US3039869A - Photographic color processes and compositions - Google Patents

Photographic color processes and compositions Download PDF

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US3039869A
US3039869A US654781A US65478157A US3039869A US 3039869 A US3039869 A US 3039869A US 654781 A US654781 A US 654781A US 65478157 A US65478157 A US 65478157A US 3039869 A US3039869 A US 3039869A
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silver halide
dye developer
developing agent
dye
photosensitive element
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Howard G Rogers
Harriet W Lutes
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Polaroid Corp
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Polaroid Corp
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Priority to NL226020D priority Critical patent/NL226020A/xx
Priority to NL110125D priority patent/NL110125C/xx
Application filed by Polaroid Corp filed Critical Polaroid Corp
Priority to US654781A priority patent/US3039869A/en
Priority to GB7219/58A priority patent/GB853481A/en
Priority to CH5773058A priority patent/CH397421A/fr
Priority to FR764045A priority patent/FR1278607A/fr
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
    • G03C8/02—Photosensitive materials characterised by the image-forming section
    • 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

Definitions

  • Diffusion-transfer reversal processes utilizing dye developers are improved by the use, in conjunction with the dye developer, of a S-pyrazolidone developing agent as disclosed and claimed in the copending application of Howard G. Rogers, Serial No. 518,979, filed June 29, 1955, now abandoned in favor of a continuation-in-part thereof, Serial No. 748,421, filed July 14, 1958.
  • diffusion-transfer reversal processes utilizing dye developers may be substantially improved by the utilization, in conjunction with a dye developer and a 3-pyrazolidone developing agent, of another or second silver halide developing agent.
  • a further object of this invention is to provide novel photographic processes, products and compositions whereby the quality of the positive image, particularly the highlights and light steps obtained in difiusion-transfer reversal processes utilizing dye developers, may be improved.
  • Another object of this invention is to provide novel photographic processes, products and compositions whereby increased density and improved contrast may be obtained in color diffusion-transfer reversal processes employing dye developers.
  • a further object of this invention is to provide photographic processes, products and compositions for use in multicolor diflusion-transfer reversal processes utilizing I dye developers whereby improved color separation may
  • Other objects of the invention will in part be obvious and will in part appear hereinafter.
  • 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 and compositions 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 this invention during processing.
  • FIG. 2 is a diagrammatic cross-sectional view of one embodiment of a photographic product for use in accordance with this invention and comprising a multilayer photosensitive element, an image-receiving element and a rupturable container holding a processing composition.
  • a photosensitive element containing a silver halide emulsion is exposed and wetted by a liquid processing composition, for example, by immersing, coating, spraying, flowing, etc., in the dark and the exposed photosensitive element is superposed prior to, during, or after wetting, on a sheetlike support element which may be utilized as an imagereceiving element.
  • the photosensitive element contains a layer of dye developer and the liquid processing composition is applied to the photosensitive element in a uniform layer as the photosensitive element is brought into superposed relationship with an image-receiving element.
  • the liquid processing composition permeates the emulsion to initiate development of the latent image contained therein.
  • the dye developer is immobilized or precipitated in exposed areas as a consequence of the development of the latent image. This immobilization is apparently, at least in part, due to a change in the solubility characteristics of the dye developer upon oxidation and especially as regards its solubility in alkaline solutions. It may also be due in part to a tanning eiiect on the emulsion by the oxidized developing agent.
  • the dye developer In unexposed and partially exposed areas of the emulsion, the dye developer is unreacted and diffusible, and thus provides an imagewise distribution of unoxidized dye developer, dissolved in the liquid processing composition, as a function of the point-to-point degree of exposure of the silver halide emulsion. At least part of this imagewise distribution of unoxidized dye developer is transferred, by imbibition, to a superposed image-receiving layer or element, said transfer substantially excluding oxidized dye developer. Under certain circumstances, the layer of the liquid processing composition may be utilized as the image-receiving layer.
  • the image-receiving element receives a depthwise diflusion, from the developed emulsion, of unoxidized dye developer without appreciably disturbing the imagewise distribution thereof to provide a 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. If the color of the transferred dye' developer is afiected by changes in the pH of the imagereceiving element, this pH may be adjusted in accordance with well-known techniques to provide a pH affording the desired color.
  • the desired positive image is revealed by stripping the image-receiving element from the photo-' sensitive element at the end of the imbibition period.
  • diifusionatransfer reversal processes utilizing dye developers may be substantially improved by the use, in conjunction with the dye developer, of a S-pyrazolidone developing agent, which may be referred to as a first developing agent, and at least one additional developing agent, which additional developing agent may be referred to as a second developing agent.
  • a S-pyrazolidone developing agent which may be referred to as a first developing agent
  • additional developing agent which additional developing agent may be referred to as a second developing agent.
  • the use of such a combination of developing agents provides color transfer images of improved density, contrast, highlight rendition and, in the case'of multicolor images, improved color separation.
  • Such a combination of developing agents provides images of superior quality as compared with images obtained by the use of a dye developer with only one developing agent whether such other developing agent is a 3-pyrazolidone developing agent or a second developing agent as set forth hereinafter.
  • 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 developing function is a hydroquinonyl group.
  • Other suitable developing functions include o-dihydroxyphenyl and oand p-amino-substituted hydroxyphenyl groups.
  • the developing function includes a benzenoid developing function. Examples of representative dye developers are given in the previously mentioned application of Howard G. Rogers, Serial No. 415,073. Additional useful dye developers are described in the following copending applications:
  • the first developing agent used in combination with a dye developer is a 3-pyrazolidone developing agent.
  • Developing agents of this class may be represented by the formula:
  • R R R R and R each represents substituents such as hydrogen, aryl or alkyl groups, including substituted alkyl and aryl groups.
  • the alkyl groups preferably contain from 1 to 4 carbon atoms, inclusive.
  • a particularly useful developing agent of this class is l-phenyl-3-pyrazolidone, which is commercially available under the trademark Phenidone from Ilford, Ltd.
  • the second developing agent utilized in combination with the dye developer may be described broadly as a benzenoid developing agent.
  • developing agents of this class contain an aryl nucleus substituted in the ortho or para positions, with respect to each other, by hydroxyl and/or amino groups, including substituted amino groups, and this nucleus also may have other nuclear substituents, e.g., alkyl, aryl, arylthio, etc.
  • suitable developing agents within this group mention may be made of the following:
  • FIG. 1 of the accompanying drawing illustrates one method of processing a silver halide emulsion to obtain a monochromatic transfer image in accordance with this invention.
  • An exposed photosensitive element 10 comprising a support 12 and a silver halide emulsion 14 is processed with a processing composition 16 while in superposed relationship with an image-receiving element 18 comprising a support 22 and an image-receiving layer 20.
  • the processing composition includes a dye developer, a first developing agent and a second developing agent.
  • the processing composition permeates the silver halide emulsion layer 14 to provide a uniform distribution of dye developer therein.
  • the dye developer In exposed areas of the silver halide emulsion layer 14, the dye developer will be immobilized as a result of development of the latent image. In unexposed areas, the dye developer will remain mobile, due to its solubility in theprocessing composition, and thus provides an imagewise distribution of mobile dye developer available for transfer to the superposed'imagereceiving layer 20.
  • the image-receiving element 18 is separated from its superposed relationship with the photosensitive element 10 after at least a portion of said imagewise distribution of dye developer has been transferred.
  • one or more of these reagents may be incorporated initially in the photosensitive element, e.g., in the silver halide emulsion or in a layer behind said emulsion.
  • a photosensitive element is prepared in a manner similar to that set forth in Example 9 of the aforementioned copending application Serial No. 612,054.
  • An imagereceiving layer of polyvinyl alcohol is applied over .a support, followed by a stripping layer and a silver halide emulsion layer.
  • This photosensitive element is exposed and processed, in superposed relationship with a spreading sheet, with an aqueous composition comprising:
  • the image-receiving element is separated after a twominute imbibition period and washed briefly to remove any traces of the processing composition.
  • the brownishblack positive image obtained is substantially better than that obtained under the same conditions using a similar processing composition which does not contain 2,5-bisethylene-imiuo-hydroquinone.
  • the image has significantly greater density and contrast, as well as substantially cleaner highlights.
  • Multicolor images may be obtained using dye developers in diffusion-transfer reversal processes by several techniques.
  • One such technique contemplates the use of a photosensitive silver halide stratum comprising at least two sets of selectively sensitized minute photosensitive elements arranged in the form of a photosensitive screen. Transfer processes of this type are disclosed in the aforementioned application of Howard G. Rogers, Serial No. 415,073 and also in the copending application of Edwin H. Land, Serial No. 448,441, filed August 9, 1954, now U.S. Patent 2,968,554 granted January 17, 1961.
  • each of the minute photo sensitive elements has associated therewith an appropriate dye developer in or behind the silver halide emulsion portion.
  • a suitable photosensitive screen In general, a suitable photosensitive screen,
  • minute redsensitized emulsion elements minute green-sensitized emulsion elements and minute blue-sensitized emulsion elements arranged in side-by-side relationship in a screen pattern and having associated therewith, respectively, a cyan dye developer, a magenta dye developer and a yellow dye developer.
  • first developing agent and the second developing agent contemplated in accordance with this invention may be incorporated in the respective photosensitive elements or in the processing composition,
  • Another process for obtaining multicolor transfer images utilizing dye developers employs an integral multilayer photosensitive element such as disclosed and claimed in the copending application of Edwin H. Land and Howard G. Rogers, Serial No. 565,135, filed February 13, 1956, wherein at least two selectively sensitized photosensitive strata are superposed on a single support and are processed, simultaneously and without separation, with a single, common image-receiving layer.
  • a suitable arrangement of thi type comprises a support carrying a redsensitive silver halide emulsion stratum, a green-sensitive silver halide emulsion stratum and a blue-sensitive silver halide emulsion stratum, said emulsions having associated therewith, respectively, 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, e.g., 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 may be separated from the other sets by suitable spacer strata, for example, by a layer of gelatin or polyvinyl alcohol.
  • a multilayer photosensitive element of the type just mentioned is illustrated in FIG. 2 of the accompanying drawing.
  • a support 66 carries a layer 64 containing a cyan dye developer; a layer 62 of a red-sensitive silver halide emulsion; a spacer layer 60, e.g., of gelatin or polyvinyl alcohol; a layer 58 containing a magenta dye developer; a layer 56 of a green-sensitive silver halide emulsion; a spacer layer 54; a layer 52 containing a yellow dye developer; and an outermost layer 50 of a bluesensitive silver halide emulsion.
  • it carries a layer 64 containing a cyan dye developer; a layer 62 of a red-sensitive silver halide emulsion; a spacer layer 60, e.g., of gelatin or polyvinyl alcohol; a layer 58 containing a magenta dye developer; a layer 56 of a green-sensitive silver halide emulsion
  • e may be desirable to incorporate a yellow filter in front of the green-sensitive emulsion layer, and such yellow filter may be incorporated in the spacer layer.
  • a separate yellow filter may be omitted.
  • the multilayer photosensitive element 46 is shown in spread-apart relationship (as, for example, during exposure) with an image-receiving element 40 having mounted thereon a rupturable container 48 holding a processing composition.
  • the image-receiving element 4% comprises a support 42 and an imagereceiving layer 44.
  • the image-receiving element 40 is brought into superposed relationship with the multilayer photosensitive element 46 and the rupturable container 48 ruptured by application of suitable pressure, e.g., by advancing between a pair of rollers, not shown, and a layer of the liquid composition spread between the superposed elements.
  • first and second developing agents are contained in the rupturable container 48 in the embodiment shown in FIG. 2, it is to be understood that one or both of said first and second developing agents may be located initially in appropriate layers of the multilayer photosensitive element, e.g., in an emulsion layer and/ or in a layer containing a dye developer. contemplated to position a portion of one or both of said first and second developing agents in the photosensitive element (whether monochrome or multicolor), and to incorporate the balance thereof in the processing composition.
  • Example 2 An integral multilayer photosensitive element similar to that shown in FIG. 2 of the accompanying drawing is prepared in a manner similar to that described in Example 2 of the aforementioned copending application Serial No. 565,135.
  • This photosensitive element com prises the following layers, laid down in the order recited,
  • a gelatin-coated film base e.g., a gelatin-coated film base
  • a layer of a cyan dye developer i.e., l,4-bis-[B-(2',5'-
  • an aqueous solution comprising:
  • a processing composition may also contain small amounts'of other photographic reagents, e.g., preservatives, restrainers, etc.
  • the photosensitive element In testing the elIect of each developing agent, the photosensitive element is exposed and then processed in superposed relationship with an image-receiving element comprising a layer of N-methoxymethyl polyhexamethylene a'dipamide (available from E. I. du Pont de Nemours & Co., Inc., Wilmington, Delaware, under the trade name Nylon Type F8) carried on a cellulose acetate-coated baryta paper.
  • the image-receiving element is stripped apart from the photosensitive element at er an imbibition period of approximately six minutes.
  • a comparison of the positive multicolor transfer images obtained in the above tests shows that the images obtained in Tests 4 and 5 using a combination of developing agents, one of which is a 3-pyrazolidone developing agent, exhibited markedly superior color separation, increased density, improved blacks and grays, and cleaner highlights than the images obtained in Tests 1, 2 and 3 using the same developing agents separately.
  • the positive image obtained in Test 6 also exhibits the abovementioned superior qualities as compared with images using only a 3-pyrazolidone developing agent.
  • a further technique for obtaining multicolor images employs a plurality of photosensitive elements associated with an appropriate number of image-receiving elements and adapted to be treated with one or more liquid processing compositions, the appropriate dye developers being incorporated in the photosensitized elements or in the liquid processing compositions.
  • Examples of film structures of this type are disclosed in U.S. Patent No. 2,647,049 issued to Edwin H. Land.
  • the dye developers utilized in the processes of this invention may be incorporated in the photosensitive element, for example, in,” on, or behind the silver halide emulsion, or they may be employed as a component of the liquid processing composition, or in the image-receiving element where monochromatic images are desired.
  • the dye developer is preferably in a coating or layer behind the'silver halide emulsion and such a layer of dye cvelop-er may be applied by the use of a coating solution containing about 0.5 to 8 percent by weight of the dye developer. Similar concentrations may be used if the dye developer is utilized as a component of the liquid processing composition.
  • the first developing agent or 3-pyrazolidone developing agent and the second developing agent may be employed as components of the liquid processing composition. It is also contemplated to employ one or both of these developing agents in the layer containing the dye developer or in the silver halide emulsion. Thus, one may utilize one of these developing agents in the liquid processing composition and the other developing agent in the silver halide emulsion or in the layer containing the dye developer.
  • the preferential oxidation and resulting immobilization of the dye developer is a consequence of its having the least soluble oxidation product. It appears that the dye developer may be oxidized and immobilized as a result of a reaction, e.g., an energy transfer reaction, with the oxidation product of a developing unit provided by the first and second developing agents, the latter developing agents being oxidized by development of the exposed silver halide. Such a reaction of oxidized developing agent with unoxidized dye developer would regenerate the first or second developing agent for further reaction with exposed silver halide.
  • a reaction e.g., an energy transfer reaction
  • the liquid processing composition herein referred to comprises at least an aqueous solution of an alkaline compound, for example, diethylamine, sodium hydroxide or sodium carbonate.
  • the liquid processing composition may also contain the first developing agent or the second develop-ing agent, or both. If the liquid processing composition is to be applied to the emulsion by being spread thereon, preferably in a relatively thin uniform layer, it might also include a viscosity-increasing compound constituting film-forming material of the type which, when said composition is spread and dried, forms 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.
  • 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.
  • Other film-forming materials or thickening agents Whose ability to increase viscosity is substantially unaffected if left in solution for along period of time may also be used.
  • the film-forming material is preferably contained in the processing composition in suitable quantifies 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.
  • the dye developers are preferably selected for their ability to provide colors that are useful in carrying out subtractive color photography, i.e., cyan, magenta and yellow. It should be noted that it is within the scope of this invention to use mixtures of dye developers to obtain a desired color, e.g., black. Thus, it is to be understood that the expression color as used herein is intended to include the use of a plurality of colors to obtain black, as well as the use of a single black dye developer.
  • Camera apparatus of this type permits successive exposure of individual frames of the photosensitive element from the emulsion side thereof as well as ndividual 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 elfect 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 imagereceiving 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 waterimpermeable subcoat over which the stratum of permeable and dyeable layer 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 image-receiving layers comprise a partially 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 onehalf oleic acid, and other materials of a similar nature, as is well known in the art.
  • a partially 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
  • cellulose acetate with filler as, for
  • a rupturable container such as container 48 in FIG. 2 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.
  • 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.
  • 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 01' contact for carrying out the transfer of nonimmobilized color-providing substances.
  • the expression positive image has been used. This expression should not be interpreted in a restrictive sense since it is used primarily for purposes of illustration, in that it defines the image produced on the image-carrying layer as being reversed, in the positive-negative sense, with respect to the image in the photosensitive element.
  • the expression positive image assume that the photosensitive element is exposed to actinic light through a negative transparency. In this case, the latent image in the photosensitive element will be a positive and the image produced on the image-carrying layer will be a negative.
  • the expression positive image is intended to cover such an image produced on the image-carrying layer.
  • a temporary stain may be observed on the image-receiving layer. This temporary stain disappears within a short time or may be removed immediately by washing or by swabbing with a slightly acidic solution. It has also been found that incorporating these developing agents in the photosensitive element, e.g., in the emulsion or in a layer behind the emulsion, minimizes or eliminates such temporary staining.
  • a process of forming transfer images in color comprising developing an exposed silver halide emulsion in the presence of (a) a dye developer, said dye developer being a compound which is both a silver halide developing agent and a dye, (b) a 3-pyrazolidone silver halide developing agent and (c) a benzenoid silver halide developing agent, said benzenoid silver halide developing agent containing an aryl nucleus substituted by at least two substituents selected from the class consisting of hydroxyl and amino groups, one of said substituents being substituted in one of the ortho and para positions with respect to the other of said substituents, oxidizing said dye developer in developed areas of said emulsion as a function of the point-to-point development thereof, whereby an imagewise distribution of unoxidized, diffusible dye developer is provided in undeveloped areas of said emulsion, and transferring, by difiusion, at least a portion of said unoxidized, diff
  • one of said substituents of said benzenoid silver halide developing agent is an amino group and said amino group is an alkyl amino group.
  • said dye develop-er contains as the silver halide developing functional group a group selected from the class consisting of para-dihydroxyphenyl, ortho-dihydroxyphenyl, paraaminohydroxyphenyl and ortho-aminohydroxyphenyl groups.
  • said dye developer contains as the silver halide developing functional group a para-dihydroxyphenyl group.
  • the process which comprises developing an exposed silver halide emulsion with an aqueous alkaline solution comprising (a) a dye developer, said dye developer being a compound which is both a silver halide developing agent and a dye, (b) a 3-pyrazolidone silver halide developing agent and (c) a benzenoid silver halide developing agent, said benzenoid silver halide developing agent con- I taining an aryl nucleus substituted by at least two substituents selected from the class consisting of hydroxyl and amino groups, one of said substituents being substituted in one of the ortho and para positions with respect to the other of said substituents.
  • a photographic developer composition comprising an aqueous alkaline solution comprising (a) a dye developer, said dye developer being a compound which is both a silver halide developing agent and a dye, (b) a 3-pyrazolidone silver halide developing agent and (c) a benzenoid silver halide developing agent, said benzenoid silver halide developing agent containing an aryl nucleus substituted by at least two substituents selected from the class consisting of hydroxyl and amino groups, one of said substituents being substituted in one of the ortho and para positions with respect to the other of said substituents.
  • a photosensitive element comprising a plurality of layers, at least one of said layers containing a photosensitive silver halide emulsion; at least one of said layers containing a dye developer, said dye developer being a compound which is both a silver halide developing agent and a dye; at least one of said layers containing a B-pyrazolidone silver halide developing agent, and at least one of said layers containing a benzenoid silver halide developing agent, said benzenoid silver halide developing agent containing an aryl nucleus substituted by at least two substituents selected from the class consisting of hydroxyl and amino groups, one of said substituents being substituted in one of the ortho and para positions with respect to the other of said substituents.
  • a photosensitive element as defined in claim 16 including a plurality of photosensitive silver halide emulsions, each of said emulsions being sensitized to different portions of the spectrum, and each of said emulsions having associated therewith a dye developer of a color substantially complementary to the portion of the visible spectrum to which said emulsion is sensitive.
  • a photographic product which comprises a. photosensitive element comprising a silver halide emulsion; an image-receiving element comprising an image-receiving layer; means interconnecting said photosensitive element for movement relative to said image-receiving element, whereby said photosensitive element is positionable in superposed relation and in relatively close proximity to 831d image-receiving element; a rupturable container holdmg at least a liquid processing composition including a solvent for (a) a dye developer, said dye developer being a compound which is both a silver halide developing agent and a dye, (b) a S-pyrazolidone silver halide developing agent and (c) a benzenoid silver halide developing agent, said benzenoid silver halide developing agent containing an aryl nucleus substituted by at least two substituents selected from the class consisting of hydroxyl and amino groups, one of said substituents being substituted in one of the ortho and para positions with respect to the other of said substituents,
  • said photosensitive element comprises a bluesensitive silver halide emulsion, a green-sensitive silver halide emulsion and a red-sensitive silver halide emulsion, said emulsions having associated therewith, respectively, a yellow dye developer, a magenta dye developer and a cyan dye developer.
  • S-pyrazolidone silver halide developing agent is 1-phenyl-3-pyrazolidone.
  • a process of forming multicolor transfer images comprising exposing a photosensitive element, said photosensitive element comprising a plurality of silver halide emulsions, each of said silver halide emulsions having associated therewith a dye developer, each said dye developer being a compound which is both a silver halide developing agent and a dye, developing said exposed photosensitive element, said development being effected in the presence of a 3-pyrazolidone silver halide developing agent and of a benzenoid silver halide developing agent, said benzenoid silver halide developing agent containing an aryl nucleus substituted by at least two substituents selected from the class consisting of hydroxyl and amino groups, one of said substituents being substituted in one of the ortho and para positions with respect to the other of said substituents, oxidizing each said dye developer as a function of the point-to-point development of the silver halide emulsion with which said dye developer is associated, thereby providing an imagewise distribution of unoxidized dye
  • said photosensitive element contains a blue-sensitive silver halide emulsion, a green-sensitive silver halide emulsion and a red-sensitive silver halide emulsion, said emulsion having associated therewith, respectively, a yellow dye developer, a magenta dye developer and a cyan dye developer.

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US654781A 1957-04-24 1957-04-24 Photographic color processes and compositions Expired - Lifetime US3039869A (en)

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NL226020D NL226020A (de) 1957-04-24
NL110125D NL110125C (de) 1957-04-24
US654781A US3039869A (en) 1957-04-24 1957-04-24 Photographic color processes and compositions
GB7219/58A GB853481A (en) 1957-04-24 1958-03-06 Photographic processes and products
CH5773058A CH397421A (fr) 1957-04-24 1958-03-31 Procédé photographique pour former des images de transfert en couleur
FR764045A FR1278607A (fr) 1957-04-24 1958-04-23 Procédé et produits photographiques

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Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3108001A (en) * 1959-08-17 1963-10-22 Polaroid Corp Novel photographic products, processes, and compositions
US3146102A (en) * 1960-08-22 1964-08-25 Eastman Kodak Co Photographic multicolor diffusion transfer process using dye developers
US3146104A (en) * 1959-12-21 1964-08-25 Eastman Kodak Co Silver halide sensitized lithographic printing plate
US3192044A (en) * 1960-08-22 1965-06-29 Polaroid Corp Multicolor diffusion transfer method and element
US3239338A (en) * 1961-03-06 1966-03-08 Polaroid Corp Photographic process
US3245789A (en) * 1961-05-05 1966-04-12 Polaroid Corp Photographic products and processes
US3253915A (en) * 1964-01-10 1966-05-31 Eastman Kodak Co Photographic dye developer image transfer systems
US3265498A (en) * 1960-08-22 1966-08-09 Polaroid Corp Diffusion transfer photographic process utilizing development restrainers
US3650749A (en) * 1968-06-10 1972-03-21 Agfa Gevaert Nv Photographic development
US4209580A (en) * 1978-10-02 1980-06-24 Eastman Kodak Company Substituted 1-phenyl-3-pyrazolidinone electron transfer agents
US4266002A (en) * 1978-10-02 1981-05-05 Eastman Kodak Company Substituted 1-phenyl-3-pyrazolidinone electron transfer agents
JPS5664339A (en) * 1979-10-29 1981-06-01 Konishiroku Photo Ind Co Ltd Silver halide color phtographic material
US4463081A (en) * 1983-08-04 1984-07-31 Eastman Kodak Company 4-Hydroxyalkyl-substituted 3-pyrazolidinone electron transfer agents
US4471046A (en) * 1983-08-04 1984-09-11 Eastman Kodak Company 4-Hydroxyalkyl-substituted 3-pyrazolidinone electron transfer agents
EP0143424A2 (de) 1983-11-25 1985-06-05 Fuji Photo Film Co., Ltd. Wärmeentwickelbares lichtempfindliches Material
EP0200011A1 (de) 1985-03-30 1986-11-05 Fuji Photo Film Co., Ltd. Wärmeentwickelbares lichtempfindliches Material
EP0200216A2 (de) 1985-04-30 1986-11-05 Fuji Photo Film Co., Ltd. Wärmeentwickelbares lichtempfindliches Material
EP0210660A2 (de) 1985-07-31 1987-02-04 Fuji Photo Film Co., Ltd. Verfahren zur Bildung eines Bildes
US4882264A (en) * 1984-01-20 1989-11-21 Olin Hunt Specialty Products Inc. Color developer composition
EP0394943A2 (de) 1989-04-25 1990-10-31 Fuji Photo Film Co., Ltd. Farbphotographisches Silberhalogenidmaterial
EP0772088A1 (de) 1991-03-05 1997-05-07 Fuji Photo Film Co., Ltd. Wärmeentwickelbares farbphotographisches Diffusionsübertragungsmaterial
EP0848287A1 (de) * 1996-12-11 1998-06-17 Imation Corp. Photographische Silberhalogenidentwicklerzusammensetzung und Verfahren zur Erzeugung photographischer Silberbilder

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2543691A (en) * 1946-06-07 1951-02-27 Gen Aniline & Film Corp Azo dyes as silver halide photographic developing agents
US2751300A (en) * 1954-07-15 1956-06-19 Eastman Kodak Co Photographic solvent transfer reproduction process
US2756142A (en) * 1953-01-22 1956-07-24 Eastman Kodak Co Photographic color reproduction process
US2774668A (en) * 1953-05-28 1956-12-18 Polaroid Corp Process and product for forming color images from complete dyes
US2892710A (en) * 1957-07-10 1959-06-30 Polaroid Corp Photographic products and processes

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2543691A (en) * 1946-06-07 1951-02-27 Gen Aniline & Film Corp Azo dyes as silver halide photographic developing agents
US2756142A (en) * 1953-01-22 1956-07-24 Eastman Kodak Co Photographic color reproduction process
US2774668A (en) * 1953-05-28 1956-12-18 Polaroid Corp Process and product for forming color images from complete dyes
US2751300A (en) * 1954-07-15 1956-06-19 Eastman Kodak Co Photographic solvent transfer reproduction process
US2892710A (en) * 1957-07-10 1959-06-30 Polaroid Corp Photographic products and processes

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3108001A (en) * 1959-08-17 1963-10-22 Polaroid Corp Novel photographic products, processes, and compositions
US3146104A (en) * 1959-12-21 1964-08-25 Eastman Kodak Co Silver halide sensitized lithographic printing plate
US3146102A (en) * 1960-08-22 1964-08-25 Eastman Kodak Co Photographic multicolor diffusion transfer process using dye developers
US3192044A (en) * 1960-08-22 1965-06-29 Polaroid Corp Multicolor diffusion transfer method and element
US3265498A (en) * 1960-08-22 1966-08-09 Polaroid Corp Diffusion transfer photographic process utilizing development restrainers
US3239338A (en) * 1961-03-06 1966-03-08 Polaroid Corp Photographic process
US3245789A (en) * 1961-05-05 1966-04-12 Polaroid Corp Photographic products and processes
US3253915A (en) * 1964-01-10 1966-05-31 Eastman Kodak Co Photographic dye developer image transfer systems
US3650749A (en) * 1968-06-10 1972-03-21 Agfa Gevaert Nv Photographic development
US4209580A (en) * 1978-10-02 1980-06-24 Eastman Kodak Company Substituted 1-phenyl-3-pyrazolidinone electron transfer agents
US4266002A (en) * 1978-10-02 1981-05-05 Eastman Kodak Company Substituted 1-phenyl-3-pyrazolidinone electron transfer agents
JPS6346406B2 (de) * 1979-10-29 1988-09-14 Konika Kk
JPS5664339A (en) * 1979-10-29 1981-06-01 Konishiroku Photo Ind Co Ltd Silver halide color phtographic material
US4463081A (en) * 1983-08-04 1984-07-31 Eastman Kodak Company 4-Hydroxyalkyl-substituted 3-pyrazolidinone electron transfer agents
US4471046A (en) * 1983-08-04 1984-09-11 Eastman Kodak Company 4-Hydroxyalkyl-substituted 3-pyrazolidinone electron transfer agents
EP0143424A2 (de) 1983-11-25 1985-06-05 Fuji Photo Film Co., Ltd. Wärmeentwickelbares lichtempfindliches Material
US4882264A (en) * 1984-01-20 1989-11-21 Olin Hunt Specialty Products Inc. Color developer composition
EP0200011A1 (de) 1985-03-30 1986-11-05 Fuji Photo Film Co., Ltd. Wärmeentwickelbares lichtempfindliches Material
EP0200216A2 (de) 1985-04-30 1986-11-05 Fuji Photo Film Co., Ltd. Wärmeentwickelbares lichtempfindliches Material
EP0210660A2 (de) 1985-07-31 1987-02-04 Fuji Photo Film Co., Ltd. Verfahren zur Bildung eines Bildes
EP0394943A2 (de) 1989-04-25 1990-10-31 Fuji Photo Film Co., Ltd. Farbphotographisches Silberhalogenidmaterial
EP0772088A1 (de) 1991-03-05 1997-05-07 Fuji Photo Film Co., Ltd. Wärmeentwickelbares farbphotographisches Diffusionsübertragungsmaterial
EP0848287A1 (de) * 1996-12-11 1998-06-17 Imation Corp. Photographische Silberhalogenidentwicklerzusammensetzung und Verfahren zur Erzeugung photographischer Silberbilder
US5998110A (en) * 1996-12-11 1999-12-07 Ferrania S.P.A. Photographic silver halide developer composition and process for forming photographic silver images

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GB853481A (en) 1960-11-09
CH397421A (fr) 1965-08-15
NL226020A (de)
NL110125C (de)

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