US3765885A - Neutralizing layer for color diffusion transfer film - Google Patents

Neutralizing layer for color diffusion transfer film Download PDF

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US3765885A
US3765885A US00214746A US3765885DA US3765885A US 3765885 A US3765885 A US 3765885A US 00214746 A US00214746 A US 00214746A US 3765885D A US3765885D A US 3765885DA US 3765885 A US3765885 A US 3765885A
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layer
film unit
image
dye
silver halide
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S Bedell
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Polaroid Corp
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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
    • G03C8/42—Structural details
    • G03C8/52—Bases or auxiliary layers; Substances therefor
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00

Definitions

  • 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 em ployed 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 func- .tion 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 desired spectral absorption characteristics.
  • the most commonly employed elements of this type are the so-called tripack structures employing a blue-, a greenand ared-sensitive silver halide layer having associated therewith, respectively, a yellow, a magenta and a cyan dye image-providing material.
  • 2,983,606 employing dye developers (dyes which are also silver halide developing agents) as the dye imageproviding materials.
  • a photosensitive element comprising at least one silver halide layer having a dye developer associated therewith (in the same or in an adjacent layer) is developed by applying an aqueous alkaline processing composition.
  • Exposedand developable silver halide is developed by the dye developer which in turn becomes oxidized to provide an oxidation product which is appreciably less diffusible-than the unreacted dye developer, thereby providing an imagewise distribution of diffusible dye developer in terms of unexposed areas of the silver jalide halide which imagewise distribution is then transferred, at least in part, by diffusion, to a dyeable stratum to impart thereto a positive dye transfer image.
  • Multicolor images may be obtained with a photosensitive element having two or more selectively sensitized silver halide layers and associated dye developers, a tripack structure of the type described above and in various patents including the aforementioned U. S. Pat. No. 2,983,606 being especially suitable for accurate color recordation of the original subject matter.
  • color images are obtained by exposing a photosensitive element or negative component comprising at least a light-sensitive layer, e.g., a gelatino silver halide emulsion layer, having a dye imageproviding 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 receiving element or positive component comprising at least a dyeable stratum to impart to this stratum a color transfer image.
  • a photosensitive element or negative component comprising at least a light-sensitive layer, e.g., a gelatino silver halide emulsion layer, having a dye imageproviding 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-
  • the negative and positive 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., integral negative-positive film units wherein the negative and positive components are laminated and/or otherwise physically retained together at least prior to image formation.
  • the present invention is applicable both to those systems wherein the dyeable stratum is contained on a separate element and to those systems wherein the dyeable stratum and the photosensitive stratacomprise a unitary structure, of particular interest are those integral negative-positive film units adapted for forming color transfer images viewable without separation, i.e.,
  • Film units intended to provide multicolor images comprise two or more selectively sensitized silver halide layers each having associated therewith an appropriate dye image-providing material exhibiting desired spectral absorptioncharacteristics.
  • the most commonly employed negative components for forming multicolor images are of the tripack structure containing a blue-, a greenand a redsensitive silver halide layer having associated therewith in the same or in a contiguous layer a yellow, a magenta and acyan dye image-providng material respectively.
  • Interlayersor spacer layers may if desired be provided between the respective silver halide layers and associated dye image-providing materials.
  • such film units further include means for providing a reflecting layer between the dyeable stratum and the negative component in order to mask effectively the silver image or images formed as a function of development of the silver halide layer or layers and any remaining associated dye image-providing material and to provide a background for viewing the color image formed in the dyeable stratum, without separation, by reflected light.
  • This reflecting layer may comprise a preformed layer of a reflecting agent included in the essential layers of the film unit or the reflecting agent may be provided after photoexposure, e.g., by including the reflecting agent in the processing composition.
  • These essential layers are preferably contained on a transparent dimensionally stable layer or support member positioned closest to the dyeable stratum so that the resulting transfer image is viewable through this transparent layer.
  • a dimensionally stable layer which may be transparent or opaque is positioned on the opposed surface of the essential layers so that the aforementioned essential layers are sandwiched or confined between a pair of dimensionally stable layers or supportmembers, at least one of each 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 the known color diffusion transfer system such as will be detailed hereinafter.
  • 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 negative component.
  • the film unit may optionally contain other layers performing specific'desired functions, e.g., spacer layers, etc.
  • Opacifying means may be provided on either side of the negative component so that the film unit may be processed in the light to provide the desired color transfer image.
  • such opacifying means comprise an opaque dimensionally stable layer or support member positioned on the free or outer surface of the negative component, i.e., on the surface of the film unit opposed from the positive component containing the dyeable stratum 'to prevent photoexposure by actinic light incident thereon from this side of the film unit and an opacifying agent applied during development between the dyeable stratum and the negative component, e.g., by including the opacifying agent in a developing composition so applied, in order to prevent further exposure (fogging) by actinic light incident thereon from the other side of the fllm unit when the thus exposed film unit is, developed in the light.
  • the last-mentioned opacifying agent may comprise the aforementioned reflecting agent which masks the negative component and provides the -requi-.
  • this reflecting agent does not by itself 4 appropriate processing composition to develop exposed silver halide and to form, as a function of development, an imagewise distribution of diffusible dye image-providing material which is transferred, at least in part by diffusion, to the dyeable stratum to impart thereto the desired color transfer image, e.g., a positive color transfer image.
  • a reflecting layer between the dyeable stratum and the photosensitive strata to mask effectively the latter and to provide a background for viewing the color image contained in the dyeable stratum, whereby this image is viewable without separation, from the other layers or elements of the film unit.
  • this reflecting layer is provided' prior to photo-exposure, e.g., as a preformed layer included in the essential layers of the laminar structure comprising the film unit, and in others it is provided at some time thereafter, e.g., by including a suitable light-reflecting agent, for example, a white pigment such as titanium dioxide, in the processing composition which is applied between thp dyeable stratum and the next adjacent layer to develop the latent image and to form the color transfer image.
  • a suitable light-reflecting agent for example, a white pigment such as titanium dioxide
  • the dyeimage-providing materials which may be employed in such processes generally are selected from those materials heretofore mentioned and disclosed in the illustrative patents which were initially soluble or diffusible in the processing composition but which are selectively rendered non-diffusible as a function of development or those which are initiallyinsoluble or nondiffusible in the processing composition but are selectively rendered diffusible as a function of development. These materials may be complete dyes or dye intermediates, e.g., color couplers.
  • a preferred opacification system to be contained in the processing composition is that described in the copending applications of Edwin H. Land, Ser. No. 43,782, filed June 5, 1970 now U.S. Pat. No. 3,647,437 and Ser. No. 101,968, filed Dec. 28, 1970, comprising an inorganic reflecting pigment dispersion containing at least one optical filter agent at a pH abovethe pKa of the optical filter agent in a concentration effective, when the processing composition is applied, to provide provide the requisite opacity it may be employed in combination with an additional opacifying agent in order to prevent further exposure of the light-sensitive silver halide layer or layers by actinic light incident thereon.
  • the reflecting pigment 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 on the copending applications of Edwin H. Land, Ser.
  • U. S. Pat. No. 3,362,819 discloses systems wherein the desired pH reduction may be effected by providing a polymeric acid layer adjacent the dyeable stratum.
  • These polymeric acids may be polymers which contain acid groups, e.g., carboxylic acid and sulfonic acid groups, which are capable of forming salts with alkali metals or with organic bases; or potentially acidyielding groups such as anhydrides or lactones.
  • the acid polymer contains free carboxyl groups.
  • An inert interlayer or spacer layer may be disposed between the polymeric acid layer and the dyeable stratum in order to control the pH reduction so that it is not premature and hence interferes with the development process, e.g., to time control the pH reduction.
  • Suitable spacer or timer layers for this purpose are de-' scribed with particularity in this patent and in others, including U. S. Pat. Nos. 3,419,389, 3,421,893; 3,433,633; 3,455,686; and 3,575,701.
  • the acid layer is preferably contained in the receiving element employed in systems wherein the dyeable stratum and photosensitive strata are contained on -separate elements, e.g., between the support for the receiving element and the dyeable stratum; or associated with the dyeable stratum in those integral film units, e.g., on the side of the dyeable stratum opposed from the negative component, the acid layer may, if desired, be disposed in a layer associated with the photosensitive strata, as is disclosed, for example, in U. S. Pat. Nos. 3,362,821 and 3,573,043.
  • U. S. Pat. No. 3,576,625 discloses integral film units containing yet another neutralizing system for lowering the pH.
  • the film unit is constructed to contain at least one layer containing a particulate dispersion of acid material.
  • this acid material may comprise any photographically nondeleterious acid material in solid or liquid state encapsulated within a polymeric wall material which is permeable to the alkaline processing composition.
  • the present invention is directed to another type of neutralizing material for lowering the environmental pH in color diffusion transfer systems of the type previously described, which material provides the distinct advantages and beneficial results which will be described hereinafter in the detailed description of the invention.
  • a layer of a graph copolymer comprising an acid moiety grafted onto a polymeric backbone is employed to lower the pH.
  • These graft copolymers are coated as aqueous emulsions, e.g., in. an aqueous medium, to provide a neutralizing layer which is characterized as being hydrophobic and possessing an extremely high peal force so as to be extremely adherent against separation or delamination from the contiguous layers of the photographic product in which it is employed.
  • FIGURE is an enlarged, fragmentary, diagrammatic, sectional view of a film unit contemplated by this invention.
  • the film unit is a socalled integral negative-positive tripack and the positive component includes the neutralizing layer of this invention in addition to the dyeable stratum. More preferably a timing or spacer layer of known description is disposed between the dyeable stratum and neutralizing layer, the preferred such timing layer being a polyvinylamide graft copolymer of the type described and claimed in U. S. Pat. No. 3,575,701 of Lloyd D. Taylor As was heretofore mentioned, the novel neutralizing layers of this invention are graft copolymers.
  • They may be defined as being monomeric or polymeric acid moieties grafted onto a polymeric backbone comprising repeating units comprising structural units capable of being oxidized by a transition metal ion catalyst of a first oxidation state, the catalyst having an oxidation potential, in acidic solution of at least about 1 volt when the transition metal is reduced to the next lowest acidic solution stable oxidation state.
  • any organic polymer or copolymer containing repeating units comprising structural units including the grouping, wherein Y- is hydroxyl, carboxyl, amino, merpolyaldehydes, polyamides, cellulose, substituted celluloses such as methyl cellulose, hydroxycthel cellulose, methyl hydroxypropyl cellulose, starch, copolymers of ethylene and acids such as maleic acid, polymeric acids such as polyacrylic acid, etc.
  • the acid moiety grafted onto this polymeric backbone may be selected from a long list of useful acids, preferred acids being acrylic acid, homologues thereof such as methacrylic acid, esters thereof such as methyl acrylate, ethyl acrylate, and polymers and copolymers including the same.
  • ethyl acrylate-acrylic acid copolymer acrylic acid, isobutyl vinyl ether/maleic acid copolymer, vinyl acetate/acrylic acid copolymer, ethyl acrylate/methacrylic acid copolymer, methyl acrylate/acrylic acid copolymer, ethyl acrylate/acrylic acid/2-hydroxy-3- methylacrylyloxypropyl-trimethylammonium chloride terpolymer, methyl acrylate, diacetone acrylamide/acrylic acid copolymer, diacetone acrylamidie/acrylic acid/2-sulfoethyl methacrylate terpolymer, diacetone acrylamide/acrylic acid/sodium 2-sulfoethyl methacrylate terpolymer, ethyl acrylate/methacrylic acid/acrylic acid terpolymer, methyl
  • EA:AAzMTC 6.3:1.8:1; monomer2PVA 0.7221.
  • Methyl acrylate graft on PVA Methyl acrylate graft on PVA.
  • Ethyl acrylate methacrylic acid diacetone acrylamide graft on HEC. EAzMAAzDAA 12221:2; monomer2HEC 3.3:1 (by wt.)
  • AMPS acrylamido-2-methylpropane sulfonic acid
  • Diacetone acrylamide 2-acrylamido-2-methylpropane sulfonic acid graft on polyacrylic acid.
  • Diacetore acrylamide 2-acrylamido-2-methyl propane sulfonic acid 2-hydroxy-3-methacryloyloxy- EXAMPLE 1 22 g. of polyvinyl alcohol were dissolved in 500 cc. of water. The mixture was cooled to room temperature and nitrogen was bubbled through for about 30 minutes. 25 g. (0.25 mole) of ethyl acrylate, 18 g. (0.25 mole) of acrylic acid and 2.15 g. of ethyl dimethyl benzyl ammonium chloride were then added. After'stirring for 15 minutes, 20 cc. of 0.2M Ce(l ⁇ l1-1.,) (NO in 1M nitric acid were added and the reaction was continued overnight at room temperature under a blanket of nitrogen to yield the graft polymer of Formula (1).
  • EXAMPLE 2 11 g. of PVA were dissolved in 500 cc. of water under nitrogen was bubbled through themixture. 25 g. (0.25 mole) of ethyl acrylateQlSg. (0.25 mole) of acrylic acid and 2.15 g. of cetyl dimethyl benzyl ammonium chloride were then addedfAfter stirring for 30 minutes, 20 cc. of 0.2M Ce(Nl-l (NO in 1m nitric acid were then added. The reaction was continued at room temperature overnight to yield the graft copolymer ofFormula (2).
  • the graft polymers of Formulae (3) through (6) were prepared in the foregoing manner by varying the amounts of reactants. For example, employment of 9 g. of acrylic acidin the procedure of Example 1 yields the polymer of Formula (3); and employment of 44 g. of PVA yields the polymer of Formula (4).
  • EXAMPLE 4 22 g. (0.5 mole) of PVA were dissolved in 500 cc. of water under nitrogen. 25 g. (0.25 mole) of isobutyl vinyl ether and 24.5 g. (0.25 mole) of maleic anhydride were added at room temperature under a blanket of nitrogen. 20 cc. of 0.1M (NH.,) Ce(NO in 1M nitric acid were added and stirring was continued overnight to yield the graft polymer of Formula (8).
  • EXAMPLE 7 To a solution of 300 g. of an isopropyl acrylamide graft on PVA (14.6% solids, 74.0% by weight isopropyl acrylamide)'in 700 cc. of water were added 25 g. (0.25 mole) of ethyl acrylate and 18 g. (0.25 mole) of acrylic acid. Nitrogen was bubbled through the mixture for one hour and the pH was adjusted to 1.5 with concentrated nitric acid. The temperature was raised to 50C. and 2.2 g. of Ce(NH.,) (N( in 10 cc. of water were then added. Stirring was continued for 2 hours to yield the graft polymer of Formula (12).
  • Varying the amounts of reagents in the foregoing Example provided the graft polymers of Formulae (14) to.
  • EXAMPLE 9 To a solution of 44 g. of PVA in 500 cc. of water were added 50 g. of ethyl acrylate, 36 g. of acrylic acid and 5 g. of 2-hydroxy-3-methylacrylyloxypropyltrimethylammonium chloride. Nitrogen was bubbled through the mixture for one hour and the pH was adjusted to 1.5 with concentrated nitric acid. The temperature was raised to 50C and 6.6 g. of Ce(NH,,)-,,('NO;,) in 50 cc. of water were then added. Stirring was continued for 2 hours to yield the graft polymer of Formula (20).
  • EXAMPLE 10 To a solution of 22 g. of PVA in 500 cc. of water were added 25 g. (0.25 mole) of ethyl acrylate, 5 g. (0.07 mole) of acrylic acid and 10 g. (0.04 mole) of 2- hydroxy-3:methylacrylyloxypropyL trimethylammonium chloride. Nitrogen was bubbled through the mixture for one hour and the pH was adjusted to 1.5 with concentrated nitric acid. The temperature was raised to 50C and 3.3 g. of Ce(NH.,) (NO in 10 cc. of water were then added. Stirring was continued for 2 hours of yield the graft polymer of Formula EXAMPLE 11 To a stirred solution of 22 g.
  • EXAMPLE 14 30 g. of HEC and 4.0 g. of Triton X-l00" (tradename of Rohm & Haas Co. for a nonionic wetting agent, isooctyl phenyl polyethoxy ethanol) were dissolved in 500 cc. of water. 36 g. (0.36 mole) of ethyl acrylate, 54 g. (0.63 mole) of methacrylic acid and 10 g. (0.14 mole) of acrylic acid were added. Nitrogen was bubbled through the mixture for one hour, after which the temperature was raised to 50C and 8.0 g. of Ce(NH (NO in 20 cc. of water were added. Stirring was continued for 2 hours to yield the graft polymer of Formula (29).
  • Triton X-l00 tradename of Rohm & Haas Co. for a nonionic wetting agent, isooctyl phenyl polyethoxy ethanol
  • EXAMPLE 15 To a solution of 30 g. of HEC in 500 cc. of water were added 4.0 g. of Triton X-lOO, 36 g. of ethyl acrylate and 54 g. of methacrylic acid. The temperature was raised to 50C and nitrogen was bubbled through 'for one hour, after which 8.0 g. of Ce(Nl-1.,) (NO in cc. of water were added. Stirring for 2 hours yielded the graft polymer ofFormula (31 EXAMPLE 1-6 To a solution of 30 g. of HEC in 500 cc. of water were added 4 g. ofTriton X-100, 36 g. of methyl acrylate and 54 g.
  • EXAMPLE 19 To a solution of 30 got BBC in 500cc. of water were added 4 g. ofTriton X-lOO, 36 g. of ethyl acrylate,.54 g. of methacrylic acid and 5 g. of diacetone acrylamide. Nitrogen was bubbled through for one hour and the temperature was raised to C, after which 8 v g. of Ce(NH (N0 in 20 cc. of water were added. Stirring for 2 hours yielded the graft polymer of Formula (40).
  • EXAMPLE 20 EXAMPLE 21 To a solution of 60 g. of soluble starch in 500 cc. of water were added 4 g. of Triton X-lOO, 72 g. of
  • trogen was bubbled through for one hour and the temperature was raised to 70C, after which 12.5 g. of Ce(NH (NO in 50 cc. of water were added. Stirring was continued for 2 hours to yield the graft polytiter of Formula (49).
  • EXAMPLE 24 To a solution of 60 g. of soluble starch in 300 cc. of water were added 40 g. of a 5 percent solution of sodium 2-sulfoethyl methacrylate, 72 g. of methyl acrylate and 108 g. of methacrylic acid. Nitrogen was bubbled through the mixture for one hour and 16 g. of Ce(Nl-I (NO in 40 cc. of water were then added. Stirring was continued for 3 1/2 hours to yield the graft polymer of-Formula (52). i
  • Example 25 was modified, employing 72 g. of ethyl acrylate instead of 72 g. of methyl acrylate and 30 g. of 5 percent sodium-2-sulfoethyl methacrylate instead of 40 g. to yield the graft polymer of Formula (53).
  • Example 25 was repeated, adding 2.75 g. of methylolated diacetone vacrylamide to the monomers employed, to yield the' graft polymer of Formula (54).
  • EXAMPLE 27 To a solution of 200 g. of ethylenelmaleic acid copolymer in one liter of water were added 4 g. of 2-acrylamido-2-methyl-propane sulfonic acid and 80 g. of methyl acrylate. Nitrogen was bubbled through for one hour, the temperature was raised to 60C and 1.1 gpof ceric ammonium nitrate was then added. Stirring was continued for hours to yield the graft polymer of Formula (57).
  • EXAMPLE 29 To a solution of 167 g. of ethylene/maleic acid copolymer in 950 cc. of water were added g. of diacetone acrylamide, 4 g. of 2-acrylamido-2-methylpropane sulfonic acid and g. of 2-hydroxy-3-methacryloyloxypropyl trimethyl ammonium chloride. Nitrogen was bubbled through for one hour, the temperature was raised to 60C and a solution of 50 cc. of water, 5 g. of nitric acid and 5.5 g. of ceric ammonium nitrate were then added. Stirring for 2 hours then yielded the graft polymer of Formula (59).
  • the neutralizing layer of this invention isuseful in systems wherein the photosensitive strata and the dyeable stratum are contained on separate elements; and in systems wherein they are contained together as a unitary film unit, e.g., in the integral negative-positive film units previously described.
  • the neutralizing layer is most preferably contained in association with the dyeable stratum, e.g., in an image-receiving element comprising a support carrying the neutralizing layer and the dyeable stratum, a spacer or timing layer preferably being disposed therebetween. It may however be contained as a layer in the photosensitive element, i.e., in the element containing the photosensitive strata, as is disclosed in U. S. Pat. No. 3,362,821.
  • the neutralizing layer is preferably associated with the dyeable stratum, e.g., on the side of the dyeable stratum opposed from the negative component, and most preferably a timing layer is disposed between the neutralizing layer and dyeable stratum.
  • the present invention is particularly useful in those film units, such as the heretofore described integral negative-positive film units, wherein the negative and positive components are at least retained together following image formation as the final print.
  • the invention will accordingly be illustrated by reference to atypical film unit of this description.
  • such a film unit may comprise, as the essential layers, a layer l3 of cyan dye developer, red-sensitive silver halide emulsion layer 14, interlayer 15, a layerof magenta dye developer 16,
  • Layers 13-21 comprise the negative component and layers 22-24 comprise the positive component.
  • These may possess a processing composition solvent vapor permeably sufficient to effect, subsequent to substan tial transfer image formation and prior to any substantial environmental image degradation to which the resulting image may be prone, osmotic transpiration of processing composition solvent in a quantity effective to decrease the solvent from a first concentration at which the color-providing material is diffusible to a second concentration at which it is not.
  • these layers may possess a vapor transmission rate of l or less gms./24 hr./l00 in.
  • /mil. they preferably possess a vapor transmission rate for the processing composition solvent averaging not less than about gms./24 hr.s/ hrs./100 in. /mil., most preferably in terms of the preferred solvent, water, a vapor transmission rate averaging in excess of about 300 grns. of water/24 hrs./l00 in. /mil., and may advantageously comprise a microporous polymeric film possessing a pore distribution which does not unduly interfere with the dimensional stability of the layers or, where required, the optical characteristics of such layers.
  • layer 12 is of sufficient opacity to prevent fogging from occurring by light passing therethrough, and layer 26 is transparent to permit photoexposure and for viewing of a transfer image formed on' receiving layer 23.
  • the silver halide layers preferably comprise photosensitive silver halide, e.g., silver chloride, bromide or iodide or mixed silver halides such as silver iodobromide or chloriodobromide dispersed in a suitable colloidal binder such as gelatin and such layers may typically be on the order of 0.6 to 6 microns in thickness.
  • photosensitive silver halide e.g., silver chloride, bromide or iodide or mixed silver halides such as silver iodobromide or chloriodobromide dispersed in a suitable colloidal binder such as gelatin and such layers may typically be on the order of 0.6 to 6 microns in thickness.
  • the silver halide layers may and in fact generally do contain other adjuncts, e.g., chemical sensitizers such as are disclosed in U. S. Pat. Nos.
  • the respective dye developers which may be any of I those heretofore known in the art and disclosed for example in U. S. Pat. No. 2,983,606, etc., are preferably dispersed in an aqueous alkaline permeable polymeric binder, e.g., gelatin as a layer from about 1 to 7 microns in thickness.
  • an aqueous alkaline permeable polymeric binder e.g., gelatin as a layer from about 1 to 7 microns in thickness.
  • Interlayers l5, l8 and 21 may comprise an alkaline permeable polymeric material such as gelatin and may be on the order of from about 1 to 5 microns in thickness.
  • alkaline permeable polymeric material such as gelatin
  • these interlayers may also contain additional reagents performing specific functions and the various ingredients necessary for development may also be contained initially in such layers in lieu of being present initially in the processing composition, in which event the desired developing composition is obtained by contacting such layers with the solvent for forming the processing composition, which solvent may include the other necessary ingredients dissolved therein.
  • the image-receiving layer may be on the order of 0.25 to 0.4 mil. in thickness.
  • Typical materials heretofore employed for this layer include dyeable polymers such as nylon, e.g., N-methoxymethyl polyhexamethylene adipamide; partially hydrolyzed polyvinyl acetate; polyvinyl alcohol with or without plasticizers; cellulose acetate with filler as, for example, onehalf cellulose acetate and one-half oleic acid; gelatin; polyvinyl alcohol'or gelatin containing a dye mordant such as poly-4-vinylpyridine, etc.
  • dyeable polymers such as nylon, e.g., N-methoxymethyl polyhexamethylene adipamide
  • partially hydrolyzed polyvinyl acetate polyvinyl alcohol with or without plasticizers
  • cellulose acetate with filler as, for example, onehalf cellulose acetate and one-half oleic acid
  • gelatin polyvinyl alcohol'or
  • Such receiving layers may, if desired, contain suitable mordants, e.g., any of the conventional mordant materials for acid dyes such as those disclosed, for example, in the aforementioned U. S. Pat. No. 3,227,5 50; as well as other additives such as ultraviolet absorbers, pH-reducing substances, etc. It may also contain specific reagents performing desired functions, e.g., a development restrainer, as disclosed,
  • the spacer or timing layer may be on the order of 0.1 to 0.7 mil thick.
  • Materials heretofore used for this pur pose include polymers which exhibit inverse temperature-dependent permeability to alkali, e.g., as disclosed in U. S. Pat. No. 3,445,686.
  • the neutralizing layer may be on the order of 0.3 to 1.5 mil. in thickness. In accordance with this invention, it will include one of the aforementioned graft polymers, most preferably contained at a coverage of less than 3000 mgs./ ft.
  • the neutralizing layers of this invention may be coated as aqueous emulsions.
  • the neutralizing layers of this invention adhere extremely well at both interfaces in the laminar structure, they resist any tendency for delamination to occu subsequent to transfer image formation.
  • an integral negative-positive film unit of the type described and claimed in U. S. Pat. No. 3,415,644 and shown in the illustrative drawing may be prepared, for example, by coating, in succession, on a gelatin subbed, 4 mil. opaque polyethylene terephthalate film base, the following layers:
  • a layer containing the copolymer referred to above in layer 3 and polyacrylamide coated coverage a coveraege of about 100 mgs./ft. of copolymer and about 12 mgs./ft. of polyacrylamide;
  • a blue-sensitive gelatino silver iodobromide emulsion layer including the auxiliary developer 4'- .methylphenyl hydroquinone coated at a coverage of about mgs./ft-. of silver, about 60 mgs./ft. of gelatin and about 30 mgs./ft. of auxiliary developer; and
  • the three dye developers employed above may be the following:
  • BIO-CHr-Ulia N-SO N N -'
  • CHa was j t XII/Hi N 0 0 0B.
  • gfl-CE-CH a magenta dye developer
  • a transparent 4 mil. polyethylene terephthalate film base may be coated, in succession, with the following illustrative layers:
  • a neutralizing layer comprising the graft polyme of Formula (28) coated at a coverage of about 2,400
  • the two components may then be laminated together to provide the desired integral film unit.
  • a rupturable container comprising an outer layer of lead foil and an inner liner or layer or polyvinyl chloride retaining an aqueous alkaline processing solution may then be fixedly mounted on the leading edge of each of the laminates, by pressure-sensitive tapes, in-
  • An illustrative processing composition to be employed in the rupturable container may comprise the following properties of ingredients:
  • This film unit may then be exposed in known manner to form a developable image and the thus exposed element may then be developed by applying compressive pressure to the rupturable container in order to distribute the aqueous I alkaline processing composition, thereby forming a multicolor transfer image which is viewable through the transparent polyethylene terephthalate film base as a positive reflection print.
  • this invention have been found to adhere extremely well, thereby obviating any tendency for delamination to occur.
  • a typical neutralizing layer heretofore known in the art has a tensile strength on the order of 80 grams peal force/inch or less.
  • the peal force/inch of the neutralizing layer prepared in the foregoing illustrative example is so great as to be immeasurable.
  • a photographic product comprising a photosensitive element including at least one light-sensitive silver halide layer having a dye image-providing material associated therewith or an image-receiving element including a stratum adapted for receiving an image by diffusion transfer, said photographic product including a neutralizing layer for lowering the environmental pH subsequent to application of an aqueous alkaline processing composition;
  • said neutralizing layer comprises a graft copolymer comprising the residue of a graftable polymer providing-an acid moiety grafted onto a polymeric backbone.
  • a photosensitive element including at least one light-sensitive silver. halide layer having a dye imageproviding material associated therewith and a neutralizing layer comprising a graft copolymer comprising the residue of a graftable polymer providing an acid moiety grafted onto a polymeric backbone.
  • a photosensitive element as defined in claim 2 including a dyeable stratum adapted for forming a color image by diffusion transfer. 7 v
  • a process for forming a visible image in color comprising the steps of exposing a photosensitive element as defined in claim 3 to form a developable image and thereafter applying an aqueous alkaline processing composition to said exposed element to form said color image.
  • an integral negative-positive film unit including a negative component comprising at least one light sensitive silver halide emulsion layer having a dye'i mage-providing material associated therewith, a positive component including at least a dyeable stratum, means for applying a reflecting layer between said positive and negative components in an amount sufficient upon development of said film unit to mask effectively said negative component and to provide a background for viewing a color image imparted to said dyeable stratum of said positive component by reflected light by applying an aqueous alkaline processing fluid to said film unit after exposure thereof, said film unit further including a neutralizing layer for lowering the environment pH subsequent to application of said alkaline processing fluid; v
  • said neutralizing layer comprises a. graft copolymer comprising the residue of a graftable polymer providing an acid moiety grafted onto a polymeric backbone.
  • a film unit as defined in claim 10 wherein said dye image-providing materials are initially soluble or diffusible in said aqueous alkaline processing fluid but are selectively rendered non-diffusible in an imagewise pattern as a function of development.
  • a fllm unit as defined in claim 6 including means for applying said aqueous alkaline processing fluid to develop said film unit.
  • a film unit as defined in claim 6 wherein said means for applying a reflecting layer comprises a layer of a white pigment disposed ina layer between said positive and negative components.
  • a film unit as defined in claim 6 wherein said means for applying a reflecting layer comprises a white pigment dispersed in said processing fluid.
  • photosensitive element including a composite structure containing,las essential layers, in sequence, 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 greensensitive 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 comprising a graft copolymer comprising the residue of a graftable polymer providing an acid moiety grafted onto a polymeric backbone in an amount sufficient to effect reduction of a processing solution 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

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US00214746A 1972-01-03 1972-01-03 Neutralizing layer for color diffusion transfer film Expired - Lifetime US3765885A (en)

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CA (1) CA1007087A (enrdf_load_stackoverflow)
DE (1) DE2300174C2 (enrdf_load_stackoverflow)
FR (1) FR2167592B1 (enrdf_load_stackoverflow)
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4389479A (en) * 1981-05-14 1983-06-21 Eastman Kodak Company Neutralizing layer for color transfer assemblages
US5212051A (en) * 1990-06-26 1993-05-18 Fuji Photo Film Co., Ltd. Photographic element with cellulose derivative polymer
US20040116628A1 (en) * 2000-12-01 2004-06-17 Roman Morschhauser Grafted comb polymers based on acryloyldimethyl taurine acid
CN107938341A (zh) * 2017-12-04 2018-04-20 宜宾惠美纤维新材料股份有限公司 一种除臭纤维素纤维的制备方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2935712A1 (de) 1978-09-07 1980-03-20 Sumitomo Chemical Co Verfahren zum herstellen von stark absorbierenden polymerisaten
JP2699013B2 (ja) * 1990-07-03 1998-01-19 富士写真フイルム株式会社 拡散転写写真要素

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3362821A (en) * 1963-05-01 1968-01-09 Polaroid Corp Diffusion transfer processes utilizing photosensitive elements containing polymeric acid spacer layers
US3384483A (en) * 1964-03-23 1968-05-21 Eastmean Kodak Company Multicolor dye developer image transfer systems
US3415644A (en) * 1967-03-10 1968-12-10 Polaroid Corp Novel photographic products and processes
US3579333A (en) * 1968-07-18 1971-05-18 Polaroid Corp Multicolor diffusion transfer photographic products and processes with a developing composition comprising a desensitizing agent
US3647434A (en) * 1970-06-05 1972-03-07 Polaroid Corp Integral negative/positive color diffusion transfer process film unit employing in situ generated visible light-reflecting agent
US3689262A (en) * 1968-05-13 1972-09-05 Polaroid Corp Photographic products and processes for color diffusion transfer

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3362819A (en) * 1962-11-01 1968-01-09 Polaroid Corp Color diffusion transfer photographic products and processes utilizing an image receiving element containing a polymeric acid layer
US3575701A (en) * 1969-01-13 1971-04-20 Polaroid Corp Polyvinylamide grafts in spacer layers for color diffusion transfer imagereceiving units

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3362821A (en) * 1963-05-01 1968-01-09 Polaroid Corp Diffusion transfer processes utilizing photosensitive elements containing polymeric acid spacer layers
US3384483A (en) * 1964-03-23 1968-05-21 Eastmean Kodak Company Multicolor dye developer image transfer systems
US3415644A (en) * 1967-03-10 1968-12-10 Polaroid Corp Novel photographic products and processes
US3689262A (en) * 1968-05-13 1972-09-05 Polaroid Corp Photographic products and processes for color diffusion transfer
US3579333A (en) * 1968-07-18 1971-05-18 Polaroid Corp Multicolor diffusion transfer photographic products and processes with a developing composition comprising a desensitizing agent
US3647434A (en) * 1970-06-05 1972-03-07 Polaroid Corp Integral negative/positive color diffusion transfer process film unit employing in situ generated visible light-reflecting agent

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4389479A (en) * 1981-05-14 1983-06-21 Eastman Kodak Company Neutralizing layer for color transfer assemblages
US5212051A (en) * 1990-06-26 1993-05-18 Fuji Photo Film Co., Ltd. Photographic element with cellulose derivative polymer
US20040116628A1 (en) * 2000-12-01 2004-06-17 Roman Morschhauser Grafted comb polymers based on acryloyldimethyl taurine acid
US6964995B2 (en) * 2000-12-01 2005-11-15 Clariant Gmbh Grafted comb polymers based on acryloyldimethyltaurine acid
CN107938341A (zh) * 2017-12-04 2018-04-20 宜宾惠美纤维新材料股份有限公司 一种除臭纤维素纤维的制备方法
CN107938341B (zh) * 2017-12-04 2020-01-10 宜宾惠美纤维新材料股份有限公司 一种除臭纤维素纤维的制备方法

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NL7300074A (enrdf_load_stackoverflow) 1973-07-05
NL177152C (nl) 1985-08-01
DE2300174A1 (de) 1973-07-26
DE2300174C2 (de) 1982-09-23
JPS5751096B2 (enrdf_load_stackoverflow) 1982-10-30
GB1415371A (en) 1975-11-26
FR2167592A1 (enrdf_load_stackoverflow) 1973-08-24
NL177152B (nl) 1985-03-01
CA1007087A (en) 1977-03-22
JPS4875236A (enrdf_load_stackoverflow) 1973-10-11
FR2167592B1 (enrdf_load_stackoverflow) 1977-04-22

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