US2607685A

US2607685A - Photographic product comprising a plurality of rupturable containers, each carrying a liquid for processing said product

Info

Publication number: US2607685A
Application number: US700931A
Authority: US
Inventors: Edwin H Land
Original assignee: Polaroid Corp
Current assignee: Polaroid Corp
Priority date: 1946-10-03
Filing date: 1946-10-03
Publication date: 1952-08-19
Anticipated expiration: 1969-08-19

Description

Aug. 19, v1952 E, D 2,607,685

PHOTOGRAPHIC PRODUCT COMPRISING A PLURALITY 0F RUPTURABLE CONTAINERS, EACH CARRYING A LIQUID FOR PROCESSING SAID PRODUCT Filed Oct. 5, 194 6 2 SHEETSSHEET 1 FIG. I

Layer Phofosensirive Layer Image Carrying Layer l4 Backing Layer Developer Pigmenf 2O Solarized Pholosensilive Layer loa Slowly Permeable Layer Backing Layer Developer Hypo FIG. 3'

Aug. 19, 1952 E. H. LAND 2,607,685

PHOTOGRAPHIC PRODUCT COMPRISING A PLURALITY OF RUPTURABLE CONTAINERS, EACH CARRYING A LIQUID FOR PROCESSING SAID PRODUCT Filed Oct. 5, 1946 z-sr-mms-smm 2 FIG. '5

glam gi Patented Aug. 19, 1952 PHOTOGRAPHIC PRODUCT COMPRISING A PLURALITY OF RUPTURABLE CONTAIN- ,ERS, EACH CARRYING,,A LIQUID FOR PROCESSING SAID PRODUCT Edwin H. Land, Cambridge, Mass.,' assignor gto Polaroid Corporation, Cambridge, Mass, a cor-' poration ofDelaware Application October 3,1946, Serial in). 766,931

23 Claims.

1 This invention relates to photography, and more particularly to novel, composite photographic film units and processes.

One objector thejjp'resent invention is to provide a photographic film unit'carrying a plurality of separate liquid compositions capable of accomplishing a number of reactions within the film unit.

Another object is to provide a film unit of the above type wherein the'mounting of said liquid compositions is suchthat by a single treatment of said unit, subsequent to exposure thereof, said reactions may be caused to take place simultaneously or in a predetermined sequence to give a final positiveimage.

Anothe object is thefprovisi'on of a composite photographic film unit comprising at least a photosentiti've layer, a liquid-containing means positioned adjacent said photosensitive layer so as to discharge its liquid in contact'with said photosensitive layer, another layer, 'said other layer being transparent, and another liquidcontaining means positioned adjacent said transparent layer so as to discharge its liquid in contact with said transparent layer, said secondnam'ed means having therein a substance adapted to alter the spectral characteristics of said transparent layer. V

Still another object is to provide a composite photographic film unit comprising a photosensitive layer and several containers for liquid compositions, one of said liquid compositions being capable of producing a visible image in said film unit and the other liquid composition being capable of forming a background of predetermined spectral characteristics for said image.

Another object is to provide a composite photographic filrn unit comprising a solarized silver halide photosensitive layer, another layer, means for developing a positive image in saidphotosensitive layer, a silver halide solvent, and means for retarding the action of the silver halide solvent on said photosensitive layer until, the development of said image is substantially completed.

Another object is to provide a composite photographic film unit of the type mentioned above wherein the photosensitive layer and the imagecarrying layer are protected by layers of lightimpervious material, so that the film unit may be removed from a camera immediately after processing without being afiected by light, at least one of said light-impervious layers having been formed in the processing of said film unit.

H Another object of the invention is to provide a novel process for treating a novel, photo- 2 graphic film unit having, a plurality of layers, one of said layers being a photosensitivelayer, which comprises introducingv between several pairs of said layers save-m1 liquid compositions,

producing by means of one of said liquid compositions a positive image, and reacting said other liquid with aportion or said film unit to increase the stability of 7 said positive image. M

These and otherpbiects of the invention will in part be obvious and will iiipart appear here- The invention accordinglycoinprises the several steps and the relation and order of one or more of such steps with respect to each 'ofthe others, and thelarticle possessing the features, properties, and the relation or e1ements,wnich are exemplified in the following,,detaile'd, disclosure and the scope of the applidationbf which wiilf be indicated in theclainisl, I Foraiullerunders'tanding of the invention,

reference should beh'ad to the following detailed one form 'of the present invention;

Fig. 2 is an exaggerated, sectional view tranother modification of the invention;

, Fig. 3 is an exaggerated sectional view of still anothe form. ofthe invention; Y

Fig. 4 is an exa gerated sectional view. of ahother modification of the invention; and

Fig. 5 is an exa'ggerated sectional viewof still another modification oi the invention.

This invention relates generally to theprocess of treating a nov el, composite. photographic film unit, containing several layers, which comprises introducing betweeh one pair of said layers a liquidcompositipn adapted to cooperate in the formation of a, positive imagem said film unit, and simultaneously or subsequently introducing between another pair of. said layers another liquid composition capablejof reacting with portions ofsaid film unit. A preferred form of film unit embodying. the present invention comprises aplurality of layers, one of said layers being a photosensitive layer. ,Said film unit also comprises a plurality of containers havin'g therein liquid compositions, said containers being so positioned with respect to said layers as to be capable of, releasin'g said liquid compositions within said film unit, said liquid compositions being capable of, assisting in the performance oi different operations in the creation of a final image in said film unit.

In such processes and products the several liquid compositions utilized may perforin'various functions. One of the liquid compositions preferably develops a latent negative image and forms at least a part of the positive image. The other liquid composition or compositions may perform one or more of several functions such for example as an image-stabilizing operation, a background-forming operation, a light-barrierforming operation, or an acidifying reaction.

A photographic product is also disclosed in my copending application .SerialNo. 662,000, filed April 13, 1946 (now Patent No. 2,584,029, issued January 29, 1952) and my copending application Serial No. 708,007, filed November 6,

i946, which product makes use of two rupturable containers each holding a liquid and wherein said liquids together contribute to the final characteristics imparted to a visible image formed during the processing of said product.

Referring now to Fig. 1, there is shown one form of the composite film unit of the present invention. This film generally comprises, in the preferred embodiment thereof, a photosensitive layer carried by an opaque base material and a transparent image-carrying layer, plus a transparent backing ,layer for the image-carrying layer.v Two containers are associated with the film'unit,.one of said containers being positioned for introducing between the photosensitive layer and image-carrying layer a liquid composition containing at least a solvent for a developer for said photosensitive layer. The liquid preferably also contains the developer. The other container is positioned so as to introduce between said two transparent layers a liquid substance which will alter the transparency of the combination of the said two layers. I n

As illustrated, said film unit comprises a layer of photo-sensitive material l mounted on a base layer l2, an imagecarrying layer [4 and a backing, layer [6. vPositioned on either side of said image-carrying layer are collapsible containers l8 and 20, holding respectively a liquid composition containing at least a solvent for a developer and a color-forming material such as a liquid suspensionof a pigment or dye-formin material. f j

.The photosensitive material [0 preferably comprises an emulsion of a noble metal halide such as a silver halide or of a mixture of silver halides, or of a mixed silver halide. However, the photosensitive material may comprise other suitable photosensitive materials such as dichromates, diazo compounds or ferric salts. The base layer l2, on which the photosensitive layer is mounted, is preferably made of an. opaque substance such as baryta-coated paper,'or of a plastic such as cellulose. acetate dyed or backed with paper to malge it light-impervious. The image-carrying layer 14 is preferably formed of a permeable, transparent material such as gelatin, polyhydroxy alkanies such as polyvinyl alcohol, sodium alginate, cellulose others, such as methyl cellulose, or their derivatives such as sodium carboxymethyl cellulose or .hydroxy-ethyl cellulose. The backing layer I6 .is preferably formed of a transparent plastic material such as a cellulose ester or a mixed ester, for example, cellulose acetate, cellulose.nitrate, cellulose acetate propionate, or celulose acetate butyrate. The imagecarrying layeris preferably permeable to some of the liquids in the liquid composition, but is not so permeable as to allow said liquids to escape therethrough. Layer l6 may be made of the same substance as layer M, or it may be made of another substance.

The liquid composition in the container 18 preferably has such a composition as to carry out the formation of a visible image in either layer as by the development of an image inthe photosensitive layer or by thedevelopment of a negative image in the photosensitive layer and the production of a positive image on the imagecarrying layer. Such latter reaction is preferred and is preferably accomplished by the transfer of image-forming components from the photosensitive layer to'the image-carrying layer. For this purpose the liquid-composition preferably comprises an aqueous solution of a developer such'as 'hydroquinone, a film-forming substance such as sodium carboxymethyl cellulose, and a substance adapted to form from a latent photosensitive image a positive image-forming component. This latter substance, in a preferred form of the invention, is sodium thiosulfate. There may also be included in this liquid composition other substances such as a preservative andanalkali. The various materials carried in solution may be included within the film unit'in solid form and the container mayinclude only a solvent therefor.

The liquid composition in container 20 may comprise a liquid. film-forming material and a pigment such as titanium dioxide, magnesium oxide, or magnesium carbonate, which will form between the image-carrying layer and the bacle ing layer an opaque, white film or layer.

The liquid composition in container 20- may, however, comprise a material which will react with another material coated on either the lower surface of layer l4 or the upper surface of layer 15 to produce an opaque, white layer. The coating material may be a substance such as colloidal zinc hydroxide, while the reactive material carried by the container may be sodium carbonate.- It is also contemplated in certain cases to have the liquid composition carried by container 20 comprising a dye, a dye coupler,-or dye base, or an aqueous solution of a film-forming material carry.- ing a dye. If the liquid carries only a portion'of the dye, such as the coupler, it is necessary to incorporate the other portion of the dye in or upon the surface of one of the layers [4 and [6. The elongated containers [8 and 20 are mounted preferably transversely of the film unit between layers It! and I4, and layers Ill and I5, respectively. These containers are positioned preferably adjacent the leading or trailing edge of each frame of film, when a plurality of such containers is provided for a roll film. When a film unit is utilized having only one frame, only two containers are provided in the preferred embodiment, one for developing the image and creating a positive and the other for creating the opaque backing for the final image. The containers are preferably formed so that the application of a compressive force thereto will release the liquid in the direction of the exposed frame. This may be accomplished by forming the containers of a single sheet of oxygen and water-vapor impervious material such as Waxcoated foil, wax-impregnated metal coated paper, or a metal foil coated with a resin, such as polyvinyl butyral, which is inert to alkalis. The sheet is folded over and filled with the liquid composition and the edges sealed by the application of heat. The seal is such that it will break before the folded edges will fracture, so that the liquid will be released from the side of the container having the seal. The seals at the end of the container are preferably formed so as to offer greater resistance to separation than the longitudinal seal. 'tained a water-vapor impervious container whose contents, for relativelylong periodswill neither become dry nor oxidize. The edge seal is preferably formed by usingethy'l cellulose-such as by painting a strip thereof so as to get a peeling bond rather than a thermoplastic unification.

In the use of theinvention asshown in Fig. '1, the photo-sensitive layer I0 is exposed to actinic light, as in a camera, the exposure being through the transparent layers l4 and 16 as shown by the arrow. The film unit is then run through pressure means such as a wringer, the end at which the containers l8 and 20 are positioned going first. As the film unit passes through the wringer, the containers are broken and their contents spread on either side of .the image carrying layer M. The liquid composition spreads between the photosensitive layer l0 and th image-carrying layer I4, the developer in the liquid composition develops the latent image in the photosensitive layer, and the substance,

such as sodium thiosulfate, forms, with the There is thus o'b- I image-forming complexes. :f-it the same time,

the container 20 is broken and the liquid composition therein is spread between theima'gecarrying layer [4 and the backing layer it, thus forming an opaque background for the positive print. After time has been allowed for the above-mentioned processes to take place, the base layer and the photosensitive layer are preferably stripped from the image-carrying, layer to reveal the positive image.

In certain cases, it is desirable to introduce into a film unit at one time two liquids which must react with portions of said'film at times spaced in relationship to each other. One means of doing this is to provide a film unit of the type shown in Fig. 2. In this film unit there are provided two containers adapted, upon the application of pressure thereto, to discharge their contents into a film unit at points spaced from each other. Between the points of entry of the two liquids there is provided a layer of controlled permeability so that one of said liquids is delayed in reaching its point of reaction by a time determined by the permeability of said layer. 1

, Such is the case where a solarized photosensitive layer is used, and the positive image is helpful to substantially completely develop the .latentimage before the undevelopable (i. e. ex-

posed) gains are dissolved. It is desirable, therefore, to provide means for retarding the action of the silver halide solvent such as sodium thiosulfate. This may be accomplished in a modification of the present invention as shown in Fig. 2, wherein Illa is a solarized photosensitive layer carried by a base layer I241. A layer 26 of a slowly permeable substance is next provided. A liquid composition is included in a container I do, betweensaid layers, and another liquid composition is included in a container 20a, between the permeable layer 26 and a backing layer Ilia. Said containers Ma and 29a are similar to the containers I8 and 20.

'6 the corresponding portions of the film units described in connection withthe discussionjof Fig. 1 above. As examples of suitable materials,.the photosensitive layer Illa. is pr'eferablyformed of asilver halide which has: *becnsolarizedby pres exposure to actinic lightyby heat treatment; or by suitable chemicaltreatmentp Thev 'baseil'ayer 12a is preferably a cellulosic film base such as cellulose acetate, and is preferably transparent. The liquid composition 'in the container Illa comprises a solvent for a'developerand preferably includes the developer in solution.- The liquid composition in container I80. also preferably comprises a film-formingmaterial and a white pigment, theliquidbeing adapted to form an opaque white permeable film 'adjacent'the photosensitive layer. Theliquid. composition in container 200 includes a solventsfor *a silver halide solvent such "as sodium 'thiosulfate and preferably carries the. silver halidev solvent in solution. The slowly permeabZreT'Iayer'ZG may be made of a substance su'chas a hardened gelatin whose degree of hardnessfor thickness is adjusted with respect to the speed of the developer so that the silver halide solvent permeates completely through said layer after the development of the solarized photosensitive layer has been substantially completed. 1 Other suitable materials of controlled permeability may be us'ed such as permeable organic plastictsheetFm'aterials. The backingtlayer-lfia, in this modification is preferably formed of an impermeablematerial suchasaplasticsheet; I;

When the film unit is p'izoce'ssedszthe. photo.- sensitive layer Iiia'i's exposed to actinic-light to create therein a latent image: There are sev- The various elements of the combination may eral ways of accomplishing this exposure. It may be either through the base'layer lZ'w or through the

transparent layers

16a and 26"; or the two ways, exposure through the base layer 12a is preferred, as shown by the arrow. The.

film unit is then subjected to mechanical stress such as by running it through a .pair of pressure When the development is substantially completed, the :silver halide solvent;.-wil1. have permeated through the slowly permeable layer 26 to dissolve out the undev'elopedsilver halide. The dissolved silver halide is precipitated in the permeable white .film where-it is substantially invisible. There is thu's'accomplished a time delay which permits the developer to develop the solarized photosensitive layerbefore-the hypo dissolves out the undeveloped silver halide.

Another example of a photographic process wherein several reactions are desired inthe same location, but spaced from eachother with respect to time, is that involving the prevention of oxidation of a surplus developer in the neighborhood of the highlights Of'aCpOSltiVe image. In such cases, it has been-'fou'ndthat such oxidation may be prevented, in a process or the typ described in connection withthe discussion of Fig. l, by reducing the alkalinity of the highlights. In order to accomplish-this result the embodiment shown in'Fig. 2 is modified somewhat. In this modification, the photosensitive layer Illa is an ordinary photosensitive layer of the type shown in Fig. 1. The liquid composition in container l8a preferably comprises a developer, a' substancecapable of creating imageforming components, such as sodium'thiosulfate, an alkali such as sodium hydroxide,'a preservative, -a film-forming material and water. The liquid composition in container 20a. comprises an acid such as maleic, citric, or hydrochloric acid, and preferably also includes an aqueous solution of a thickening 'o'r film-forming material to impart a high viscosity to the liquid composition and permit accurate spreading thereof.

A preferred embodiment of this feature of the invention comprises 'theiuse of a slowly permeable layer 26. This layer is preferably formed by casting a hydroxyethyl cellulose sheet .03 inch thick. This sheet is cast from a mixture of 200 grams of hydroxyethyl cellulose and 30 grams of lead acetate. The hydroxyethyl cellulose used is preferably Cellosize, WSlOO, manufactured by Carbide &. Carbon Chemicals Corporation. This mixture is preferably heated to assist in dissolving the lead acetate. It is next cooled to removeai'r bubbles and then cast into a layer of desired thickness. A preferred liquid composition for the container 201: comprises 100 grams of a percent solution of sodium carboxymethyl cellulose containin'g .5 gram of citric acid.

' -A film unit of this type is processed in the same-manner as described in connection with the film unit of Fig. 1. The photosensitive layer is exposed and the film unit run through a-pair of pressure rollers. The positive image is formed in the same manner as described in connection with the first embodiment of Fig. 1. This positiv image exists at least partially in the'formed image-receiving layer carried by the image carrying layer. 7

At the same time that the image-forining reaction is taking place, the acid is slowly permeating through the layer 26. By the time that the. acid reaches the image-receiving layer between layers Illa and 26, the image-forming reaction is substantially complete. The acid then lowers the pH of the liquid between layers Illa and 26 to such a pointthat the excess developer cannot oxidize. The image-carrying layer having thereonthe positive image may then be separated from the photosensitive layer and thus exposed to air. Due to the acid condition of the developer in solution, it cannot oxidize and it rapidly. dries out to'foim 'a stable, finished 'image.

There is thus-provideda photographic-process where ahighly concentrated, easily oxidizable developer is used and an excess amount of developer is employed, aerial oxidation being prevented, during the developing process, due to the fact that substantially all air is excluded from the region'of the developer and the" alkalinity of the developer is lowered below its oxidation point before the excess developer is exposed" to aerial oxidation.

In some cases it is desirable to have a black backing for the entire film unit, in addition to the white pigment'whichisprovided as a direct background for the image of the type discussed in connection with Fig. 1. It is desirable in some cases to form this black background after the exposure of the photosensitivelayer, since it is preferred in many cases to expose the photosensitive layer through a transparent image-carrying layer. This black backing; together with the opaque base. layer on which the photosen-i 'sitive layer is preferably mounted, makes the film unit completely light-imperviousso that it maybe removed from the camera immediately after passing through the pressure rollers. In order to form this black backing, a modification of 1 the invention as shown in Fig. 3 is provided. This modification of the invention isv similar to the embodiment of .the invention described in connection WithgFig. l, with like numbers corresponding to like parts thereof. As can be seen, a third container 22 having therein a black dye and another transparent backing or cover layer 24 have been added to the modification shown in Fig. 1. I

In the preferred modification of the invention as shown in Fig. 3, the various elements thereof are, formed of materials mentioned as being preferable in thediscussion of Fig. 1. The layer 25 can be an organic plastic transparent film which preferably is substantive to the dye carried in a container 22.,

In the use of the film unit of Fig. 3, the photosensitive layer H] is exposed to actinic light preferably, as shown by the arrow, through the trans parent layers l4, I6 and 24 to create in said layer ill a' latent image. The film unit is then processed by applying a mechanical stress thereto such as by passing it through a pair of pressure rollers, the container end going first. The pressure rollers releasethe liquid carried bythe respective containers and the liquids are spread between the various layers. The developer-containing liquid composition is spread between layers l0 and Hi, the pigment-carrying liquid is spread between layers It and I6, and the dye-carrying liquid is spread between layers l6 and 24. In the preferred form of the invention the developing liquid develops the photosensitive layer, creates image-forming components, and transfers these image-forming components to the stable film that is formed by the action of the film-forming material preferably included within container I 8. Meanwhile, the'pigment liquid forms an opaque White background for the positive image being formed on the image-carrying layer. The liquid dye forms an opaque black, light barrier behind the white background and the film can be ejected from a camera directly into daylight.

In some cases it is desirable to have in a film unit'separate solutions 'of materials which cannot be maintained in the same solution Without 'a deleterious reaction therebetween. In such cases, it is preferred to maintain a solution of one of the materials in onecontainer, and to have a solution of the other. material in another container. This condition arisesin certain instances such as when it'is, desirable to use a film-forming material in a developer solution. As an'example,

such a film-forming material may be sodium.

carboxymethyl cellulose. The developer solution preferably also contains a substance such as sodium hydroxide and a developer such as hydroquinone. When a film-forming material, such as sodium carboxymethyl cellulose is used, it is desirable to form this film into a relatively insoluble, dimensionally stable film adjacent an image-carrying layer. To insolubilize this filmforming material it has been found that a lead salt such as lead acetate is particularly advantageous. In some instances it is desirable to carry the lead salt in solution so that it may be spread across the surface ofthe image-carrying layer after the liquid composition, containing the developer and sodiumcarboxymethyl cellulose, has beenspread across the image-carrying layer. In these cases, the leadsalt cannot be carried in the same container with the sodium carboxymethyl cellulose or the sodium hydroxide, since it will react with these substances and form insoluble compounds therewith. Therefore, the

lead salt is carried in a separate solution-which droxide. As an example of a film unit incorporating this modification of the invention, there is shown in Fig. 4 a film unit having two containers mounted in a position to discharge the contents thereof between .a photosensitive layer and another layer. In a preferred modification ofthe invention the film unit comprises a photosensitive layer Ii! which corresponds to the photosensitive layers of Figs. 1 and 3, a base layer 42 which may also correspond to the base layer E2 of Fig. ,1, and an image-carrying layer M which, may'correspond to the image-carrying layer is of Fig. 1. Two containers l8 and 20b" carry the developer liquid composition and the lead salt solution, respectively. The various elements of the film unit may be made of suitable materials as described previously.-

In the use of the invention of Fig. 4, the film unitis exposed as shown by the arrov.z-,preferably through the layer I4, and after exposure the film is processed by the application thereto of mechanical stress, such asby running the film unit through a pair of pressure rollers, the end of the. filmhaving therein container is going throughfirst. The container 18 is ruptured by the pressure rollers, and theliquid composition contained thereinis spread in va uniform film between the photosensitive layer and the image-carrying layer I4. In this instance, the lead salt such aslead acetate is released by reversing the film unit end running itthrough the pressure rollers again, the end having thereinthe container, 20?) ,going first, The lead salt reacts with the film-forming'material to create therewith an insoluble, stable filmand the other reactionsmentionedin connection W th 2. 3 di cussion of Fig. 1 occur in thesame manner. The finalpositive" image is created within and upon the: film. formed. by. the sodium; carbo vmethy cellulose. v. .2. It is also desirable,- insome cases; tohave not only a time differential in release of; the liqu compositionsv but also. to have the releas b tween different layers. "Such a situation is desirable in thoseinstanceswhere it is preferred to have a liquid react with a formed. positive image but wherein it is desired not to interfere with the image'by spre'adingthe liquid across the. surface thereof. -A film unit whereby theabovemay be accomplished is shown in Fig. 5. 'In this modification of. the invention, where like numbers correspond to like numbers of Fig, 4, there is provided the usual base layer l2, having thereon a layer I 0 of a suitable photosensitive material. There is also an image-carrying layer I4 preferably made of a transparent, permeable material such as gelatin and preferably having a coating'of a lead salt on'its upper surface. There is also included an additional "backing layer [6. Two containers is and 200 are included; one at each end'of the film unit. Container 18-, between layers l6 and [4 preferably 'cont'ains'a liquid composition of the type mentioned previously and includes a developer, a film-formingmaterial, etc. Container 200', between layers I4 and i6,

preferably contains an aqueous solutionof an acid such as citric acid which prevents oxidation of the developer remaining in. the highlights and thus prevents-staining of thehighlights of the positive image. I I

In the use of the film unit of Fig. 5, the photosensitive layer I0 is exposed to actinic light, preferably through layers l6 and M. The film unit is then processed by releasing the liquid composition from container I8 and spreading it between layers If) and I4. explained previously, the

liquid composition from container [8 develops the latent negative image contained in the photosensitive layer and also forms a positive image of the subject matter of said latent image, the positive image being formed at least partially in the film created by the film-forming material. After a sufficient time for the formation of the positive image in the formed film, the container 200 is ruptured and the liquid therefrom is spread between layers [-6 and I l and permeates through layer M to stabilize the positive in age. This stabilization is believed to bed-he to the capability of the above-mentioned acid incon-tainer ziicof lowering the pH of the liquid composition in the positive image, at least in the highlights thereof, to the point where oxidation of any excess developer cannot-takeplace. It is also possible to form the layerld from a water-soluble linear polymer such as sodium. earbo xyrnethyl cellulose which has been cross-linked by lead to form a relatively insoluble material. this case the layer I4 is reacted upon by the alkaline liquid composition from container [=3 and the lead is apparently released in ionic condition, The sodium carboxymethyl cellulosein the liquidcomposition forms a unitary film with the sodium carboxymethyl cellulose in layer [4 and the positive image is rm d n is unitaryla r- It o d be n stood t a the mb d me t of the n now in Fi s- 1 t rou h 5 may be in the, form of individual'filrn pack units or ay o mise po t ons: o a roll: or film Since certain changes may be madein the above duc and p o es d id iier nt mbodiments of the invention could be madewithout departing from the scope thereof, it is intended that all matter contained in the above description or shown in the accompanyinng drawings Shall be nt r r d as: l u rat ve and not in a limiting sense,

What is claimed is; i

.1. A photographic product comprisin a'first liquid-confining layer including at least a photo,- sensitive silver halide portion, a second liquidconfining layer, a rupturable container holding a liquid, said producthaving Positioned, therein photographic, processing material, including a soluble silverhalide developer, said developer layer w th a posit e ima e by transfer, a third q fi in la e and a e ond r ptu a container llQldl-Ilgfi llQllid said two containers and said' three liquid-confining layers being rranged so that said three liquid-confining layers may be superposed withsaid two'containers posined. b w en dif n Pe -rs o id iquid-99 fining layers, said first container being arranged ll for releasing its contained liquid for spreading between said first two liquid-confining layers, said second container beingarranged to release its contained liquid for spreading between. said third liquid-confining layer and one of said first two liquid-confining layers, said second liquid, upon release and spreading, creating an effect supplementary to said image transfer.

2. A photographic product comprising a first liquid-confining layer including at least a photosensitive silver halide 'portion, asecond liquidconfining layer, a rupturable container holding a liquid,: s'aid product having positioned therein photographic processing material, including a soluble silver'halide developer and a silver halide solvent for' developing exposed silver halide and providing said secondliquid-confining layer with a positive image by transfer, a third liquid-confining layer, and a second rupturable container holding a liquid, said two containers and said three liquid-confining layers being arranged so that said three liquid-confining layers may be superposed with saidtwocontainers positioned between different pairs or said liquid-confining layers, said first container being arranged for releasing its contained liquid for spreading between said first two liquid-confining layers, said second container being arranged to release its contained liquid for spreading between said second and third liquid-confining layers, said second liquid, upon release andspreading, creating an efiect supplementary to said image transfer.

3, The product of claim 2 wherein said second liquid includes an image-stabilizing material and said second liquid-confining layer is permeable to said second liquid.

4. The product of claim 2 wherein said second and third liquid-confining layers are transparent and said second liquid includesa material which is capable of forming a background '-for said positive image when spread between said second and third liquid-confininglayers.

5. The product of claim 2'whereinsaid second and third liquid-confining layers are transparent and said second liquid includes a material which is capable of forming a light barrier when spread between said second and third liquid-confining layers. f t

6. The product of claim 2'wherein said second and third liquid-confining layers are transparent and said second liquid includes a pigment." I

'7. The product of claim 2 wherein said second and third liquid-confining layers are transparent and said second liquid includes a dye.

8. The product of claim 2 wherein said second and third liquid-confining layers are transparent,

said second liquid includes a dye component and one of said second and third liquid-confining layers includes a material'capable of reacting with said component to form a dye. I r i 9. The product of claim 2 wherein said second liquid includes an acid and said second liquidconfining layer is slowly permeable to said second liquid.

10. The product of claim 18 wherein a relatively slowly permeable barrier layer is positioned between said two liquid-confining layers, said first container is positioned between said first liquid-confining layer and said barrier layer and said second container is positioned between said second liquid-confining layer and said barrier layer.

11. The product of claim 1 wherein a third rupturable container and a fourth liquid-confining layer are provided} said third container being positioned betweensaid third and fourth liquid-confining layers. t 4

12. A photographic productcomprising a runturable container holding a liquid, a sheetsupport upon which said container-is mounted, said sheet supportproviding a spreading surface having a liquid-receiving area adjacent said container onto which said liquid is spreadable directly from said container, said liquid-receiving area being greater than the area covered by said container, the liquid in the container'being sufficient in amount to cover said liquid-receiving area, said product containing-a reducing-agent for developing the exposed portion-eta photosensitive element having as its photosensitive material a heavy metal salt capable of forming a latent image upon photoeXpos'ure and capable ofbeing developed by said reducing agent topr'oduce a visible image comprising the metal of said salt, said reducing agent being inan amount sufiicient to develop an'image in an area of said photosensitive element equivalent to said liquid-receiv ing area, the container contents, when spread on said liquid-receiving area,'placing said reducing agent in condition to efiect the development, a second rupturablefcontainer holding a liquid, and a second sheet support providing a spreading surface having a liquid-receivingarea substantially coextensive in area with said first liquidreceiving area, said two" containers being positioned adjacentopposite surfaces of said first sheet support, said second container being positioned between said two sheet supports for release and spreading of its contained liquid between said two sheet supports, said second liquid creating, when spread, an effect supplementary to said image development and being in an'amount sufficient to cover said second-mentioned liquid- I receiving" area. I i V 13. A photographic productcomprising a first liquid-confining layer, a photosensitive material capable of having a photographic record formed therein upon photoexposure and supported upon said first liquid-confining layerita; second'liquidconfining layer, a first rupturable container holding a liquid, and a second rupturablecont'ainer holding a liquid, said product containing a photographic reagent adapted to'participate' in transforming a photographic record in saidphotosensitive material to a picture image, said reagent I being rendered effective for "transforming'zsaid photographic record by liquid-permeated into said photosensitive material from atleast one of said containers, means holding said two liquidconfining layers together so that saidliquidconfining layers may be superposed with said containers positioned therebetweenfor releasing their contained liquidfor spreading; between said liquidconfining layersiupon-"rupture of said containers, each of said liquids contributing 'to the final characteristics of said picture iinage, and said photosensitive material comprising a salt of the class consisting of (a) the 'photosensitive ferric salts; (b) the photosensitive diazonium salts; (0) the photosensitive dichromates; and (d) heavy metal salts capable. of torrning a latent image upon photoexposurejand capableof development to produce a visible imagecomprising the metal of said-salt.

l4. Aphotographic product, as defined in claim 13 wherein said photosensitive material comprises a silver halide emulsion coated; on said first liquid-confining-layer.r

15; photographic produt asdefined claim 14 wherein said photographic reagent is a'silver halidedeveloper. 1 v

l6, nphotographicproduct as defined in claim 13 wherein another liquid-confining layer is positioned between said first and second liquid-confining layers to provide an intermediate'layer therebetween andwherein said first container is located between said first and --intermediate liquid-confining layers and said secondcontainer is located between said-second and intermediate liquid-confining layers, i v T 17, A photographic product comprising a first liquid-confining layer including at least a solarized silver halide portion, a second liquid-confining layer, a third liquid confining layer, a first rupturable container holding a first liquid, a silver halide developer being included in said first liquid, and a second rupturable. container holding a second liquid, a silver halide solvent being included in said second liquid,said two containers and said three liquid-confining layers being arranged so that the liquid-confining layers may be superposed with said first container positioned between said first and second liquid-confining layers and with said second container positioned between said second andthird liquid-confining layers for releasing their contained liquids for spreading between the layers with which each respective container is associated, said second liquid-confining layer being slowly permeable to said second liquid and said liquids being rendered effective to transform an image-in said solarized silver halide portion upon rupture of said containers and permeation of ;said liquids into said first liquid-confining layer, including said solarized silver halide portion. v

18. A photographic product containing material, including a photographic reagent, for producing a transformation of an image in said product, said reagent being present in an amount sufiicient to effect said transformation, said product comprising a first liquid-confining layer including at least a photosensitive silver halide portion, a second liquid-confining layer, a rupturable container holding a liquid, and a second 45 forming a latent image upon photoexposure and rupturable container holding a liquid, said liquid in said two containers being in an amount sufficient for transforming said image in said photosensitive portion, said liquid, upon permeation of said photosensitive portion, rendering said transforming material effective to transform said image, said two containers and said two liquidconfining layers being arranged so that said two liquid-confining layers may be superposed with said two containers positioned between different portions of said liquid-confining layers for releasing their contents for spreading therebetween, each said container having a liquid-releasing mouth, one of said containers being positioned at a location adjacent one edge of said photosensitive portion and the other of said containers being positioned at a location adjacent the opposite edge of said photosensitive portion, the mouths of said containers facing each other, each of said liquids being effective to contribute to the final characteristics of the image produced by said transformation.

19. A photographic product comprising a first a sheet support, a secondsheet support arranged in superposed relation thereto, a first rupturable container mounted on the side of said first sheet support which is furthest removed from the second support, said first container holding a liquid, the contents of said first container including a silver halide developer, and a second rupturable container holding a liquid, said second container tially similar and the liquid in each container being sufficient in amount to cover the liquidreceiving area'w-ith which said container is associated and to provide-a continuous filmof liquid thereon, said silver-halide developer being in an amount sumcient-to develop alatent-image in a silver halide photosensiti-ve stratum equivalent in area-to" a liquidereceiving area,- each said liquid upon-its release being adapted to cooperate with the other liquidto impart the final characteristics to the i'jage. resulting from silver halide development;

' '20. A-photographic product as defined in.- claim 19 wherein -the-liqu-id= in saidsecond container includes a 'silver 'halidesolvent. 1 V

7 2i." A photographicproduct for carrying out a photographic processresultingin the formation of a visible imageand-comprising a sheet support, a first rupturable container holding a liquid, and a secondrupturablecontainer holding a liquid, each'said container having a liquidreleasing mouth, each; said container being mountedon'thes'ame side off said support and extending transversely thereof, said support being providedjwith asurface area'on said side having said containers thereon and which is adapted to receive theliqui'dcontentsbf the containers' upon rupture thereofand: the spreading of liquid released therefrom, said containers also being positioned on said sheet-support to have their respective liquid-releasing mouths each facing an edge of said surface area for dispensing the liquid contents of the containers for spreading over said surface area. and each container holding liquid in an amount sufficient to cover said surface area, said product containing a reducing agent for developing the exposed portion of a photosensitive element having as its photosensitive material a heavy metal salt capable of 22.'A photographic product comprising a rupturable container holding a liquid, a sheet sup-- port upon which said container is mounted, said sheet support providing a spreading surface having a liquid-receiving area adjacent said container onto which said liquid is spreadable directly from said container, said liquid-receiving area being greater than the area covered by said container, the liquid in the container being sufficient in amount to cover said liquid-receiving area, said product containing at least one photographic processing agent from the class consisting of the silver halide developers and the silver halide fixing solvents, said processing agent being in an amount sufiicient to process an image in an area of a photosensitive, silver halide element equivalent to said liquid-receiving area, the container. contents, when, spread on said liquid-re ceivingfl area; placing said processing agent in condition toeffect. the processing of said element, a second rupturablecontainer holdinga liquid, and a second sheet support providinga spreading surface having a. liquid-receiving area, substantially "coextensive in area with said first liquidreceiving area, said 'two containers being positioned adjacent opposite surfaces of said first sheet support, said second container being positionedbetweensaid two sheet supports for release and spreading of its contained liquid between said two sheetgsl pports, said secondliquid creating, when ,spread,,;an,; efiect supplementary to said image processing 'an'dbeing; in an amount suflicient to, cover. said second-mentioned liquidreceiving area" H I V 23. A photographic product for carrying'out a photographic process resulting in the formation of a visible image and comprising a sheet support, a first rupturable container holding a liquid, and a second rupturable container holding a liquid, each said containenhaving a liquid-releasing mouth, each said container being mounted on the same side of; said support and extending transversely thereof, said support being provided with a surface areaon said side having said containers thereon and which is adapted to receive the liquid contents of the containers upon rupture thereof and the spreadin of liquid released therefrom, said containers also being positioned on said sheet support to have their respective liquid-releasing mouths each facing an edge of said surface area for dispensing the liquid contents of the containersforspreading over said surface area and each container holding liquid in an amount sufiicient ,to cover said surface area, said ment. 7

V EDWIN I-I. LAND,

' REFERENCES CITED The following referencesare of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,207,042 Hochstetter 1- Dec. 5', 1916 2,071,821 Eckardt Feb. 23,1937 2,315,966 Knott Apr. 6,1943 2,322,005 'Fierke et a1. June 15, 1943 2,322,006 Fierke et a1. June 15, 1943 2,322,027 Jelley et a1. June 15, 1943 2,352,014 Rott June 20, 1944 2,358,246 Nicolle Sept. 12, 1944 2,378,004 Duell June 12, 1945 2,388,894 Yackel Nov. 13, 1945 2,397,015 Kendall Mar. 19, 1946 2,410,644 Fierke Nov. 5, 1946 FOREIGN PATENTS Number Country a Date- France Mar; 10, 1943

Claims

12. A PHOTOGRAPHIC PRODUCT COMPRISING A RUPTURABLE CONTAINER HOLDING A LIQUID, A SHEET SUPPORT UPON WHICH SAID CONTAINER IS MOUNTED, SAID SHEET SUPPORT PROVIDING A SPREADING SURFACE HAVING A LIQUID RECEIVING AREA ADJACENT SAID CONTAINER ONTO WHICH SAID LIQUID IS SPREADABLE DIRECTLY FROM SAID CONTAINER, SAID LIQUID-RECEIVING AREA BEING GREATER THAN THE AREA COVERED BY SAID CONTAINER, THE LIQUID IN THE CONTAINER BEING SUFFICIENT IN AMOUNT TO COVER SAID LIQUID-RECEIVING AREA, SAID PRODUCT CONTAINING A REDUCING AGENT FOR DEVELOPING THE EXPOSED PORTION OF A PHOTOSENSITIVE ELEMENT HAVING AS ITS PHOTOSENSITIVE MATERIAL A HEAVY METAL SALT CAPABLE OF FORMING A LATENT IMAGE UPON PHOTOEXPOSURE AND CAPABLE OF BEING DEVELOPED BY SAID REDUCING AGENT TO PRODUCE A VISIBLE IMAGE COMPRISING THE METAL OF SAID SALT, SAID REDUCING AGENT BEING IN AN AMOUNT SUFFICIENT TO DEVELOP AN IMAGE IN AN AREA OF SAID PHOTOSENSITIVE ELEMENT EQUIVALENT TO SAID LIQUID-RECEIVING AREA, THE CONTAINER CONTENTS, WHEN SPREAD ON SAID LIQUID-RECEIVING AREA, PLACING SAID REDUCING AGENT IN CONDITION TO EFFECT THE DEVELOPMENT, A SECOND RUPTURABLE CONTAINER HOLDING A LIQUID, AND A SECOND SHEET SUPPORT PROVIDING A SPREADING SURFACE HAVING A LIQUID-RECEIVING AREA SUBSTANTIALLY COEXTENSIVE IN AREA WITH SAID FIRST LIQUIDRECEIVING AREA, SAID TWO CONTAINERS BEING POSITIONED ADJACENT OPPOSITE SURFACES OF SAID FIRST SHEET SUPPORT, SAID SECOND CONTAINER BEING POSITIONED BETWEEN SAID TWO SHEET SUPPORTS FOR RELEASE AND SPREADING OF ITS CONTAINED LIQUID BETWEEN SAID TWO SHEET SUPPORTS, SAID SECOND LIQUID CREATING, WHEN SPREAD, AN EFFECT SUPPLEMENTARY TO SAID IMAGE DEVELOPMENT AND BEING IN AN AMOUNT SUFFICIENT TO COVER SAID SECOND MENTIONED LIQUID RECEIVING AREA.