CA1036857A - Photographic products and processes - Google Patents

Abstract

Abstract of the Disclosure The present invention relates to photography, particularly, to photographic products specifically adapted for employment in specified photographic diffusion transfer color processes and, more particularly, to photographic products which comprise a fixed or permanent composite photosensitive structure including, as essential layers, in sequence, a first dimensionally stable layer transparent to actinic radiation; a polymeric layer dyeable by a diffusion transfer process dye image-forming material;
a processing composition permeable opaque layer; a photo-sensitive silver halide layer having associated therewith a diffusion transfer process dye image-forming material;
a processing composition permeable layer impermeable to a diffusion transfer process dye image-forming material;
a second dimensionally stable layer transparent to actinic radiation; and means for providing a diffusion transfer process processing composition preferably retaining opacifying agent intermediate the dye image-forming material impermeable polymeric layer and the next adja-cent second transparent dimensionally stable layer; and to specified photographic diffusion transfer color processes employing such products.

Description

103~;857 The present inYention is directed to providing new and improved diffusion transfer color process photo-graphic film units adapted to provide, as a function of the point-to-point degree of photoexposure, by diffusion transfer processing dye transfer image formation.
As disclosed in United States Patent No.
3,672,890 a composite photosensitive structure, particularly adapted for reflection type photographic diffusion transfer color process employment, which comp~ises a plurality of essential layers including, in sequence, a dimensionally stable layer preferably opaque to incident radiation; one or more silver halide emulsion layers having associated there-with a diffusion transfer process dye image-providing mate-rial; a polymeric layer adapted to receive solubilized dye image-providing material diffusing thereto; and a dimension-ally stable transparent layer, may be exposed to incident actinic radiation and processed by interposing intermediate the silver halide emulsion layer and the reception layer, a processing composition and an opacifying agent, which may reflect incident radiation, in a quantity sufficient to mask dye image-prov~ding material associated with the silver halide emulsion.
In a preferred embodiment, the composite photo-sensitive structure includes a rupturable container, retain-ing an alkaline processing composition and the opacifying agent, fixedly positioned extending transverse a leading edge of the composite structure in order to effect, upon application of compressive pressure to the container, - 1 - - q~

10~i8~7 discharge of the processing composition intermediate the opposed surfaces of the reception layer and the next adja-cent silver halide emulsion.
The liquid processing composition, distributed intermediate the reception layer and the silver halide emulsion, permeates the silver halide emulsion layers of the composite photosensitive structure to initiate develop-ment of the latent images contained therein resultant from photoexposure. As a consequence of the development of the latent images, dye image-providing material associated with each of the respective silver halide emulsion layers is individually mobilized as a function of the point-to-point degree of the respective silver halide emulsion layer's photoexposure, resulting in imagewise distributions of mobile dye image-providing materials adapted to transfer, by diffusion, to the reception layer to provide the desired transfer dye image. Subsequent to substantial dye image formation in the reception layer, means associated with composite structure are adapted to convert the pH of the film unit from a first processing pH at which dye image-providing material is diffusible as a function of the film - unit's photoexposure to a second pH at which the transfer dye image exhibits increased stability, preferably a sufficient portion of the ions of an alkaline processing composition transfers, by diffusion, to a polymeric neutralizing layer to effect reduction in the alkalinity of the composite film unit from a first alkaline process-.i ing pH to t~e second pH at which dye image providing material is substantiall~ nondiffusible, and further dye image-providing material transfer is thereby substantially obviated.
The transfer dye image is viewed, as a reflection image, through the dimensionally stable transparent layer against the background provided by the opacifying agent, distributed as a component of the processing composition, intermediate the reception layer and next adjacent silver halide emulsion layer. The thus-formed opacifying stratum effectively masks residual dye image-providing material retained in association with the silver halide emulsion layer subsequent to processing.
In United States Patent No. 3,415,644, the di-mensionally stable layer of the film unit next adjacent the photosensitive layer or layers is disclosed to be opaque, the opacifying agent is initially disposed in an aqueous alkaline processing composition and the film unit's pH modulating means are disclosed to comprise a polymeric layer disposed intermediate the dimensionally stable transparent layer and the reception layer and adapted to reduce, subsequent to substantial dye transfer image formation; the pH of an aqueous alkaline processing composition from a first processing pH at which the dye image-forming material or materials are soluble and diffusible in the composition as a function of the photoexposure of the photosensitive silver halide layer associated therewith to a second pH
at which the dye image-forming material or materials are substantially nondiffusible and, as disclosed in United States Patent No. 3,415,646, the dimensionally stable layer of the film unit next adjacent the photosensitive silver halide 10368g7 layer or layers is disclosed to be transparent to incident actinic radiation and, as further disclosed in United States Patent No. 3,415,645, in such instance the opacifying agent may be initially disposed in the film unit intermediate the reception layer and next adjacent silver halide layer.
As disclosed in United States Patents Nos.
3,615,421 and 3,661,585, the opacifying component of the film unit may optionally be initially disposed as a preformed proces-sing composition permeable layer, intermediate the reception lo layer and next adjacent silver halide layer, in a concentra-tion which prior to photoexposure is insufficient to prevent transmission therethrough of exposing actinic radiation and which, subsequent to processing, possesses an opacifying capacity effective to mask residual dye image-providing material retained associated with the film unit's silver halide emulsion layers, and in United States Patent No.
3,647,435, the opacifying component of the film unit may op-tionally be initially formed in s _ , intermediate the recep-tion layer and next adjacent silver halide layer, during photo-graphic processing of the film unit.
~n United States Patent No. 3,647,437, the opacify-ing component is disclosed to optionally comprise a light-absorbing reagent such as a dye which is present as an ab-sorbing species at the first pH and which may be converted to a substantially non-absorbing species at the second pH, and in United States Patents Nos. 3,473,925, 3,573,042 and 3,576,626, opacifying and reflecting component, respectively, may be individually interposed intermediate the silver halide layer and reception layer by selective distribution from a composite or a plurality of rupturable containers.

103~57 , ' In United States Patent No. 3,573,043, the poly-meric neutralizing layer is dlsclosed to be optionally disposed intermediate the dimensionally stable opaque layer and next adjacent essential layerJ i.e., next adjacent silver halide/
dye image-providing material component, to effect the design-ated modulation of film unit's environmental pH; United States Patent No. 3,576,625 discloses the employment of particulate acid distributed within the film unit to effect the modula-tion of the environmental pH, and United States Patent No.
3,573,044 discloses the employment of processing composition solvent vapor transmissive dimensionally stable layers to effect process modulation of dye transfer as a function of sol-vent concentration.
~here desired, the film unit may also be construc-ted in accordance with the disclosure of United States Patents Nos. 3,594,164; 3,594,165; 3,689,262 and 3,701,656 to com-prise a composite photosensitive structure including a trans-parent dimensionally stable layer carrying a reception layer, a processing composition permeable opaque layer and a photo-sensitive silver halide layer and the film unit may include a separate dimensionally stable sheet element adapted to be superposed on the surface of the photosensitive structure opposite the dimensionally stable layer and may further in-clude means such as a rupturable container retaining proces-sing composition for distribution of a processing composition intermediate the sheet and photosensitive structure to effect processing. As further disclosed in certain of the last-cited patents and applications, in structures wherein the receptor is positioned next adjacent the transparent layer or the pro-cessing composition and/or the sheet is to be separated 103685q from the remainder of the film unit subsequent to proces-sing, the latter elements may optionally include opacifying component.
As disclosed in United States Patent No.
3J620S724~ the dimensionally stable layer referred to may be opaque and in which instance the photosensitive silver halide layer is positioned next adjacent the opaque support layer and the opacifying component of the film unit's processing composition permeable opaque layer will be disposed in the unit in a concentration insufficient to prevent transmission therethrough of exposing actinic radiation and which, sub-sequent to processing, possesses an opacifying capacity effective to mask residual dye image-providing material re-tained associated with the silver halide layer, and as dis-closed in United States Patent No. 3,647,434, the opacifying agent may be optionally formed in such film unit, in s _ , during processing of the unit.
As disclosed in British Patent No. 874,046, two or more separate diffusion transfer process images may be simultaneously provided by exposure and diffusion transfer processing of a film unit which includes a transfer process image-receiving layer located contiguous one major surface of a silver halide emulsion and an image-receiving element superposed contiguous the opposite major surface of the emulsion during processing and, subsequent to processing, separating the image-receiving element from its superposed relationship with the emulsion and, where required, the emulsion fr~m its contiguous relationship with the image-receiving layer for viewing of the respective transfer images.

m e present inventlon is directed to novel photographic diffusion transfer color process film units and specifically to integral negative/posi-tive, diffusion transfer process photographic film units adapted to provide, by diffusion transfer processing, photographic color image reproduction as a function of exposure of such film unit to incident actinic radiation.
Thus, in a first e~bodiment this invention seeks to provide a com-posite photographic diffusion transfer process film unit which comprises, in combinatlon, a first dimensionally stable transparent layer; a first dyeable layer adapted to receive diffusion transfer process dye image-forming material diffusing thereto; an opaque layer; a photosensitive silver halide layer hav-ing associated therewith a diffusion transfer process dye image-forming mat-erial; a processing composition permeable diffusion transfer process dye image-forming material impermeable layer; a second dimensionally stable transparent layer; means for providing a processing composition intermediate the second dimension~lly stable transparent layer and the dye image-forming material impermeable layer; and means for maintaining the composite unit intact sub-sequent to diffusion transfer processing.
Preferably, the composite photographic diffusion transfer process film unit also includes means for providing opacifying agent intermediate the second dimensionally stable layer and the next ad~acent silver halide layer in a quantity effective to prevent exposure of said photosensitive silver hal-ide layer during processing of said film unit in the presence of radiation actinic to said photosensitive layer and incident on said second dimensionally stable transparent layer and said opaque layer is effective to prevent expo-sure of said photosensitive layer during processing of said film unit in the presence of radiation actinic to said photosensitive layer and incident on said first dimensionally stable layer.
Ihus, in a second embodiment this invention seeks to provide a pro-cess for providing ccmposite photographic diffusion transfer process dye images which comprises, in combination, the steps of:
(a) exposing to incident actinic radiation a photographic diffusion transfer process film unit which comprises, in combination, a dimensionally ~ _ 7 _ B!
.

103~857 stable transparent layer; a dyeable layer adapted to receive diffusion trans-fer process dye image-forming material diffusing thereto; an opaque ]ayer; a photosensitive silver halide layer having associated therewith a diffusion transfer process dye image-forming material; a processing composition perme-able dye image-forming material impermeable layer, (b) contacting the surface of the dye image-forming material imper-meable layer opposite the dimensionally stable transparent layer with a pro-cessing composltion and effecting development of the photoexposed sllver hal-ide layer and formation of an imagewise distribution of mobile dye image-forming material as a function of the point-to-point degree of silver halide layer photoexposure; and tc) transferring, by diffusion, at least a portion of said imagewise distribution of mobile dye image-forming material to said dyeable layer adapted to receive dye image-forming material diffusing thereto to thereby provide to said dyeable layer a dye image in terms of said imagewise distribution.
In accordance with the present invention, the film units will com-prise a plurality of layers including, in relative order, a first dimensionally stable layer transparent to incident actinic radiation; a diffusion transfer process dye image-forming material impermeable layer permeable to processing composition; one or m~re photosensitive silver halide layers having associated therewith one or more diffusion transfer process dye image-forming materials;
an opaque layer; a second transparent layer adapted to receive dye image-forming material diffusing thereto and a second dimensionally stable layer transparent to incident actinic radiation; means for providing, intermediate the first dimensionally stable layer and next ad~acent dye image-forming mat-erial impermeable layer, opacifying agent; and means for providing a processing composition in contact with the photosensitive layers, and, in a particularly preferred embodiment, a processing composition posessing a first pH at which the diffusion transfer process dye image-forming material is diffusible during processing and means for modulating the pH of the film unit from the first pH
to a second pH at which dye image-forming material is substantially nondif-fusible subsequent to substantial dye transfer image formation.

- 7a -,..~B~

10;~6857 In the accompanying drawings;
Figure 1 is a fragmentary perspective view of one embodiment of a photographic filn unit in accordance with the invention;
Figures 2, 4 and 6 are diagrammatic enlarged cross-sectional views of the filn unit of Figure 1, along section line 2-2, illustrating the association of elements during the three illustrated stages of the performance of a diffusion transfer process, for the production of a multicolor transfer lmage according to the invention, the thickness of the varlous materials being exaggerated, and wherein Figure 2 represents an exposure stage, Figure 4 .~'.

1036~g7 j represents a processing stage and Figure 6 represents a product of the process; and Figures 3, 5 and 7 are diagrammatic, further enlarged cross-sectional views of the film unit of Figures

2, 4 and 6, along section lines 3-3, 5-5 and 7-7, respec-tively, further illustrating, in detail, the arrangement of layers comprising the photosensitive laminate during the three illustrated stages of the transfer process;
Figure 8 is a perspective view of a film pack comprising an assemblage of film units; and Figure 9 is a longitudinal sectional view taken substantially midway between the sides of the film pack of Figure 8.
Diffusion transfer photographic processing in accordance with the present invention may be employed to provide a positive reflection dye image, as a direct function of actinic radiation incident on a film unit assemblage which unit is preferably constructed to comprise a plurality of sequential layers including a first dimen-sionally stable layer transparent to incident radiation;
a first transparent layer permeable to processing composi-tion and impermeable to diffusion transfer process dye image-forming material diffusing thereto; one or more photosensitive silver halide layers having associated therewith one or more diffusion transfer process dye image-forming materials; an opaque layer; a layer adapted to receive dye image-forming material diffusing thereto; a second dimensionally stable layer transparent to incident radiation; means for interposing intermediate the first dimensionally stable layer and the next adjacent dye image-forming material impermeable layer opacifying agent, pre-ferably an inorganic reflecting pigment dispersion, in a concentration effective to provide, subsequent to selec-tive photoexposure of the silver halide layer, protection of the silver halide layer from further exposure to actinic radiation incident on the dimensionally stable layer; and means for converting the pH of the film unit from the first processing pH to a second pH at which the dye image-forming material is substantially nondiffusible subsequent to substan-tial dye image-forming material diffusion to the reception layer.
In view of the fact that the preferred dye image-forming materials comprise dyes which are silver halide developing agents, as stated above, for purposes of simpli-city and clarity, the present invention will be further described hereinafter in terms of such dyes, without limitation of the invention to the illustrative dyes denoted, and, in addition the photographic film unit structure will be detailed hereinafter employing the last-mentioned pre-ferred structural embodiment, without limitation of the invention to the preferred structure denoted.
The dye developers are compounds which contain, in the same molecule, both the chromophoric system of a dye and also a silver halide developing function. By "a silver halide developing function" is meant a grouping adapted to develop exposed silver halide. A preferred silver halide developing function is a hydroquinonyl group.
Other suitable developing functions include ortho-dihydroxy-phenyl and ortho- and para-amine substituted hydroxyphenyl ~0;168g7 groups. In general, the developing function includes a benzenoid developing function, that is, an aromatic developing group which forms quinonoid or quinone substances when oxidized.
me dye developers are preferably selected for their ability to provide colors that are useful in carrying out subtractive color photography, that is, the previously men~ioned cyan, magenta and yellow. m e dye developers employed may be incorporated in the respective silver halide emulsion, in a preferred embodiment, or in a separate layer contiguous the respective silver halide stratum. Specifically, the dye developer may, for example, be in a coating or layer behind or directly disposed in the respective silver halide stratum and such dye developer structure may be applied by use of a coating solution containing about 0.5 to 8 percent, by weight, of the respective dye developer distributed in a film-forming natural, or synthetic, polymer, for example, gelatin, polyvinyl alcohol, and the li~e, adapted to be permeated by the chosen diffusion transfer fluid processing composition.
An extensive compilation of specific dye developers particularly adapted for employment in photographic diffusion transfer processes is set forth in United States Patent No. 2,983,606. As examples of additional Uhited States patents detailing specific dye developers for photographic transfer process use, mention may be made of United States Patent Nos.
2,983,605; 2,992,106; 2,047,386; 3,076,808;

10368g7

3,076,820, 3,077,402; 3,126,280; 3,131,061; 3,134,762;
3,134,765; 3,135,604; 3,135,605; 3,135,606; 3,135,734;
3,141,722; 3,142,565; and the like.
The silver halide strata comprising the multi-color photosensitive laminate preferably possess predominant spectral sensitivity to separate regions of the spectrum and each has associated therewith a dye developer which is, most preferably, substantially soluble in the reduced form only at a first pH possessing, subsequent to processing, a spectral absorption range substantially complementary to the predominant sensitivity range of its associated emulsion. ~
In a preferred embodiment of the present invention, the film unit is specifically adapted to provide for the production of a multicolor dye transfer image and the photo-sensitive laminate comprises, in order, at least two selec-tively sensitized silver halide emulsion strata each having dye image-providing material of predetermined image color subsequent to processing associated therewith which is solub}e and diffusible substantially only at a first pH
as a function of the photoexposure of its associ-ated silver halide emulsion stratum.
The silver halide emulsions comprising the multi-color photosensitive laminate preferably possess predominant spectral sensitivity to separate regions of the spsctrum and each has associated therewith a dye, which is a silver halide developing agent and is, most preferably, substantially soluble in the reduced form only at a first pH, possessing subsequent to photoexposure or processing a spectral absorp-tion range ~ubstantially complementary to the predominant sensitivity range of its associated emulsion. Specifically preferred dyes comprise dyes which exhibit major spectral absorption outside of the primary regions of the spectrum to which the associated silver halide emulsion is sensitive and a spectral transmission substantially complementary to that absorption, during exposure of the emulsion, and major spectral absorption within the spectral range to which the associated silver halide emulsion is sensitive and a spectral transmission substantially complementary to that absorption, subsequent to exposure or processing of said emulsion, for example, of the type disclosed in United States patent No.
3,307,947.
In one embodiment each of the emulsion strata, and its associated dye, may be spaced from the remaining emsulion strata, and their associated dye, by separate alka-line solution permeable polymeric interlayers and the dyeable polymeric layer next adjacent the polymeric acid layer may be separated from that layer by an alkaline solution permeable polymeric spacer layer, most preferably a polymeric spacer layer having decreasing permeability to alkaline solution with increasing temperature.
In such preferred embodiments of the invention, the silver halide emulsion comprises photosensitive silver halide dispersed in gelatin and is about 0.6 to 6 microns in thickness; the dye itself may be dispersed in an aqueous alkaline solution permeable polymeric binder, preferably gelatin, as a separate layer about 1 to 7 microns in thick-ness; the alkaline solution permeable polymeric interlayers, for example,~gelatin, may be about 1 to 5 microns in thick-ness; the alakline solution permeable and dyeable polymeric layers are transparent and may be about 0.25 to 0.4 mil in thickness; the alkaline solution polymeric spacer layers 10;}68g7 are transparent and may be about 0.1 to 0.7 mil in thickness;
the alkaline solution permeable polymeric acid layers are transparent and may be about 0.3 to 1.5 mils in thickness;
and the dimensionally stable transparent layers are alkaline solution imperméable and may be about 2 to 6 mils in thick-ness. It will be specifically recognized that the relative dimensions recited above may be appropriately modified, in accordance with the desires of the operator, with respect to the specific product to be ultimately prepared.
In the preferred embodiment of the present inven-tion's film unit for the production of a multicolor transfer image, the respective silver halide/dye developer units of the photosensitive element will be in the form of a tripack configuration which will ordinarily comprise a yellow dye developer/blue-sensitive emulsion unit, a cyan dye developer/
red-sensitive emulsion unit and a magenta dye developer/
green-sensitive emulsion unit intermediate those units, recognizing that the relative order of such units may be varied in accordance with the desires of the operator.
In those instances, where either or both the respective yellow and magenta dye developers, employed in a preferred tripack configuration which positions the yellow dye developer/blue-sensitive emulsion unit distal the opaque layer dimensionally stable transparent layer and the cyan dye developer/red-sensitive emulsion unit proximal the opaque layer to provide the multicolor transfer image, comprise a dye developer which exhibits major spectral absorption outside of the primary region of the spectrum to which its associated silver halide emulsion is sensitive and a spectral transmission substantially complementary to that absorption, during exposure ~03685 7 of the emulsion, then, in many circumstances, it may be advantageous to incorporate filter agents adapted to insure the correct selective exposure of the respective emulsions less proximal the exposure surface of the laminate. Speci-fically, in the instance where the yellow dye developer exhibits major spectral transmission within the primary regions of the spectrum to which its associated silver halide emulsion is sensitive, that is, the blue region of the visible spectrum, during exposure of the emulsions, then a yellow filter agent may advantageously be incorporated intermediate the blue-sensitive emulsion and the remaining green- and red-sensitive emulsions, in order to prevent undesired exposure of the latter emulsions by reason of their inherent sensitivity to actinic radiation within the blue range of the spectrum generally present. In the instance where the magenta dye developer employed exhibits major spectral transmission within the primary region of the spectrum to which its associated silver halide emulsion i9 sensitive, that is, the green region of the visible spectrum, during exposure of the emulsions, a magenta filter agent may be advantageously incorporated intermediate the green- and red-sensitive emulsions in instances wherein the red-sensitive emulsion possesses sensitivity to actinic radiation within the green region of the spectrum.
Reference is now made to Figures 1 through 7 of the drawings wherein there is illustrated a preferred film unit of the present invention and wherein like numbers, appearing i~ the various figures, refer to like components.
As illustrated in the drawings, Figure 1 sets forth a perspective view of the film unit, designated 10, -~0368g7 and each of Figs. 2 through 7 illustrate diagrammatic cross-sectional views of film unit 10, along the stated section lines 2-2, 3-3, 5-5 and 7-7, during the various depicted stages in the performance of a photographic diffu-sion transfer process as detailed hereinafter.
Film unit 10 comprise~ rupturable container 11, retaining, prior to processing, aqueous alkaline solution 12, and photosensitive element 13 including, in order, dimen~ionally stable transparent layer 24a neutralizing layer 23a; spacer layer 23a; processing composition permeable, dye image-forming material barrier layer 25:
blue-sensitive silver halide emulsion layer 15 containing yellow dye developer: interlayer 16; green-sensitive silver halide emulsion layer 17 containing magenta dye developer;
interlayer 18; red-sensitive silver halide emulsion layer 19 containing cyan dye developer opaque layer 20 image-receiving layer 21 spacer layer 22b: neutralizing layer 23b and dimensionally stable transparent layer 2~b, both layer 24a and layer 24b comprising an actinic radiation transparent and processing composition impermeable flexible sheet material.
~ Photosensitive element 13 may be provided with a binding member 26 extending around, for example, the specified edges of the element maintaining the element intact except at the interface between spacer layer 22a and barrier layer 25 during distribution of processing composition 12. As illustrated in the figures, the binding member may comprise a pressure-se~nsitive tape 26 securing the photosensitive element's components together at film unit lO's specified edges. Tape 26 will also act to maintain processing 1036~7 composition 12 intermediate first spacer layer 22a/barrier layer 25 and upon application of compressive pressure to container 11 and distribution of its contents intermediate stated components 22a and 25. Under such circumstances, binder tape 26 will act to prevent leakage of processing composition from the film unit during and subsequent to photographic processing.
As illustrated, binding sheet 26 overlying and secured to the trailing edge sections of transparent layer 24a and transparent layer 24b cooperates with the trailing edge of each of the transparent layers to provide an enclosed chamber or trap area 2 adapted to secure and retain excess processing composition 12, employed to insure adequate processing composition coverage upon distribution. To further facilitate distribution of processing composition 12 between transparent layer 24a and transparent layer 24b, binding member 26 may be provided with one or more air release vents 1 associated with the trailing edge section of the film unit and preferably in direct communication with trap chamber 2 in order to facilitate release of air from the film unit during distribution of processing composi-tion 12.
Rupturable container 11 may be of the type shown and described in any of U. S. Patents Nos. 2,543,181; 2,634, 886; 2,653,732; 2,723,051; 3,056,491; 3,056,492; 3,152,515;
and the like. In general, such containers will comprise a rectangular blank of fluid- and air-impervious sheet material folded longi~udinally upon itself to form two walls 27 which are sealed to one another along their longitudinal and end margins to form a cavity in which processing solution 12 is .1~36~ , retained. The longitudinal marginal seal 28 is made weaker than the end seals 29 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 pres-sure to walls 27 of the container.
As illustrated in Figures 1, 2 and 4, container 11 is fixedly positioned and extends transverse a leading edge of photosensitive laminate 13 whereby to effect unidirection-al discharge of the container's contents 12 intermediate first spacer layer 22a and barrier layer 25, upon applica-tion of compressive force to container 11. Thus, container 11, as illustrated in Fig. 2, is fixedly positioned and extends transverse a leading edge of laminate 13 with its longitudinal marginal seal 28 directed toward the ieading edge of the stated interface. As shown in Figures 1, 2 and 4, container 11 is fixedly secured to laminate 13 by extension 30 of tape 26 extending over a portion of one wall 27 of the container, in combination with a separate retaining member such as illustrated retaining tape 31 extending over a portion of the other wall 27 of the container and a portion of laminate 13's surface generally equal in area to about that covered by tape 26.
As illustrated in Figures 1, 2 and 4, extension flap 30 of tape 26 may be of such area and dimensions that upon, for example, manual separation of container 11 and leader 31, subsequent to distribution of the composition, from the remainder of film unit 10, flap 30 may be folded over the edge~of laminate 13, previously covered by leader 31, in order to facilitate maintenance of the laminate's structural integrity, for example, during the flexations -18~-lQ368g7 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 24. Preferably, however, the film unit will be maintained intact subsequent to processing includ-ing retention of the exhausted container, the processing composition in the spacial position assumed during process-ing. In such instance, the processing composition employed ~hould possess the requisite adhesive capacity, in both the fluid and dry states, to enhance the integrity and stability of the spacial arrangement assumed.
In general, in a particularly preferred embodi-ment, the opacity of processing composition 12 when distri-buted will be sufficient to prevent further exposure of lS the film unit's silver halide emulsion or emulsions, by actinic radiation incident on transparent layer 24a during processing of the unit in the presence of radiation actinic to the emulsion or emulsions. Accordingly, the film unit may be processed, subsequent to exposure, in the presence of such radiation, in view of the fact that the silver halide emulsion or emulsions of the laminate are appropriately protected from incident radiation, at one major surface by the opaque layer or layers 20 and at the remaining major surface by opaque processing composi-tion 12 as further described`hereinafter. If the illus-trated binder tapes are also opaque, as stated abo~e, edge leakage of actinic radiation incident on the emulsion or emulsions will also be prevented. The selected opaque layer or layers 20, however, should be one providing a background suitable for viewing the respective dye lQ36Bg7 developer transfer image formed in the dyeable polymeric layer. In general, while substantially any opaque process-ing composition and permeable opaque layer may be employed, it is preferred that a processing composition and layer be selected that will not interfere with the color inte-grity of the dye transfer image carried by the reception layers, as viewed by the observer, and, most preferably, an opa~ue processing composition and opaque layer which is aesthetically pleasing to the viewer and does not provide a background noise signal degrading, or detracting from, the information content of the dye image. Particularly desirable opaque compositions will be those providing a white background, for viewing the transfer image, and specifically those adapted to be employed to provide back-ground for reflection photographic prints and, especially, those layers possessing the optical properties desired for reflectance of incident radiation.
The opaque layer may comprise substantially any opacifying agent compatible with the photographic system, such as, for example, barium sulfate, titanium dioxide, barium stearate, silver flake, zirconium oxide, and the like, which may be distributed in a permeable polymeric matrix or binder, such as, for example, gelatin, polyvinyl alcohol, and the like.
2S A particularly preferred opaque layer comprises titanium dioxide due to its highly effective reflection properties. In general, a coating composition, for example, hydroxyethylcellulose, containing sufficient titanium dioxide to provide a precent reflectance of about 85 to 90 percent, respectively, will be employed. In the most ~0368~7 preferred embodiments, the percent reflectance desired thus will be in the order of ~ about 85 percent.
Where it is desired to increase the opacifying capacity of a layer containing, for example, titanium dio-xide, beyond that ordinarily obtained, an additionalopacifying agent such as carbon black, for example, in a concentration of about one part carbon black to one hundred to five hundred part~ titanium dioxide may be provided to the layer. Preferably, however, such addi-tional opacifying capacity will be provided by constitut-ing the opacifying layer as a plurality of more or less discrete layers, the layer next adjacent the transparent support comprising a reflection layer and the succeeding layer or layer~ comprising one or more opacifying agents possessing greater opacifying capacity than that ordinarily obtained from the reflecting agent or agents employed.
Such additional opacifying agent may be any of the multiplicity of ~uch agents known in the art such as carbon black, iron oxide, titanium (III) oxide, titanium ~III) hydroxide, and the like. In preferance, the agent or agents should be selected which possess the maximum opacifying capacity per unit weight, is photographically nondeleterious and is substantially nondiffusible through-out the film unit subsequent to distribution. A particu-larly preferred agent has been found to comprise carbonblack employed in a concentration effective, taken together with the selected reflecting agent, to provide the opacity required to~prevent undesired physical fogging of the emul-sion formulations selected and employed by radiation transmitted through the spread processing composition.

103685q The fluid contents of the container preferably comprise an aqueous alkaline solution having a pH and solvent concentration at which the dye developers are soluble and diffusible and contains inorganic light-reflecting pigment in a quantity sufficient, upon distri-bution, to provide a layer exhibiting optical transmission density ~ about six to prevent exposure of photosensitive silver halide emulsion layers 15, 17 and 19 by actinic radiation incident on dimensionally ~table transparent layer 24a during processing in the presence of such radiation and to afford immediate viewing of dye image formation in image-receiving layer 21 during and ~ubse-quent to dye transfer image formation. 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 emulsion or emul-sions of film unit 10 are appropriately protected by incident radiation, at one major surface of the opaque processing composition and at the remaining major surface by opaque layer 20. If the illu~trated binder tapes are also opaque, edge leakage of actinic radiation incident on the emulsion or emulsions will also be prevented.
As examples of pigments adapted for employment in processing composition 12, mention may be made of those specifically identified above.
A particularly preferred proce~sing composition reflecting agent comprises carbon black due to its highly effective li~ht-absorption properties.
In general, the opacifying adjuvants to be employed are those which remain substantially immobile 103~8S~
within their respective compositionq during and subsequent to photographic processing and particularly those reflecting agents which comprise insoluble and nondiffusible inorganic pigment dispersions within the composition in which they are disposed.
Where desired, opacifying adjuvants constituting layer 20 accordingly may thu8 be distributed within a proce~sing composition permeable polymeric matrix such as gelatin and/or any other such polymeric matrixes as are specifically denoted throughout the specification as suitable for e~ployment as a matrix binder and may be distributed in one or more of the film unit layers which may be separated or contiguous, intermediate the image-receiving layer and next adjacent silver halide layer, provided that its distribution and concentration is effec-tive to provide the denoted post processing mas~ing function, and the opacifying agent component of the processing composition may be ultimately dispo~ed within the processing composition residuum located intermediate barrier layer 25 and transparent layer 24a.
In the performance of a diffusion transfer multi-color process employing film unit 10, the unit is exposed to radiation, actinic to photosensitive laminate 13, inci-dent on the laminate'q exposure surface 34, as illustrated by Fig. 2.
Subsequent to exposure as ililustrated by Figs.
2 and 4, film unit lO is processed by being passed through opposed suitable gapped rolls 33 in order to apply compres-sive pressure to frangible container 11 and to effect rupture of longitudinal seal 28 and distribution of processing 103~;8g7 composition 12, containing opacifying agent and having a pH
at which the cyan, magenta and yellow dye developer~ are soluble and diffusible, intermediate first spacer layer 22a and barrier layer 25 coextensive their respective surfaces.
Processing composition 12 permeates through barrier layer 25 and into emulsion layers 15, 1~ and 19 to initiate development of the latent images contained in the respective emulsions. The cyan, magenta and yellow dye developers, of layers 15, 17 and 19, are immobilized, as a function of the development of their respective as~oc-iated silver halide emulsions, preferably substantially as a result of their conversion from the reduced form to their relatively insoluble and nondiffusible oxidized form, thereby providing imagewise distributions of mobile, soluble and diffusible cyan, magenta and yellow dye developer, as a function of the point-to-point degree of their a~sociated emulsion~' exposure. At least part of the imagewise distributions of mobile cyan, magenta and yellow dye developer transfer, by diffusion, to proce~s-ing composition dyeable polymeric layer 21 to provide tosuch layer a multicolor dye transfer image vie*able through dimensionally stable transparent layer 24b.
Subsequent to substantial transfer image formation, a sufficient portion of the ions comprising aqueous compo-sition 12 transfer, by diffusion, through permeablespacer layers 22a and 22b and to permeable polymeric acid layers 23a and 23b whereby solution 12 decreases in pH, as a funGtion of neutralization, to a pH at which the cyan, magenta and yellow dye developers, in the reduced form, are substantially insoluble and nondiffusible, ~03685q to thereby provide increased stability to the multicolor dye transfer image.
Subsequent to distribution of processing solution 12, container 11, optionally, may be manually dissociated from the remainder of the film unit, as described above.
As previously stated, the multicolor dye transfer image i~ viewable through dimensionally stable transparent layer 24b both during and subsequent to transfer image formation, in the preferred embodiment detailed above.
The present invention will be further illustrated and detailed in conjunction with the following illustrative constructions which set out representative embodiments and photographic utilization of the novel photographic film units of this invention, which, however, are not limited to the details therein set forth and are intended to be illustrative only.
Film units ~imilar to that shown in the drawings may be prepared, for example, by providing, in ~ucce~sion, on a first 4 mil. transparent polyester film base, the follow-ing layers:
1. the partial butyl ester of polyethylene/
maleic anhydride copolymer at a coverage of about 2500 mgs./ft.2 to provide a polymeric acid layer;
2. a timing layer containing about a 49:1 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./ft.2; and 3. a 2:1 mixture, by weight, of polyvinyl alcohol and poly-4-vinylpyridine, at a coverage of about 300 mgs./ft.2 to provide a polymeric image-receiving layer;

1~36~S7 , ,,

4. a 25:1 mixture of titanium dioxide and a 60/30/4/6 copolymer of butyl acrylate, diacetone acryl-amide, styrene and methacrylic acid at a coverage of about 1800 mgs./ft.2;

5. gelatin at a coverage of about 50 mg8./ft.2;

6. a 1:0.8:0.1 mixture of carbon black, Rhoplex E-32*(an acrylic latex sold by Rohm and Haa~ Co., Philadelphia, Pa., U.S.A.) and polyacrylamide at a coverage of about 240 mgs./ft.2 measured a8 carbon;

7. a 1:1 mixture of ~a) a ~olid disper~ion of the cyan dye developer HO ~ H ~ \ N ~ ¦ l CIN3 ~C .~ C~ _~
HC - NH - 02S ! N

No ~ N ~ S02 - NN - CN

~ OH
HO ~

gelatin and polyvinyl hydrogen phthalate coated to provide * Irade Mbrk -26-- 103~i85~
a coverage of about 67 mgs./ft.2 dye developer, about 97 mgs./ft~2 of gelatin and about 5 mg~./ft.2 of polyvinyl hydrogen phthalate and (b) a red-sensitive gelatino silver iodobromide emulsion coated to provide a coverage of about 67 mgs./ft. silver iodobromide measured as silver and about 29 mgs./ft.2 gelatin;

8. a red-sensitive gelatino silver iodo-bromide emulsion and polyvinyl hydrogen phthalate coated at a coverage of about 62 mgs./ft.2 silver iodobromide measured as silver, about 60 mgs./ft.2 gelatin and about O.8 mgs./ft. polyvinyl hydrogen phthalate;

9. a layer of butyl acrylate/diacetone acrylamide/styrene/methacrylic acid (60/30/4/6) and poly-acrylamide coated in a ratio of about 29:1, respectively, ' a,t a coverage of about 162 mgs./ft.2;

10. a 1:1 mixture of (a) a solid dispersion of the magenta dye developer . ~
HO--CH2 cH2\ )='<
S2 ~\ / ~ = N I I CH3 HO - CH2 CH2 ~ ~ N~
O\ /0 ~

/ ~
O o OlH
~C--CH2 CH2~
~ .
OH
d and gelatin coated to provide a coverage of about 100 mgs./ft.2 of dye developer and about 87 mgs./ft.2 of _27-~0368S7 gelatin and (b) a green-sensitive gelatino silver iodobromide emulsion coated to provide a coverage of about 30 mgs./ft.2 silver iodobromide measured as silver and about 22 mgs./ft.2 gelatin;

11. a green-sensitive gelatino silver iodo-bromide emulsion and polyvinyl hydrogen phthalate coated at a coverage of about 40 mgs./ft.2 silver iodobromide measured as silver, about 87 mgs./ft.2 gelatin and about 1.3 mgs./ft.2 polyvinyl hydrogen phthalate;

12. a layer of butyl acrylate/diacetone acrylamide/styrene/methacrylic acid (60/30/4/6) and poly-acrylamide coated in a ratio of about 29:4, respectively, at a coverage of about 110 mgs./ft.2 and succindialdehyde coated at a coverage of about 10 mgs./ft. ;

13. a 1:1 mixture of (a) a solid dispersion of the yellow dye developer oC3H7 ~2 Cr--H20 / \O OH
~C-C1l2-cl~2~

OH

and gelatin ~oated to provide a coverage of about 120 mgs./ft.2 dye developer and about 48 mgs./ft.2 of gelatin;
and (b) a blue-sensitive gelatino silver iodobromide emulsion 10368g7 and polyvinyl hydrogen phthalate coa*ed to provide a coverage of about 50 mgs.jft.2 ~ilver iodobromide measured as silver, about 22 mgs./ft.2 gelatin and about 0.3 mgs./ft.2 polyvinyl hydrogen phthalate;

14. a blue-sensitive gelatino silver iodo-bromide emulsion, polyvinyl hydrogen phthalate and 4'-methyl-phenyl hydroquinone in N,N-diethyl lauramide coated at a coverage of about 100 mgs./ft.2 silver iodobromide measured as silver, about 66 mgs./ft.2 gelatin, about 0.6 mgs./ft.2 polyvinyl hydrogen phthalate and about 25 mgs./ft.2 4'-methyl-phenyl hydroquinone;

15. a layer of butyl acrylate/diacetone acrylamide/styrene/methacrylic acid (60/30/4/6) coated at a coverage of about 100 mgs./ft.2.
A second 4 mil. transparent polyester film base may then be taped to the photosen~itive element in laminate form, at their respective lateral and trailing edges, by means of a pressure-sensitive binding tape extending around, in contact with, and over the edges of the resultant laminate.
A rupturable container comprising an outer layer of lead foil and an inner liner or layer of polyvinyl chloride retaining an aqueou~ alkaline processing solution such as, for example, about 0.8 cc. of 0.5 cc. of lN
sodium hydroxide and about 0.8 cc. of water, about 100 cc.
of 10.5 grams of potassium hydroxide, about 2.3 grams of carboxymethyl cellulose, about 95.6 grams of titanium dioxide, abouf 2.9 grams of N-benzyl-a-picolinium bromide, about 1.7 grams of N-phenethyl-a-picolinium bromide, about 1.7 grams of an aqueous silica dispersion comprisin~

1036~3~7 about 30 percent SiO2, one or more antifoggants ~uch aq about 1.3 grams of benzotriazole and about 0.06 gram of 6-methyl-5-bromo-4-azabenzimidazole, about 0.67.gram of 6-methyl uracil, about 0.47 gram of bis-(~-aminoethyl)-sulfide, about 0.94 gram of 6-benzyl-amino purine, about 1.22 grams of polyethylene glycol, about 1.9 grams of 1-hydroxyethyl-ethylene diamine tetra acetic acid, about 0.22 gram of lithium nitrate, and about 0.25 gram of lithium hydroxide may then be fixedly mounted on the leading edge of each of the laminates, by pressure-sensitive tapes interconnecting the respective containers and laminates, such that, upon application of compressive pressure to the container, its contents may be distributed, upon rupture of the container's marginal seal, between the second trans-parent polyester film base and its next adjacent layer 15.
The photosensitive composite film units may beexposed through radiation incident on the second trans-parent polyester film base and processed by passage of the exposed film units through appropriate pressure-applying members, such as suitably gapped, e.g., 50 to 60 mils, opposed rolls, to effect rupture of the container and distribution of its contents. Subsequent to processing, multicolor dye transfer image formation may be viewed through the first transparent polyester layer against a titanium dioxide reflection layer.
Film units, fabricated essentially as denoted above, may be processed in the stated manner, subsequent to exposure ~hrough a conventional step wedge, to provide graphic illustration of the characteristic curves of the respective dye transfer images forming the multicolor dye positive images. Specifically, the detailed characteri~tic curves may be determined by plotting the density of the respective imàges to red, green and blue light, as a function of the log exposure of the photosensitive element, e.g., the characteristic cyan, magenta and yellow transfer image dye curves (read to red, green and blue ref}ected light) of the test film units.
By addition of an effective concentration of OH OH
~ ~Cla837~n .~0 and HOO H ~H-S02-C16H33-n ,,~
to the processing composition, for example, 6.17 and 1.37 grams, respectively, to the second processing composition component identified above, image formation in the second image-receiving layer may be immediately viewed upon distr$-bution of the processing composition by reason of the protec-tion against incident radiation afforded the photosensitive silver halide emulsion layers by the composition's optical transmission density of > about six density units and against the titanium dioxide's effective reflective background afforded by reason of the composition possessing an optical reflection density of < about one density units.
Processing composition permeable dye impermeable layer 15 of the structure detailed, in accordance with the present invention, allows passage of the fluid processing composition including processing adjuvants of a molecular size less than that of the stated yellow, magenta and cyan dye developers simultaneously preventing passage or extrac-tion of processing compositon solubilized dye developer from the photosensitive laminate into the processing compo-sition in accordance with differential dye concentration gradients between the laminate and the composition's initial distribution locus and the dye sink capacity of processing compositions generally employed in dye diffusion transfer photographic systems. By restriction of diffusion of the dye to the photosensitive laminate during processing of the film unit, there is provided the efficiencies and economic advantages resultant from decreased dye required per unit dye transfer density of the resultant transfer image in addition to optimized control of the dye employed by its associated silver halide layer, as a function of the point-to-point degree of the layer exposure to actinic radiation, with the resultant increased acuity of the resultant dye transfer image generated.

1~36857 As examples of additional polymeric composition~
specifically adapted to provide the required processing composition permeable layer of the present invention impermeable to dye developer for the effective duration of the processing of a film unit constructed as detailed immediately above, mention may be made of, for example, butyl acrylate/diacetone acrylamide/styrene/methacrylic acid (60/30/4/6) + polyacrylamide at 1 to 2 percent by weight of the tetrapolymer coated at a coverage of about 100 mgs./ft.2; butyl acrylate/diacetone acrylamide/
styrene/methacrylic acid (60/30/4/6) + polyvinyl alcohol at a 10:1 ratio coated at a coverage of about 100 mgs./ft.2;
2-sulfoethyl methacrylat-/ethylacrylate/methacrylic acid;
Rhoplex E-32, HA-12 or HA-16 (trade designation of Rohm and Haas Co., Philadelphia, Pennffylvania, U.S.A., for certain acrylic latices) + less than 1 percent polyacryl-amide; and the like.
The pH a~d solvent concentration of the alkaline processing solution initially employed will preferably possess a pH above the pKa of the optical filter agents where the latter are employed, that is, the pH at which about fifty percent of the agents are present as the lesser absorbing species and about fifty percent are present as the greater absorbing species, preferably a pKa of > about 11 and most preferably > about 12 and a pH at which the dye developers 1~368g7 employed are soluble and diffusible. Although it has been found that the specific pH to be employed may be readily determined empirically for any dye developer and optical filter agent, or group of dye developers and filter agents, most particularly desirable dye developers are soluble at pH's above 9 and relatively insoluble at pH's below 9, in reducedform, and the system can be readily baIanced accordingly for such dye developers. In addition, although as previously noted, the processing composition, in the preferred embodiment, will include the stated film-forming viscosity-increasing agent, or agents, to facilitate spread-ing of the composition and to provite maintenance of the spread composition as a structurally stable layer of the laminate, subsequent to distribution, it is not necessary that such agent be employed as a component of the composition.
In the latter instance, however, it will be preferred that the concentration of solvent, that is, water, etc., compris-ing the composition be the minimum amount necessary to conduct the desired transfer process, in order not to adverse-ly effect the structural integrity of the laminate and that the layers forming the laminate can readily accommodate and dissipate the solvent throughout during processing and drying without effecting undesirable dimensional changes in the layers forming the laminate.
As disclosed in the previously cited patents, the liquid processing composition referred to for effecting multicolor diffusion transfer processes comprises at least an aqueous solution of an alkaIine material, for example, diethyla~ine, sodium hydroxide or sodium carbonate and the like, and preferably possessing a pH in excess of 12, 1C~368g7 and most preferably includes a vi~cosity-~ncrea~ing 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 weightpolymers such as polymeric, water-soluble ethers which are insert to an alkaline solution such a~, for example, a hydroxyethyl cellulose or sodium carboxymethyl cellulose.
Additionally, film-forming materials or thickening agents whose ability to increase viscosity i8 sub~tantially unaf-fected if left in solution for a long period of time are also disclosed to be capable of utilization. A~ stated, the film-forming material i8 preferably oontained in the processing compo~ition in such ~uitable quantities a8 to lS impart to the composition a visco~ity in excess of 100 cps.
at a temperature of approximately 24 C. and preferably in the order of 100,000 Cp8. to 200,000 cps. at that tempera-ture.
Neutralizlng means, for example, a polymeric acid layer of the type discus~ed above will be incorporated, as ~tated, in the film unit of the present invention, to provide reduction of the alkalinity of the processing solution from - a p~ at which the dyes are soluble a~ a function of film unit photoexposure and above the pKa of selected optical filter agents where desired to a pH below the pKa of the filter agent selected and at which the dyes are substantially nondiffusible, in order to advantageously further stabilize and optimize reflectivity of the respective dye transfer images. In ~uch instance, the neutralizing layer may comprise particulate acid reacting reagent di~posed within the film 1~368S7 unit or a polymeric acid layer, for example, a polymeric acid layer approximately 0.3 to 1.5 mils in thickness, positioned intermediate the first ant/or second transparent support and the next adjacent functional layer and the film unit may also contain a polymeric spacer or barrier layer, for example, approximately 0.1 to 0.7 mil in thickness, next adjacent the respective polymeric acid layer or layers, opposite the respective support layer, as previously described.
Specifically, the film units may employ the pre-sence of a polymeric acid layer such as, for example, of the type set forth in United States Patent No. 3,362,819 which, most preferably, includes the presence of an inert timing or spacer layer intermediate the polymeric acid layer carried on a support and the image-receiving layer.
As previously noted, the pH of the processing compo-sition preferably is of the order of about least 12 to 14 and the pKa of the selected optical filter agents will accortingly preferably be in the order of 12 or greater.
The polymer layer is disclosed to contain at least suffi-cient acid groups to effect a reduction in the pH of the image layer from a pH of about 12 to 14 to a pH of at least 11 or lower at the end of the imbibition period, and prefer-ably to a pH of about 5 to 8 within a short time after imbibition, thus requiring, of course, that the action of the polymeric acid be accurately so controlled as not to interfere with either development of the negative or image transfer of unoxidized dye developers. For this reason, the pH of the image layer must be kept at a functional transfer~ level, for example, 12 to 14 until the dye image has been formed after which the pH is reduced very rapidly 10368g7 to a pH below that at which dye transfer may be accomplished, for example, at least about 11 and preferably about pH 9 to 10. Unoxidized dye developers containing hytroquinonyl developing radicals diffuse from the negative to the posi-tive as the sodium or other alkali salt. The diffusion rate of such dye image-forming components thus is at least partly a function of the alkali concentration, and it is necessary that the pH of the image layer remain on the order of, for example, 12 to 14 until transfer of the necessary quantity of tye has been accomplished. The subsequent pH reduction, in addition to its tesirable effect upon image light stability, serves a highly valu-able photographic function by substantially terminating further dye transfer.
In order to prevent premature pH reduction during transfer processing, as evidenced, for example, by an undesired reduction in positive image density, the acid groups are disclosed to be so distributed in the polymer layer that the rate of their availability to the alkali is controllable, e.g., as a function of the rate of swell-ing of the polymer layer which rate in turn has a direct relationship to the diffusion rate of the alkali ions.
The desired availability of the acid groups in the polymer layer may be effected by mixing acid polymer with a polymer free of acid groups, or lower in concentration o~ acid groups, and compatible therewith, as a modulated system~ or by using only an acid polymer but selecting one having a predetermined acid group availability rate.
~ne layer containing the polymeric acid may also contain a water insoluble polymer, preferably a cellulose 10~57 ester, which acts to control or modulate the rate at which the alkali salt of the polymer acid is formed. As examples of cellulose esters contemplated for use, mention is made of cellulose acetate, cellulose acetate butyrate, etc.
The particular polymers and combinations of polymers employed in any given embodiment are, of course, selected so as to have atequate wet and dry strength and when necessary or desirable, suitable subcoats are employed to help the various polymeric layers adhere to each other during storage and use.
The inert spacer layer of the last-mentioned patent, for example, an inert spacer layer comprising polyvinyl alcohol or gelatin, acts to "time" control the pH reduction by the polymeric acid layer. This timing is disclosed to be a function of the rate at which the alkali diffuses through the inert spacer layer. It is there stated to have been found that the pH does not drop until the alkali has passed through the spacer layer, i.e., the pH is not reduced to any significant extent by the mere diffusion into the interlayer, but the pH drops quite rapidly once the alkali diffuses through the spacer layer.
As disclosed in aforementioned United States Patent No. 3,362,819, the presence of an inert spacer layer was found to be effective in evening out the various reaction rates over a wide range of temperatures, for example, by preventing premature pH reduction when imbibition is effected at temp-eratures above room temperature, for example, at 95 to 100F.
By providing an inert spacer layer, that application discloses that the rate at which alkali is available for capture in the polymeric acid layer becomes a function of the alkali diffu-sion rates.

~~

103~57 However, as disclosed in United States Patent No.
3,455,686, preferably the aforementioned rate at which the cations of the alkaline processing composition, i.e., alkali ions, are available for capture in the polymeric acit layer should be decreased with increasing transfer processing temp-eratures in orter to provide diffusion transfer color processes relatively independent of positive transfer image variations over an extended range of ambient temperatures.
Specifically, it is there stated to have been found that the diffusion rate of alkali through a permeable inert polymeric spacer layer increases with increased process-ing temperature to the extent, for example, that at relatively high transfer processing temperatures, that is, transfer processing temperatures above approximately 80F., a pre-mature decrease in the pH of the transfer processing compo-sition occurs due, at least in part, to the rapid diffusion of alkali from the dye transfer environment and its subse-quent neutralization upon contact with the polymeric acid layer. This was stated to be especially true of alkali traversing an inert spacer layer possessing permeability to alkali optimized to be effective with the temperature range of optimum transfer processing. Conversely, at temperatures below the optimum transfer processing range, for example, te~peraturesbelow approximately 40F., the last-mentioned inert spacer layer was disclosed to provide an effective diffusion barrier timewise preventing effective traverse of the inert spacer layer by alkali having tempera-ture depressed diffusion rates and to result in maintenance of the transfer processing environment's high pH for such an extended time interval as to facilitate formation of 1036B5~7 transfer image stain and its resultant degradation of the positive transfer images' color definition.
It is further stated in the last-mentioned United States Patent No. 3,455,686 to have been found, however, that if the inert spacer layer of the print-receiving ele-ment is replaced by a spacer layer which comprises a permeable polymeric layer exhibiting permeability inversely dependent on temperature, that is, a ~olymeric film-forming material which exhibits decreasing permeability to solubilized alkali derived cations such as alkali metal and quaternary ammonium ions under conditions of increasing temperature, that the posi-tive transfer image defects resultant from the aforementioned overextended pH maintenance and/or premature pH reduction are obviated.
As examples of materials, for use as the image-receiving layer, mention may be made of solution dyeable polymers such as nylon as, for example, N-methoxymethyl polyhexamethylene adipamide; partially hytrolyzet polyvinyl acetate; polyvinyl alcohol with or without plasticizers;
cellulose acetate with filler as, for example, one-half cellu}ose acetate and one-half oleic acid; gelatin; ant other materials of a similar nature. Preferred materials comprise polyvinyl alcohol or gelatin containing a tye mordant such as poly-4-vinylpyridine, as disclosed in United States Patent No. 3,148,06I, issued September 8, 1964.
It will be noted that the liquid processing compo-sition employed may contain an auxiliary or accelerating developing agent, such as p-methylaminophenol, 2,4-diamino-phenol, ~-benzylaminophenyl, hydroquinone, toluhydroquinone, phenylhydroquinone, 4' methylphenylhydroquinone, etc. It l0~
is also contemplated to employ a plurality of auxiliary or accelerating developing agents, such as a 3- W razolidone developeing agent and a benzenoid developing agent, as disclosed in United States Patent No. 3,039,869, issued June 19, 1962. As exa~ples of suitable combinations of aux-iliary developing agents, mention may be made of l-phenyl-3-pyrazolidone in combination with p-benzylaminophenol and l-phenyl-3-pyrazolidone in combination with 2,5-bis-ethyl-enimino-hydroquinone. Such auxiliary developing agents may be employet in the liquid processing composition or they may be initially incorporated, at least in part, in any one or more of the silver halide emulsion strata, the strata containing the dye developers, the interlayers, the image-receiving layer, or in any other auxiliary layer, or layers, of the film unit.
It may be noted that a* least a portion of the dye developer oxidized during development may be oxidized and immobilized as a result of a reaction, e.g,, an energy-transfer reaction, with the oxidation product of an oxi-dized auxiliary developing agent, the latter developing agent being oxidized by the development of exposed silver halide. Such a reaction of oxidized developing agent with unoxidized dye developer would regenerate the auxiliary developing agent for further reaction with the exposed silver halide.
In addition, development may be effected in the presence of an onium compound, particularly a quaternary ammonium compound, in accordance with the processes disclosed in Unite~ States Patent No. 3,173,786, issued March 16, 1965.
It will be apparent that the relative proportions of the agents of the diffusion transfer processing composition 103~
may be altered to suit the requirements of the operator.
Thus, it is within the scope of this invention to modify the herein described developing compositions by the substi-tution of preservatives, alkalies, etc., other than those specifically mentioned, providet that the pH of the compo-sition is initially at the first pH required. ~hen desir-sble, it is also contemplated to include, in the developing composition, components such as restrainers, accelerators, etc. Similarly, the concentration of various components aay be varied over a wide range and when desirable adapt-able components may be disposed in the photosensitive element, prior to exposure, in a separate permeable layer of the photosensitive element and/or in the photosensitive e ulsion.
The dimensionally stable layers or sheets referred to may comprise any of various types of conventional trans-parent rigid or flexible materials, for example, papers and polymeric films of both synthetic types and those derived from naturally occurring products. Suitable materials include alkaline solution imper eable materials such as polymethacrylic acid methyl and ethyl esters; vinyl chloride polymers, polyvinyl acetal; polyamides such as nylon;
polyesters such as polymeric films derived from ethylene glycol and terephthalic acid; and cellulose derivatives such as cellulose acetate, triacetate, nitrate, propionate, butyrate, acetate-propionate or acetate-butyrate. It will be recognized that one or more of the designated layers may not be required where th~e remaining layers of the laminate are such as to provide the functions of these layers in the absence of same, for example, where the remaining layers of the laminate ~0368~7 .
provide the requisite dimensional stabllity and radiation filtering properttes.
In all examples of this ~pecification, percentage~
o_ components are given by weight unle~s otherwise indicated.
Although the invention has been discuYsed in detail throughout employing dye developers, the preferred image-providing materials, it will be readily recognized that other, le~ pre~erred, diffusion transfer process dye image-providing material~ may be substituted in replacement of the preferred dye developers in the practice of the inven-tion. Por example, there may be employed dye image-fonm;ng materials such as those disclosed tn V. S. Patents Nos.
2,647,049; 2,661,293; 2,6g8,244; 2,698,798; 2,802,735;
3,148,062; 3,227,550; 3,227,55i; 3,227,552; 3,227,554;
3,243,294; 3,330,655; 3,347,671; 3,352,672; 3,364,022;
3,443,939; 3,443,940; 3,443,941; 3,443,943; etc., wherein color diffusion transfer processes are described which employ color coupling techniques comprising, at lea~t in part, rea¢ting one or more dye ~mage-providing color developing agents and one or more dye image-providing color formers or couplers to provide a dye transfer image to a superposed image-receiving layer and those disclosed in U. S. Patent Nos. 2,774,668 and 3,087,817, wherein color diffusion transfer processes are described which employ the imagewise differential transfer of complete dyes by the mechanisms therein described to provide a transfer dye image to a contiguous image-receiving layer, and thus including the employment of dye image-providing materials in whole or in part initially insoluble or nondiffusible as disposed in the film unit which diffuse during processing as a direct or indirect function of exposure.

1036Bg7 Where desired, the film unit may also contain ultraviolet absorbing materials to protect the mordanted dye transfer image from fading due to ultraviolet light such as those selected from the general class of benzotriazoles and benzophenones as, for example, the substituted 2-phenyl-benzotriazole agents disclosed in United States Patents Nos.
3~004~896; 3~189~615; etc.; the 2-hydroxybenzophenones such as 2-hydroxy-4-methoxybenzophenone; 2,2~-dihydroxy-4-methoxybenzo-phenone; 2-hydroxy-4-octyloxybenzophenone; etc., both water and organic solvent soluble agents being comtemplated, and/or bri-ghtening agents such as those selected from the general class of triazinestilbenes, coumarins, anthrocenes, terphenyls, tet-raphenylbutadienes, quinoxalines, conventional for use as fluor-escent agents and as optical brightening agents. Suitable tri-asinestilbene optical brightening agents are disclosed in Unites States Patent No. 2,933,390; coumarines are disclosed in British Patent No. 786~234; and various agents are disclosed in United States Patents Nos. 2,171,427; 2,473,475; 2,595,030;
3,660,578; and British Patents Nos. 595,065; 623,849;
624,051; 624,052; 678,291; 681,642; 705,406; etc.
Commercially available brightening agents are distributed under the trade designation Tinopal (SP, WR, SFG, BV277, 2B, GS, NG) Leucophor B, Calcoflour White MR, Blaneofor SC, Hitamine (BSP, N, SOL., 6T6), and the like, and commeraially available ultraviolet absorbing agents are distributed under the trade designation Tinuvin and the like.
In general, ultraviolet absorbing and optical brightening agents may be employed in concentrations varying over an extended range. Suitable concentrations include ln36ss7 these within the range of about 0.2 to 10 mgs./ft. of receptor layer surface area and, preferably, between about 1 to 5 mgs./ft. .
The agents may be incorporated in any one or more of the layers of the f~m unit preferably intermediate an opaque layer forming the background against which an image is viewed and the viewing surface in any suitable manner as, for example, a constituent component of the casting and/or coating solution or formulation employed to provide such layer or layers employing an organic solvent or water carrier or as a latex dispersion.
In the circumstances wherein the receptor layer or layers possess the dimensional stability to provide a self-sustaining layer conformation, the layer may optionally be coated on or carried by an appropriate dimensionally stable support layer of the various types and classes specifically designated hereinbefore or not at the elec-tion of the operator.
Ordinarily, when the image receptor stratum comprises a la~er carried on a separate dimensionally stable support layer, the receptor stratum will comprise in the order of about 0.1 to 0.4 mil in thickness whereas such stratum employed as a self-sustaining layer will comprise in the order of about 3 to 6 mils in thickness.
In addition to conventional techniques for the direct dispersion of a particulate solid material in a polymeric, or colloidal, matrix such as ball-milling and the like techniques, the preparation of the dye developer and color coupler dispersions may also be obtained by dissolving the dye and/or coupler in an appropriate solvent, or mixture of solvents, and the resultant solution distributed in the polymeric binder, with optional subsequent removal of the solvent, or solvents, employed, as, for example, by vapor-ization where the selected solvent, or solvents, possesses a - sufficiently low boiling point or washing where the selected solvent, or solvents, possesses a sufficiently high differ_ ential solubility in the wash medium, for example, water, when measured against the solubility of the remaining composition components, and/or obtained by dissolving both the polymeric binder and dye in a common solvent.
For further detailed treatment of solvent distri-bution systems of the types referred to above, and for an extensive compilation of the conventional solvents tradi-tionally employed in the art to effect distribution of photographic color-providing materials in polymeric binders, specifically for the formation of component layers of photo-graphic film units, reference ~ay be made to United States Patents Nos. 2,269,158; 2,322,027; 2,304,939; 2,304,940; 2,801,171;
and the like.
For the production of the photosensitive gelatino silver halide emulsions employed to provide the film unit, the silver halide crystals may be prepared by reacting a water-soluble silver salt, such as silver nitra~e, with at least one water-soluble halide, such as ammonium, potassium or sodium bromide, preferably together with a corresponding iodide, in an aqueous solution of a peptizing agent such as a colloidal gelatin solution; digesting the dispersion at an elevated temperature, to provide increased crystal growth;
washing the resultant water-soluble salts by chilling the dispersion, noodling the set dispersion, and washing the noodles with cold water, or alternatively, employing any of the various flocc systems, or procedures, adapted to effect removal of un-desired components, for example, the procedures described in United States Patents Nos. 2,614,928; 2,614,929; 2,728,662;
and the like; after-ripening the dispersion at an ele~ated temperature in combination with the addition of gelatin and various adjuncts, for example, chemical sensitizing agents of United States Patents Nos. 1~574,944; 1~623,499; 2,410~689;
2~597,856; 2,597,915; 2,487,850; 2,518,698; 2,521,926; and the like; all according to the traditional procedures of the art, as described in Neblette, C.B., Photo~raph~ Its Materials and Processes, 6th Ed., 1962.
Optical sensitization of the emNlsion's sil~er halide crystals may be accomplished by contact of the emulsion composition with an effecti~e concentration of the selected optical sensitizing dyes dissolved in an appropriate dispersing solvent such as meth-anol, ethanol, acetone, water, and the like; all according to the traditional procedures of the art, as described in Hammer, F.M., me Cyanine es and Related Compounds.
Additional optional additives, such as coating aids, hardeners, viscosity-increasing agents, stabilizers, preservatives, and the like, for example, those set forth hereinafter, also may be incorporated in the emulsion formula-tion, according to the conventional procedures known in the photographic emulsion manufacturing art.
~The photoresponsive material of the photographic emulsion will, as previously described, preferably comprise a crystal of silver, for example, one or more of the silver - ' 10~
halides such as silver chloride, silver iodide, silver bromide, or mixed silver halides such as sil~er chlorobromide, silver chloroi-odobromide or silver iodobromide, of varying halide ratios and varying silver concentrations.
As the binder for the respective emulsion strata, the aforementioned gelatin may be, in whole or in part, replaced with some other colloidal material such as albumin; casein; or zein; or resins such as a cellulose derivative, as described in United States Pàtents Nos. 2,322~085 and 2,327,808, polyacrylamides, as described in United States Patent No. 2,541,474; and vinyl polymers such as described in an extensive nultiplicity of readily available United States and foreign patents.
Although the preceding description of the invention has been couched in terms of the preferred photosensitive component construction wherein at least two selectively sensitized photosen-sitive strata are in contiguous coplanar relationship and, speci-fically~ in terms of the preferred tripack type structure comprising a red-sensitive silver halide emulsion stratum, a green-sensitive silver halide emulsion stratum and a blue-sensitive silver halide emulsion stratum having associated therewith, respectively, a cyan dye developer, a magenta dye developer and a yellow dye developer, the photosensitive component of the film unit may comprise at least two sets of selectively sensitized minute photosensitive elements arranged in the form of a photosensitive screen where-in each of the minute photosensitive elements has associated therewith, for example, an appropriate dye image-forming material in or behind its respective silver halide emulsion portions.
In general , a suitable photosensitive screen may comprise minute red-sensitized emuision elements, minute green sensitized emulsion _ 48 -~036BS~
elements and minute blue-sensitized emulsion elements arranged in side-by-side relationship in a screen pattern and having associated therewith, respectively, for example, a cyan, a magenta and a yellow dye developer.
me present invention also includes the employment of a black dye image-providing material and the use of a mixture of, for example, dye developers adapted to provide a black-and-white transfer image, for example, the employ-ment of dye developers of the three substractive co~ors in an appropriate mixture in which the quantities of the dye developers are proportioned such that the colors combine to provide black.
Where in the specification, the expression "posi-tive image" has been used, this expression should not be interpreted in a restrictive sense since it is used primarily for purposes of illustration, in that it defines the image produced on the image-carrying layers as being reversed, in the positive-negative sense, with respect to the image in the photosensitive emulsion layers. As an example of an alternative meaning for "positive image", assume that the photosensitive element is exposed to actinic light through a negative transparency. In this case, the latent image in the photosensitive emulsion layers will be a positive and the dye image produced on the image-carrying layers will be negative. The expression "positive image" is intended to cover such an image produced on the image-carTying layer.
In addition to the described essential layers, it will be recognized that the film unit may also contain one or more subcoats or layers, which, in turn, may contain one ~036~g7 or more additives such as plasticizers, intermediate essential layers for the purpose, for example, of improving adhesion, and that any one or more of the described layers may comprise a composite of two or more strata of the same, or different, components and which may be contiguous, or separated from, each other, for example, two or more neutralizing layers or the like.
Where desired sheet 24a, illustrated in the figures as transparent and superposed coextensive the exposure surface of the photosensitive laminate in the preferred embodiment, may be adapted to be superposed on the laminate subsequent to photoexposure of the film unit as, for example, by fixedly positioning a leading edge of the sheet extending transverse a leading edge of the photosensitive laminate and adapted to be superposed, subsequent to photoexposure, on and coexten-sive the exposure surface of the laminate, at least during proces~ing, to facilitate distribution of processing compo-sition upon, for example, rupture of the container and uni-directional discharge of its processing composition contents contiguous the exposure surface of the laminate. In such embodiment the displaceable sheet may be transparent or opaque and the processing composition may or may not retain opacify-ing agent, at the election of the operator. Subsequent to distribution of the processing composition, the sheet may be manually dissociated from the remainder of the film unit individually and/or in combination with the processing composition employed and/or the expended processing compo-sition rupturable container.
In accordance with the present invention, the preferred form of the film assemblage for the production _50-:

103685'7 of a dye re~lection print comprises a photosensltive film unit constructed as described above and specifically adapted to be processed in the presence of ambient radiation and the dye reflection print image to be viewed during and subsequent to processing without separation of film unit component~ and includes leader means for coupling film units and selectively withdrawing the units sequentially from a fllm pack or magazine and opaci~ying agent, preferably dlsposed in whole or in part in the processing composition, taken together with the opaque layer, adapted to prevent exposure of the first sheet element's photoresponsive material by radiation actinic thereto incident on the film unit in the processing mode.
A preferred-form of film pack or magazine embody-ing the designated film units comprises a plurality of the film assemblies, each adnpted to be individually expo~ed in a camera, enclosed in an initialiy light-proof container which allows the film units to be se~uentially exposed. The container includes a forward wall having a light-transmltting section, e.g., an exposure aperture, therein and an opening in one wall through which film assemblies can be individually withdrawn. The photosensitive film units are positioned together in stacked relationship within the container under-lying the exposure aperture with the exposure surface of each film unit uppermost and the rupturable container positioned adjacent the opening through which the film units are with-drawn so that following the exposure of each film unit, the unit is moved, by drawing on the leader of the film unit, and withdrawn from the container through the opening. The film pack is initially provided with a cover element or sheet mounted within the container and extending across the exposure aperture for closing the aperture aga~nst the admission of light. The cover element also includes a leader extending from the container through the opening and being removable therethrough.
~ he film pack is employed by being positioned in a camera, including a pair of juxtaposed pressure-applying members, with the opening located adjacent the pressure-applying members and the exposure aperture disposed approxi-mately in the exposure plane of the camera. A leader forthe cover element extends from the pack and from the camera where the last-mentioned leader may be grasped for withdrawing the cover element from the pack through the pressure-applying members and camera to allow the film units of the pack to be selectively exposed. After each successive film unit iq exposed, that film unit is then individually withdrawn from the container and camera between the pressure-applylng members by withdrawlng the leader of the first film unit and of successive film unlts from the container and camera.
Reference is now made to Figures 1, 8 and 9 of the drawings wherein there are illustrated film units and an assemblage of film units in the form of a film pack.
Each film unit 10 includes a leader sheet 31 having a leading end sec~ion designated 38 and a trailing end section 40 at which the leader sheet 31 is coupled with the film unit near the leading end thereof. Leader sheet 31 including leading and trailing end qections 38 and 40 is approximately equal in width to ~he film unit 10 and leading end section 38 of each leader sheet 31 i5 secured to the trailing end of the ~0368g7 next preceding film unit or, in the case of the first film unit, to the cover sheet, preferably near the trailing end section of the preced$ng element (cover sheet or film unit).
The length of leader sheet 31 between its leading edge attachment to one film unit and the trailing edge to the next succeeding film unit is sub~tantially equal to the length of the film units between their }eading and trailing edges; ana the connected film units and leader~ are arranged in zig-zag folted relation.
A film pack or a~semblage of f~lm unit~ lO embody-ing the invention is shown in Figs. 8 and 9 of the drawings.
This film pack, designated 44, compri~es all of the component~
and structure incl~ding pressure-applying means required to produce a plurality of diffusion transfer proces~ color prints. Film pack 44 comprises a generally parallelepiped-shaped container or box 46 for holding and enclosing a plurality of film unit~ 10 arranged in stacked relation.
Container 46 i5 ~hown a~ comprising a forward wall 48, side wall~ 50, a trailing end wall 52, a leading end wall 54, and a rear wall 56 and is preferably formed of plastic material that is at least semi-rigid and adapted to conven-tional molding techniques. Forward wall 48 is provided with a generally rectangular exposure aperture 58 for trans-mitting light for exposing the forwardmost of the film units carried in stacked relation within the container. Leading end wall 54 is provided with a generally rectangular with-drawal slot or exit opening 60 the forward edge of which is defined by forward wall 48 and through which film units lO carried b~ the container are adapted to be withdrawn one at a time following exposure. In order to help in~ure 103~'7 that only one film unit at a time passes through opening 60, restrainlng means in the form of one or more projections or extensions 62 of end wall 54 may be provided. Projections 62, which as illustrated are integral parts of end wall 54, project forwardly part way acro~s opening 60 to positions whereat they suffuciently obstruct the opening to the extent that they must be deformed in order to permit the passage of the forwardmost film unit in the stack, that i8~ the film unit positioned for exposure across aperture 58 against forward wall 48. Projections 62 comprise a resilient cons-truction ~uch that as the leading film unit i8 withdrawn through opening 60, the leading edge of the film unit will engage and deflect projections 62 outward sufficiently to penmit the forward film unit only to move through slot 60, lS while preventing the next succeeding film unit from moving through the slot.
The film pack of the invention is initially pro-v~ded with a dark slide or cover sheet 64 formed of an actinic light-impermeable ~heet material for preventing 20 admission of light through exposure aperture 58 prior to loading of the film pack into a camera or attachment of the film pack to the rear of the camera. Cover sheet 64 includes a section at least coextensive in area with forward wall 48 for preventing the admission of light and a leading end section 66 which may be tapered, as shown, extending from the film pack and providing a leader which may be grasped for manually withdrawing the cover sheet from the film pack to permit exposure of film units arranged in ! ~tacked rela~-ion underlying the exposure opening and cover sheet. A lip 68 is provided on forward wall 48 surrounding ~54-lV36~g~
opening 58 for cooperating with the camera to properly locate the film pack and exposure opening therein with respect to the exposure systems of the camera and in in~tance~ where the ilm pack is coupled to the rear of the camera rat~er than being completely enclosed therein, llp 68 also cooperates to form a light-tight seal between the interior of the camera and the interior of the film pack container.
As previously noted, the film units 10 are arranged in stacked relation between the forward and rear walls of the fi~m pack with sheets 24a facing forwardly and the exposure areas of the film units aligned with exposure opening 58. Means are provided for resiliently biasing the fil~ units 10 and cover sheet 64 forwardly against the rear surface of forward wall 48 to light-seal the exposure aperture when the cover sheet is in place and following cover sheet removal, iocate the forwardmost film unit in proper position for exposure in the image plane of the camera, i.e., against the rear surface of forward wall 48. ~hese means include a spring and pressure plate assembly designated 70, preferably formed of resilient sheet metal and including a generally rectangular frame 72 for engaging and supporting the rearwardmost film unit ~ and a transverse portion 74 from which extend rearwardly biased spring sections 76 engaged with the rear wall 56 of the film pack for biasing frame 72 and the film units supported thereby, forwardly toward forward wall 48.
As previously noted, each film unit 10 includes a leader 31 ~attached at its trailing end 40 to the forward surface of the film unit near the leading end thereof.

The film units and leaders are arranged in the f~lm pack containex with the trailing end of each leader 31 folded back upon itself 80 that the leader extend~ toward the trailing end of the film unit and pack container between the forward surface of the film unit of which it is a component and the rear surface of the cover sheet 64 (in the case of the forwardmo~t film unit) or the rear surface of the preceding film unit next ad~acent forward wall 48 and exposure aperture 58. The leading end 38 of each leader is folded forwardly upon itself and attached to the rear surface Of the component, i.e., cover sheet 64 or film unit 10, located next adjacent the forward wall and is secured to said component near the trailing end thereof. Thus the cover sheet 64 and succession of film units 10 are joined by leaders 31, each of which extends from the trailing end of the component to the leading end of the next component (film unit) to be withdrawn from the pack. The leaders 31 are folded in zig-zag fashion to provide a stack comprising cover ~heet 64, a leader 31, a fllm unit lO, another leader 31, and so forth. Each leader 31 may be weakened by perforations, precutting, or the like so that the portion of a leader attached to a film unit within the pack and extendi~g from the pack to provide a leader for withdrawing the last-mentioned film unit may be severed from the portion of the leader attached to the precedlng component, i.e., cover sheet 64 or film unit 10 .
In accordance with the invention, film pack 44 includes means for compressively engaging each film unit as it is wit:ldrawn therefrom following exposure, to rupture container 11 causing the discharge of its liquid contents 103~85~7 intermediate layers 21a and 15 and spread the liquid content-of the container as a thin layer between the aforementioned layers. As shown in Figs. 8 and 9, these pressure-applying means take the form of an integral pressure-applying unit or device 70 coupled to box 46 at the leading end thereof.
Pressure-applying device ? is preferably formed of a sheet material such as metal which i~ both structurally strong and rlgid while h~ving flexibility sufficient to accommodate the varying thickne~s of a film unit as the latter i8 withdrawn from the film pack. Device 70 is shown ~8 hav$ng a generally parallelepiped shape including a forward wall 72, rear wall 74 and side walls 97 adapted to encompass the ieading end portion of the forward, rear and side walls of container 46, to provide additional strength and rigidity and to cooperate in retaining pressure-applying device 70 on box 46 as a component of film pack 44. Forward wall 72 is provided with a rearwardly extending dependent lip 96 and rear wall 74 is provided with a forwardly ~xtending dependent lip 78. The spreading device includes a le~ding end wall including a forward section 80 and a rear section 82 separated from one another by a withdrawal opening or passage. Forward section 80 and rear 6ection 82 lnclude edge portions rolled upon themselves to form cylinders or pressure-applying members designated 90 and 92, respectively, having substantial resistance to flexure or bending and adapted to function as a pair of pressure-applying members.
~ ips 96 and 78 are engaged with ridges 86 and 88 formed on the leading end portions of forward wall 48 and rear wall 56,~respectively, of the film pack container 46.
Ridges 86 and 88 are inclined or tapered toward the leading 10368g7 end of the film unit to facilitate coupling of the pres~ure-applying device 7Q to the film pack container simply by pressing the pressure-applying device onto the end of the container slightly deforming the forward and rear walls of the container and/or pressure-applying device as re~uired to permit lip8 96 and 78 to pass over the ridges 86 and 88 into the position shown in Fig. 9 in which the rear portion of forward wall 82 is disposed against end wall 54 of the film pac~ container.
A~ previously noted, and as will be apparent from the drawings, the minimum or compressed thickness of the film unit will vary throughout the length of the fi}m unit so that the depth of the gap or passage 84 between pressure-applying members 90 and 92 should be variable so that the pressure-applying members apply compressive pressure regard-less of the variatlon in the film unit thickness. Io facili-tate relative movements of the cylindrical pressure-applying members which are preferably located with their axis parallel and coplanar, rear portion 82 is ~ormed with slits 94 at the ends of cylindrical pressure-applying members 92 to facilitate movement of member 92 relative to pres~sure-applying member 90 toward and away from the latter.
While a zig-zag folded arrangement of interconnected leaders and film units i8 illustrated, it should be understood that means other than those shown in the drawings may be pro-vided for assi~ting in the manual withdrawal of the film units, one at a time, from the film pack between the pressure-applying members. Such means are disclosed, for example, in U. S. Pate~ts Nos. 2,903,951; 2,909,977; and 2,946,270.
Other qystems in which a leader of one film unit i8 withdrawn 103~i857 from the pack to a position at which it can be gripped by and in response to withdrawal of the previou~ film unit or the cover sheet are al80 well known in the art and can be employed in place of the leader sy~tem shown.
It will be seen from the foregoing that the inven-tion provides a simple and inexpensive film pack structure including all of the components required to produce a plurality of color prints; and that ~uch prints are produced simply and ea~ily ~y manually withdrawing exposed film units one at a time from the pack between a pair of pressure-applying members wh~ch are an integral part of the pack. m e only other ~external) structure reguired in order to produce color prints i8 an exposure system including, for example, a lens, ~hutter, view finder, etc. in con~unction with which the pack is adapted to be employed. Each film unit comprises an lntegral unit which ~mains intact prior to, during and subsequent to exposure and processing so that the only manip-ulative step is film unit withdrawal which is effective to discharge the proces~ing li~uid contents of a container within the film unit and distribute the processing liquid therewithin so as to effect dye transfer image formation while the film unit i8 outside of the pack, and of the camera if the pack is enclosed therein.
Withdrawal of each film unit 10 in effect succeeds in projecting leader 31 secured to the next succeeding film unit through passage 71 for the distance neces3a~y to selec-tively withdraw that film unit for processing subsequent to photoexposure in the manner stated above. Where desired the leader may be selectively detached from the preceding and succeeding film unit subsequent to the selected film units' withdrawal from the camera.

_59_ ~036W7 It will be recognized that although in the preferred embodiment of the present invention the leading end ~ection 38 of the leader sheet 31 is secured to either major surface of the preceding elements trailing end section provided that by po~ition or composition when ~ecured to the exposure ~urface it does not interfere with exposure of the unit.
Leading end section 38 of leader sheet 31 may be secured to the preceding element, i.e., film unit or dark slide, on its surface opposite the exposure aperture forward that element' 8 trailing end section provided that the length of the leader is sufficient to extend through the withdrawal orifice a sufficient distance to be grasped, possesses the reguisite 81ip capacity, e.g., by composition or coating, to allow its withdrawal from the cas~ette including between the opposed pressure-applying members and is readily dis-~ociated from the preceding element external tbe camera and w~thin grasping capacity of the operator.
The da~rk slide and leader sheet material~ employed may comprl~e any one or more of the conventional paper and/
or polymer~c materials, for example, those previously identi-fied, sufficiently flexible to perform the function denoted with respect to the leader material, be opaque, translucent or transparent, and may optionally be either separated from the film unit subsequent to processing, for example, with or 2S without separation of the frangible container, or alternatively adhered to either film unit surface, and where transparent, to the viewing surface, of the film unit, preferably coexten-sive therewith for aesthetic purposes by means of convention-! al selectiveJly adhering adhesives available from a multipli-city of commercial sources which may be carried by a proposed ~036857 contact surface. In those instances wherein the leader is maintained with the processed film unit, the decorative aspects of the leader ~heet, i.e., color, texture and design will be selected to provide the desired visual appearance.
S Since certain changes may be made in the above produce without departing from the scope of the invention herein involved, it is intended that all matter contained in the above description or shown in the accompanying drawings shall be interpreted as illustrative and not in a limiting sen~e.

Claims (27)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A composite photographic diffusion transfer process film unit which comprises, in combination, a first dimensionally stable transparent layer; a first dyeable layer adapted to receive diffusion transfer process dye image-forming material diffusing thereto; an opaque layer;
a photosensitive silver halide layer having associated therewith a diffusion transfer process dye image-forming material; a processing composition permeable diffusion transfer process dye image-forming material impermeable layer; a second dimensionally stable transparent layer:
means for providing a processing composition intermediate the second dimensionally stable transparent layer and the dye image-forming material impermeable layer; and means for maintaining the composite unit intact subsequent to diffusion transfer processing.

2. A composite photographic diffusion transfer color process film unit as defined in claim 1 wherein said processing composition possesses a first processing pH and said film unit includes means for converting, subsequent to substantial dye transfer image formation in said dyeable layer, said processing composition from said first processing pH to a second pH at which each of said dye transfer images exhibit increased stability.

3. A composite photographic diffusion transfer process film unit as defined in claim 2 wherein said first processing pH is an alkaline pH and said second pH is lower than said first pH.

4. A composite photographic diffusion transfer process film unit as defined in claim 3 wherein said second pH is > one pH unit less than said first pH.

5. A composite photographic diffusion transfer process film unit as defined in claim 2 wherein said means for converting said processing composition from said first to said second pH subsequent to substantial dye transfer image formation in each of said first and said second dyeable layers comprise a polymeric neutralizing layer positioned intermediate at least one of said first dimensionally stable transparent layer and said dyeable layer, and said second dimensionally stable transparent layer and said dye image-forming material impermeable layer.

6. A composite photographic diffusion tran.sfer process film unit as defined in claim 1 including means for providing opacifying agent intermediate the second dimensionally stable layer and the next adjacent silver halide layer in a quantity effective to prevent exposure of said photosensitive silver halide layer during process-ing of said film unit in the presence of radiation actinic to said photosensitive layer and incident on said second dimensionally stable transparent layer and said opaque layer is effective to prevent exposure of said photosensi-tive layer during processing of said film unit in the presence of radiation actinic to said photosensitive layer and incident on said first dimensionally stable layer.

7. A composite photographic diffusion transfer process film unit as defined in claim 1 wherein said opaque layer is actinic radiation reflective.

8. A composite photographic diffusion transfer process film unit as defined in claim 7 wherein said opaque layer comprises titanium dioxide dispersed in a processing composition permeable polymeric binder.

9. A composite photographic diffusion transfer process film unit as defined in claim 8 wherein said opaque layer comprises a composite including a layer containing carbon black dispersed in a processing composition permeable polymeric binder positioned intermediate said opaque layer comprising titanium dioxide and the photosensitive silver halide layer next adjacent thereto.

10. A composite photographic diffusion transfer process film unit as defined in claim 6 wherein said opacify-ing agent is actinic radiation absorptive.

11. A composite photographic diffusion transfer process film unit as defined in claim 10 wherein said opacify-ing agent comprises an inorganic pigment.

12. A composite photograhic diffusion transfer process film unit as defined in claim 11 wherein said opacify-ing agent including said inorganic reflecting pigment and is disposed in said processing composition.

13. A composite photographic diffusion transfer process film unit as defined in claim 1 wherein said means for providing said processing composition comprises ruptur-able container means retaining said processing composition extending transverse an edge of said film unit to effect, upon application of compressive pressure to the container means, discharge of said container means processing composi-tion contents intermediate said second dimensionally stable transparent layer and the dye image-forming material impermeable layer.

14. A composite photographic diffusion transfer process film unit as defined in claim 1 wherein said diffu-sion transfer process dye image-forming material is a dye which is a silver halide developing agent.

15. A composite photographic diffusion transfer process film unit as defined in claim 14 wherein said dye is soluble and diffusible at a first pH and substantially nondiffusible at a second pH.

16. A composite photographic diffusion transfer process film unit as defined in claim 1 including intermediate said opaque layer and said second dyeable layer at least two selectively sensitized silver halide layers each having associated therewith a dye image-forming material adapted to provide a dye image of predetermined color as a function of the photoexposure of its associated silver halide layer.

17. A composite photographic diffusion transfer process film unit as defined in claim 16 wherein each of said selectively sensitized silver halide layers of said each film unit possesses predominant spectral sensitivity to separate regions of the spectrum and said dye image-forming material associated with each of said silver halide layers is adpated to provide a dye transfer image possessing a spectral absorption range subsequent to processing substan-tially complementary to the predominant sensitivity range of its associated silver halide layer.

18. A composite photographic diffusion transfer process film unit as defined in claim 17 wherein said process-ing composition and said color film units each include means for converting the pH of said processing composition, subse-quent to substantial diffusion dye image-forming materials to said receiving layer, from a first alkaline process pH
to a second pH less than said first pH at which the dye transfer image provided by said dye-image-forming materials exhibits increased stability.

19. A composite photographic diffusion transfer process film unit as defined in claim 18 wherein said selec-tively sensitized silver halide layers include, as essential layers, a red-sensitive silver halide emulsion layer having associated therewith a diffusion transfer process cyan dye image-forming material, a green-sensitive silver halide emulsion layer having associated therewith a diffusion transfer process magenta dye image-forming material and a blue-sensitive silver halide emulsion layer having associated therewith a diffusion transfer process yellow dye image-forming material.

20. A photographic diffusion transfer process film unit as defined in claim 1 wherein said processing composition permeable diffusion transfer process dye image-forming material impermeable layer is butyl acrylate/
diacetone acrylamide/styrene/methacrylic acid (60/30/4/6).

21. A process for providing composite photographic diffusion transfer process dye images which comprises, in combination, the steps of:
(a) exposing to incident actinic radiation a photo-graphic diffusion transfer process film unit which comprises, in combination, a dimensionally stable transparent layer;
a dyeable layer adapted to receive diffusion transfer process dye image-forming material diffusing thereto; an opaque layer; a photosensitive silver halide layer having associated therewith a diffusion transfer process dye image-forming material, a processing composition permeable dye image-forming material impermeable layer;
(b) contacting the surface of the dye image-forming material impermeable layer opposite the dimensionally stable transparent layer with a processing composition and effecting development of the photoexposed silver halide layer and formation of an imagewise distribution of mobile dye image-forming material as a function of the point-to-point degree of silver halide layer photoexposure; and (c) transferring, by diffusion, at least a portion of said imagewise distribution of mobile dye image-forming material to said dyeable layer adapted to receive dye image-forming material diffusing thereto to thereby provide to said dyeable layer a dye image in terms of said image-wise distribution.

22. A process for providing a photographic diffusion transfer process dye image as defined in claim 21 including the step of converting the pH of said film unit, subsequent to substantial dye image formation in said dyeable layer, from a first processing pH provided by said processing composition to a second pH at which said dye images exhibit increased stability.

23. A process for providing a photographic diffusion transfer process dye image as defined in claim 22 wherein said dye image-forming material comprises a dye which is a silver halide developing agent and is soluble and diffusible in said processing composition at said first pH as a function of the photoexposure of said film unit and is substantially nondiffusible at said second pH.

24. A process for providing a photographic diffusion transfer process dye image as defined in claim 22 wherein said first processing pH is an alkaline pH and said second pH is > about one pH unit lower than said first pH.

25. A process for providing a photographic diffusion transfer process dye image as defined in claim 21 including the step of providing opacifying agent contiguous the surface of said silver halide layer opposite the dimensionally stable transparent layer.

26. A process for providing a photographic diffusion transfer process dye image as defined in claim 21 which comprises, in combination, the steps of:
(a) exposing to incident actinic radiation a composite photographic film unit which comprises a plurality of sequen-tial layers including a first dimensionally stable layer transparent to incident actinic radiation; a dyeable layer;
an opaque layer; at least two selectively sensitized silver halide emulsion layers possessing predominant spectral sensitivity to separate regions of the visible electro-magnetic spectrum and a dye image-forming material associated with each of the silver halide emulsion layers and providing a dye possessing spectral absorption range, subsequent to processing, substantially complementary to the predominant sensitivity range of its associated silver halide emulsion layers; a processing composition permeable dye image-forming material impermeable layer; a second dimensionally stable layer transparent to incident actinic radiation;
and means for securing the layers in substantially fixed relationship;
a rupturable container retaining a processing composi-tion possessing substantially uniformly dispersed therein opacifying agent present in a quantity sufficient, upon distribution of the processing composition pH as a layer intermediate the second dimensionally stable transparent layer and next adjacent selectively sensitized silver halide emulsion layer, to substantially prevent transmission there-through of incident exposure radiation actinic to the silver halide emulsion layers and the rupturable container is posi-tioned and extends transverse an edge of the photosensitive element to effect discharge of the container's alkaline processing composition intermediate the second dimensionally stable transparent layer and the dye image-forming material impermeable layer;
(b) effecting discharge of the container's processing composition intermediate the second dimensionally stable transparent layer and the dye image-forming material imperm-eable layer;
(c) effecting thereby development of each of the selec-tively sensitized silver halide emulsions;
(d) forming thereby imagewise distributions of mobile dye as a function of development;
(e) transferring, by diffusion, at least a portion of each of the imagewise distributions of mobile dye to said dyeable layer to provide a dye image in terms of the image-wise distributions; and (f) maintaining the composite structure intact subse-quent to processing.

27. A process for providing composite photographic diffusion transfer process dye images as defined in claim 26 which comprises, in combination, the steps of:
(a) exposing to incident actinic radiation a photo-graphic film unit which comprises a composite structure containing, as essential layers, in sequence, a first dimen-sionally stable alkaline solution impermeable transparent layer; an alkaline solution dyeable polymeric layer; an alkaline solution permeable inorganic light-reflecting pigment layer comprising titanium dioxide; an alkaline solu-tion permeable opaque layer comprising carbon black; 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 dye impermeable polymeric layer; a second dimen-sionally stable alkaline solution impermeable transparent layer; a polymeric layer containing sufficient acidifying capacity to effect reduction of a processing composition having the first pH at which the cyan, magenta and yellow dyes are soluble and diffusible to a second pH at which the dyes are substantially nondiffusible positioned intermediate at least one of said dimensionally stable transparent layers and next adjacent layers; and means securing said layers in substantially fixed relationship; and a rupturable container retaining an aqueous alkaline processing composition having the first pH and containing substantially uniformly disposed therein opacifying agent substantially nondiffusible from said processing composition and present in a quantity sufficient, upon distribution of the aqueous alkaline processing composition possessing the first pH as a layer intermediate the second dimensionally stable transparent layer and the dye impermeable layer, to provide a layer possessing an optical transmission density > about six density units with respect to incident radiation actinic to the silver halide emulsion layers, and the container is fixedly positioned and extends transverse a leading edge of the photosensitive element to effect upon application of compressive force unidirectional discharge of the container's aqueous alkaline processing composition possessing the first pH intermediate the second dimension-ally stable transparent layer and dye impermeable layer;
(b) applying compressive force to the rupturable container to effect unidirectional discharge of the container's aqueous alkaline processing composition intermediate the second dimensionally stable transparent layer and the dye impermeable layer;
(c) effecting thereby development of the red-, green-and blue-sensitive silver halide emulsion layers;
(d) immobilizing the cyan, magenta and yellow dyes as a result of development of their associated silver halide emulsion layers;
(e) forming thereby an imagewise distribution of mobile cyan, magenta and yellow dye as a function of the point-to-point degree of exposure of their associated silver halide emulsion layers;
(f) transferring, by diffusion, at least a portion of each of the imagewise distributions of mobile cyan, magenta and yellow dye to said alkaline solution permeable polymeric layer dyeable by said dyes to provide thereto a multicolor dye image;
(g) transferring, by diffusion, subsequent to substan-tial dye transfer, a sufficient portion of the ions of the aqueous alkaline processing solution to the polymeric acid layer to thereby reduce the alkalinity of the film unit from the first pH, at which the cyan, magenta and yellow image dyes are soluble and diffusible to a second pH, at which the cyan, magenta and yellow image dyes are substantially non-diffusible; and (h) maintaining the composite structure intact subse-quent to processing.