US3754910A - Neutralizing layers in diffusion transfer photographic film - Google Patents

Neutralizing layers in diffusion transfer photographic film Download PDF

Info

Publication number
US3754910A
US3754910A US00208616A US3754910DA US3754910A US 3754910 A US3754910 A US 3754910A US 00208616 A US00208616 A US 00208616A US 3754910D A US3754910D A US 3754910DA US 3754910 A US3754910 A US 3754910A
Authority
US
United States
Prior art keywords
layer
film unit
image
dye
silver halide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US00208616A
Other languages
English (en)
Inventor
L Taylor
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Polaroid Corp
Original Assignee
Polaroid Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Polaroid Corp filed Critical Polaroid Corp
Application granted granted Critical
Publication of US3754910A publication Critical patent/US3754910A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • 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

Definitions

  • 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-diffusibl'e 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 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 particularly useful system for forming color images by diffusion transfer is that described in U. S. Pat. No. 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.
  • Exposed and 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 halide layer, 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 elementor 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.
  • While 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 strata comprise a unitary structure, of particular interest are those integral negative-positive film units adapted for forming color transfer images viewable without separation, i.e., wherein the positive component need not be separated from the negative component for viewing purposes.
  • film units comprise a plurality of essential layers including a negative component comprising at least one light-sensitive silver halide and associated dye image-providing material and a positive component comprising dyeable stratum. These components may be laminated together or otherwise secured together in physical juxtaposition as a single structure.
  • 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 absorption characteristics.
  • the most commonly employed negative components for forming multicolor images are of the tripack structure containing a blue-, a greenand aredsensitive silver halide layer having associated therewith in the same or in a contiguous layer a yellow, a magenta and a cyan dye image-providing material respectively.
  • lnterlayers or 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 ing 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 support members, 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 development composition so applied, in order to prevent further exposure (fogging) by actinic light incident thereon from the other side of the film 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 requisite background for viewing the transfer image formed thereover. Where this reflecting agent does not by itself 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 integral negative-positive film units of the foregoing description are exposed to form a developable image and thereafter developed by applying the 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.
  • this reflecting layer is provided prior to photoexposure, 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 lightreflecting agent, for example, a white pigment such as titanium dioxide, in the processing composition which is applied between the dyeable stratum and the next adjacent layer to develop the latent image and to form the color transfer image.
  • a suitable lightreflecting agent for example, a white pigment such as titanium dioxide
  • the dye image-providing materials which may be employed in such processes generally are selected from those materials heretofore mentioned and disclosed in the illustra-tive 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 initially insoluble 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, SOr. No. 43,782, filed June 5, 1970 (now abandoned) and S0r. No. 101,968, filed Dec. 28, 1970, now U.S. Pat. No. 3,647,437, comprising an inorganic reflecting pigment dispersion containing at least one optical filter agent at a pH above the pKa of the optical filter agent in a concentration effective, when the processing composition is applied, to provide a layer exhibiting optical transmission density than about 6.0 density units with respect to incident radia-tion actinic to the photosensitive silver halide layer and optical reflection density than about 1.0 density with respect to incident visible radiation.
  • 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.
  • the reflecting pigment may be generated in situ as is disclosed in the copending applications of Edwin H. Land, Ser. Nos. 43,741 and 43,742, both filed June 5, 1970, now U. S. Pat. Nos. 3,647,434 and 3,647,435, respectively.
  • 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.
  • 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., the time" control the pH reduction. Suitable spacer or timer" layers for this purpose are described 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.
  • FIG. is an enlarged, fragmentary, diagrammatic. sectional view of a film unit contemplated by this invention.
  • a layer comprising a polymeric salt of a strong acid and a weak base is employed to lower the pH.
  • This salt hydrolyzes to give an acid reaction and as a function thereof and the subsequent lowering of the pH forms a polymeric base, as distinguished from neutralization reactions wherein an acid reacts with a base to form a salt.
  • the film unit is a socalled integral negative-positive tripack employing dye developers as the dye image-providing materials and the positive component includes the aforementioned neutralizing layer in addition to the dyeable stratum.
  • the present invention contemplates film units including a neutralizing layer for lowering the environmental pH, which layer comprises an acid salt of a polymeric base, i.e., the polymeric salt of a strong acid and a weak base which will hydrolyze to give an acid reaction.
  • the neutralizing layers of this invention thus distinguish chemically as well as in the reaction product formed as a function of the neutralization from the acids heretofore employed for this purpose in that the salts of this invention form polymeric bases following neutralization, rather than salts.
  • the respective reactions by which acids and salts effect neutralization may be illustrated as follows:
  • the bases employed to form the salts of this invention generally are the amines, primary, secondary or tertiary, including aliphatic, aromatic or heterocyclic amines.
  • aminated polysaccharides such as deacetylated chitin, aminoethyl ether derivatives of cellulose, and the like.
  • the acids employed to form the salts generally have a pKa less than 4, preferably less than 3, and include the strong mineral acids such as nitric, hydrochloric, phosphoric and sulfuric, as well as strong organic acids such as lactic, chloroacetic, trifluoroacetic, p-toluene sulfonic, etc. Most preferred is nitric acid, since the nitrate salts are non-tacky and are not hygroscopic, as compared, for example, to the chlorides or sulfates.
  • the polymeric salts may be formed by reacting the amine monomer with the desired amount of acid and then polymerizing to form the polymeric salt; or by reacting the polyamine with the acid. Both reactions are 7 well known and per se comprise no part of this invention; and the salts obtained thereby are generally also old.
  • the amount of acid employed will depend upon the degree of neutralization or protonation desired. For example, if fully neutralized salts are contemplated, stoichiometric amounts of acid will be employed.
  • the amount or degree of neutralization of the salts will be at least in part dependent upon the degree of pH reduction contemplated in the particular film unit and system in which these salts areemployed. The lesser the amount of neutralization, the fewer the acidic ions which will be present for a given coverage of the salt.
  • the salt employed in this layer should preferably be at least SO'percent neutralized, i.e., atleast 50 percent of the basic groups should be neutralized, and most preferably at least 75 percent neutralized.
  • salts having a lesser degree of neutralization may be completey adequate and hence'are also contemplated. In any event,
  • the absence of sufiicient acid ions at a given coverage of the salt may be compensated for by other means, including the use of higher coverages in the salt neutralizing layer. Accordingly, it is to be expressly understood that the polymeric salts of this invention include those bases which are not .fully neutralized or protonated.
  • the neutralizing layer of this invention is useful in systems wherein the photosensitive strataand the dyeable stratum are contained on separate elements; and in'systems wherein theyare contained together as a unitary film unit, e.g., in the integral negative-positive film units previously described. In the former type, the neutralizing layer is most preferably containediin association with the dyeable stratum,
  • 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 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 a typical film unit of this description.
  • such a film unit may comprise, as the essential layers, a layer 13 of cyan dye developer, red-sensitive silver halide emulsion layer 14,
  • Layers 13-21 comprise the negative component and layers 22-24 comprise the positive component.
  • These essential layers are shown to be confinedbetween a dimensionally stable layer or support member 12 which is preferably opaque so as to permit development in the light and dimensionally stable layer 'or support member 25 which is effectively transparent to permit viewing of a color transfer image formed as a functionof develop ment in receiving layer or dyeable stratum 22.
  • Layers 12 and 25 are preferably dimensionally stable liquid-impermeable layers which when taken together may possess a processing composition solvent vapor permeably sufficient to effect, subsequent to substantial 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. Although these ing in excess of about 3O,0 gms.
  • 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 suchlayers.
  • useful materials of this nature mention may be made of those having the aforementioned characteristics and which are derived from ethylene glycol terephthalic acid; vinyl chloride polymers;polyvinyl-acetate; cellulos'ede v rivatives, etc.
  • layer12 is of suffisensitive silver halide, e.g., silver chloride, bromide or neutralizing 1 cient opacity to prevent fogging from occurring-by light passing therethroug'h, and layer 26 is transparent to pennitphotoexposure and for viewing of a transfer image formed on receiving layer 23.
  • layer12 is of suffisensitive silver halide, e.g., silver chloride, bromide or neutralizing 1 cient opacity to prevent fogging from occurring-by light passing therethroug'h
  • layer 26 is transparent to pennitphotoexposure and for viewing of a transfer image formed on receiving layer 23.
  • the silver halide layers preferablycomprise photoiodide 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.
  • a suitable colloidal binder such as gelatin
  • the silver halidelayers may and in fact generally do contain other adjuncts, e.g., chemical sensitizers such as are disclosed inU. S. Pats. Nos. 1,574,944; l,623,4'99;: 2,410,689; 2,597,856; 2,597,915; 2,487,850; 2,518,698; 2,521,926; etc.; as
  • coating aids e.g., coating aids, hardeners, viscosityincreasing agents, stabilizers, preservatives, ultraviolet absorbers and/or speed-increasing compounds.
  • the preferred binder for the silver halide is gelatin, others such as albumin, casein, zein, resins such as cellu- 9 lose derivatives, polyacrylamides, vinyl polymers, etc., may replace the gelatin in whole or in part.
  • the respective dye developers which may be any of 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.
  • lnterlayers 15, 18 and 21 may comprise an alkaline permeable polymeric material such as gelatin and may be on the order of from about 1 to microns in thickness.
  • alkaline permeable polymeric material such as gelatin
  • other materials for forming these interlayers mention may be made of those disclosed in U. S. Pats. Nos. 3,421,892 and 3,575,701 and the copending applications of Richard J. Haberlin, Ser. No; 854,491, filed Sept. 2, 1969 now US Pat. No. 3,615,422, and Avtges et al., Ser. No. 119,331, filed Feb. 26, 1971, and now U. S. Pat. No. 3,625,685 etc.
  • 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., Nmethoxymethyl 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., Nmethoxymethyl 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
  • 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. 3,227,550; 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, for example, in U. S. Pat. No. 3,265,498.
  • 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. 3,227,550; 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, for example, in U. S. Pat. No. 3,265,498.
  • the spacer or timing layer may be on the order of 0.1 to 0.7 mil. thick.
  • Materials heretofore used for this purpose include polymers which exhibit inverse temperature-dependent permeability to alkali, e.g., as disclosed in U. S. Pat. No. 3,445,686.
  • Materials previously employed for this layer include polyvinyl alcohol, cyanoethylated polyvinyl alcohol, hydroxypropyl polyvinyl alcohol, polyvinyl methyl ether, polyethylene oxide, polyvinyl oxazolidinone, hydroxypropyl methyl cellulose, partial acetals of polyvinyl alcohol such as partial polyvinyl butyral and partial polyvinyl propional, polyvinyl amides such as polyacrylamide, etc.
  • 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 salts, preferably one which is at least 75 percent neutralized, and the salt is most preferably contained at a coverage of less than 3000 mgs./ft.
  • the salts of this invention may be applied in accordance with knowncoating techniques to prepare the desired neutralizing layer, e.g., layer 24 of the illustrative film unit. It is most preferable to employ polymeric salts which are watersoluble and which may therefore be applied from aqueous coating solutions, thereby obviating the need for organic solvents and the obvious manufacturing disadvantages inherent in the use of organic coating solutions, e.g., the need for special equipment to handle these solvents which are typically volatile, including the storage thereof before use, and the involved danger in the use of such solvents.
  • the coating disadvantages do not preclude the use of water-insoluble polymeric salts which need be coated from organic solutions, and from a photographic standpoint, these water-insoluble salts are equally applicable and are therefore contemplated by the present invention.
  • the reaction product i.e., the polymeric base, formed by the pH reduction within the film unit is characterized as being hydrophobic. This hydrophobicity in turn provides certain distinct advantages over the use of prior hydrophilic acids in the neutralizing layer, e.g., the water-soluble polymeric acids described and claimed in the aforementioned Schlein et al application Ser. No. 165,171.
  • the present invention permits one to apply the neutralizing layer as an aqueous coating, thereby obtaining all the advantages of aqueous coating systems during the manufacture of the film unit, while at the same time obtaining the advantages following development of hydrophobicity, due to the conversion of the polymeric salt from an initially hydrophilic material to a hydrophobic one.
  • Poly-4-vinyl pyridinium lactate was prepared by neutralizing 10.5 g. of poly-4-pyridine dispersed in water by adding 10.6 g. of 85 percent lactic acid.
  • EXAMPLE 2 To a dispersion of 16 g. of deacetylated chitin (prepared by acid hydrolyzing natural chitin) 9 g. of percent nitric acid was added to form deacetylated chitin hydronitrate.
  • EXAMPLE 3 A solution of 31.4 g. of dimethylaminoethyl methacrylate was neutralized by adding 18 g. of nitric acid. The resulting mixture was polymerized by the addition of 0.062 g. of ammonium persulfate and 0.062 g. of sodium bisulfite to form poly-dimethylaminoethyl methacrylate hydronitrate.
  • EXAMPLE 4 Forty-fourg. of 4-vinyl pyridine were added to a deaerated solution of 11 g. of polyvinyl alcohol in 500 cc. of water under a blanket of nitrogen. After raising the temperature to 50C, the pH was adjusted to 1.5 with concentrated nitric acid and 6.6 g. of ceric ammonium nitrate was added. After several hours polymerization was complete, forming the graft copolymer of 4-vinyl pyridinium nitrate on polyvinyl alcohol.
  • the polymeric salts were not isolated from the reaction mixture.
  • Coating solutions for preparing the neutralizing layers of this invention may, if desired, by obtained from these reaction mixtures including the desired polymeric salt, or alternatively, if desired, the polymeric salt may first be isolated or recovered from the reaction mixture by standard procedures.
  • the neutralizing layers of this invention may be prepared by standard coating techniques employing polymeric salts such as those prepared in the foregoing illustrative Examples.
  • 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 blue-sensitive gelatino silver iodobromide emulsion layer including the auxiliary developer 4'- met-hylphenyl hydroquinone coated at a coverage of about 120 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:
  • a transparent 4 mil. polyethylene terephthalate film base may be coated, in succession, with the following illustrative layers:
  • 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 of 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, interconnecting the respective container and laminates so that, upon application of compressive pressure to the container to rupture the container's marginal seal, its contents may be distributed between the dyeable stratum (layer 3 of the positive component) and the gelatin layer (layer 9) of the negative component.
  • 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 alkaline processing composition. thereby forming a multicolor transfer image which is viewable through the transparent polyethylene terephthalate film base as a positive reflection print.
  • a solution of deacetylated chitin hydronitrate (as prepared in Example 2) was coated on a clear film base at a coverage of about 16 mgsJft. to provide a neutralizing layer.
  • Similar film units may be prepared, for example, by applying the polymeric salt prepared in Example 3 at a coverage of about 2,400 mgs./ft. or the salt prepared in Example 4 at a coverage of about 2,300 mgsJft.
  • 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 compositon;
  • said neutralizing layer comprises a polymeric salt of a monomeric strong acid and a polymeric weak base.
  • 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 polymeric salt of a strong acid and a weak base.
  • a photosensitive element as defined in claim 3 including a dyeable stratum adapted for forming a color image by diffusion transfer.
  • an integral negative-positive film unit including a negative component comprising at least one lightsensitive silver halide emulsion layer having a dye image-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 environmental pH subsequent to application of said alkaline processing fluid;
  • said neutralizing layer comprises a polymeric salt of a strong acid and a weak base.
  • a film unit as defined in claim 6 wherein said salt is the salt of an amine and an acid having a pKa less than 4.
  • said amine is a polymer, copolymer or graft copolymer of a member of the group consisting of 2-vinyl pyridine, 4- vinyl pyridine, Z-methyl-S-vinyl pyridine, dimethylamino-ethyl acrylate, dimethylaminoethyl methacrylate, N-vinylimidazole, t-butylaminoethyl methacrylate and aminoethylvinyl ether, aminated polysaccharides or aminoethyl ether derivatives of cellulose.
  • a film unit as defined in claim 7 wherein said acid is selected from the group consisting of nitric, hydrochloric, sulfuric, phosphoric, lactic, chloroacetic, trifluoroacetic and p-toluene sulfonic acids.
  • a film 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 in a 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.
  • a photosensitive element including a composite structure containing, as 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 polymeric salt of a strong acid and a weak base 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 non-diffusible, 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 retaining an aqueous
  • a film unit as defined in claim 19 including a timing layer disposed between said dyeable stratum and said neutralizing layer.
  • 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.
  • a process for forming a color transfer image comprising the steps of exposing a film unit as defined in claim 6 to form a developable image and thereafter applying an aqueous alkaline processing composition to develop said image and to form, as a function of development, an imagewise distribution of dye imageproviding material which is transferred, at least in part, by diffusion, to said dyeable stratum to impart thereto a color transfer image viewable, without separation, by

Landscapes

  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
US00208616A 1971-12-16 1971-12-16 Neutralizing layers in diffusion transfer photographic film Expired - Lifetime US3754910A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US20861671A 1971-12-16 1971-12-16

Publications (1)

Publication Number Publication Date
US3754910A true US3754910A (en) 1973-08-28

Family

ID=22775282

Family Applications (1)

Application Number Title Priority Date Filing Date
US00208616A Expired - Lifetime US3754910A (en) 1971-12-16 1971-12-16 Neutralizing layers in diffusion transfer photographic film

Country Status (9)

Country Link
US (1) US3754910A (enrdf_load_stackoverflow)
JP (1) JPS5544937B2 (enrdf_load_stackoverflow)
AU (1) AU459598B2 (enrdf_load_stackoverflow)
CA (1) CA992788A (enrdf_load_stackoverflow)
DE (1) DE2261588C2 (enrdf_load_stackoverflow)
FR (1) FR2163732B1 (enrdf_load_stackoverflow)
GB (1) GB1415009A (enrdf_load_stackoverflow)
IT (1) IT974084B (enrdf_load_stackoverflow)
NL (1) NL177048C (enrdf_load_stackoverflow)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3833370A (en) * 1973-01-05 1974-09-03 Polaroid Corp Color diffusion transfer with development controlling polymeric salt
US4191572A (en) * 1975-06-03 1980-03-04 E. I. Du Pont De Nemours And Company Process for image reproduction using multilayer photosensitive element with solvent-soluble layer

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6291829U (enrdf_load_stackoverflow) * 1985-11-29 1987-06-12

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3415646A (en) * 1967-05-16 1968-12-10 Polaroid Corp Novel photographic products and processes

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3833370A (en) * 1973-01-05 1974-09-03 Polaroid Corp Color diffusion transfer with development controlling polymeric salt
US4191572A (en) * 1975-06-03 1980-03-04 E. I. Du Pont De Nemours And Company Process for image reproduction using multilayer photosensitive element with solvent-soluble layer

Also Published As

Publication number Publication date
IT974084B (it) 1974-06-20
GB1415009A (en) 1975-11-26
AU5001772A (en) 1974-06-13
DE2261588A1 (de) 1973-06-28
DE2261588C2 (de) 1982-07-01
JPS4866826A (enrdf_load_stackoverflow) 1973-09-13
NL7217096A (enrdf_load_stackoverflow) 1973-06-19
FR2163732B1 (enrdf_load_stackoverflow) 1976-06-04
AU459598B2 (en) 1975-03-27
JPS5544937B2 (enrdf_load_stackoverflow) 1980-11-14
NL177048C (nl) 1985-07-16
CA992788A (en) 1976-07-13
NL177048B (nl) 1985-02-18
FR2163732A1 (enrdf_load_stackoverflow) 1973-07-27

Similar Documents

Publication Publication Date Title
US3594165A (en) Novel photographic products and processes
US3415644A (en) Novel photographic products and processes
US3415646A (en) Novel photographic products and processes
US3415645A (en) Opaque permeable polymeric layer in photo-sensitive element
US3785815A (en) Spacer or timing layer in color diffusion transfer film
US3384483A (en) Multicolor dye developer image transfer systems
US3706557A (en) Color diffusion transfer film unit containing a temporary barrier for developer restrainers
US3625685A (en) Photographic color diffusion-transfer element comprising aqueous film-forming synthetic polymer suspension layers intermediate its sensitive layers and processes for their use
US4009031A (en) Diffusion transfer image-receiving element having polyvinylpyridine layer treated with hydrophilic colloid/ammonia solution
US3421892A (en) Novel photographic products and processes
US3856521A (en) Diffusion transfer color film and process
US3776726A (en) Color diffusion transfer photographic products,processes and compositions
US3594164A (en) Photographic color diffusion transfer process and film unit for use therein
US3445228A (en) Dye diffusion transfer process and element
US3754910A (en) Neutralizing layers in diffusion transfer photographic film
US4401746A (en) Stripping layer consisting of a mixture of cellulose acetate hydrogen phthalate and straight chain saturated polyester of adipic acid
US3756815A (en) Binder photographic color diffusion transfer units which utilize neutralizing layer comprising a water soluble polymeric acid and a water soluble
US3765885A (en) Neutralizing layer for color diffusion transfer film
US3778265A (en) Novel photographic products and processes
US3833367A (en) Novel photographic products and processes
US3772026A (en) Colorless precursor of alkyl viologen as filter agent in photographic film
US3418117A (en) Multicolor dye developer image transfer systems
US3647435A (en) Integral negative/positive color diffusion transfer process film unit employing in-situ generated visible light-reflecting agent
US3756816A (en) Orming polymer dispersion photographic film units including a layer comprising an aqueous filmf
US3816125A (en) Photographic products and processes