US3802881A - Color diffusion transfer film with whitening agent - Google Patents

Color diffusion transfer film with whitening agent Download PDF

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Publication number
US3802881A
US3802881A US00247048A US24704872A US3802881A US 3802881 A US3802881 A US 3802881A US 00247048 A US00247048 A US 00247048A US 24704872 A US24704872 A US 24704872A US 3802881 A US3802881 A US 3802881A
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layer
image
processing composition
diffusible
silver halide
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US00247048A
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E Land
S Bloom
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Polaroid Corp
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Polaroid Corp
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Priority to US00247048A priority Critical patent/US3802881A/en
Priority to GB1813673A priority patent/GB1432805A/en
Priority to DE2319718A priority patent/DE2319718C2/de
Priority to CA169,127A priority patent/CA1007508A/en
Priority to FR7314463A priority patent/FR2181937B1/fr
Priority to JP4605873A priority patent/JPS5319408B2/ja
Priority to NLAANVRAGE7305707,A priority patent/NL181758C/xx
Application granted granted Critical
Publication of US3802881A publication Critical patent/US3802881A/en
Priority to CA256,097A priority patent/CA1011150A/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
    • G03C1/00—Photosensitive materials
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/815—Photosensitive materials characterised by the base or auxiliary layers characterised by means for filtering or absorbing ultraviolet light, e.g. optical bleaching
    • G03C1/8155—Organic compounds therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
    • G03C8/24—Photosensitive materials characterised by the image-receiving section
    • G03C8/246—Non-macromolecular agents inhibiting image regression or formation of ghost images

Definitions

  • ABSTRACT This invention relates to photographic film units adapted for forming color transfer images viewable by reflected light and to diffusion transfer processes employing these film units wherein a non-fluorescent optical whitening reagent is provided in association with the transfer image to offset the color stain that tends to form in the image highlights during aging.
  • the whitening reagent may be a non-fluorescent pigment or a non-fluorescent dye capable of absorbing visible light in a wavelength range complementary to the wavelength range absorbed by the color stain and is used in a concentration such that the highlights, i.e.. D,,,,-,,
  • areas of the transfer image appear substantially white initially and after aging, as observed by the eye.
  • the present invention relates to photography, and more particularly, it relates to diffusion transfer photographic film units adapted to provide reflection prints with improved highlights and to diffusion transfer photographic processes employing the same.
  • color images are obtained by exposing a photosensitive component comprising at least one photosensitive layer, e.g., a light-sensitive silver halide layer, having a dye image-providing material associated therewith in the same or in an adjacent layer, to form a developable image; developing this exposed element with a processing composition to form an imagewise distribution of a soluble and diffusible image-providing material; and transferring this imagewise distribution, at least in part, by diffusion, to a superposed imagereceiving component comprising at least a dyeable stratum to impart to this stratum a color transfer image.
  • a photosensitive component comprising at least one photosensitive layer, e.g., a light-sensitive silver halide layer, having a dye image-providing material associated therewith in the same or in an adjacent layer, to form a developable image
  • developing this exposed element with a processing composition to form an imagewise distribution of a soluble and diffusible image-providing material
  • transferring this imagewise distribution at least in part
  • the photosensitive and image-receiving components may be separate elements which are brought together during processing and thereafter either retained together as the final print or separated following image formation; or they may together comprise a unitary structure, e.g., an integral negative-positive film structure wherein the negative, i.e., photosensitive component and the positive, i.e., the image-receiving component are laminated and/or otherwise physically retained together at least prior to image formation.
  • the essential layers namely, the photosensitive layer(s) and associated dye image-providing material and dyeable stratum are preferably contained on a transparent dimensionally stable layer or support member positioned closest to the dyeable stratum so hat the resulting transfer image is viewable through this transparent layer.
  • a transparent dimensionally stable layer or support member positioned closest to the dyeable stratum so hat the resulting transfer image is viewable through this transparent layer.
  • another dimensionally stable layer which may be transparent or opaque is positioned on the opposed surface of the essential layers so that these layers are sandwiched or confined between a pair of dimensionally stable layers or support members, at least one of which is transparent to permit viewing therethrough of a color transfer image obtained as a function of development of the exposed film unit in accordance with known color diffusion transfer processes.
  • These film units optionally may contain other layers capable of performing specific desired functions and preferably also include a neutralizing layer to reduce the pH following substantial transfer of dye image-providing material to a pH at which said image-providing material is substantially non-diffusible.
  • a neutralizing layer to reduce the pH following substantial transfer of dye image-providing material to a pH at which said image-providing material is substantially non-diffusible.
  • such film units are employed in conjunction with a rupturable container of known description containing the requisite processing composition and adapted upon application of pressure of applying its contents to develop the exposed film unit, e.g., by applying the processing composition in a substantially uniform layer between the dyeable stratum and the photosensitive component.
  • This reflecting layer may comprise a preformed processing composition permeable layer of a lightreflecting agent included in the essential layers of the film unit or the light-reflecting agent may be provided after photoexposure, e.g., by including the reflecting agent in the processing composition.
  • the reflecting layer In addition to masking the photosensitive component and providing a background for viewing the transfer image as a color reflection print, the reflecting layer also helps to protect the photoexposed silver halide layers from postexposure fogging by light passing through the transparent support member if the photoexposed film unit is removed from the camera before image formation is complete.
  • U.S. Pat. No. 3,647,437 in the name of Edwin H. Land is concerned with improvements in the abovedescribed composite film units and diffusion transfer processes employing these unitary structures and discloses the provision of light-absorbing materials to permit such processes to be performed outside of the camera in which photoexposure is effected and under'much more intense ambient light conditions.
  • a lightabsorbing material or reagent preferably a dye, is provided so positioned and/or constituted as not to interfere with photoexposure but so positioned between the photoexposed silver halide layers and the transparent support during processing after photoexposure as to absorb light which otherwise might fog said photoexposed layers. After processing, the light-absorbing material is so positioned and/or constituted as not to interfere with viewing the desired image shortly after said image has been formed.
  • the light-absorbing material also sometimes referred to as an optical filter agent
  • the lightabsorbing dye selected as the optical filter agent is highly colored at the initial pH of the processing composition but is substantially non-light-absorbing in the visible spectrum at a lower pH which is attained after substantial transfer of dye image-providing material and which is effected by an acid-reacting reagent, e.g., the neutralizing layer mentioned previously.
  • Color changing, i.e., pH sensitive dyes, especially useful as optical filter agents in this embodiment form the subject matter of copending U.S. Pat. applications Ser. No. 103,392.0f Myron S. Simon and David P.
  • fluorescent dyes are commonly used as optical brighteners in various photographic products to counteract staining in the image highlights, such dyes are subject to certain disadvantages. Because they depend upon irradiation with ultraviolet light for emitting visible light, their efficiency is reduced when used in conjunction with conventional UV absorbers and their visual effectiveness differs according to the light, i.e., natural or artificial illumination used for viewing the photographic image. Also, most of the fluorescent dyes used as optical brighteners tend to decompose upon prlonged exposure to irradiation.
  • the present invention is concerned with enhancing the whiteness of the non-image or highlight areas of color reflection prints without the use of fluorescent materials by adding to the photographic system, a non-fluorescent optical whitening reagent, i.e., a non-fluorescent reagent which has a color complementary to that of the stain such that the combination of reagent color plus stain color reflects substantially white light.
  • a non-fluorescent optical whitening reagent i.e., a non-fluorescent reagent which has a color complementary to that of the stain such that the combination of reagent color plus stain color reflects substantially white light.
  • 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.
  • FIG. 1 is a perspective view of a photographic film unit embodying the invention
  • FIGS. 3, 5 and 7 are diagrammatic, further enlarged cross-sectional views of the film unit of FIGS. 2, 4 and 6, along section lines 33, 55 and 77, respectively, further illustrating, in detail, the arrangement of layers comprising the photosensitive laminate during the three illustrated stages of' the transfer process.
  • the non-fluorescent reagent employed in the present invention should be capable of absorbing visible radiation within a predetermined wavelength range complemen tary to the wavelength range absorbed by the color stain and should be added in a concentration such that the light reflected from the highlights, i.e., the D,,,,,, areas of the transfer image both initially and upon aging appears to be substantially white, as observed by the eye. Also, it has been found that adding color to the photographic system in this manner does not cause any apparent darkening of the highlights, i.e., any darkening that is visually discernible to the viewer.
  • the whitening reagent employed may be any nonfluorescent pigment or non-fluorescent dye having a color complementary to that of the stain, or it may be a substantially colorless dye precursor, such as, a temporarily shifted dye which assumes a color complementary to that of the stain when contacted with the aqueous alkaline processing composition.
  • the whitening reagent may be soluble or insoluble in the aqueous alkaline processing composition, it should be nondiffusible in the processing composition or capable of being rendered substantially non-diffusible in the appropriate layer or layers of the film unit associated with the transfer image subsequent to processing.
  • the whitening reagent is distributed in a substantially uniform layer, i.e., in a non-imagewise fashion, and as discussed hereinafter, the whitening reagent should be finally positioned in the reflecting layer and/or in the image-receiving component.
  • Suitable whitening reagents having the necessary color characteristics may be selected from arylmethane, anthraquinone, indigoid, indanthrone, methine, azomethine, quinoline, azo, phthalocyanine and any of the various other classes of pigments and dyes known in the art. If desired, acombination of pigments and/or dyes may be used for obtaining the appropriate color characteristics needed for absorbing light in the wavelength range complementary to the wavelength range absorbed by the stain.
  • the pigment and/or dye selected should be stable in the photographic system under the processing conditions encountered and should be stable to prolonged exposure to light.
  • the dye precursors if employed should be stable in their colored form.
  • the whitening reagent should be finally positioned in the lightreflecting layer and/or in the image-receiving component, i.e., in a layer or layers between the reflecting layer and the source of light used for viewing the color transfer image.
  • the whitening reagent is ultimately positioned in the reflecting layer and/or in the next adjacent layer of the image-receiving component, i.e., the dyeable stratum and preferably, is contained within the light-reflecting layer.
  • the whitening reagent may be disposed in a layer of the film unit provided that it does not absorb actinic radiation intended to expose the photosensitive strata.
  • a whitening reagent in its colored form may be disposed in the image-receiving component and/or in a preformed light-reflecting layer without interfering with photoexposure.
  • the whitening reagent disposed in the image-receiving component and/or in a preformed reflecting layer should be substantially colorless, such as, the temporarily shifted dyes mentioned above and then rendered colored after photoexposure.
  • the whitening reagent may be located outside of the photoexposure optical path by being initially disposed in the processing composition.
  • the whitening reagent is colored intially and is introduced as a component of the processing composition.
  • the reagent may be substantially nondiffusible and thus, retained substantially within the processing composition layer, or it may be diffusible and capable of being rendered substantially nondiffusible in a layer or layers of the image-receiving component, for example, by mordanting to the dyeable stratum.
  • the whitening reagent should be diffusible to the light-reflecting layer and/or a layer or layers of the image-receivingcomponent and there rendered non-diffusible.
  • the amount of optical whitening reagent to be added will depend primarily upon the degree of color staining together with the final location of the reagent in the film unit. For example, if the final position on the reagent is substantially within the light-reflecting layer, a larger amount of reagent will be needed than if it is finally disposed in the dyeable stratum due to the hiding properties of the light-reflecting pigment.
  • the appropriate amount of whitening reagent may be readily determined empirically for a given photographic system by measuring the minimum transfer reflection densities for red, green and blue light initially and again after prolonged standing at room temperature or after accelerated aging at elevated temperatures and then adding a pigment or dye having the requisite light absorption characteristics in an amount'that will maintain the difference between the minimum densities both initially and after aging within a range such that the light reflected from the highlights appears substantially white to the viewer.
  • the whitening reagent is added in an amount sufficient to maintain the final 6 densities, i.e., the densities after aging within about 0.08 or 0.09 density units while keeping the difference in initial densities preferably within about 0.03 or 0.04 density units.
  • the initial minimum transfer reflection densities usually are about 018 or 0.19 density units for red and green light and about 0.21 density units for blue light.
  • the densities measured after aging show a decrease in red light to about 0.16 density units and increases to about 0.23 and 0.27 density units in green and blue light, respectively. (All density measurements were referenced against magnesium carbonate as 0.00)
  • a blue pigment or dye in amounts sufficient to adjust the initial minimum density for red light to about 0.20 to 0.22 density units, the light reflected from the D,,,,,, areas of the transfer image appears substantially white both initially and after aging.
  • the adjustment in the'minimum transfer reflection density for red light in such film units may be achieved, for example, by including a soluble blue dye in the aqueous alkaline processing composition which is diffusible therein but capable of being rendered substantially non-diffusible in the dyeablestratum in a substantially uniform distribution and in a concentration such that the optical reflection density of the resulting stratum does not exceed about 0.04 density units and preferably is between about 0.03 and 0.04 density units.
  • the adjustment may be achieved by including an insoluble and substantially non-diffusible blue pigment in the processing composition substantially uniformly dispersed therein in a concentration such that a layer of the composition approximately 0.0025 inch thick has an optical reflection density not exceeding about 0.04 density units and preferably between about 0.03 and 0.04 density units.
  • the whitening reagent may be initially included in a layer of the film unit, but preferably in the aforementioned composite film units, the whitening reagent is introduced as a component of the processing composition.
  • Particularly useful pigments and dyes which reflect red light and which may be conveniently used to add the 0.03 to 0.04 density units to bring the initial minimum reflection density for red light up to about 0.20 to 0.22 are pigments and dyes of the phthalocyanine class.
  • various diffusion transfer systems for forming color images have heretofore been disclosed in the art.
  • such systems rely for color image formation upon a differential in mobility or solubility of a dye image-providing material obtained as a function of development so as to provide an imagewise distribution of such material which is more diffusible and which is therefore selectively transferred, at least in part, by diffusion, to a superposed dyeable stratum to impart thereto the desired color transfer image.
  • the differential in mobility or solubility may for example be obtained by a chemical action such as a redox reaction or a coupling reaction.
  • the dye image-providing materials which may be employed in such processes generally may be characterized as either (I) initially soluble or diffusible in the processing composition but are selectively rendered non-diffusible in an imagewise pattern as a function of development; or (2) initially insoluble or non-diffusible in the processing composition but which are selectively rendered diffusible in an imagewise pattern as a function of development.
  • These materials may be complete dyes or dye intermediates, e.g., color couplers.
  • multicolor images are obtained by employing a film unit containing at least two selectively sensitized silver halide layers each having associated therewith a dye image-providing material exhibiting the desired spectral absorption characteristics.
  • the most commonly employed elements of this type are the so-called tripack structures employing a blue-, a greenand a red-sensitive silver halide layer having associated therewith, respectively, a yellow, a magenta and a cyan dye image-providing material.
  • a suitable arrangement of this type comprises a support carrying a red-sensitive silver halide stratum, a green-sensitive silver halide stratum and a bluesensitive silver halide stratum, said emulsions having associated therewith, respectively, for example, a cyan dye developer, a magenta dye developer and a yellow dye developer.
  • the dye developer may be utilized in the silver halide stratum, for example, in the form of particles, or it may be employed as a layer behind the appropriate silver halide strata.
  • Each set of silver halide strata and associated dye developer strata optionally may be separated from other sets by suitable interlayers, for example, by a layer of gelatin or polyvinyl alcohol.
  • a yellow filter in front of the green-sensitive emulsion and such yellow filter may be incorporated in an interlayer.
  • a yellow dye developer of the appropriate spectral characteristics and present in a state capable of functioning as a yellow filter may be employed.
  • a separate yellow filter may be omitted.
  • These film units may, and preferably, further contain pH modulating or adjusting means, e.g., a layer or layers containing a reagent for adjusting the pH following substantial transfer image formation.
  • pH modulating or adjusting means e.g., a layer or layers containing a reagent for adjusting the pH following substantial transfer image formation.
  • such film units may contain a neutralizing layer or layers, e.g., a polymeric acid layer of the type described, for example, in U.S. Pat. No. 3,362,819.
  • a spacer layer in conjunction with the neutralizing layer in order to time control the pH adjustment by the neutralizing layer. Spacer layers of this description are disclosed, for example, in the v 8 aforementioned U.S. Pat. No. 3,362,819, as well as in other patents, e.g., U.S. Pat. Nos. 3,455,686;
  • the neutralizing and spacer layers are preferably contained in the image-receiving component, e.g., as layers disposed on the side of the dyeable stratum opposed from the photosensitive component. However, they may be disposed in the photosensitive component, as is described and claimed in U.S. Pat. No. 3,573,043. Also, modulation of the environmental pH may be effected by employing particulate acid distributed within the film unit as disclosed in U.S. Pat. No. 3,576,625.
  • a preferred unitary film structure contains, as essential layers, in sequence, a dimensionally stable alkali solution impermeable opaque layer, a layer containing a cyan dye developer, a red-sensitive silver halide emulsion layer, a layer containing a magenta dye developer, a green-sensitive silver halide emulsion layer, a layer of yellow dye developer, a blue-sensitive silver halide emulsion layer, a dyeable stratum, a spacer layer, a neutralizing layer and a dimensionally stable alkali solution impermeable transparent layer, the composite structure being employed in combination with a rupturable container retaining an aqueous alkaline processing composition including a light-reflecting agent and preferably, further including at least one optical filter agent, the container being fixedly positioned and extending along a leading edge of the composite structure so as to be capable of effecting unidirectional discharge of its contents between the dyeablestratum and the blue-sensitive silver halide emulsion layer upon application of compress
  • the aforementioned dye developers are compounds which contain, in the same molecule, both the chromophoric system of a dye and also a silver halide developing function.
  • a silver halide developing function is meant a grouping adapted to develop exposed silver halide.
  • a preferred silver halide development function is a hydroquinonyl group.
  • Other suitable developing functions include ortho-dihydroxyphenyl and orthoand para-amino substituted hydroxyphenyl groups.
  • the development functions includes a benzenoid developing function, that is, an aromatic developing group which forms quinonoid or quinone substances when oxidized.
  • the dye developers are preferably selected for their ability to provide colors that are useful in carrying out subtractive color photography, that is, the previously mentioned cyan, magenta and yellow.
  • the silver halide strata possess predominant spectral sensitivity to separate regions of the spectrum, and the dye developer associated with each of the strata possesses a spectral absorption range substantially complementary to the predominant sensitivity of its associated silver halide emulsion.
  • each of the silver halide strata, and its associated dye developer is separated from the remaining strata, and their associated dye developers by separate processing solution permeable polymeric interlayers.
  • FIGS. 1 through 7 of the drawings wherein there is illustrated a preferred film unit of the present invention and wherein like numbers, appearing in the various figures, refer to like components.
  • FIG. 1 sets forth a perspective view of the film unit, designated 10, and each of FIGS. 2 through 7 illustrate diagrammatic crosssectional views of film unit 10, along the stated section lines 2-2, 3-3, 55 and 77, during the various depicted stages in the performance of a photographic diffusion transfer process as detailed hereinafter.
  • Film unit 10 comprises rupturable container 11, retaning, prior to processing, aqueous processing composition l2, and photosensitive laminate 13 including, in order, dimensionally stable opaque layer 14, preferably an actinic radiation-opaque flexible sheet material; cyan dye developer layer 15; red-sensitive silver halide emusion layer 16; interlayer l7; magenta dye developer layer 18; green-sensitive silver halide emulsion layer 19; interlayer 20; yellow dye developer layer 21; blue-sensitive silver halide emulsion layer 22; auxiliary layer 23, which may contain an auxiliary silver halide developing agent; image-receiving layer 24; spacer layer 25; neutralizing layer 26; and dimensionally stable transparent layer 27, preferably an actinic radiation transmissive flexible sheet material.
  • cyan dye developer layer 15 red-sensitive silver halide emusion layer 16; interlayer l7; magenta dye developer layer 18; green-sensitive silver halide emulsion layer 19; interlayer 20; yellow dye developer layer 21; blue
  • the structural integrity of laminate 13 may be maintained, at least in part, by the adhesive capacity exhibited between the various layers comprising the laminate at their opposed surfaces.
  • the adhesive capacity exhibited at an interface intermediate imagereceiving layer 24 and the silver halide emulsion layer next adjacent thereto, for example, image-receiving layer 24 and auxiliary layer 23 as illustrated in FIGS. 2 through 7, should be less than that exhibited at the interface between the opposed surfaces of the remainder of the layers forming the laminate, in order to facilitate distribution of processing solution 12 intermediate the stated image-receiving layer 24 and the silver halide emulsion layer next adjacent thereto.
  • the laminates structural integrity may also be enhanced or provided, in whole or in part, by providing a binding member extending around, for example, the edges of laminate l3, and maintaining the layers comprising the laminate intact, except at the interface between layers 23 and 24 during distribution of processing composition 12 intermediate those layers.
  • the binding member may comprise a pressure-sensitive tape 28 securing and/or maintaining the layers of laminate 13 together at its respective edges. Tape 28 will also act to maintain processing solution 12 intermediate image-receiving layer 24 and the silver halide emulsion layer next adjacent thereto, upon application of compressive pressure to pod 11 and distribution of its contents intermediate the stated layers. Under such circumstances, binder tape 28 will act to prevent leakage of fluid processing composition from the film units laminate during and subsequent to photographic processing.
  • Rupturable container 11 may be of the type shown and described in any of U.S. Pat. Nos. 2,543,181; 2,634,886; 3,653,732; 2,723,051; 3,056,492; 3,056,491; 3,152,515; and the like.
  • such containers will comprise a rectangular blank of fluidand air-impervious sheet material folded longitudinally upon itself to form two walls 29 which are sealed to one another along their longitudinal and end margins to form a cavity in which processing composition 12 is retained.
  • the longitudinal marginal seal 30 is made weaker than the end seals 31 so as to become unsealed in response to the hydraulic pressure generated within the fluid contents 12 of the container by the application of compressive pressure to walls 29 of the container.
  • container 11 is fixedly positioned and extends transverse a leading edge of photosensitive laminate 13 whereby to effect unidirectional discharge of the containers contents 12 between image-receiving layer 24 and the stated layer next adjacent thereto, upon application of compressive force to container 11.
  • container 1 l as illustrated in FIG. 2, is fixedly positioned and extends transverse a leading edge of laminate 13 with its longitduinal marginal seal 30 directed toward the interface between image-receiving layer 24 and auxiliary layer 23.
  • FIGS. 1 l is fixedly positioned and extends transverse a leading edge of laminate 13 with its longitduinal marginal seal 30 directed toward the interface between image-receiving layer 24 and auxiliary layer 23.
  • container 11 is fixedly secured to laminate 13 by extension 32 of tape 28 extending over a portion of one wall 29 of the container, in combination with a separate retaining member such as illustrated retaining tap 33 extending over a portion of laminate 13s surface generally equal in area to'about that covered by tape 28.
  • extension flap 32 of tape 28 is preferably of such area and dimensions that upon, for example manual separation of container 11 and tape 33, subsequent to distribution of processing composition 12, from the remainder of film unit 10, flap 32 may be folded over the edge of laminate 13, previously covered by tape 33, in order to facilitate maintenance of the lamin'ates structural integrity, for example, during the flexations inevitable in storage and use of the processed film unit, and to provide a suitable mask or frame, for viewing of the transfer image through the picture viewing area of transparent layer 27.
  • the fluid contents of the container comprise a liquid processing composition, having a pH and solvent concentration at which the dye developers are soluble and diffusible, which contains a light-reflecting agent in a quantity sufficient to mask the positive component, i.e., the silver halide emulsions and associated layers subsequent to processing and additionally contains one or more optical filter agent(s) having an absorption spectrum such that the filter agent(s) are capable of absorbing incident actinic radiation between about 400 nm. and 700 nm.
  • the optical filter agent(s) comprise a pH sensitive dye or dyes, such as those disclosed and claimed in aforementioned U.S. Pat. applications Ser. Nos. 103,392 and 108,260,
  • the liquid processing composition used for effecting color diffusion transfer processes comprises at least an aqueous solution of an alkaline material, for example, diethylamine, sodium hydroxide or sodium carbonate and the like, and preferably possesses a pH in excess of 12, and most preferably includes a viscosity-increasing compound constituting a film-forming material of the type which, when the composition is spread and dried, forms a relatively firm and relatively stable film.
  • the preferred film-forming materials disclosed comprise high molecular weight polymers such as polymeric, watersoluble ethers which are inert to an alkaline solution such as, for example, a hydroxyethyl cellulose or sodium carboxymethyl cellulose.
  • filmforming materials or thickening agents whose ability to increase viscosity is substantially unaffected if left in solution for a long period of time are also disclosed to be capable of utilization.
  • the film-forming material is preferably contained in the processing composition in such suitable quantities as to impart to the composition a viscosity in excess of cps. at a temperature of approximately 24 C. and preferably in the .ture
  • the aqueous alkaline processing composition releasably retained in said rupturable container includes the above-described whitening reagent in a concentration such that, upon application of the processing composition and subsequent development and dye transfer image formation, the light reflected from the D,,,,-,, areas of the dye transfer image visually appears substantially white both initially and after aging.
  • the pigment or dye selected as the whitening reagent may be substantially non-diffusible in the aqueous alkaline processing composition so that it will remain substantially within the layer of processing composition distributed intermediate the image-receiving layer 24 and the silver halide layer next adjacent thereto.
  • the whitening reagent selected may be diffusible in the aqueous alkaline processing composition provided that it is capable of being rendered substantially non-diffusible in the appropriate location in the film unit, i.e., in the layer containing the light-reflecting agent, ifpreformed, and/or in a layer of the imagereceiving component, preferably, a layer of the imagereceiving component next adjacent the light-reflecting layer, e.g., the dyeable stratum.
  • a sufficient portion of the ions comprising aqueous alkaline processing composition 12 transfer, by diffusion, throughpermeable polymeric reception layer 24, permeable spacer layer 25 to polymeric neutralizing layer 26 whereby the environmental pl-I of the system decreases as a function of neutralization to a pH at which the cyan, magenta and yellow dye developers, in the reduced form, are substantially nondiffusible to thereby provide a stable multicolor dye transfer image and discharge of the pH-sensitive optical filter agent by reduction of the pH substantially below the pKa of such agent to thereby provide maximum reflectivity in terms of the pigment concentration present.
  • the alkaline processing composition positioned intermediate the photosensitive element and the imagereceiving layer, thus permeates the emulsions to initiate development of the latent images contained therein.
  • the respective associated dye developers are immobilized-or precipitated in exposed areas as a consequence of the development of the latent images. This immobilization is apparently, at least in part, due to a change in the solubility characteristics of dye developer upon oxidation and especially as regards itssolubility in alkaline solutions. It may also be due in part to a tanning effeet on the emulsion by oxidized developing agent, and
  • the unit is exposed to radiation, actinic to photosensitive laminate 13, incident on the laminates exposure surface 34, as illustrated in FIG. 2.
  • film unit 10 is processed by being passed through opposed'suitably gapped rolls 35 in order to apply com pressive pressure to frangible container 11 and to effect rupture of longitudinal seal and distribution of alkaline processing composition 12, possessing inorganic light-reflecting pigment and optical filter agent at a pH above the pKa of the filter agent and a pH at which the cyan, magenta and yellow dye developers are soluble and diffusible as a function of the point-to-point degree of exposure of red-sensitive silver halide emulsion layer 16, green-sensitive silver halide emulsion layer 19 and blue-sensitive silver halide emulsion layer 22, respectively, intermediate space layer 25 and auxiliary layer Alkaline processing composition 12 permeates emulsion layers 16, 19 and 22 to initiate development of the latent images contained in the respective emulsions.
  • the cyan, magenta and yellow dye developers, of layers 15, 18 and 21, are immobilized, as a function of the development of their respective associated silver halide emulsions, preferably substantially as a result of their conversion from the reduced form to their relatively insoluble and nondiffusible oxidized form, thereby pro-.
  • the associated dye developer is unreacted and diffusible and thus provides an imagewise distribution of unoxidized dye developer dissolved in the liquid processing composition, as a function of the point-to-point degree of exposure of the silver halide emulsion.
  • At least part of this imagewise distribution of unoxidized dye developer is transferred, by imbibition, to a superposed image-receiving layer or element, said transfer substantially excluding oxidized dye developer.
  • the image-receiving element receives a depthwise diffusion, from the developed emulsion, of unoxidized dye developer without appreciably disturbing the imagewise distribution thereof to provide the reversed or positive color image of the developed image.
  • container 11 may be manually dissociated from the remainder of the film unit, as described above, to provide the product illustrated in FIG. 6.
  • optical filter agent(s) selected for use in diffusion transfer processes should exhibit at the initial pH of the processing, maximum spectral absorption of radiation at the wavelengths to which the film units photosensitive silver halide layer or layers are sensitive and preferably, should be substantially immobile or nondiffusible within the pigment dispersion, during performance of its radiation filtration function, in order to maintain and enhance the optical integrity of the dispersion as a radiation filter unit and to prevent its diffusion into and localized concentration within the image-receiving layer.
  • the dye or dyes selected as the optical filter agents should possess absorption complementary to said sensitivity range of such silver halide layers in order to provide effective protection against physical fog providing radiation during processing.
  • the selected agents should be those exhibiting major spectral absorption at the pH at which processing is effected and minimal absorption at a pH below that which obtains during transfer image formation.
  • the pI-I-sensitive dyes selected as the optical filter agent or agents should possess a pKa below that of the processing pH and above that of the environmental pI-I subsequent to transfer image formation.
  • the selected light-reflecting agent should be one providing a background suitable for viewing the dye developer transfer image formed in the dyeable polymeric layer.
  • substantially any reflecting agent may be employed, it is preferred that the agent selected will not interfere with the color integrity of the dye transfer image, as viewed by the observer, and will be aesthetically pleasing to the viewer without detracting from the information content of the image.
  • Particularly desirable reflecting agents will be those providing a white background for viewing the transfer image, and specifically, those conventionally employed to provide a background for reflection photographic prints and, especially, those agents possessing the optical properties desired for reflection of incident radiation.
  • reflecting agents suitable for use in the practice of the present invention include barium sulfate, zinc sulfide, titanium dioxide, barium stearate, silver flake, silicates, alumina, zirconium oxide, zirconium acetyl acetate, sodium zirconium sulfate, kaolin, mica, and the like.
  • a particularly preferred reflecting agent comprises titanium dioxide due to its highly effective reflection properties.
  • the reflecting agent needed to mask the photosensitive strata and to provide the requisite background for viewing the color transfer image formed in the receiving layer may be contained initially in whole or in 'part as a preformed layer in the film unit.
  • a preformed layer mention may be made of that disclosed in U.S. Pat. No. 3,615,421 and in US. Pat. No. 3,620,724.
  • the light-reflecting agent may be generated in situ as is disclosed in US. Pat. Nos. 3,647,434 and 3,647,435.
  • the optical filter agent(s) may be dispersed in any processing composition permeable layer of the composite film unit structure intermediate the photosensitive silver halide layer(s) to be protected from incident actinic radiation and the exposure surface of the film unit.
  • any processing composition permeable layer of the composite film unit structure intermediate the photosensitive silver halide layer(s) to be protected from incident actinic radiation and the exposure surface of the film unit.
  • the optical filter agents are initially disposed within the alkaline pro cessing solution, in order to obviate the necessity of converting the filter agent from a substantially nonabsorber of actinic radiation desired to effect photoexposure of the film unit to the desired light-absorbing form during processing, by alkaline processing composition contact, subsequent to selective photoexposure of the film unit and to thus maximize isolation of their effects from the photosensitive silver halide crystals prior to photoexposure.
  • the light-reflecting agent also is initially disposed in the alkaline processing solution.
  • the concentration of light-reflecting agent or agents and optical filter agent or agents selected will be that sufficient to prevent further exposure of the film units silver halide layer or layers by actinic radiation traversing through the dimensionally stable transparent layer, subsequent to distribution of processing solution intermediate the dyeable polymeric layer and the stated layer next adjacent thereto. Accordingly, the film unit may be processed, subsequent to distribution of the composition, in the presence of such radiation, in view of the fact that the silver halide layer or layers of the laminate are appropriately protected from incident radiation, at one major surface by the distributed light-reflecting and optical filter agents andat the remaining major surface by the dimensionally stable opaque layer.
  • the concentration of optical filter agent is selected to provide the optical transmission density required, in combination with other layers including the light reflecting layer intermediate the silver halide layer(s) and the incident radiation, to prevent nonimagewise exposure, i.e., fogging, by incident actinic light during the performance of the photographic process. It has been found, by interposing neutral density (carbon containing) filters over a layer of titanium dioxide, that a transmission density of approximately 6.0 from'said neutral density filters was effective to prevent fogging of a diffusion transfer multicolor film unit of the type described in said U.S. Pat. No.
  • 3,415,644 having a transparent support layer and an Equivalent ASA Exposure Index of approximately when processed for one minute in 10,000 foot candles of color corrected light, a light intensity approximating the intensity of a noon summer sun.
  • the transmission density required to protect such a film unit under the stated conditions may also be expressed in terms of the system transmission density of all the layers intermediate the silver halide layer(s) and the incident light;
  • color film units of the aforementioned type and photographic speed has been found to be on the order of 7.0
  • the silver halide layers shouldbe protected in all visible and non-visible regions of the spectrum to which they are sensitive.
  • Ultraviolet and infra-red absorbers are well known in the photographic art and any of the compounds conventionally used for this purpose may be employed in the present invention.
  • the absorbers should provide the desired protection against post-exposure fogging during at least the initial stages of development but should not absorb radiation intended to selectively expose the photosensitive material or detract from the brilliance hues and other properties of the final image.
  • the absorber or absorbers may be initially disposed in a layer of the film unit and/or the processing solution and subsequent to processing may be retained in or separated from the final product.
  • the film units described above including the photosensitive component comp'rising the photosensitive strata and associated dye image-forming material; the image-receiving component comprising the dyeable and other layers, and the processing composition including its components, such as, the alkaline material and various addenda are described in detail in aforementioned U.S. Pat. Nos. 3,415,644, 3,415,645, 3,415,646, 3,373,043, 3,573,044, 3,594,164, 3,594,165 and 3,647,437 which patents, for convenience, are specifically incorporated herein.
  • timing layer containing about a 40:1 ratio of a 60-30-4-6 copolymer of butylacrylate, diacetone acrylamide, styrene and methacrylic acid and polyacrylamide at a coverage of about 500 mgs./ 1.
  • a polymeric image-receiving layer containing a 2:1 mixture, by weight, of polyvinyl alcohol and poly- 4-vinylpyridine, at a coverage of about 300 mgs./ft?
  • the two components thus prepared were then taped together in laminate form, at their respective edges to provide the desired integral film unit.
  • a rupturable container comprising an outer layer of lead foil and an inner liner or layer of polyvinyl chloride retaining an aqueous alkaline processing solution was fixedly mounted on the leading edge of each of the laminates, by pressure-sensitive tapes, interconnecting the respective container and laminates so that, upon application of compressive pressure to the container to rupture the containters marginal seal, its contents were distributed between the dyeable stratum (layer 3 of the image-receiving component) and the gelatin layer (layer 9) of the photosensitive component.
  • aqueous alkaline processing composition employed in the rupturable container comprised the following:
  • H000 NHSOaCuHu-n OH OH OOH HOOC is a1 To g of the above processing composition was added approximately 40 mgs. of copper phthalocyanine pigment as the whitening reagent, which pigment was insoluble and non-diffusible in the composition.
  • the unitary film structure was totally exposed, i.e., exposed overall to incident actinic radiation and then developed by applying compressive pressure to the rupturable container in order to distribute the aqueous alkaline processing composition. Without separating the superposed photosensitive and image-receiving components, the integral densities were measured by reflectance through the transparent support layer of the image-receiving component using red, green and blue filters to give the initial minimum reflection densities. The film unit was then stored for 18 hours at a temperature of about F and after aging in this manner, the integral densities were measured again.
  • a control was prepared and tested as described above except that the copper phthalocyanine pigment was omitted.
  • whitening reagent used was a copper phthalocyanine dye, soluble and diffusible in the processing composition, and having the formula:
  • optical reflection densities measured for this example and a control are set out below.
  • the reflection prints representing the control prints in the two comparisons described above appeared substantially white initially but appeared yellow after aging.
  • the reflection prints prepared using the copper phthalocyanine pigment and the copper phthalocyanine dye, respectively appeared substantially white to the eye both initially and after aging.
  • the essence of the present invention resides in adding color in the form of a light-absorbing reagent to achieve a balance between the initial and final integral minimum reflection densities of the transfer image such that the build up of color stain in time is not visually discernible.
  • the highlight areas of the transfer image appear substantially white both initially and afterprolonged standing.
  • the prior art methods employed for correctingcolor stain employ a light-emitting, i.e., a fluorescent reagent rather than a light-absorbing reagent.
  • a fluorescent reagent rather than a light-absorbing reagent.
  • the fluorescent materials because they arelight emitters, subtract ratherthan add color, and depending upon their location with respect to the light source used for viewing the image, may cause undesirable lowering of the maximum densities of the transfer image.
  • a photographic film unit adapted for forming a color transfer image viewable as a reflection print ineluding a photosensitive component comprising at least one light-sensitive silver halide layer having a dye image-providing material associated therewith, an imagereceiving component including at least a dyeable stratum, means for providing a reflecting layer between said photosensitive and image-receiving components in an amount sufficient after development of said film unit to mask effectively said photosensitive component and to provide a background for viewing a color transfer image by reflected light;
  • the improvement which comprises including in said film unit a non-fluorescent optical whitening reagent so positioned after transfer image formation as to be substantially uniformly distributed in at least one of said reflecting layer and said imagereceiving component, said whitening reagent being capable of absorbing visible light within a predetermined wavelength range complementary to the wavelength range absorbed by the color stain that forms during aging and being present in a concentration such that the light reflected from the D areas of said transfer image visually appears substantially white initially and after aging.
  • a film unit as defined in claim 1 including a rupturable container releasably holding an aqueous alkaline processing composition, said whitening reagent being included in said processing composition.
  • a film unit as defined in claim 2 wherein said means for providing a reflecting layer comprises including a light-reflecting agent in said processing composition.
  • a film unit as defined in claim 8 including a neutralizing layer disposed in the image-receiving component between said transparent support layer and said dyeable stratum.
  • a film unit as defined in claim 12 wherein said aqueous alkaline processing composition includes at least one optical filter agent which is colored at the pH of said alkaline processing composition but which is capable of being rendered substantially colorless by lowering the pH of said processing composition subsequent to transfer image formation.
  • a film unit as defined in claim 13 wherein said light-reflecting agent included in said processing composition is titanium dioxide.
  • a composite photographic film unit containing,
  • a dimensionally stable alkaline solution impermeable opaque layer a layer containing a cyan dye developer, a red-sensitive gelatino silver halide emulsion layer, a layer containing a magenta dye developer, a green-sensitive gelatino silver halide emulsion layer, a layer containing a yellow dye developer, a blue-sensitive gelatino silver halide emulsion layer, a dyeable stratum, a neutralizing layer for effecting reduction of an alkaline processing composition having a first pH at which said dye developers are soluble and diffusible to a second pH at which said dye developers are substantially insoluble and nondiffusible, a dimensionally stable alkaline solution impermeable transparent layer, means securing at least the side edges of said opposed layers in fixed relationship and a rupturable container releasably holding an aqueous alkaline processing composition having said first pH and containing dispersed therein a lightreflecting agent in
  • a process for providing a photographic diffusion transfer image which comprises, in combination, the steps of:
  • a photographic film unit adapted for forming a colortransfer image viewable as a color reflection print including a photo-sensitive component comprising at least one light-sensitive silver-halide layer having a dye image-providing material associated therewith, an image-receiving component including at least a dyeable stratum and means for providing a reflecting layer between said photosensitive and image-receiving components in an amount sufficient after development of said film unit to mask effectively said photosensitive component and to provide a background for viewing said color transfer image by reflected light;
  • g. providing, as a result of contacting said photoexposed layer with said processing composition, a substantially uniform distribution of a nonfluorescent optical whitening reagent in at least one of said reflecting layer and said imagereceiving component, said whitening reagent being capable of absorbing visible light within a predetermined wavelength range complementary to the wavelength range absorbed by the color stain that forms during aging and being present in a concentration such that the light reflected from the D areas of said transfer image visually appears substantially white initially and after aging; and
  • said photosensitive component includes a dimensionally stable opaque support layer, a red-sensitive silver halide emulsion layer having a cyan dye image providing material associated therewith, a green-sensitive silver halide emulsion layer having a magenta dye imageproviding material associated therewith and a bluesensitive silver halide emulsion layer having a yellow dye image-providing material associated therewith.
  • said aqueous alkaline processing composition additionally includes at least one optical filter agent which is colored at the pH of said alkaline processing composition but which is capable of being rendered substantially colorless by lowering the pH of said processing compo- I sition subsequent to transfer image formation.
  • a process for providing a photographic diffusion transfer multicolor image viewable as a color reflection print which comprises, in combination, the steps of:
  • exposing to incident actinic radiation a photographic film unit which comprises a composite structure containing, as essential layers, in sequence, a dimensionally stable alkaline solution impermeable opaque layer; a red-sensitive silver halide emulsion layer having associated therewith cyan dye; a green-sensitive silver halide emulsion layer having associated therewith magenta dye; a blue-sensitive silver halide emulsion layer having associated therewith yellow dye, each of the cyan, magenta, and yellow dyes being silver halide developing agents and being soluble and diffusible, in alkali, at a first pH; an alkaline solution permeable and dyeable polymeric layer; a polymeric neutralizing layer containing sufficient acidifying capacity to effect reduction of a processing composition having the first pH at which thecyan, magenta and yellow dyes are soluble and diffusible to a second pH at ,which the dyes are substantially nondiffusible; a dimensionally stable alkaline solution impermeable transparent layer; and means

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Spectroscopy & Molecular Physics (AREA)
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  • Investigating Or Analysing Biological Materials (AREA)
US00247048A 1972-04-24 1972-04-24 Color diffusion transfer film with whitening agent Expired - Lifetime US3802881A (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
US00247048A US3802881A (en) 1972-04-24 1972-04-24 Color diffusion transfer film with whitening agent
GB1813673A GB1432805A (en) 1972-04-24 1973-04-16 Diffusion transfer photographic products and processes
DE2319718A DE2319718C2 (de) 1972-04-24 1973-04-18 Photographisches Aufzeichnungsmaterial
FR7314463A FR2181937B1 (enrdf_load_stackoverflow) 1972-04-24 1973-04-19
CA169,127A CA1007508A (en) 1972-04-24 1973-04-19 Photographic products and processes
JP4605873A JPS5319408B2 (enrdf_load_stackoverflow) 1972-04-24 1973-04-23
NLAANVRAGE7305707,A NL181758C (nl) 1972-04-24 1973-04-24 Fotografische filmeenheid voor het vormen van een kleuroverdrachtsbeeld, alsmede breekbare houder die geschikt is om in combinatie met die filmeenheid te worden gebruikt.
CA256,097A CA1011150A (en) 1972-04-24 1976-06-30 Photographic products and processes

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US (1) US3802881A (enrdf_load_stackoverflow)
JP (1) JPS5319408B2 (enrdf_load_stackoverflow)
CA (1) CA1007508A (enrdf_load_stackoverflow)
DE (1) DE2319718C2 (enrdf_load_stackoverflow)
FR (1) FR2181937B1 (enrdf_load_stackoverflow)
GB (1) GB1432805A (enrdf_load_stackoverflow)
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3853562A (en) * 1973-09-24 1974-12-10 Polaroid Corp Container for diffusion transfer films with whitening agent containing processing solution
JPS50147330A (enrdf_load_stackoverflow) * 1974-04-23 1975-11-26
US5213951A (en) * 1990-07-20 1993-05-25 Minnesota Mining And Manufacturing Company Silver halide photographic material with reduced sensitizing dye stain
US5262286A (en) * 1992-07-31 1993-11-16 Eastman Kodak Company Reduction of yellow stain in photographic prints
US6556889B2 (en) * 1998-03-20 2003-04-29 The Coca-Cola Company Vending machine

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS55156956U (enrdf_load_stackoverflow) * 1979-04-27 1980-11-11
JPS61152449U (enrdf_load_stackoverflow) * 1985-03-14 1986-09-20

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3558315A (en) * 1966-08-31 1971-01-26 Fuji Photo Film Co Ltd Edge-fog-prevention method for photographic light-sensitive films
US3547640A (en) * 1967-03-09 1970-12-15 Eastman Kodak Co Multicolor photographic elements
US3415645A (en) * 1967-03-10 1968-12-10 Polaroid Corp Opaque permeable polymeric layer in photo-sensitive element
US3415644A (en) * 1967-03-10 1968-12-10 Polaroid Corp Novel photographic products and processes
CA874918A (en) * 1967-08-30 1971-07-06 J. Weyerts Walter Color prints of improved brightness
US3594165A (en) * 1968-05-13 1971-07-20 Polaroid Corp Novel photographic products and processes
CA928559A (en) * 1969-10-24 1973-06-19 E. Cole Harold Photographic film unit for diffusion transfer processing

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3853562A (en) * 1973-09-24 1974-12-10 Polaroid Corp Container for diffusion transfer films with whitening agent containing processing solution
JPS50147330A (enrdf_load_stackoverflow) * 1974-04-23 1975-11-26
US3996050A (en) * 1974-04-23 1976-12-07 Polaroid Corporation Whitening agents in color diffusion transfer film units
US5213951A (en) * 1990-07-20 1993-05-25 Minnesota Mining And Manufacturing Company Silver halide photographic material with reduced sensitizing dye stain
US5262286A (en) * 1992-07-31 1993-11-16 Eastman Kodak Company Reduction of yellow stain in photographic prints
US6556889B2 (en) * 1998-03-20 2003-04-29 The Coca-Cola Company Vending machine

Also Published As

Publication number Publication date
NL181758C (nl) 1987-10-16
NL7305707A (enrdf_load_stackoverflow) 1973-10-26
DE2319718C2 (de) 1983-10-27
JPS4948327A (enrdf_load_stackoverflow) 1974-05-10
FR2181937B1 (enrdf_load_stackoverflow) 1982-06-04
CA1007508A (en) 1977-03-29
JPS5319408B2 (enrdf_load_stackoverflow) 1978-06-21
GB1432805A (en) 1976-04-22
FR2181937A1 (enrdf_load_stackoverflow) 1973-12-07
NL181758B (nl) 1987-05-18
DE2319718A1 (de) 1973-11-15

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