US3345163A - Photographic diffusion transfer color processes - Google Patents

Photographic diffusion transfer color processes Download PDF

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Publication number
US3345163A
US3345163A US565135A US56513556A US3345163A US 3345163 A US3345163 A US 3345163A US 565135 A US565135 A US 565135A US 56513556 A US56513556 A US 56513556A US 3345163 A US3345163 A US 3345163A
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Prior art keywords
color
layer
dye
emulsion
image
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US565135A
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English (en)
Inventor
Edwin H Land
Howard G Rogers
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Polaroid Corp
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Polaroid Corp
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Priority to NL214522D priority Critical patent/NL214522A/xx
Priority to NL105917D priority patent/NL105917C/xx
Priority to NL214523D priority patent/NL214523A/xx
Priority to BE554933D priority patent/BE554933A/xx
Priority to BE558821D priority patent/BE558821A/xx
Priority to NL105919D priority patent/NL105919C/xx
Priority to BE554935D priority patent/BE554935A/xx
Priority to NL293714D priority patent/NL293714A/xx
Priority to DENDAT1287717D priority patent/DE1287717B/de
Priority to NL214521D priority patent/NL214521A/xx
Priority to BE554934D priority patent/BE554934A/xx
Priority to NL105918D priority patent/NL105918C/xx
Priority to NL218146D priority patent/NL218146A/xx
Priority to NL103316D priority patent/NL103316C/xx
Priority to US565135A priority patent/US3345163A/en
Application filed by Polaroid Corp filed Critical Polaroid Corp
Priority claimed from US607820A external-priority patent/US2997390A/en
Priority to US612051A priority patent/US3019107A/en
Priority to GB11261/59A priority patent/GB853482A/en
Priority to GB2738/57A priority patent/GB853480A/en
Priority to GB2737/57A priority patent/GB853479A/en
Priority to GB2736/57A priority patent/GB853478A/en
Priority to FR1185401D priority patent/FR1185401A/fr
Priority to FR1185402D priority patent/FR1185402A/fr
Priority to CH4257957A priority patent/CH418826A/fr
Priority to DEI12826A priority patent/DE1036640B/de
Priority to CH4257757A priority patent/CH396630A/fr
Priority to CH615266A priority patent/CH444344A/fr
Priority to DEI12825A priority patent/DE1047620B/de
Priority to DEI12824A priority patent/DE1151176B/de
Priority to CH4257857A priority patent/CH398311A/fr
Priority to GB18671/57A priority patent/GB858673A/en
Priority to FR1196814D priority patent/FR1196814A/fr
Priority to DEI13400A priority patent/DE1026172B/de
Priority to CH361194D priority patent/CH361194A/de
Priority to US98287A priority patent/US3236893A/en
Priority to US196463A priority patent/US3134811A/en
Priority to SE10918/65A priority patent/SE335061B/xx
Publication of US3345163A publication Critical patent/US3345163A/en
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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
    • G03C8/32—Development processes or agents therefor
    • G03C8/36—Developers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
    • C07C205/27—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups
    • C07C205/35—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups having nitro groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
    • C07C45/46—Friedel-Crafts reactions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
    • C07C49/84—Ketones containing a keto group bound to a six-membered aromatic ring containing ether groups, groups, groups, or groups
    • 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
    • C09B39/00—Other azo dyes prepared by diazotising and coupling
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
    • C10L1/223—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond having at least one amino group bound to an aromatic carbon atom
    • C10L1/2235—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond having at least one amino group bound to an aromatic carbon atom hydroxy containing
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/232—Organic compounds containing nitrogen containing nitrogen in a heterocyclic ring
    • C10L1/233—Organic compounds containing nitrogen containing nitrogen in a heterocyclic ring containing nitrogen and oxygen in the ring, e.g. oxazoles
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3008—Polarising elements comprising dielectric particles, e.g. birefringent crystals embedded in a matrix
    • 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
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/29—Development processes or agents therefor
    • G03C5/30—Developers
    • G03C5/3021—Developers with oxydisable hydroxyl or amine groups linked to an aromatic ring
    • 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
    • G03C8/02—Photosensitive materials characterised by the image-forming section
    • G03C8/08—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of organic compounds
    • G03C8/10—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of organic compounds of dyes or their precursors
    • G03C8/12—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of organic compounds of dyes or their precursors characterised by the releasing mechanism
    • G03C8/14—Oxidation of the chromogenic substances
    • G03C8/16—Oxidation of the chromogenic substances initially diffusible in alkaline environment
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
    • G03C8/02—Photosensitive materials characterised by the image-forming section
    • G03C8/08—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of organic compounds
    • G03C8/10—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of organic compounds of dyes or their precursors
    • G03C8/12—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of organic compounds of dyes or their precursors characterised by the releasing mechanism
    • G03C8/14—Oxidation of the chromogenic substances
    • G03C8/16—Oxidation of the chromogenic substances initially diffusible in alkaline environment
    • G03C8/18—Dye developers
    • 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
    • G03C8/30—Additive processes using colour screens; Materials therefor; Preparing or processing such materials
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups

Definitions

  • This invention relates to the art of photography, and more particularly to novel processes for the formation of color images and to photographic products for use with such processes.
  • the present invention is concerned with improvements in the formation of color images by diffusion transferreversal processes and especially processes for the formation of such images using an integral, multilayer, negative photosensitive element.
  • Another object of this invention is to provide difiusion transfer-reversal processes wherein diffusion of the colorproviding substances associated with at least one emulsion layer of an integral multilayer photosensitive element to an image-receiving layer is controlled in such a way as to be deferred until at least substantial development of the latent color record contained in said emulsion layer has occurred.
  • the invention accordingly comprises the processes involving the several steps and the relation and order of one or more of such steps with respect to each of the others, and the products possessing the features, properties and the relation of elements which are exemplified in the following detailed disclosure, and the scope of the application of which will be indicated in the claims.
  • FIGURE 1 is a diagrammatic cross-sectional view of one embodiment of a multilayer photosensitive element suitable for use in the process of this invention in association with an image-receiving element and a rupturable container holding a liquid processing composition;
  • FIG. 2 is a diagrammatic cross-sectional view of another embodiment of a multilayer photosensitive element
  • FIG. 3 is a dagrammatic cross-sectional view of a further embodiment of a multilayer photosensitive element wherein one photosensitive layer comprises a photosensitive screen;
  • FIG. 4 is a diagrammatic cross-sectional view of a furthe; embodiment of a multilayer photosensitive element; an
  • FIG. 5 is a diagrammatic cross-sectional view of still another embodiment of a multilayer photosensitive element in association With an image-receiving element and a rupturable container similar to that of FIGURE 1.
  • an exposed photosensitive silver halide emulsion layer containing a latent color record image is processed by a liquid processing composition to obtain an imagewise distribution of diffusible color-providing substances.
  • the imagewise distribution of diffusible colorproviding substances results from the immobilization or trapping of color-providing substances in exposed areas, in situ with the developed silver, as a result of development of the latent image.
  • a positive image may be obtained by the transfer of such difiusible, nonimmobilized color-providing substances, by imbibition, from the developed photosensitive layer to a superposed image-receiving layer.
  • the desired positive image is revealed by stripping the image-receiving layer from the developed photosensitive layer after a suitable imbibition period.
  • Diffusion transfer-reversal color processes described in the prior art have found it necessary to employ separate, independent negative layers to record each portion of the spectrum, process them separately and form the respective positive color images on separate, independent imagereceiving layers which must thereafter be superposed in registered relationship to obtain the desired multicolor image.
  • the multicolor positive image might be formed by successively bringing each separate negative layer, individually processed, into superposed registered relationship with an image-receiving element.
  • a positive multicolor image may be formed on a common image-receiving element by the use of a negative element comprising a plurality of superposed emulsion layers, said negative element being processed as an integral unit and superposed on said common image-receiving element without separation of the several emulsion layers.
  • the novel, integral multilayer photosensitive elements contemplated offer great advantages over the prior art in producing superior multicolor images as well as increased simplicity in manufacture and use.
  • this invention comprises the discovery that superior multicolor positive images may be imparted to a single image-receiving layer from an integr al multilayer photosensitive element comprising a plurality of superposed photosensitive emulsion layers Which are processed as a unit in conjunction with a common image-receiving element, by suitably controlling the diffusibility, i.e., availability for transfer, of at least the colora providing substances associatedwith the inner emulsion layer or layers and which have not been immobilized as a result of development of said emulsion, whereby such nonimmobilized color-providing substances are not rendered diffusible until after at least substantial development of the latent image in the next outermost emulsion layer.
  • the diffusibility i.e., availability for transfer
  • Such control of the diffusion of color-providing substances may be effected by restricting their outward diffusibility, i.e., deferring or retarding their ability to diffuse to the image-receiving layer, until after the desired development has occurred, whereby participation of such nonimmobilized color-prodiving substances in the development of other emulsion layers may be avoided.
  • deferred diffusibility it is intended to cover situations where nonimmobilized color-providing substances associated with an inner emulsion are rendered diifusible after at least substantial development of an outer emulsion has occurred but simultaneously with the development of said inner emulsion, or where development of both said inner and outer emulsion layers has been substantially completed.
  • color-providing substances as used herein is intended to include all types of reagents which may be utilized to produce a color image, and such reagents may initially possess the desired color or may undergo a reaction after transfer to give the desired color.
  • the color-providing substances are dye developers, that is, complete dyes which have a silver halide developing function, as disclosed in the copending application of Howard G. Rogers, Ser. No. 415,- 073, filed Mar 9, 1954, now abandoned and replaced by a continuation-in-part thereof, Ser. No. 748,421, filed July 14, 1958 now US. Patent No. 2,983,606 issued May 9, 1961.
  • color formers or couplers which react with the oxidation product of color developers to produce a dye is also contemplated within the term color-providing substances.
  • color-providing substances The use of complete dyes per se as colorforming substances is also within the scope of this invention. The nature of these and other color-providing substances will be referred to in more detail hereinafter.
  • integral multilayer photosensitive element as used herein is intended to include photosensitive elements comprising at least two separate, superposed layers of photosensitive material, each layer being selectively sensitized to an appropriate portion of the spectrum, at least the inner layer or layers having associated therewith appropriate color-providing substances.
  • the integral multilayer photosensitive element is intended to be processed without separation of the layers. The imagewise distribution of diffusible color-forming substances present in each layer as a result of the development of latent images therein is transferred to a single, common image-receiving element to provide the desired multicolor image.
  • the term layer is intended to include a stratum comprising a mixture of two differently sensitized photosensitive emulsions, as well as a stratum comprising a photosensitive screen comprising two sets of differently sensitized, minute photosensitive elements.
  • multicolor positive images are formed in accordance with this invention by suitable control of the diffusibility or availability for diffusion of colorproviding substances associated with at least the inner photosensitive layer or layers to other photosensitive layers of an integral multilayer photosensitive element or to the image-receiving layer.
  • This control of the availability of color-providing substances may be described as deferred mobility, deferred diffusibility or retarded mobility.
  • Such control of the nonimmobilized color-providing substances is necessary to insure that they do not participate in the development of the latent color record image in a photosensitive layer or stratum other than that with which they are associated. This is particularly essential where the nonimmobilized color-providing substance is capable of developing exposed silver halide.
  • Color-providing substances whose ability to diffuse has not been impaired by the development of the latent image are termed diffusible or nonimmobilized color-providing substances.
  • Those color-providing substances, which are no longer free to diffuse as a result of development of exposed silver halide, are termed immobile or immobilized colorproviding substances. It is to be understood that, prior to development, all of the color-providing substances present are considered mobile in that they are potentially diffusible.
  • Various mechanisms may be utilized to create the desired deferred diffusibility of the color-providing substances, and a particular integral multilayer photosensitive elements may utilize the same or several different mechanisms for creating the desired deferred diffusibility in the several layers.
  • the color-providing substances in the inner layer or layers may transfer or diffuse to the image-receiving element at any stage in the processing thereof. It is necessary, however, to insure that such color-providing substances do not diffuse inwardly.
  • the color-providing substances to be associated with the outermost layer may, if desired, be introduced as ingredients of the liquid processing composition.
  • the deferred diffusibility of the nonimmobilized color-providing substances associated wtih an inner layer should be such that said substances do not become available for diffusion until development of at least the latent color record image in the next outer emulsion layer is substantially complete, it is only necessary that this deferred diffusibility be of such duration as to restrict diffusion until after at least substantial development of said latent image has occurred.
  • substantial development is meant the minimum development of the latent image, i.e., negative density, adapted to produce substantially clean highlights of a color record in the transferred, positive image and to be substantially unaffected by diffusion into said emulsion of an unoxidized developing agent originally associated with a differently sensitized emulsion.
  • the desired deferred diffusibility of color-providing substances may be obtained by two types of processing.
  • the latent color record images in the several emulsion layers are substantially simultaneously developed prior to the time the nonimmobilized color-providing substances in unexposed areas achieve the requisite diffusibility.
  • the integral multilayer photosensitive element is processed layerwise, one emulsion layer being develop-ed and the color-providing substances associated therewith, but not immobilized by development, rendered diffusible to the image-receiving layer substantially prior to the time development and diffusion occurs in another layer.
  • an integral multilayer photosensitive element may be so constructed as to utilize both types of processing techniques.
  • certain embodiments of this invention utilize the ability of a developing agent to develop a latent image contained in an exposed silver halide emulsion before a color-providing substance associated with said emulsion is sufficiently dissolved by a liquid processing composition to become diffusible.
  • the color-providing substance is also the developing agent, e.g., a dye developer, such developer may be rendered effective to reduce adjacent exposed silver halide before unoxidized dye developer is sufficiently solubilized to be rendered diffusible.
  • development of a latent color record image results in an imagewise distribution of diffusible or nonimmobilized color-providing substance in unexposed areas of the emulsion.
  • Immobilization of a color-providing substance may be due to a change in solubility resulting from the development, particularly where the color-providing substance is also a developer; to a barrier erected by tanning or hardening of the emulsion carrier due to the development; to a reaction with an immobile oxidized developer agent; etc.
  • the preferred color-providing substances are dye developers.
  • the desired imagewise distribution of diffusible dye developer results from the immobilization of the dye developer oxidized in developing the latent image.
  • Suitable dye developers mention may be made of 2 naphthylazohydroquinone, 1 phenyl 3- methyl 4 [p (2',5 dihydroxyphenethyl) phenylazoJ-S-pyrazolone and phenylazohydroquinone, for yellow; 2-hydr0xynaphthylazohydroquinone, 2-[p-(2',5'-dihydroxyphenethyl)-phenylazo] 4 methoxy-l-naphthol and 1-amino-4-phenylazo-2-naphthol, for magenta; 1,4- bis (2,S dihydroxyanilino) anthraquinone, 1,4 bis- [[3 (2",5' dihydroxyphenyl) ethylamino] anthraquinone and 1,4 bis [/3 (2',5' dihydroxyphenyl)- propylamino]-anthraquinone, for cyan.
  • a nondilfusing silver halide color developer is disposed in the photosensitive emulsion and a suitable phenolic or naphtholic type coupler is associated with said emulsion.
  • Each coupler employed should be of a character which is dispersible or soluble in a processing liquid and reactable with the oxidation prodnet of the silver halide color developer and also of a character which is reactable with the stabilized diazotized salt to provide a dye of the desired color.
  • the diazotized salt is disposed in the image-receiving layer and is available for reaction and coupling with unreacted color coupler which diffuses from unexposed portions of the negative.
  • coupling dye i.e., a complete dye which is capable of coupling with the oxidation product of a color developer, e.g., diethy-l p-phenylene diamine, to form an immobile dye.
  • the desired imagewise distribution of diffusible color-providing substance results from the immobilization of the coupling dye in situ with the developed image as a result of the coupling reaction.
  • the coupling dye possesses the requisite color and may be utilized in the image-receiving layer without further reaction.
  • Dyes i.e., coupling dyes, which are particularly suited for reaction with an oxidation product of a color developer are found in those dyes having an open position on a ring, which position is para to a hyd-roxyl or an amino group, or those dyes having a reactive methylene group.
  • Many suitable dyes coming within this classification are found among the azo, pyrazolone and triphenyl methane dyes, as is well known in the art.
  • waterand alkalisoluble dyes such as Fast Crimson 6BL (Cl. 57) as well as water-insoluble but alkali-soluble dyes such as 1,5-dihydroxynaphthalene-4-azobenzene.
  • dyes having an azo substitutent which is displaceable by reaction with oxidized photographic developer.
  • dyes having an azo substitutent are open chain reactive methylene compounds having an azo substituent attached to the reactive methylene group, compounds having a heterocyclic system containing an azo substituted methylene group and an adjacent carbonyl group as part of the ring structure, and phenolic compounds having an azo substituent attached to the phenol nucleus in a position para to the hydroxyl group; see U.S. Patents 2,453,661; 2,455,169; 2,455,170 and 2,521,908.
  • solubilizing groups e.g., sulfo
  • a complete dye which is immobilized by tanning or by otherwise reducing the permeability of the emulsion by oxidized developer, whereby outward diffusion of the dye is prevented.
  • Preferred couplers for this embodiment of the invention are those which form azomethine, indaniline and indophenol dyes when reacted with a silver halide secondary color developer in the presence of an oxidizing agent.
  • Such couplers may comprise nitriles, acyl nitriles. thioindoxyls, cyanaoetanilides, pyrazolones, phenols, naphthols, substituted ketones, esters and acyl acetanilides.
  • Particularly suitable coupers which react with the oxidation product of a color developer to provide dyes are 2,4-dichloro-1-naphthol, for cyan; 1-p-nitrophenyl-3-methyl-5-pyrazolone and 1-phenyl-3-butyramido-5-pyrazo1one, for magenta; and acetoacet-Z,5-dichloranilide, acetoacet-Z- 'chloranilide and benzoylacetanilide, for yellow.
  • Suitable silver halide color developers for use with the just-described couplers comprise such secondary developing agents as the p-phenylene diamines and other characterized by their ability when oxidized to condense with couplers to form dyes of the above type. Combinations of color developers and couplers which form the least mobile dyes are preferred since such combinations give the cleanest highlights and the sharpest detail to the positive image.
  • a standard color developer with which the invention may be practiced mention may be made of Z-amino-S-diethylamino toluene.
  • leuco dyes which are capable of developing a latent silver halide image and whose oxidation product is a dye.
  • leuco dyes include leuco indophenols, e.g., 2-chloro- 4-(4-diethylamino-2'-methylanilino)-5-nitro-l naphthol hydrochloride, for cyan; leu-coquinizarin, for yellow; and leuco azomethines, e.g., l-phenyl-3-methyl-4-(2'-methyl- 4'-diethylamino)-anilino-5-pyrazolone hydrochloride, for magenta.
  • the image-receiving element has incorporated therein an oxidizing agent for the purpose of speeding up dye image formation, and providing full density insmediately upon stripping.
  • an oxidizing agent for the purpose of speeding up dye image formation, and providing full density insmediately upon stripping.
  • suitable oxidizing agents mention may be made of peroxy compounds such as sodium or potassium perborate, and compounds having polyvalent metallic elements in higher valent form, such as copper, iron or cerium, wherein the metallic element is in higher valent form. Examples of these latter mentioned agents are cupric salts such as cupric sulfate.
  • Another suitable oxidizing agent is benzoyl peroxide.
  • Deferred diifusibility may be provided by incorporating the color-providing substances in an environment which initially prevents diffusion but which, by action of a liquid processing composition thereon, permits diffusion to occur after a suitable initial development period.
  • the environment is so constituted that application of a liquid processing composition renders the developing agent substantially immediately effective for development without rendering said color-providing substances soluble enough to be immediately diffusible.
  • the color-providing substances which are not immobilized as a result of development are released for transfer.
  • a color-providing substance may be incorporated in a water-immiscible material which is slowly permeable by alkaline solutions.
  • One means of so incorporating color-providing substances is to emulsify them in particles of a liquid plasticizer which is preferably a high boiling, waterand alkali-immiscible liquid. Due to a greater afiinity of the color-providing substance for the liquid processing composition than for the liquid plasticizer in which it is emulsified, the color-providing substance is rendered increasingly ditfusible by a differential extraction process.
  • a suitable liquid plasticizer is tricresyl phosphate.
  • a color-providing substance When a color-providing substance is incorporated in the form of particles or droplets, it isdesirable that such particles be of a relatively coarse nature such that their covering power is relatively low and therefore they do not substantially affect the speed of the silver halide emulsion with which they are associated.
  • Another method of effecting deferred diffusibility by utilizing the difference between the rate of development and the rate of solubilization of color-providing substances is by incorporating the color-providing substance, e.g., a dye developer, in a particle such that the color-providing substance is surrounded by silver halide. In exposed areas the color-providing substance would be immobilized by the development reaction before it became sufficiently solubilized to diffuse.
  • Such particles may be utilized in a binder, e.g., carboxymethyl cellulose, in which the nonimmobilized color-providing substance may move freely.
  • Particles containing redand green-sensitive silver halide are preferably provided with a suitable yellow filter.
  • a color-providing substance e.g., a dye developer, which is solubilized immediately but has a slow rate of diffusion, so that it may be immobilized in exposed areas before it is able to diffuse.
  • ground particles of dye developer should be of a relatively coarse nature, so as to have a relatively low covering power.
  • a white pigment may be utilized in forming particles of color-providing substances in lieu of a high boiling liquid plasticizer or a slowly hydrolyzable material. This may be accomplished by treating a pigment wettable by organic solvents, such, for example, as titanium dioxide, with an organic solution of the desired color-providing substance, after which the pigment is dried in the form of fine particles. These particles may then be finely dispersed in a photosensitive silver halide emulsion without adversely affecting the emulsion speed.
  • the nonimmobilized color-providing substances are rendered diffusible by being dissolved in the liquid processing composition.
  • a slowly hydrolyzable material may be used as a barrier layer separating an outer emulsion layer and its associated colorproviding substance from an inner emulsion layer and its associated color-providing substance.
  • Permeation by the liquid processing composition initiates development of the latent color record image and also hydrolysis of the barrier material.
  • a barrier material whose rate of hydrolysis is slower than the rate of development of the latent image, it is possible to effect the processing in a stepwise or layerwise manner.
  • the color-providing substances may be associated with the appropriate emulsions in any suitable manner, for example in a layer in, on or behind the emulsion, in the form of particles dispersed through the emulsion, etc.
  • stepwise processing e.g. by the use of a barrier layer between each set of photosensitive emulsion layers and their associated color-providing substances, permits development of the latent color record image in an emulsion layer and diffusion of the resulting imagewise distribution of diffusible color-providing substances to be substantially completed prior to initiation of development and diffusion in another emulsion layer.
  • the color-providing substances are dye developers
  • an unoxidized dye developer being diffused from an inner emulsion layer is not trapped by development of exposed but undeveloped silver halide grains in an outer emulsion layer, while unoxidized dye developer from an outer emulsion layer has diffused to the image-receiving layer and is unavailable for rearward diffusion to participate in the development of an inner emulsion layer.
  • Another means of effecting this type of layerwise processing is by theuse of a barrier layer which is slowly permeated by the liquid processing composition, such that permeation of the liquid processing composition from an outer emulsion layer into the next inner emulsion layer is deferred until processing of said outer emulsion layer is substantially complete.
  • a barrier layer which is slowly permeated by the liquid processing composition, such that permeation of the liquid processing composition from an outer emulsion layer into the next inner emulsion layer is deferred until processing of said outer emulsion layer is substantially complete.
  • One may employ, as a slowly permeable barrier layer, a layer of material which is slowly dissolved by a solvent therefor contained in the liquid processing composition.
  • An example of another suitable layer for this purpose is a copolymer of methyl methacrylate and methacrylic acid which is rendered permeable more slowly than development occurs.
  • barrier layers may be prepared by incorporating a slowly alkali-soluble material, such as benzoic anhydride, into a polymer so that the permeability of such polymer to an alkaline solution is dependent on the rate at which the slowly alkali-soluble material is dissolved.
  • a slowly alkali-soluble material such as benzoic anhydride
  • a weak alkali such as sodium carbonate or phosphate to initiate development without rendering the color-providing substances diffusible.
  • a stronger alkali such as sodium hydroxide may be released to render the nonimmobilized color-providing substances diffusible.
  • a film unit containing two pods or containers rupture of one such container being utilized to apply the weak alkali followed by rupture of the second container after a suitable interval to apply the stronger alkali.
  • the use of two containers to release different compositions at different stages of processing is disclosed and claimed in the copending application of Edwin H. Land, Ser. No. 299,358, filed July 17, 1952 now US. Patent No. 2,846,309 issued Aug. 5, 1958.
  • Such a two-stage application may be modified by having the liquid processing composition contained in the first ruptured container merely an aqueous composition effective to permeate the photosensitive element and release a weak alkali contained therein.
  • One may also incorporate the strong alkali in the integral multilayer photosensitive element in such a way as to be slowly released by the action of a liquid processing composition containing a weak alkali.
  • a further method of utilizing a weak alkali to initiate development followed by the introduction of a strong alkali to render the nonimmobilized color-providing substances diffusible utilizes an outermost layer which permits water, but not an alkali, to pass through.
  • the water of the liquid processing composition permeates this layer and solubilizes a weak alkali present in the photosensitive element, whereby development of the latent color record images is initiated.
  • This outer layer reacts slowly with a strong alkali initially present in the liquid process ing composition and, after an interval of time sufficient to permit the necessary minimum development, becomes sufiiciently permeable to the strong alkali to permit it to permeate the photosensitive element and render the nonimmobilized color-providing substances dilrusible.
  • Such a layer may be a thin layer of cellulose acetate or cellulose nitrate, which is slowly saponified by the strong alkali.
  • Another suitable material is a polymeric substance containing a slowly alkali-soluble material, such as the previously mentioned benzoic anhydride-containing polymers.
  • Deferred dilfusibility of color-providing substances may be accomplished also by the use of a temporary mordant mechanism, i.e., a color-providing substance may be associated with a substituent or substance which renders it temporarily insoluble, in lieu of the previously discussed barrier-type mechanism.
  • Application of a liquid processing composition slowly renders the temporary mordanted color-providing substances difiusible, as by hydrolyzing off an insolu'bilizing substituent such as an amine mordant.
  • One may also utilize a layer of hydrolyzable nylon dispersed throughout the emulsion to temporarily mordant a color-providing substance. In lieu of destroying the temporary mordant, one may use an image-receiving layer which has substantially more aflinity for the nonimmobilized color-providing substance than does the temporary mordant.
  • Still another method of deferring the diffusibility of nonimmobilized color-providing substances is by the temporary formation of salts of such color-providing substances, which salts are substantially insoluble in the liquid processing composition.
  • the liquid processing composition may contain a reagent which forms an insoluble salt of the dye developer as it permeates the photosensitive element, thus temporarily preventing unoxidized dye developer from diffusing to the image-receiving element without interfering in the development of the latent image.
  • a reagent capable of converting this insoluble salt to a salt soluble in the liquid processing composition is disposed behind the innermost strata of emulsion and/or dye developer.
  • the insoluble-salt-forming reagent may be a metal hydroxide which is soluble in water and forms an alkaliinsoluble salt, e.g., barium or calcium hydroxide, and which may replace a part of the alkali in the liquid processing composition, and the soluble-salt-forming reagent may be a source of sodium ions.
  • the dye developer may initially be present in the photosensitive element in the form of such an insoluble salt.
  • the suppressed solubility may be eliminated by precipitating the sodium sulfate, or by reacting it with a material, contained in an innermost layer, which will form a salt having less solubility suppression efiect.
  • materials include barium citrate and barium acetate.
  • the colorproviding substance may be incorporated in aparticle or envelope of pre-exposed silver bromide which is more slowly developable than the exposed silver halide .of tilt emulsion.
  • the developer In exposed areas, the developer is exhauster without developing the pre-exposed silver bromide of sucl particles, thus keeping immobile the color-providing substance in such particles.
  • the developer In unexposed areas the developer reduces the pre-exposed silver bromide, so changing the nature of the particle as to release the color-providing substance for diffusion.
  • the color-providing substance may be incorporated in a particle or envelope or a silver complex precipitant, such as zinc sulfide, and a silver halide solvent incorporated in the liquid processing composition.
  • a silver complex precipitant such as zinc sulfide
  • a silver halide solvent incorporated in the liquid processing composition.
  • silver bromide is dissolved and migrates to the particles containing the color-providing substance where it reacts with the silver complex precipitant, releasing the color-providing substance contained therein for diffusion.
  • a further modification of the above use of the unexhausted developer to effect the desired deferred diffusibility involves the use of a color-providing substance, e.g., a dye of desired color, containing a reducible component, e.g., a quinone group, which component in its unreduced state renders the dye immobile, such dye being made diffusible by the reducing action of the unoxidized developer.
  • a reducible component is more slowly reducible by the unoxidized developing agent than is the exposed silver halide but faster than the unexposed silver halide. In unexposed areas, the developing agent reduces this component, rendering the dye dilfusible.
  • the reduced quinone is preferably a weak developing agent and thus does not interfere with normal development.
  • Such uses of unexha-usted developer comprise the subject matter of the c-opending application of Howard G. Rogers, Ser. No. 599,122, filed July 20, 1956 (now abandoned in favor of a continuation-in-part thereof, Ser. No. 825,359, filed July 6, 1959, now US. Patent No. 3,185,567 issued May 25, 1965).
  • a process of this type may be described as a noninterfering process, since the several developing agents cannot interfere in the development of emulsions other than the one with which they are associated. Diffusion of the color-providing substances is deferred until after at least substantial development has occurred. This deferred difiusibility may be effected by utilizing the various techniques set forth in this specification.
  • the innermost emulsion layer of a three-color integral multilayer photosensitive element may utilize a nondiflusing tanning developer to develop the latent color record image therein. Tanning of the emulsion by the oxidized, nondiffusing tanning developer would be effective to prevent transfer, in exposed areas, of a dye initially present in a layer behind said emulsion.
  • the middle and outermost emulsion layers may utilize a nondifiusing couplin developer, such, for example, as 4- amino-S-n-butoxydiethyl aniline or decyloxyamiuophenol, to control the transfer of a coupling dye associated therewith.
  • Coupling dyes are dyes containing substituents which permit coupling thereof with the oxidation product of a color developer to form an immobile dye, as previously described.
  • the outermost emulsion layer maybe developed by a dye developer which may be introduced as an ingredient of the liquid processing composition. It may be desirable to utilize a layer behind this emulsion layer which will prevent permeation of the dye developer into inner emulsion layers.
  • an image-receiving layer which is only slowly permeated by the dye developer whereby imbibition of the dye developer is delayed and dye developer stain in the highlights is avoided.
  • nondiffusible tanning developer in the innermost layer, one may alsouse a nondiffusible developer which possesses a free amino group as part of its developing function to harden a carrier material for silver halide such, for example, as a polymer which is normally permeable to alkaline Solutions but which can be made less permeable by a coupling reaction with an oxidized amino developer.
  • a carrier material for silver halide such as a polymer which is normally permeable to alkaline Solutions but which can be made less permeable by a coupling reaction with an oxidized amino developer.
  • a polymer of this nature is a modified polyvinyl alcohol wherein positions on its chain have been substituted with phenol or naphthol groups and wherein the substituted phenols or naphthols have open positions for coupling, which positions are para to hydroxyl groups.
  • processing is preferably effected in the presence of a small amount of a short induction period-accelerating developing agent, for example, Metol (p-methylaminophenol) or Phenidone (lphenyl-3-pyrazolidone), hereinafter referred to as accelcrating developers.
  • a short induction period-accelerating developing agent for example, Metol (p-methylaminophenol) or Phenidone (lphenyl-3-pyrazolidone), hereinafter referred to as accelcrating developers.
  • accelcrating developers an amount insufficient to give any appreciable negative density by it self.
  • Such an accelerating developer may be incorporated in the liquid processing composition or in the emulsion so that it is substantially immediately available for development upon application of the liquid processing composition.
  • the accelerating developer appears to initiate development of the latent color record image before the principal developing agent, e.g., the dye developer, present in the photosensitive element, is sufficiently activated, e.g., solubilized, to begin development and the colorproviding substance rendered diffusible.
  • the principal developing agent e.g., the dye developer
  • solubilized e.g., solubilized
  • the oxidized accelerating developer is reduced or regenerated by reaction with unoxidized dye developer, apparently by an energy-transfer mechanism, immobilizing the dye developer substantially where the accelerating developer was oxidized by the exposed silver halide.
  • the regenerated accelerating developer is thus made available to repeat the cycle.
  • This reaction between the oxidized accelerating developer and the unoxidized principal developer may occur while the latter is still in an immobile condition, i.e., prior to its being solubilized by the liquid processing composition.
  • the use of such accelerating developers has been found to greatly improve the contrast of the color record image and to give increased development rates with low mobility principal developing agents. It has been found to be particularly useful in controlling transfer of a dye developer disposed in an emulsion, since part of the dye developer nearest to the outer surface of the emulsion might otherwise transfer before it was immobilized by adjacent exposed silver halide.
  • This priming development illustrated by accelerating developers, and explainable by an energy-transfer mechanism, facilitates the creation of the desired deferred diffusibility by rapidly initiating the imagewise development necessary to control the transfer of the color-providing substances.
  • a dye developer in the form of a continuous layer
  • Such spots may be approximately 0.0001 of an inch in thickness.
  • a suitable carrier material for the dye developers mention may be made of cellulose acetate hydrogen phthalate.
  • a carrier material which will control the release of the dye developer e.g.. a copolymer of methyl methacrylate and methacrylic acid, as previously discussed. Utilization of the dye developer in such spots has the advantages over a continuous layer of permitting faster permeation of the liquid processing composition as well as reduced danger of inward diffusion of dye developer.
  • a two-layer integral multilayer photosensitive element may also be constructed and processed in a similar manher.
  • the techniques of this invention may be utilized in both two-color and three-color photographic processes.
  • the sensitivities of the several emulsions may be selected in accordance with well-known photographic principles.
  • an integral multilayer photosensitive element suitable for use in two-color processes may have one emulsion sensitized to the blue and green portions of the spectrum, and the other emulsion to the orange and red portions of the spectrum.
  • the color-providing substances associated with such two-color photosensitive elements are, respectively, orange and cyan.
  • Suitable three-color integral multilayer photosensitive elements may comprise an outer blue-sensitive emulsion separated by a yellow filter layer from inner red-sensitive and green-sensitive emulsion layers. Where a yellow dye developer is utilized in processing the blue-sensitive outer emulsion layer, a layer of such dye developer behind the blue-sensitive emulsion may be utilized as an efficient yellow filter. Where the color-providing substance associated with the blue-sensitive emulsion is dispersed therein or otherwise utilized in such a way as to be incapable of effectively functioning as a yellow filter, a suitable yellow filter layer may be used.
  • a yellow filter layer may be prepared using a pigment comprising a suspension of a benzidine yellow, such as that commercially avialable under the name of Padding Yellow GL from Textile Colors Division, Interchemical Corporation, Hawthorne, NJ.
  • the liquid processing composition utilized to process the exposed photosensitive element comprises at least an aqueous solution, and may contain an alkaline reagent. If the liquid processing composition is to be applied to the exposed photosensitive element by being spread thereon, preferably in a relatively thin, uniform layer, it may also include a viscosity-increasing compound constituting a film-forming material of the type which, when said composition is spread and dried, will form a relatively firm and relatively stable film.
  • a preferred film-forming material is a high molecular weight polymer such as a polymeric water-soluble ether which is inert to an alkaline solution as, for example, a hydroxyethyl cellulose or sodium carboxymethyl cellulose.
  • film-forming materials or thickening agents whose ability to increase viscosity is substantially unaffected when left in solution for a long period of time may also be used.
  • the filmforming material is preferably contained in the processing composition in suitable quantities to impart to said composition a viscosity in excess of 1,000 centipoises at a temperature of approximately 24 C. and preferably of the order of 1,000 to 200,000 centipoises at said temperature.
  • suitable liquid processing compositions may be found in the several patents and copending applications herein mentioned, and also in the examples hereinafter given. Under certain circumstances, it may be desirable to apply the liquid processing composition to the integral multilayer photosensitive element prior to exposure in accordance with the technique described in the copending application of Edwin H. Land, Ser. No. 498,672, filed Apr. 1, 1955 now US. Patent No. 3,087,- 816 issued Apr. 30, 1963.
  • alkaline material is present in the liquid processing composition, and whether such alkaline compound is a strong or weak alkali, will depend upon the nature of the technique employed to create the desired deferred mobility as discussed above.
  • FIGURE 1 of the accompanying drawings diagram matically illustrates in cross section one example of an integral multilayer photosensitive element constructed in accordance with this invention.
  • a support has coated thereon an innermost layer 11 of a cyan dye developer over which has been coated a layer 12 of a red-sensitive silver halide emulsion.
  • a middle layer 14 of a greensensitive emulsion 14a containing discrete particles 14b of a magenta dye developer is separated from the innermost red-sensitive emulsion layer 12 by a gelatin interlayer 13.
  • the outermost layer 16 comprises a blue-sensitive silver halide emulsion 16a having dispersed therein discrete particles 16b of a yellow dye developer, and has been applied over a gelatin layer containing a yellow filter.
  • a container 17 is ruptured and a liquid processing composition contained therein is spread between the exposed, integral, multilayer photosensitive element and a superposed image-receiving element 18.
  • the alkaline liquid processing composition is permeated into the exposed photosensitive element whereby the dye developers are rendered eifective to develop the exposed silver halide.
  • Particles 14b and 16b containing magenta and yellow dye developers comprise particles, globules or droplets of a material which permits the liquid processing composition to activate dye developer contained therein to reduce exposed silver halide but which restricts the ability of unreacted dye developer contained therein to diffuse and transfer to the imagereceiving element until after at least substantial development of the exposed silver halide has occurred, at which stage of processing, diflusion of unreacted dye developer from an inner layer may be etfected without interfering in the development of I a dilferently sensitized emulsion.
  • the particles may be prepared from suitable plasticizers, or suitable, slowly hydrolyzable materials, such as esters, or mixtures thereof.
  • suitable plasticizers such as esters, or mixtures thereof.
  • tricresyl phosphate other suitable materials and mixtures for use in forming such particles include:
  • emulsion sensitivities as well as the color prop erties of the color-providing substances, e.g., dye de velopers, employed in the following example and alsc in the other examples of this specification are intended only to illustrate the techniques employed, without trying to obtain accurate color reproduction of the photographed subject matter.
  • Example 1 An integral multilayer photosensitive element is prepared by coating a gelatin-coated film base with a composition comprising 4% of a yellow dye developer (napht-hylazohydroquinone) in a 4% solution of cellulose acetate hydrogen phthalate in an :20 mixture, by volume, of acetone and methanol. After this coating has dried, a green-sensitive silver halide emulsion is applied, followed by a thin layer of gelatin using a 2% gelatin solution. A layer of red-sensitive emulsion containing a cyan dye developer dispersed therein is applied over the dried gelatin layer. The dispersion of cyan dye developer in the red-sensitive emulsion is prepared by emulsifying 1.35 g.
  • a yellow dye developer napht-hylazohydroquinone
  • the integral multilayer photosensitive element is processed by spreading an aqueous liquid proc essing composition comprising:
  • an image-receiving element comprising a coating of 4% Nylon Type F8 (trade name of E. I. du Pont de Nemours & 00., Wilmington, Del., for N-methoxymethyl polyhexamethylene adipamide) applied over a cellulose acetate-coated baryta paper, as said elements are brought into superposed relationship. After an imbibition period of approximately five minutes, the imagereceiving element is stripped from the developed photosensitive element revealing a yellow, cyan and green positive image.
  • Nylon Type F8 trade name of E. I. du Pont de Nemours & 00., Wilmington, Del.
  • FIG. 2 Suitable structure for a two-color diffusion transferreversal process is illustrated in FIG. 2, wherein an inner layer 21 containing particles 21a of a cyan dye developer and particles 21b of an orangeand red-sensitive emulsion has been applied to a support layer 20.
  • the exposed blueand green-sensitive emulsion particles of said outer layer 22 are developed by the orange dye developer dispersed therein. Unoxidized orange dye developer is ditfused to a suitable image-receiving layer, not shown.
  • the liquid processing composition permeates said inner layer 21 and renders the cyan dye developer dispersed therein as particles 21a eifective to develop exposed orangeand red-sensitive emulsion particles 21b,
  • the term layer as herein used also contemplates a stratum containing a combination of two differently photosensitized emulsions.
  • a stratum may comprise a mixture of two sets of particles of hardened gelatin, each encasing particles of a suitably sensitized emulsion together with its appropriate colorproviding substance.
  • hardened gelatin particles may be formed by procedures similar to those taught in US. Patent No. 2,618,553.
  • layer also contemplates a stratum comprising two sets of selectively sensitized minute photosensitive elements arranged in the form of a photosensitive screen, such as illustrated in FIG. 3 of the drawings.
  • a photosensitive screen 38 comprising minute red-sensitized emulsion elements 32 and minute green-sensitized emulsion elements 34 arranged in side-by-side relationship in a screen pattern, and having associated therewith strata 31 and 33 of cyan and magenta dye developers, respectively, is disposed on a support layer 30.
  • Suitable photosensitive screens for use in this embodiment may be prepared as disclosed in the aforementioned application Ser. No. 415,073 (now abandoned in favor of a continuation-in-part thereof, Ser. No. 748,421, now US. Patent No. 2,983,606 issued May 9, 1961) and also in the copending .application of Edwin H. Land, Ser. No. 448,441, filed Aug.
  • a barrier layer 35 separates said screen layer 38 from a layer 36 of a yellow dye developer over which is applied an outer layer 37 of a blue-sensitive emulsion.
  • the liquid processing composition permeates the blue-sensitive emulsion layer 37 and its associated layer 36 of yellow dye developer.
  • the barrier layer 35 serves to delay permeation of the liquid processing composition into the photosensitive screen layer 38 until at least substantial development of the blue-sensitive emulsion layer 37 has occurred.
  • the redand green-sensitized elements of the photosensitive screen layer 38 are then developed simultaneously and unoxidized cyan and magenta dye developers simultaneously rendered diffusible from the unexposed areas thereof. It will be apparent that the color-providing substances associated with the photosensitive screen may be incorporated in the emulsion or in separate strata behind the emulsion strata.
  • each unit portion of such color-providing substance transferred to the image-receiving layer be disposed over a surface area of the image-receiving layer which is greater in magnitude than the surface layer of the negative from which said unit portion of color-providing substance originates.
  • the extent of the overlap is controlled by the spacing employed between the negative and positive elements while undergoing processing. This spacing apart of the negative and positive elements will, of course, be dependent upon the thickness of the liquid processing composition spread between and in contact with said elements. The thickness of the layer of liquid composition will, in turn, be dependent, as will be well understood by the art, upon the liquid volume being spread, the viscosity of the liquid, the separation or gap between the pressure rolls or other spreading means and similar interrelated factors.
  • FIG. 4 of the accompanying drawings illustrates an integral, multilayer, photosensitive element wherein development and diffusion of the nonimmobilized color-providing substances is performed layerwise, i.e., development and diffusion of nonimmobilized color-providing substances is substantially completed in one layer before being initiated in an adjacent layer.
  • Support layer 40 has coated thereon a layer 41 of a cyan dye developer and a layer 42 of a red-sensitive emulsion.
  • Barrier layer 43 separates the layer 42 of red-sensitive emulsion from a layer 44 of a magenta dye developer and its associated layer 45 of a green-sensitive emulsion.
  • a blue-sensitive emulsion layer 48 and its associated layer 47 of a yellow dye developer is separated from the green-sensitive emulsion by a barrier layer 46.
  • An example of a suitable material for barrier layers 43 and 46 is gelatin.
  • the structure shown in FIG. 4 may be modified by disposing a layer of dye developer between two layers of commonly sensitized emulsion, e.g., a layer of a yellow dye developer may be cast between two layers of a blue-sensitive emulsion.
  • the layer of magenta dye developer may be similarly cast between two layers of a green-sensitive emulsion.
  • the layer of dye developer may effectively serve as a filter for an inner emulsion layer.
  • Casting the layer of dye developer between two layers of a commonly sensitized emulsion may also permit one to use thinner barrier layers between the several emulsion layers or to even omit such barrier layers completely, since the innermost of the two emulsion layers will function as a barrier layer to reduce or eliminate inward diffusion of the dye developer.
  • Example 2 An integral, multilayer, photosensitive element is prepared by coating a gelatin-coated film base with a 4% solution of 1,4 bis [,8 (2',5'-dihydroxyphenyl)-propylamino]-anthraquinone in a solution of 4% cellulose acetate hydrogen phthalate in a 50:50 mixture, by volume, of acetone and tetrahydrofuran. A red-sensitive emulsion is then applied, followed by a gelatin layer cast from a 4% aqueous gelatin solution.
  • a layer of yellow dye developer is then applied using a solution of 1.5% of naphthylazohydroquinone in a 4% solution of cellulose acetate hydrogen phthalate in a 50:50 mixture, by volume, of acetone and tetrahydrofuran, followed by a layer of a slightly diluted, green-sensitive emulsion.
  • the thus prepared photosensitive element is exposed and processed by application of an aqueous liquid processing composition comprising:
  • the liquid processing composition is applied by spreading between the exposed, integral, multilayer, photosensitive element and an image-receiving element, similar to that described in Example 1, as said elements are brought into superposed relationship. After an imbibition period of ap-' proximately 1 /2 minutes, the image-receiving element is stripped from the developed photosensitive element. The positive dye image in the image-receiving element has yellow, cyan and green portions, thus indicating that the desired color separation has been accomplished.
  • Permeation of the liquid processing composition into the exposed, integral, multilayer, photosensitive element whereby that element is processed layerwise may be effected by appropriate selection of the thickness of each photosensitive layer, as well as by the selection of emulsions which are of themselves slowly permeable, or by a combination of both of these practices. Additionally, one may utilize the increase of thickness of a photographic emulsion due to its swelling when wetted with the processing composition as a means of controlling the permeation of the'liquid processing composition. Furthermore, various materials may be added to a photosensitive emulsion layer to retard the rate of permeation by the liquid processing composition. Examples of suitable materials for this purpose include gum arabic, polyvinyl alcohol, and other materials which are compatible with gelatin.
  • a support layer 50 carries a layer 51 of a cyan dye over which is coated a layer 52 of a red-sensitive emulsion containing a nondiffusing, tanning developer, such as a long chain alkyl-substituted hydroquinone.
  • a layer 53 of a magenta coupling dye associated with a layer 54 of a green-sensitive emulsion containing a nondiffusing color developer is next applied.
  • a yellow dye developer is contained in a liquid processing composition disposed in a rupturable container 57 which is adapted, upon rupture, to release its contents for spreading across the exposed photosensitive element.
  • Application of the liquid processing composition containing the yellow dye developer simultaneously effects development of the bluesensitive emulsion layer 56 and permeation of the greenand red-sensitive emulsion layers 54 and 52.
  • the bluesensitive emulsion layer 56 is so constituted as to permit permeation of the alkaline processing composition, but not the yellow dye developer, to the inner greenand redsensitive emulsion layers 54 and 52.
  • the emulsion is tanned by the oxidized, nondilfusing tanning developer, thus preventing the cyan dye from dilfusing therethrough.
  • Development of the exposed green-sensitive emulsion layer 54 by the nondiffusing color developer disposed therein immobilize's the magenta coupling dye in the exposed portions thereof. Unoxidized yellow dye developer remains free to diffuse from the unoxidized portions of the bluesensitive emulsion layer 56.
  • FIG. 6 Suitable structure utilizing an insoluble-salt-forming mechanism for obtaining the desired deferred diffusibility is illustrated in FIG. 6.
  • a support 70 has coated thereon a layer 69 comprising a soluble-salt-forming reagent or material, for example sodium sulfate or an ion exchange resin capable of yielding sodium ions. Over this is applied a layer '68 of a cyan dye developer followed by a layer 67 of a red-sensitive silver halide emulsion.
  • a soluble-salt-forming reagent or material for example sodium sulfate or an ion exchange resin capable of yielding sodium ions.
  • a spatial barrier layer 66 which may be a layer of gelatin, silver halide emulsion or other material adapted to restrict inward diffusion of dye developer without restricting permeation of the liquid processing composition, separates the red-sensitive emulsion layer from a layer 65 of a magenta dye developer and its associated green-sensitive emulsion layer 64.
  • a spatial barrier layer 63 similar to the previously mentioned spatial barrier layer 66, separates the green-sensitive emulsion layer 64 from a layer 62 of a yellow dye developer and its associated layer 61 of a blue-sensitive emulsion.
  • an insoluble-salt-forming reagent such as barium hydroxide
  • an alkaline material such as sodium hydroxide or diethylamine
  • Permeation of the liquid processing composition into the innermost layer releases a soluble-salt-forming reagent or ion, which, as it dilfuses outwardly, converts the temporarily insolubilized, unoxidized dye developer into a salt which is soluble in the liquid processing composition and therefore ditfusible to the image-receiving element, and precipitates the insoluble-salt-forming reagent, e.g., the barium ion.
  • the pH of the liquid processing composition may be increased due to the greater alkalinity of sodium hydroxide. Release of the soluble-salt-forming reagent is effected only after at least substantial development has occurred.
  • the following example illustrates the preparation and processing of a two-color, integral, multilayer, photosensitive element similar in structure to the three-color element shown in FIG. 6, and is given only as an illustration of this technique.
  • Example 3 An integral, multilayer, photosensitive element is prepared by coating a film base with an aqueous gelatin solution containing 1% sodium sulfate. Over this is applied a layer of a yellow dye developer cast from a solution of 4% naphthylazohydroquinone in a 4% solution of cellulose acetate hydrogen phthalate in a 50:50 mixture, by volume, of acetone and tetrahydrofuran, followed by a layer of a green-sensitive emulsion. A gelatin layer is then applied, using a 4% aqueous gelatin solution.
  • a layer of cyan dye developer using a solution comprising 3% of 1,4-bis-[fl-(2,5'-dihydroxyphenyl)-propylaminoJ-anthraquinone in a solution of 4% cellulose :acetate hydrogen phth-alate in a 50:50 mixture, by volume, of acetone and tetrahydrofuran, followed by a layer of a red-sensitive emulsion.
  • this photosensitive element is processed by application of an aqueous liquid processing composition comprising:
  • the liquid processing composition is applied by spread ing between the exposed, integral, multilayer, photosensitive element and an image-receiving element, similar to that described in Example 1, as said elements are brought into superposed relationship. After an imbibition period of approximately two minutes, the image-receiving element is stripped from the developed photosensitive element.
  • the positive dye image in the image-receiving element has yellow, green and cyan portions, indicating that color separation has been effected.
  • the carrier or binder material of the silver halide emulsion be rendered impermeable as by tanning, hardening, etc.
  • Such hardening of the emulsion would prevent color-providing substances from diffusing outwardly from unexposed areas of an inner layer or layers.
  • the structure of the integral, multilayer, photosensitive element has been illustrated as having emulsion layers from top to bottom sensitized to blue, green, and red portions of the spectrum, respectively, it is to be understood that the order of these emulsions may vary in accordance with well known practices in the art.
  • the emulsion layers or strata are approximately 0.0001 to 0.0005 of an inch in thickness, while the barrier layers may be approximately 0.00005 to 0.0002 of an inch thick. It will be apparent that the thickness of the barrier layer will vary according to the nature of the material used and the nature of the liquid processing composition.
  • the color-providing substances are preferably selected for their ability to provide colors useful in carrying out subtractive color photography.
  • the color-providing substances are used in a quantity per unit portion of emulsion sufficient to be completely immobilized by the development reaction as said unit portion is fully exposed. When one relies upon tanning or hardening of the emulsion to restrict diffusion of the color-providing substance, then such color-providing substance may be used in excess of said quantity.
  • the color-providing substances are intended to be so distributed as to have a substantially uniform concentration for each unit surface area of the emulsion layer with which they are associated.
  • the color-providing substance in the form utilized in the integral multilayer photosensitive element may effectively function as a filter for the light reaching an inner emulsion layer.
  • the color-providing substance may be placed in, on or behind its respective emulsion layer. Preferably it is placed behind the emulsion, since dispersing such a colored substance in an emulsion may possibly reduce the exposure given inner portions of that emulsion layer.
  • a camera apparatus suitable for processing roll film of the type just mentioned is provided by the Polaroid Land Camera Model 95A, sold by Polaroid Corporation, Cambridge, Massachusetts, or similar camera structure such, for example, as the camera forming the subject matter of US. Patent No. 2,435,717.
  • Camera apparatus of this type permits successive exposure of individual frames of the photosensitive elements 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 image-receiving element while drawing these portions of the film assembly between a pair of pressure rollers 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 image-receiving element comprises an image-receiving layer of opaque or transparent material which is liquid permeable and dyeable from alkaline solutions and which has been illustrated for purposes of simplicity as comprising a single sheet of permeable material, for example paper.
  • This element may comprise a support upon which at least one liquid-permeable and dyeable layer is mounted.
  • the support layer may have a water-impermeable subcoat over which the stratum of permeable and dyeable material is applied.
  • the dyeable layer may comprise a layer of liquid processing composition which is adapted to remain adhered to the support layer upon stripping.
  • a preferred material for the image-receiving layer is a nylon and preferably a nylon such as N-methoxymethyl polyhexamethylene adipamide which is available under the trade name of Nylon Type F8 from E. I. du Pont de Nemours & Co.
  • Suitable for imagereceiving layers comprise a paritally hydrolyzed polyvinyl acetate such as that commercially available under the trade name of Vinylite MA-28-18 from Bakelite Division, Carbide and Carbon Chemicals Co.; polyvinyl alcohol with or without plasticizers; baryta paper, i.e., a support having a baryta coating thereon; cellulose acetate with filler as, for example, one-half cellulose acetate and one-half oleic acid, and other materials of a similar nature, as is well known in the art.
  • a paritally hydrolyzed polyvinyl acetate such as that commercially available under the trade name of Vinylite MA-28-18 from Bakelite Division, Carbide and Carbon Chemicals Co.
  • polyvinyl alcohol with or without plasticizers polyvinyl alcohol with or without plasticizers
  • baryta paper i.e., a support having a baryta coating thereon
  • a rupturable container 17 such as has been illustrated with the film unit of FIG. 1, 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 this invention may be otherwise effected.
  • an integral, multilayer, 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.
  • a nonviscous liquid processing composition is particularly applicable with the processing technique last mentioned above and may be applied to the exposed photosensitive element by imbibition or coating practices and may be similarly applied to the image-receiving element before said elements are brought into superposed relation or contact for carrying out the transfer of nonimmobilized color-providing substances.
  • tripack film structure for the negative photosensitive element in a diffusion transfer-reversal process.
  • a tripack film structure utilizes a plurality of separable, individual emulsion layers held together in superposed relationship during exposure but processed separately, in conjunction with separate image-receiving layers, which layers are thereafter superposed in registered relationship on a common support.
  • Such structure is readily distinguishable from the herein contemplated integral, multilayer, photosensitive element which is processed as a unit and in conjunction with a common image-receiving layer or element, and is in the nature of a monopack material.
  • 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 element.
  • 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 element will be a positive and the image produced on the imagecarrying layer will be a negative.
  • the expression posi tive image is intended to cover such an image produced on the image-carrying layer.
  • a process of forming positive transfer images in color comprising the steps of: exposing an integral, multilayer, photosensitive monopack element comprising a support carrying a plurality of continuous, coextensive, superposed photosensitive silver halide emulsion layers, each said emulsion having associated with it a color-providing substance selected from the class consisting of an image dye and an intermediate for said image dye, each said silver halide emulsion being sensitized to different portions of the spectrum, developing each of said emulsions, immobilizing in developed areas, as a function of said development, said color-providing substance associated wit] each said emulsion thereby providing in undevelopet areas of each said emulsion an imagewise distributior of nonimmobilized, diifusible color-providing substance transferring by imbibition at least a portion of each 0: said imagewise distributions of nonimmobilized, diffusible color-providing substance to a single, superposed image receiving layer to impart thereto a plurality
  • said integral, multilayer, photosensitive element comprises a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer, said emulsion layers being continuous, coextensive and superposed over each other and carried on a common support, said blue-sensitive silver halide emulsion layer being positioned most distant from said support and having associated therewith a yellow dye developer, said green-sensitive silver halide emulsion layer having associated therewith a magenta dye developer, and said red-sensitive sil ver halide emulsion layer having associated therewith a cyan dye developer, each of said dye developers being a compound which is, respectively, a yellow dye, a magenta dye, and a cyan dye, each said compound also being a silver halide developing agent, permeating said exposed integral, multilayer, photosensitive element with a liquid alkaline composition to so
  • a process of forming positive transfer images in color comprising the steps of: exposing an integral, multilayer, photosensitive monopack element comprising a support carrying a plurality of continuous, coextensive, superposed photosensitive silver halide emulsion layers, each said emulsion having associated with it a color-providing substance selected from the class consisting of an image dye and an intermediate for said image dye, each said silver halide emulsion being sensitized to different portions of the spectrum, developing each of said emulsions, immobilizing in developed areas, as a function of said development, said color-providing substance associated with each said emulsion thereby providing in undeveloped areas of each said emulsion an imagewise distribution of nonimmobilized, diffusible color-providing substance, transferring by imbibition at least a portion of each of said imagewise distributions of nonimmobilized, diffusible color-providing substance to a single, superposed imagereceiving layer to impart thereto a plurality of dye images, thereby
  • a process of forming positive transfer images in color comprising the steps of: exposing an integral, multilayer, photosensitive monopack element comprising a support carrying a plurality of continuous, coextensive, superposed photosensitive silver halide emulsion layers, each said emulsion having associated with it a color-providing substance selected from the class consisting of an image dye and an intermediate for said image dye, each said silver halide emulsion being sensitized to different portions of the spectrum, developing each of said emulsions, immobilizing in developed areas, as a function of said development, said color-providing substance associated with each said emulsion thereby providing in undeveloped areas of each said emulsion an imagewise distribution of nonimmobilized, diffusible color-providing substance, transferring by imbibition at least a portion of each of said imagewise distributions of nonimmobilized, diffusible color-providing substance to a single, superposed image-receiving layer to impart thereto a plurality of dye images,
  • a photographic product comprising an integral, multilayer photosensitive monopack element comprising a support carrying a plurality of continuous, coextensive, superposed photosensitive silver halide emulsion layers and adapted to be processed wtihout separation of said layers, each of said photosensitive emulsion layers being sensitized to different portions of the spectrum and having associated therewith a color-providing substance selected from the group consisting of an image dye and an intermediate for said image dye, said color-providing substance being nondilfusible from developed areas of said emulsion and diffusible from undeveloped areas of said emulsion as a function of the development of said emulsion, an image-receiving element comprising an imagereceiving layer for receiving by diffusion transfer mobile, ditfusible color-providing substance from each of said superposed silver halide emulsion layers to provide a plurality of dye images, means interconnecting said integral, multilayer, photosensitive element for movement relative to said image-receiving element whereby said
  • said integral, multilayer photosensitive element comprises a support having superposed thereon, in sequence, a red-sensitive silver halide emulsion stratum, a green-sensitive silver halide emulsion stratum, and a blue-sensitive silver halide emulsion stratum, each of said emulsions being continuous and coextensive and having associated therewith, respectively, a cyan dye developer, a magenta dye developer and a yellow dye developer, each of said dye developers being a compound which is a dye of the aforesaid color, which compound is also a silver halide developing agent.

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US565135A 1956-02-13 1956-02-13 Photographic diffusion transfer color processes Expired - Lifetime US3345163A (en)

Priority Applications (36)

Application Number Priority Date Filing Date Title
NL105917D NL105917C (zh) 1956-02-13
BE554934D BE554934A (zh) 1956-02-13
BE558821D BE558821A (zh) 1956-02-13
NL105919D NL105919C (zh) 1956-02-13
BE554935D BE554935A (zh) 1956-02-13
NL293714D NL293714A (zh) 1956-02-13
NL214522D NL214522A (zh) 1956-02-13
NL214523D NL214523A (zh) 1956-02-13
BE554933D BE554933A (zh) 1956-02-13
NL105918D NL105918C (zh) 1956-02-13
NL218146D NL218146A (zh) 1956-02-13
NL103316D NL103316C (zh) 1956-02-13
NL214521D NL214521A (zh) 1956-02-13
DENDAT1287717D DE1287717B (de) 1956-02-13 Verfahren zur Herstellung von Azofarbstoffen
US565135A US3345163A (en) 1956-02-13 1956-02-13 Photographic diffusion transfer color processes
US612051A US3019107A (en) 1956-02-13 1956-09-25 Novel photographic products, processes and compositions
GB2737/57A GB853479A (en) 1956-02-13 1957-01-25 Photographic processes and azo dye developers for use therein
GB2738/57A GB853480A (en) 1956-02-13 1957-01-25 Processes and products for forming photographic images in colour
GB11261/59A GB853482A (en) 1956-02-13 1957-01-25 Aminoaralkyldihydroxybenzenes, their o-acyl derivatives and their use in photographic processes
GB2736/57A GB853478A (en) 1956-02-13 1957-01-25 Colour photographic processes and products therefor
FR1185401D FR1185401A (fr) 1956-02-13 1957-02-11 Perfectionnements à la photographie en couleurs et à ses procédés
FR1185402D FR1185402A (fr) 1956-02-13 1957-02-11 Perfectionnements aux procédés pour former des images photographiques en couleurs
DEI12824A DE1151176B (de) 1956-02-13 1957-02-12 Verfahren zur Herstellung mehrfarbiger UEbertragungsbilder
DEI12826A DE1036640B (de) 1956-02-13 1957-02-12 Photographisches Verfahren zur Herstellung von monochromatischen oder mehrfarbigen Bildern, z. B. nach einem Diffusionsuebertragungsverfahren, und Material zur Durchfuehrung des Verfahrens
CH4257757A CH396630A (fr) 1956-02-13 1957-02-12 Procédé pour obtenir des images en couleurs par transfert
CH615266A CH444344A (fr) 1956-02-13 1957-02-12 Procédé de préparation de nouveaux colorants azoïques
DEI12825A DE1047620B (de) 1956-02-13 1957-02-12 Verfahren zur Herstellung von photographischen Farbbildern nach dem Diffusionsuebertragungsumkehrverfahren
CH4257957A CH418826A (fr) 1956-02-13 1957-02-12 Procédé photographique pour la formation d'images monochromatiques ou multicolores
CH4257857A CH398311A (fr) 1956-02-13 1957-02-12 Procédé pour former des images photographiques en couleurs
GB18671/57A GB858673A (en) 1956-02-13 1957-06-13 Process of forming transfer images in colour
DEI13400A DE1026172B (de) 1956-02-13 1957-06-26 Verfahren zur Herstellung von farbigen UEbertragungsbildern nach Diffusionsuebertragungs-Umkehrverfahren
FR1196814D FR1196814A (fr) 1956-02-13 1957-06-26 Procédé d'obtention d'images en couleurs par transfert
CH361194D CH361194A (de) 1956-02-13 1957-07-01 Verfahren zur Herstellung von farbigen Übertragungsbildern
US98287A US3236893A (en) 1956-02-13 1961-03-27 2-aminoarylalkylene-dihydroxy-benzenes
US196463A US3134811A (en) 1956-02-13 1962-05-21 Aminophenyl hydroquinones
SE10918/65A SE335061B (zh) 1956-02-13 1965-08-20

Applications Claiming Priority (12)

Application Number Priority Date Filing Date Title
US565135A US3345163A (en) 1956-02-13 1956-02-13 Photographic diffusion transfer color processes
US59912256A 1956-07-20 1956-07-20
US607820A US2997390A (en) 1956-09-04 1956-09-04 Novel color processes and products
US61205356A 1956-09-25 1956-09-25
US61206356A 1956-09-25 1956-09-25
US61204556A 1956-09-25 1956-09-25
US61205456A 1956-09-25 1956-09-25
US61205556A 1956-09-25 1956-09-25
US61205256A 1956-09-25 1956-09-25
US612051A US3019107A (en) 1956-02-13 1956-09-25 Novel photographic products, processes and compositions
US98287A US3236893A (en) 1956-02-13 1961-03-27 2-aminoarylalkylene-dihydroxy-benzenes
US196463A US3134811A (en) 1956-02-13 1962-05-21 Aminophenyl hydroquinones

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US3345163A true US3345163A (en) 1967-10-03

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US565135A Expired - Lifetime US3345163A (en) 1956-02-13 1956-02-13 Photographic diffusion transfer color processes
US612051A Expired - Lifetime US3019107A (en) 1956-02-13 1956-09-25 Novel photographic products, processes and compositions
US98287A Expired - Lifetime US3236893A (en) 1956-02-13 1961-03-27 2-aminoarylalkylene-dihydroxy-benzenes
US196463A Expired - Lifetime US3134811A (en) 1956-02-13 1962-05-21 Aminophenyl hydroquinones

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US612051A Expired - Lifetime US3019107A (en) 1956-02-13 1956-09-25 Novel photographic products, processes and compositions
US98287A Expired - Lifetime US3236893A (en) 1956-02-13 1961-03-27 2-aminoarylalkylene-dihydroxy-benzenes
US196463A Expired - Lifetime US3134811A (en) 1956-02-13 1962-05-21 Aminophenyl hydroquinones

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US (4) US3345163A (zh)
BE (4) BE558821A (zh)
CH (5) CH418826A (zh)
DE (5) DE1036640B (zh)
FR (3) FR1185401A (zh)
GB (5) GB853478A (zh)
NL (9) NL103316C (zh)
SE (1) SE335061B (zh)

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Also Published As

Publication number Publication date
CH418826A (fr) 1966-08-15
GB858673A (en) 1961-01-11
FR1185402A (fr) 1959-07-31
US3134811A (en) 1964-05-26
GB853479A (en) 1960-11-09
NL214522A (zh) 1900-01-01
BE554935A (zh) 1900-01-01
GB853478A (en) 1960-11-09
SE335061B (zh) 1971-05-10
DE1151176B (de) 1963-07-04
DE1287717B (de) 1969-01-23
GB853480A (en) 1960-11-09
US3019107A (en) 1962-01-30
CH396630A (fr) 1965-07-31
FR1196814A (fr) 1959-11-26
NL105918C (zh) 1900-01-01
NL103316C (zh) 1900-01-01
CH444344A (fr) 1967-09-30
DE1026172B (de) 1958-03-13
CH361194A (de) 1962-03-31
NL105919C (zh) 1900-01-01
CH398311A (fr) 1966-03-15
GB853482A (en) 1960-11-09
NL105917C (zh) 1900-01-01
FR1185401A (fr) 1959-07-31
US3236893A (en) 1966-02-22
BE554933A (zh) 1900-01-01
BE558821A (zh) 1900-01-01
DE1036640B (de) 1958-08-14
NL214523A (zh) 1900-01-01
DE1047620B (de) 1958-12-24
NL214521A (zh) 1900-01-01
BE554934A (zh) 1900-01-01
NL293714A (zh) 1900-01-01
NL218146A (zh) 1900-01-01

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