US3314792A

US3314792A - Photographic film assemblage including processing liquid

Info

Publication number: US3314792A
Application number: US499703A
Authority: US
Inventors: Edwin H Land
Original assignee: Polaroid Corp
Current assignee: Polaroid Corp
Priority date: 1963-07-31
Filing date: 1965-10-21
Publication date: 1967-04-18
Anticipated expiration: 1984-04-18
Also published as: BE651210A; NL6408793A; BE660445A

Description

April 18, 1967 E. H. LAND 3,314,792 PHOTOGRAPHIC FILM ASSEMBLAGE INCLUDING PROCESSING LIQUID Original Filed July 51, 1963 I NVENTOR. 5.4% 4 .43%

ATTORNEYS April 18, 1967 E. H. LAND 3,314,792

PHOTOGRAPHIC FILM ASSEMBLAGE INCLUDING PROCESSING LIQUID Original Filed July 31, 1963 5 Sheets-Sheet 2 FIG. 3

INVENTOR.

BY W M wallet M $29M 6. 25M

ATTORNEYS April 18, 1967 E. H. LAND 3,314,792

PHOTOGRAPHIC FILM ASSEMBLAGE INCLUDI NG PROCESSING LIQUID Original Filed July 51, 1963 3 Sheets-Sheet :5

INVENTOR BY 624% ZXM ATTORNEYS United States Patent 25 Claims. (Cl. 96-76) This application is a division of copending application Ser, No. 298,968 filed July 31, 1963, in the name of Edwin H. Land.

This invention relates to photographic products, and particularly to a product including a photosensitive imagerecording sheet, a second sheet, and a processing liquid for treating the image-recording sheet following exposure thereof.

A number of different types of photographic apparatus have been proposed for exposing a succession of areas of a photosensitive image-recording sheet, superposing each exposed area with an area of a second sheet and distributing a processing liquid between the superposed sheets in order to produce a positive transfer print in an imagereceiving layer on the sec-0nd sheet by difiusion-transfer process. The materials employed in the process comprise an image-recording sheet including an image-forming material such as a heavy metal salt (e.g., silver halide), a second or image-receiving sheet for supporting an imagereceiving layer containing a diffusion-transfer image, and a processing liquid including a developing agent for the photosensitive material and an alkali for rendering the developing agent reactive. It has been proposed to in corporate all of the materials for producing a transfer print including the photosensitive image-recording material, image-receiving material, developing agent, alkali, transferable image-forming substances, and/or agents capable of forming transferable image-forming substances and even water, in layers or strata comprising the imagerecording and second sheets. However, when water or more particularly, an aqueous alkaline liquid, has been included in a stratum or component of one of the two sheets, it has been necessary to provide a barrier for isolating the liquid from other strata and agents incorporated therein, together with means for removing the barrier and bringing all of the reagents into association when processing is to be effected. Heretofore, film assemblages of this general type have had a mechanically complex and expensive construction and have required correspondingly complex and expensive apparatus to achieve their exposure and processing,

Objects of the invention are: to provide a novel and improved photographic product in the form of a film assemblage comprising an image-forming material and a developing agent therefor, 21 second sheet including an image-receptive stratum carrying an aqueous alkaline liquid, and a gas and liquid-tight container holding the second sheet and the liquid; and to provide a product of the character described including means cooperating with components of the apparatus in which the image-recording sheet is exposed and processed for opening a container to permit withdrawal movement of the second sheet and closing and sealing the container against the admission of gas at other times.

Another object of the invention is to provide photographic products as described which make possible the storage and withdrawal from storage of successive sections of a sheet impregnated with a liquid having a very high pH, i.e., at least 12, and maintaining the pH of the liquid at a predetermined high level.

Other objects of the invention will in part be obvious and will in part appear hereinafter.

The invention accordingly comprises the product possessing the features, properties and the relation of components which are exemplified in the following detailed dis-closure, and the scope of the application of which will be indicated in the claims.

For a fuller understanding of the nature and objects of the invention, reference should be 'had to the following detailed description taken in connection with the accompanying drawings wherein:

FIGURE 1 is a perspective view, partially in section, of a film assemblage embodying the invention;

FIG. 2 is a fragmentary sectional view of a portion of the film assemblage of FIG. 1;

FIG. 3 is a sectional view of a camera useful with the film assemblage of FIG. 1 showing the film assemblage within the camera, the section being taken midway between the upper and lower sides thereof;

FIG. 4 is a perspective view, partially in section, of another form of film assemblage embodying the invention; and

FIG. 5 is a view, similar to FIG. bodiment of the camera of FIG. 4.

The film assemblage of the invention is especially designed for producing multicolor photographic transfer prints according to the process disclosed in US. Patent No. 2,983,606 issued May 9, 1961, to Howard G. Rogers; and utilizing integral multilayer negatives incorporating dye developers such as are disclosed in the copending US. application of Edwin H. Land and Howard G. Rogers, Ser. No. 565,135, filed Feb. 13, 1956. In this process the multilayer negative (sheet) is exposed to form a latent image, is superposed with -a second sheet including a receiving layer for image-forming dyes transferred by diffusion from the negative sheet; and a liquid reagent is permeated into the layers of the negative containing the photosensitive materials and dye developers and the imagereceiving layer. The liquid reagent is alkaline in nature and serves to render the other reagents, particularly the developers, reactive to develop the latent image, or images thereby immobilizing image-forming dyes in areas where image devolpment occurs and causing image-forming dyes in unexposed areas to transfer by diffusion to the image (dye)receiving layer. The process performed by the products of the invention differ from known processes and products basically in the manner in which the liquid is supplied for permeation into the negative layers. Heretofore, this has been accomplished by providing a quantity of the liquid including a thickening agent in a layer between the two sheets and spreading the thickened (viscous) liquid in a thin layer over each exposed area by moving the sheets in superposition relative to and between a pair of pressure-applying members. It has been the practice to provide the liquid for processing successive areas in either of two ways, these being in a succession of rupturable containers mounted on one of the sheets for movement together with the sheets between the pressureapplying members, or in separate containers which are moved with respect to the sheets for dispensing their liquid contents between the sheets for subsequent distribution.

According to the present invention, the aqueous alkaline liquid required for processing is carried by the image-receiving layer itself thus making possible a very simple film assemblage essentially comprising two sheets and a container for the image-receiving sheet and liquid; as compared With existing film assemblages including such components as masks, containers, liquid-trapping devices, indexing members and the like, requiring careful and precise 3, of a modified emincorporating the film assemblage fabrication and assembly to insure proper operation, registration and location of the various components during processing. The processing components of the camera designed to employ this film assemblage may be correspondingly simple since they are not required to dispense and/ or distribute a viscous processing liquid in a precise manner and trap excess processing liquid, but are required only to press the two sheets into face-to-face contact since the liquid is already distributed in the required amount in the image-receiving layer on one of the sheets.

The liquid, an example of which is given hereinafter, carried by the image-receiving layer is highly alkaline, this alkalinity being achieved by the inclusion in the liquid of an alkali metal hydroxide, such as sodium hydroxide or potassium hydroxide, preferably in sufficient quantity to achieve a pH of at least 12. In order to maintain the liquid in this highly alkaline condition, it is necessary to exclude carbon dioxide, such as is found in the atmosphere, from the liquid and for this reason the camera includes a container and/ or a container closure for protecting the liquid-carrying, image-receiving sheet from the atmosphere while allowing successive areas of the image-receiving sheet to be withdrawn from a container (gas impermeable) in the camera and pressed into super position with successive exposed areas of the imagerecording sheet. The container and container closure may comprise components of the camera or cooperating components of both the camera and film assemblage employed therein, while achieving a primary object in providing the simplest and least expensive (expendable) film assemblage capable of being processed in the least complicated and expensive camera.

The film assemblage of the invention comprises a multilayer negative or image-recording sheet and image-receiving sheet including an image-receiving layer impregnated with an aqueous alkaline liquid, with the two sheets being joined to one another at their leading ends, and a container for the liquid impregnated receiving sheet. A typical multilayer negative for producing multicolor transfer prints includes blue sensitive, green sensitive and red sensitive silver iodobromide emulsion layers having positioned behind them, respectively, a yellow dye developer, a magenta dye developer and a cyan dye developer; gelatin interlayers positioned between the yellow dye developer layer and the green sensitive emulsion and between the magenta dye developer layer and the red sensitive emulsion; and a support for the emulsion layers, dye developer layers, and gelatin inner layers. Multilayer negatives of this type are disclosed, for example, in Fig. 9 of the aforementioned US. Patent No. 2,983,606.

The image-receiving sheet comprises a support, preferably of a material which is chemically inert to, is insoluble in and impermeable to aqueous alkaline liquids, and an image-receiving layer of a material receptive to the aforementioned dye developers, securely adhered to the support and so constituted, by virtue of its composition and thickness, as to retain an amount of liquid sufficient to process the negative. In a preferred embodi ment of the image-receiving sheet, the aqueous alkaline liquid-permeable layer has a graded permeability ranging from an impermeable material on a support such as paper, to a highly permeable material swollen by the aqueous alkaline liquid. Such an image-receiving layer comprises a combination of strata of different composition and permeability bonded to one another and the support with the degree of swelling increasing progressively outward from the support. By way of example, a suitable image-receiving sheet was prepared by coating a support sheet of et-paper or baryta paper with a solution comprising g. of polyvinyl butyral in 100 cc. of ethanol. The paper is preferably coated on both sides and/ or impregnated with the polyvinyl butyral solution in order to render the support impermeable to the aqueous alkaline liquid. In the alternative, polyvinyl butyral sheet has been employed as the support. To the polyvinyl butyral coating (or sheet), was applied a coating of a solution comprising:

Polyvinyl butyral -g 5 Poly-4-vinylpyridine g 5 Ethanol cc 200 To the foregoing coating was applied a coating of a solution comprising 10 g. of poly-4-vinylpyridine in 200 cc. of ethanol. Three additional coating were then applied comprising in order 3:1, 2:1 and 1:1 mixtures of, respectively, Solutions A and B comprising:

Water Each of the aforesaid 3:1, 2:1 and 1:1 mixtures was diluted by an equal quantity of water before application. All of the layers were applied by a conventional reverse roll coating technique in which a doctor was employed spaced from the coating roll by a .003 inch gap; and the six layers comprising the image-receiving layer were found after drying to have an aggregate thickness of about .0007 inch.

The image-receiving sheet thus prepared was immersed for 5 minutes in an aqueous alkaline processing composition comprising:

KOH g 7.26 Sodium tetraborate g 2.0 Benzotriazole 2.3 N-benzyl-wpicolinium bromide "g" 2.3 Water cc 100 Before pressing the liquid-containing, image-receiving sheet into contact with the exposed photosensitive sheet to effect the processing of the latter and the formation of a dye transfer image on the image-receiving sheet, either or both surfaces of the image-receiving sheet are squeegeed to remove excess liquid from the image-receiving layer and render the surface of the support actually dry. The processing liquid required for treating the photosensitive sheet is contained entirely within the swollen, imagereceiving layer so that this layer too may appear to be substantially dry to the touch; and, in any event, no free liquid need remain on the surface of the image-receiving layer following the squeegeeing operation.

The sandwich comprising the two superposed sheets may be advanced directly from the camera in which exposure and processing is accomplished and, accordingly, the supports of both the photosensitive and image-receiving sheets are formed of a material or provided with a layer which is opaque to actinic light.

The photosensitive image-recording sheet, designated 44, is supplied in a coiled container within the camera. Such a camera is shown in FIG. 3, as comprising a housing including three relatively movable sections designated a forward section 12, a rear section 14 and an end section 16. The forward section of the camera housing comprises a forward wall 18 having a generally rectangular opening therein including a recessed section defined by upper and lower side walls 22,

end walls

24 and 26 and a rear wall 28 provided with a rectangular exposure aperture 39. The camera is of the folding type and includes a conventional lens and shutter assembly 32 coupled with rear wall 28 by a bellows 34 which is collapsible (the usual erecting mechanism is not shown) to permit the bellows and the lens and shutter assembly to be contained within the recess in the forward housing section.

The rear housing section includes a rear wall 36 having a curved end section 38 at which the rear housing section is pivotally secured to the forward housing section by a hinge 40. The forward and rear housing sections, specifically forward wall 18, upper and lower side walls 22 and wall 24 and end section 38 of rear wall 36 cooperate to provide a storage chamber 42 for mounting and enclosing a roll of a photosensitive image-recording sheet 44 of the type described. The rear housing section also includes a portion designated 46 located at the end of rear wall 36 opposite end section 38 which projects rearwardly from rear wall 36 and includes a wall 48 having an L- shaped cross section and upper and lower side walls 50 which are disposed above and below upper and lower side walls 22. The rear housing section is pivotable between the closed or operative position shown in which the forward and rear housing section cooperate to provide closed storage chamber 42; and an open position at which access is provided to chamber 42 for loading a roll of image-recording sheet 44 into the storage chamber and threading the sheet or a leader attached thereto through the camera between

rear walls

28 and 36 across exposure aperture 30. The rear surface of rear wall 28 and the forward surface of rear wall 36 are located generally at the focal surface of the lens of assembly 32 and cooperate to locate successive areas of the image-recording sheet in position for exposure to light transmitted by the lens through aperture 30.

Forward housing section 12 includes an enlarged end section comprising outer upper and lower, walls spaced from and cooperating with upper end lower walls 22 to define chambers at an end of the forward housing section in the upper and lower portions thereof for enclosing components of the operating mechanism of the camera. The forward housing section also includes an end wall designated 60 spaced from end wall 26 and cooperating with the latter, forward wall 18 and upper and lower walls 22 to provide another chamber 62 for enclosing components of the apparatus. End wall 69 also functions to provide a wall for a sealed container (to be described hereinafter). End walls 26 and '60 extend rearwardly to join rear wall 36 at the end of the forward housing section 12 furthest from chamber 42.

End section 16 of the camera housing includes a forward wall 64, a curved end wall 66, and a rear wall 63, inner and outer, upper and lower walls (not shown). The inner upper and lower walls, forward wall 64, end wall 66, and rear wall 68 cooperate to provide an open storage chamber 82 for holding a supply of the imagerecording sheet designated 84. End section 16 is coupled with forward housing section 12 by a l inge 86 constructed to provide for limited linear movement of the end section relative to the forward section as well as pivotal movement of the two sections with respect to one another. Hinge 86 is secured to forward

walls

18 and 64 of, respectively, the forward and end housing sections and permits the end section to be pivoted with respect to the forward section between the operative or closed position shown, in which end walls '60 of the forward section cooperate with the end section to provide a closure for storage chamber 82, and the open position of the end section in which chamber 82 is open to permit loading of a supply of an image-receiving sheet 84 into chamber -82.

End section 16 of the housing includes a rearwardly projecting portion 88 comprising upper and lower walls 90 joined by an L-shaped wall 92 extending rearwardly from rear wall 68 and then parallel with the rear wall and cooperating with the upper and lower walls to provide a chamber 94 for enclosing components of the apparatus.

In the operative position of the housing sections, walls 48 and 92 cooperate to define a slot 114 connecting with chamber 94 dimensioned to permit withdrawal of the image-recording and image-receiving sheets in superposition from the camera housing and a cutting bar 116 having a sharpened, serrated edge is provided within slot 114 on wall 48 for facilitating the severance of sheet materials extending from the camera housing through the slot.

The photosensitive image-recording sheet, designated 44, is supplied in a coiled condition in the usual manner, e.g., on a spool, and the liquid impregnated imagereceiving sheet, designated 84, is supplied in a coiled condition in a container which is substantially impermeable to the processing liquid, water vapor and gasses, particularly carbon dioxide. A typical container for the liquid impregnated image-receiving sheet is illustrated in FIGS. 1, 2 and 3 of the drawings. This container, designated 118, includes a generally cylindrical peripheral wall 120 and two circular end walls 122. Wall 120 is provided with an axial slot defined by a pair of overlapping outer and inner lips designated, respectively, '124 and 126. The edge portion of the outer lip is thickened and the inner lip is provided with a rib to stiffen the two lips and retain them in a closed position in engagement with a portion of image-receiving sheet 84 ex tending from the container through the passage between the lips. The edge 128 of inner lip 126 closest the outer lip is provided with a sharpened corner designed to function as a squeegee for removing liquid from a surface of image-receiving sheet '84. Container 118 may be form-ed of any suitable material particularly organic plastics, such as polyethylene, which are air and Water vapor impervious and are compatible with aqueous alkaline liquids. The image-receiving sheet is supplied in a coiled condition in container 118 with a leading end portion of the sheet extending from the container through the passage between

lips

124 and 126. Additional means may be provided for sealing the passage against the admission of air and the leakage of water or water vapor and in the form shown these sealing means may comp-rise a seal of some material, such as wax, which may be introduced in a softened or molten condition into the passage between

lips

124 and 126 in surrounding relation to the sheet to fill the passage and form a rupturable bond between the sheet and container to prevent the passage of air and water between the lips.

Receiving sheet 84 may be coiled with the liquid impregnated image-receiving layer facing inwardly or outwardly and is shown in FIGS. 1 and 3 with the liquid impregnated layer facing outwardly. Since the container must be opened to permit the withdrawal of the image receiving sheet and thus possibly permit escape of water vapor and/or admission of air, it may be desirable to provide a reservoir of excess processing liquid within the container together with means for gettering carbon dioxide so that any carbon dioxide gaining admission to the container does not react with the hydroxide in the processing liquid to reduce the pH thereof. The image-receiving sheet is preferably coiled tightly upon itself to help prevent contact between the liquid impregnated image-receiving layer and the atmosphere of the container. In order to prevent loss (by evaporation) of processing liquid from the image-receiving layer, the atmosphere of the container is preferably maintained saturated with water vapor by the provision of a reservoir of water or processing liquid. This reservoir of excess processing liquid or water may comprise the image-receiving layer itself which may be impregnated with excess liquid which could be removed by squeegeeing during withdrawal of the receiving sheet from the con tainer. In this embodiment, squeegees would be provided on both

lips

124 and 126 for removing liquid from both surfaces of the image-receiving sheet so that the sheet, upon withdrawal from the container, is substantially dry to the touch with all the liquid required for processing being retained within the image-receiving layer. In an alternative embodiment, water or process ing liquid may be provided in a reservoir apart from the image-receiving sheet. Such a reservoir may comprise, for example, a liquid impregnated absorbent material such as a sheet shown and designated 132 in FIG. 4. Liquid impregnated sheet 132 is shown wrapped around the outside of the coiled image-receiving sheet, but in an alternative embodiment could be disposed within the coiled receiving sheet.

In order to maintain the high pH level of the liquid carried by the image-receiving layer, it may be necessary to provide a getter for any carbon dioxide which enters the container. Since hydroxides, particularly the hydroxides comprising the processing liquid are highly reactive with carbon dioxide, such a getter may also comprise an hydroxide contained, for example, within the reservoir of liquid which provides for the water vapor saturated atmosphere within the container. Alkali metal hydroxides are suggested for use as getters and include hydroxides which combine with carbon dioxide to form carbonates which are less soluble than the carbonates formed by the hydroxide in the processing liquid. For example, when potassium hydroxide is used in the processing liquid, calcium hydroxide may be provided for reacting with carbon dioxide in order to prevent reaction of the potassium hydroxide with carbon dioxide within the container. Barium hydroxide is also sugegsted as a getter when potassium hydroxide is employed in the processing liquid. Sodium hydroxide may be incorporated in the processing liquid instead of potassium hydroxide to provide for the high pH thereof, in which case any of potassium hydroxide, barium hydroxide and calcium hydroxide may be incorporated in the container as a getter for carbon dioxide.

Container 1118 in which liquid impregnated sheet 84 is supplied is unsealed at the commencement of withdrawal of the image-receiving sheet therefrom and in the form shown remains unsealed thereafter. Accordingly, the camera in which the container is employed includes either: means for sealing the container against the escape of water vapor and the admission of carbon dioxide, or a container for holding container 11 8 and which may be sealed against the escape of water vapor and the admission of carbon dioxide, between times when the image-receiving sheet is being withdrawn from container 118 and/ or the container within the camera.

Camera 10 includes a container which is substantially impervious to water vapor and carbon dioxide and may be sealed against the admission or escape of water vapor and carbon dioxide and may be opened to permit the withdrawal movement of the image-receiving sheet therefrom. This container provides a storage chamber 82 defined by end wall 60, upper and lower walls, and end walls 66. Means are provided for sealing storage chamber 82 and, in the form shown in FIG. 3, comprise a pair of seals 134 and 1 36.

Seals

134 and 136 are preferably formed of an elastomeric material which is compatible with and unaffected by alkalies, is substantially impervious to water vapor and carbon dioxide, and is highly resistant to assuming a permanent set. Seal 134 is generally rectangular in shape and includes a thin rectangular medial membrane 138 surrounded by marginal engagement portions termed and designated a forward sealing section 140, a rear sealing section 142 and end sealing sections (not shown). Seal 134 is secured to the surface of end wall 60 within storage chamber 82 and not only functions as a seal for the chamber but cooperates to protect end wall 60 from the highly corrosive processing liquid.

Seal 136 includes a membrane 148 in the form of an open, tube-shaped container adapted to fit within storage chamber 82 against the walls thereof. Seal 136 includes a forward sealing flange 150, end sealing flanges (not shown), and a rear sealing flange 154 which cooperate with respectively forward sealing section 140, the end sealing section and rear sealing section 142 to seal chamber 82 in the closed position thereof. Rear sealing section 142 and flange 154 are preferably designed to function as squeegees for removing liquid from either or both surfaces of the image-receiving sheet during withdrawal of the image-receiving sheet from storage chamber 82.

The camera includes separately movable housing sections retained in closed position by suitable latching means designed to cause compression of the mutually engageable sections of

seals

134 and 136 when the camera housing sections are in closed position. In order to withdraw the image-receiving sheet from chamber 32, the chamber is opened at rear sealing section 142 and rear sealing flange 154 by pivoting the end housing section, designated 16, with respect to forward housing section 12 about an axis intermediate the forward and rear seals and extending approximately through the axis of studs 1.12. This pivotal movement is achieved by further compressing forward sealing section .140 and for ward sealing flange which, being elastorneric, function as a spring to close the seal at the rear of the storage chamber when the force tending to pivot the end housing section is removed.

To process an exposed area of image-recording sheet 44 to produce a transfer image in a corresponding area of the image-receiving sheet, the two sheets are pressed into superposition with one another. This processing is accomplished by a pair of pressure rolls 164 and 166. Each of rolls 16 4 and 156 is shown as comprising a metal shaft covered by an elastomeric material such that the rolls are slightly compressible and, in fact, the resiliency of the elas-tomeric material may be employed to apply the necessary pressure to the two sheets. Roll 164 is pivotally mounted on rear housing section 14 between upper and lower side walls 50 for movement into juxtaposition with roll 16 6 which is also mounted within chamber 94 on inner upper wall 70 and inner lower wall 74. In the operation of the camera, image-receiving sheet 84 extends from chamber 82 into superposition with image-recording sheet 44 between rolls 164 and [1-66. The rolls are rotated in engagement with the superposed sheets in order to superpose an exposed area of the photosensitive sheet with an area of receiving sheet and simultaneously advance the sandwich thus formed from the camera through slot 114 and advance the next succeeding area of the image-recording sheet into position for exposure in alignment with aperture 30.

The film assemblage, including the sheet materials employed in the camera shown and described, is supplied with a leading end portion thereof, or leader attached thereto, extending from container 1113 and coupled with a leader or the leading end of the image-recording sheet. To load the camera, the coil of image-recording sheet is introduced into chamber 42; the rear housing section is pivoted into closed position; the container of imagereceiving sheet is loaded into chamber 32; end housing section 11 6 is then pivoted into closed position, and latching arms 98 are pivoted in a counterclockwise direction to retain the camera in closed position. The camera housing sections are thus closed with the coupled leaders extending between rolls 164 and 1 66 through slot 114. An area of the image-recording sheet is then advanced into position for exposure and following exposure of this and each succeeding area of the image-recording sheet, each exposed area of the image-recording sheet is pressed into superposition with an area of the image-receiving sheet to form a sandwich and advanced from the camera through slot 114. The superposed areas of the two sheets comprising the sandwich may be severed from portions of the sheets remaining within the camera housing by drawing the sandwich against cutting bar v116. The sheets are retained in superposition during a processing period of predetermined duration at the end of which the sheets are separated to reveal a transfer print on the image-receiving sheet.

In another embodiment of the product of the invention and a camera useful therewith, a seal, which may be opened and closed, is provided for the container in which the image-recording sheet is supplied, rather than a complete container in itself, so that the camera and film assemblage combine to form a container which can be sealed and unsealed. In the form shown in FIG. 4, image-receiving sheet 8 4 is supplied in a coiled condition in a container in the form of a bag 1196. The image-receiving sheet is coiled within a cylindrical sleeve 198 having an axial slot and designed to retain the imagereceiving sheet in a coiled condition and allow it to be withdrawn from the coil. Bag .196 is formed by wrapping .a generally rectangular sheet of a water vapor, alkali and gas impervious material around the coiled imagereceiving sheet, bringing the edges of the sheet material comprising the bag together and sealing or adhering the edges to one another and to the sheet which is allowed to extend from the bag. The sheet material comprising the bag may be a multi-ply material formed, for example, of paper and/or metal foil .with an inner ply of a polymeric material, preferably one which is thermoplastic and can be bonded to itself and other materials by application of heat and pressure. The completed container is formed with a pair of lips designated Ztit) releasably secured to the image-receiving sheet and defining a mouth through which the image-receiving sheet may be withdrawn. Alternatively, a clip or other means may be provided for holding lips 200 in a closed position prior to loading of the container into a camera. The film assemblage shown in FIG. 8 also includes a reservoir for excess water or processing liquid and a getter for carbon dioxide. This reservoir takes the form of sheet 132 of an absorbent material impregnated with the desired liquid disposed within sleeve 198 in surrounding relation to the coiled image-receiving sheet.

The camera for use with this film assemblage is shown in FIG. and, in most respects, is substantially the same as the camera shown in FIG. 3, differing therefrom primarily with regard to the sealing of storage chamber 82 and a seal for bag 1%. Storage chamber 82 is provided without any means for sealing the chamber but instead, is provided with a container seal comprising a pair of shoes 2G4 and 2%. Shoe 204 is mounted in fixed position on end Wall '60 and shoe 266 is mounted on a block 212 mounted on rear wall 68 in juxtaposition with shoe 204 or movement toward and away from the latter. Each of the shoes comprises an elongated member formed of a pliant and/or elastomeric material such that when the shoes are pressed together with lips 2M engaged therebetween, the shoes effectively seal the lips against the admission of gas into the container or the escape of water vapor therefrom. The film assembly of FIG. 4 is positioned within storage chamber 82 with the edges of the lips disposed between the shoes, shoe 2% being urged toward shoe 204 by resilient means such as a spring or springs 208. The form of camera shown in FIG. 5 is somewhat simpler than the one previously described inasmuch as chamber 82 is not required to function as a container thereby making

seals

134 and 136 unnecessary and eliminating the necessity for a slidable hinge as shown in FIG. 3 and inner upper and lower walls 70 and 74. In most other respects the camera of FIG. 5, particularly the operating mechanism, is substantially the same as that previously described.

The film assemblage described herein together with the camera are intended for intermittent frame by frame exposure and processing, with the film assemblage itself being substantially simplified, as compared to existing self-developing roll film assemblages, in that its essential elements are limited to an image-recording sheet, a liquid impregnated image-receiving sheet and a container for the latter. Masks, fluid collecting and retaining devices, indexing references and the like, heretofore associated with this type of roll film assemblage, have been made unnecessary.

Since certain changes may be made in the above product 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 sense.

What is claimed is:

1. An externally dry photographic film assemblage for treating successive exposed areas of a photosensitive image-recording sheet with an aqueous alkaline liquid having a high pH, said assemblage comprising, in combination:

a substantially gas and water impermeable container having a narrow opening therein through which a sheet is movable;

an elongated second sheet coiled within said container with an end portion of said second sheet extending from said container through said opening;

means for engaging said container and said second sheet at said opening for substantially sealing said opening against the admission of carbon dioxide to said container;

said second sheet including a layer impregnated with an aqueous alkaline liquid having a high pH, said liquid being distributed within said layer in mmcient quantity to effect the treatment of said imagerecording sheet and in the formation of an image wherein when said layer is pressed into face-to-face contact with said image-recording sheet; and

a reagent within said container for combining with carbon dioxide entering said container through said opening and thereby maintaining the pH level of said liquid impregnated into said layer.

2. The photographic film assemblage of claim 1 in which said liquid includes an alkali metal hydroxide and said reagent for combining with carbon dioxide comprises an aqueous solution of a heavy metal containing compound which reacts with carbon dioxide and the carbonate of said alkali metal to form a carbonate less soluble than said carbonate of said alkali metal impregnated into said layer.

3. The photographic film assemblage of claim 1 in which a squeegee is provided within said container adjacent said opening for engaging said second sheet within said container during withdrawal movement of said second sheet to remove said liquid from at least one surface thereof.

4. An externally dry photographic film assemblage for treating successive exposed areas of a photosensitive image-recording sheet with an aqueous alkaline liquid having a high pH, said assemblage comprising, in combination:

an elongated image-receiving sheet coiled within said container with an end portion of said image-receiving sheet extending from said container through said opening;

means for engaging said container and said imagereceiving sheet at said opening for substantially sealing said opening against the admission of carbon dioxide to said container;

said image-receiving sheet comprising a support and an image-receiving layer carried on said support and impregnated with an aqueous alkaline liquid having a high pH, said liquid being distributed within said image-receiving layer in sufiicient quantity to effect the treatment of said image-recording sheet when said image-receiving layer is pressed into face-to-face contact therewith; and

a source of water vapor within said container for maintaining the atmosphere of said container substantially in a saturated condition.

5. The photographic film assemblage of claim 4 in which said aqueous alkaline liquid has a pH of at least 12.

6. The photographic film assemblage of claim 4 in which a reagent is provided within said container (for lll combining with carbon dioxide entering said container" through said opening and thereby maintaining the pH level of said liquid impregnated into said image-receiving layer.

7. The photographic film assemblage of claim 6 in which said image-receiving layer is disposed innermost, and said reagent for combining with carbon dioxide is disposed outside of said coiled image-receiving sheet.

8. The photographic film assemblage of claim 6 in which said liquid includes an alkali metal hydroxide and said reagent for combining with carbon dioxide oomprises an aqueous solution of a heavy metal containing compound which reacts with carbon dioxide and the carbonate of said alkali metal to form a carbonate less soluble than said carbonate of said alkali metal impregnated into a liquid permeable element within said container.

9. The photographic film assemblage of claim 8 in which said image-receiving sheet is coiled upon itself with said image-receiving layer disposed innermost and said liquid permeable element impregnated with an aqueous solution of said agent for reacting with carbon dioxide is disposed in surrounding relation to at least a portion of said coiled image-receiving sheet in the region of said opening in said container.

110. The photographic film assemblage of claim 8 in which said heavy metal containing compound is a compound selected from the class consisting of hydroxides of alkali metals and alkaline earth metals.

11. The photographic film assemblage of claim 4 in which a squeegee is provided within said container adjacent said opening for engaging said image-receiving sheet within said container during withdrawal movement of said image-receiving sheet to remove said liquid from at least one surface thereof.

12.. The photographic film assemblage of claim 11 in which said squeegee engages and removes said liquid from the surface of said support opposite said imagereceiving layer.

13. The photographic film assemblage of claim 4 in which said means for sealing said opening comprise a gasimpermeable material adhered to said image-receiving sheet and said container within said opening and rupturable to permit withdrawal of said image-recording sheet from said container through said opening.

14. The photographic film assemblage of claim 4 in which said source of water vapor comprises a water containing element separate from said image-receiving sheet.

15. An externally dry photographic film assemblage for treating successive exposed areas of a photosensitive image-recording sheet with an aqueous alkaline liquid having a high pH to produce a succession of photographic transfer prints, said assemblage comprising, in combination:

an image-recording sheet including a photosensitive heavy metal salt capable of forming .a latent image upon photoexposure and a developing agent in substantially dry form capable of reducing exposed portions of said heavy metal salt;

an elongated image-receiving sheet coiled within said container with an end portion of said image-receiving sheet extending :from said container through said opening;

said image-receiving sheet comprising a support and an image-receiving layer carried on said support and impregnated with an aqueous alkaline liquid having a high pH, said liquid being distributed within said image-receiving layer uniformly laterally in sufficient quantity to render said developing agent reactive when said image-receiving layer is pressed into face-to-face contact with said image-recording sheet;

said end portion of said image-receiving layer being 12. coupled with the leading end of the image-recording sheet exterior of said container adjacent said opening with said image-receiving layer facing said image-recording sheet;

means for engaging said container and said imagereceiving sheet at said opening for substantially sealing said opening against admission of carbon dioxide to said container; and

a reagent within said container for combining with carbon dioxide entering said container through said opening and thereby maintaining the pH level of said liquid impregnated into said image-receiving layer.

16. The photographic film assemblage of claim 15 in which said aqueous alkaline liquid has a high pH of at least 12.

17. The photographic film assemblage of claim 15 in which a source of water vapor is provided within said container for maintaining the atmosphere of said container substantially in a saturated condition.

1%. The photographic film assemblage of claim 15 in which said liquid includes an alkali metal hydroxide and said reagent for combining wtih carbon dioxide comprises an aqueous solution of a compound of a heavy metal which reacts with carbon dioxide and the carbonate of said alkali metal to form a carbonate less soluble than said alkali metal carbonate, impregnated into a permeable element within said container.

19. The photographic film assemblage of claim 18 in which said image-receiving sheet is coiled upon itself with said image-receiving layer disposed innermost, and said liquid permeable element impregnated with an aqueous solution of said agent for reacting with carbon dioxide is disposed in surrounding relation to at least a portion of said coiled image-receiving sheet in the region of said opening in said container.

20. The photographic film assemblage of claim 18 in which said heavy metal containing compound is selected from the class consisting of hydroxides of alkali metals and alkaline earth metals.

21. An externally dry photographic film assemblage for treating successive exposed areas of a photosensitive image-recording sheet with an aqueous alkaline liquid having a high pH to produce a succession of photographic transfer prints, said assemblage comprising, in combination:

an image-recording sheet including a photosensitive heavy metal salt capable of forming a latent image upon photoexposure and a developing agent in substantially dry form capable of reducing exposed portions of said heavy metal salt;

said image-receiving sheet comprising a support and an image-receiving layer carried on said support and impregnated wtih an aqueous alkaline liquid having a high pH, said liquid being distributed within said image-receiving layer in sufficient quantity to render said developing agent reactive when said image-receiving layer is pressed in face-to-face contact with said image-recording sheet;

said end portion of said image-receiving layer being coupled outside of said container with the leading end of said image-recording sheet with said imagereceiving layer facing said image-recording sheet;

closure means comprising portions of said container for engaging said image-receiving sheet at said opening to substantially seal said opening against admission of carbon dioxide to said container, said closure means being movable to an open position to permit withdrawal movement of said image-receiving sheet from said container through said opening; and

a squeegee within said container adjacent said opening for engaging said image-receiving sheet within said container during Withdrawal movement of said image-receiving sheet to remove said liquid from at least one surface thereof.

22. The photo-graphic film assemblage of claim 21 in which said squeegee engages and removes said liquid from the surface of said support opposite said image-r ceiving layer so that the last-mentioned surface is essentially dry upon withdrawal from said container.

23. The photographic film assemblage of claim 21 in which said sealing means are movable from said open position to a closed position to seal said opening against the admission of gas when withdrawal movement of said image-receiving sheet from said container is discontinued.

24. The photographic film assemblage of claim 21 in which said container is semi-rigid and said sealing means include a liquid and gas impervious thermoplastic material.

25. The photographic film assemblage of claim 21 in which said container comprises a bag formed of a liquid and gas impervious sheet material, said bag has a mouth providing said opening, and said closure means comprise edge portions of said bag at said mouth adhered to one another and to a portion of said image-receiving sheet extending vbetween said edge portion.

No references cited.

NORMAN G. TORCHIN, Primary Examiner. R. MARTIN, Assistant Examiner.

Claims

21. AN EXTERNALLY DRY PHOTOGRAPHIC FILM ASEMBLAGE FOR TREATING SUCCESSIVE EXPOSED AREAS OF A HOTOTSENSITIVE IMAGE-RECORDING SHEET WITH AN AQUEOUS ALKALINE LIQUID HAVING A HIGH PH TO PRODUCE A SUCCESSION OF PHOTOGRAPHIC TRANSFER PRINTS, SAID ASSEMBLAGE COMPRISING, IN COMBINATION: AN IMAGE-RECORDING SHEET INCLUDING A PHOTOSENSITIVE HEAVY METAL SALT CAPABLE OF FORMING A LATENT IMAGE UPON PHOTOEXPOSURE AND A DEVELOPING AGENT IN SUBSTANTIALLY DRY FORM CAPABLE OF REDUCING EXPOSED PORTIONS OF SAID HEAVY METAL SALT; A SUBSTANTIALLY GAS AND WATER IMPERMEABLE CONTAINER HAVING A NARROW OPENING THEREIN THROUGH WHICH A SHEET IS MOVABLE; AN ELONGETED IMAGE-RECEIVING SHEET COILED WITHIN SAID CONTAINER WITH AN END PORTION OF SAID IMAGE-RECEIVING SHEET EXTENDING FROM SAID CONTAINER THROUGH SAID OPENING; SAID IMAGE-RECEIVING SHEET COMPRISING A SUPPORT AND AN IMAGE-RECEIVING LAYER CARRIED ON SAID SUPPORT AND IMPREGNATED WITH AN AQUEOUS ALKALINE LIQUID HAVING A HIGH PH, SAID LIQUID BEING DISTRIBUTED WITHIN SAID IMAGE-RECEIVING LAYER IN SUFFICIENT QUANTITY TO RENDER SAID DEVELOPING AGENT REACTIVE WHEN SAID IMAGE-RECEIVING LAYER IS PRESSED IN FACE-TO-FACE CONTACT WITH SAID IMAGE-RECORDING SHEET; SAID END PORTION OF SAID IMAGE-RECEIVING LAYER BEING COUPLED OUTSIDE OF SAID CONTAINER WITH THE LEADING END OF SAID IMAGE-RECORDING SHEET WITH SAID IMAGERECEIVING LAYER FACING SAID IMAGE-RECORDING SHEET; CLOSURE MEANS COMPRISING PORTIONS OF SAID CONTAINER FOR ENGAGING SAID IMAGE-RECEIVING SHEET AT SAID OPENING TO SUBSTANTIALLY SEAL SAID OPENING AGAINST ADMISSION OF CARBON DIOXIDE TO SAID CONTAINER, SAID CLOSURE MEANS BEING MOVABLE TO AN OPEN POSITION TO PERMIT WITHDRAWAL MOVEMENT OF SAID IMAGE-RECEIVING SHEET FROM SAID CONTAINER THROUGH SAID OPENING; AND A SQUEEGEE WITHIN SAID CONTAINER ADJACENT SAID OPENING FOR ENGAGING SAID IMAGE-RECEIVING SHEET WITHIN SAID CONTAINER DURING WITHDRAWAL MOVEMENT OF SAID IMAGE-RECEIVING SHEET TO REMOVE SAID LIQUID FROM AT LEAST ONE SURFACE THEREOF.