, and method of making the same
US20090071908A1 (en) * 2005-05-06 2009-03-19 Fujifilm Corporation Method of concentrating nanoparticles and method of deaggregating aggregated nanoparticles
US8679341B2 (en) 2005-05-06 2014-03-25 Fujifilm Corporation Method of concentrating nanoparticles and method of deaggregating aggregated nanoparticles
US20090045535A1 (en) * 2005-05-09 2009-02-19 Yousuke Miyashita Method of producing organic particles and production apparatus usable for the same
US20090069473A1 (en) * 2005-05-09 2009-03-12 Takayuki Kusano Method of producing organic-particles-dispersion liquid
US8283395B2 (en) 2005-05-09 2012-10-09 Fujifilm Corporation Method of producing organic-particles-dispersion liquid
US20090059138A1 (en) * 2006-01-23 2009-03-05 Keisuke Matsumoto Method of producing organic nanoparticles, organic nanoparticles thus obtained, inkjet ink for color filter, colored photosensitive resin composition and photosensitive resin transfer material, containing the same, and color filter, liquid crystal display device and ccd device, prepared using the same
US8319916B2 (en) 2006-01-23 2012-11-27 Fujifilm Corporation Method of producing organic nanoparticles, organic nanoparticles thus obtained, inkjet ink for color filter, colored photosensitive resin composition and photosensitive resin transfer material, containing the same, and color filter, liquid crystal display device and CCD device, prepared using the same

Also Published As

Publication number Publication date
NL166798C (nl) 1981-09-15
NL166798B (nl) 1981-04-15
DE2058545B2 (de) 1980-12-18
DE2058545A1 (de) 1971-06-09
CA944207A (en) 1974-03-26
FR2143984A5 (fr) 1973-02-09
NL7017019A (fr) 1971-06-02
JPS492617B1 (fr) 1974-01-22
BE758825A (fr) 1971-05-12
DE2058545C3 (de) 1981-09-24
GB1333415A (en) 1973-10-10

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