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US2565377A - Hinged photographic film unit containing a liquid - Google Patents

Hinged photographic film unit containing a liquid Download PDF

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US2565377A
US2565377A US167832A US16783250A US2565377A US 2565377 A US2565377 A US 2565377A US 167832 A US167832 A US 167832A US 16783250 A US16783250 A US 16783250A US 2565377 A US2565377 A US 2565377A
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liquid
layer
image
layers
container
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US167832A
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Edwin H Land
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Polaroid Corp
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Polaroid Corp
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    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C8/00Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
    • G03C8/42Structural details

Definitions

  • This invention relates to photography and more particularly to novel, composite photographic film units and materials.
  • One object of the present invention is to provide a novel, composite photographic film unit comprising a photosensitive layer and a base layer forming a, photosensitive layer assembly, another layer, and a liquid container, said other layer and said assembly being hinged together for separation during exposure of the photosensitive layer and rejoinder after exposure.
  • Still another object of the invention is to provide a composite photographic film unit comprising a photosensitive layer assembly, an image-carrying layer and a container for a liquid composition positioned betweensaid assembly and said image-carrying layer, said image-carrying layer and said photosensitive layer assembly being hinged for separation during exposure and rejoinder after exposure.
  • Another object is to provide a novel, composite photographic film of the above type wherein the to prevent the layers from separating while allowing manual separation thereof.
  • Another object of the present invention is to provide a novel, composite photographic film unit having a photosensitive layer assembly connected to an image-carrying layer by a hinge, and having a, container between said assembly and said image-carrying layer, the thickness and compressibility of the composite film in that portion including said container being the same as the thickness and compressibility of the composite film in that portion including said hinge.
  • Fig. 2 is a cross-sectional view of a, novel, composite photographic material showing another feature of the present invention.
  • Fig. 3 is a cross-sectional view of another modification of the present invention.
  • Fig. '1 which is similar. to one of the film units described in my copending application mentioned above, there is shown one form of the present invention.
  • a base layer In carrying thereon a photosensitive layer ll, these two layers comprising a photosensitive assembly.
  • an image-carrying layer I2 and a container or pod l3 mounted on said image-carrying layer and having therein. a liquid composition or reagent.
  • this hinge allows the base layer l0, along with the photosensitive layer H, to be moved relative to the image-carrying layer l2, so that, when the composite film unit is positioned within a camera, the inner surface of the photosensitive layer H may be exposed to actinic light.
  • the base layer In comprises paper or other opaque substance. It may be a cellulosic film base such as a sheet of cellulose acetate, cellulose nitrate or cellulose acetate butyrate where the cellulosic film base has been treated to make it opaque to light.
  • Photosensitive layer II is preferably of the type which is rendered developable by exposure to light, e. g., an emulsion of silver halide or of a mixture of silver halides or of a mixed silver halide.
  • the image-carrying layer [2 is preferably formed of a substance such as paper, including alpha and barytapaper, or a substance like hardened opaque gelatin, although it may be formed of a material such as opaque glass.
  • Container I3 of the liquid composition is preferably formed of an elongated, water-vapor-impervious and oxygen-impervious material such as a wax coated metal foil.
  • This container is so formed that the application of a suitable mechanical stress thereto as, for example, the squeezing together of the faces of the composite film unit will release the liquid composition in said container in only one direction, longitudinally of the film unit, so as to spread said liquid composition between the photosensitive layer ii and the layer l2.
  • the iiquid composition is preferably viscous and preferably contains therein a water-soluble film-forming material such as a high molecular weight polymer or protein as, for example, gelatin or a polymeric water-soluble ether, inert to an alkali solution, such as hydroxy-methyl cellulose, or a metal salt of carboxymethyl cellulose, for example, sodium or aluminum carboxymethyl cellulose.
  • a water-soluble film-forming material such as a high molecular weight polymer or protein as, for example, gelatin or a polymeric water-soluble ether
  • an alkali solution such as hydroxy-methyl cellulose, or a metal salt of carboxymethyl cellulose, for example, sodium or aluminum carboxymethyl cellulose.
  • This film-forming substance such as sodium carboxymethyl cellulose, when spread between the photosensitive layer I l and the image carrying layer 52, quickly forms a dimensionally stable, firm film, which is known as, and hereafter referred to as, an image-receiving layer.
  • This film-forming substance acts as an adhesive to hold the image-carrying layer to the photosensitive layer assembly, so that the two will not be separated after the film unit has been processed.
  • the liquid composition in the container 13 also preferably has included therein a developer such as hydroquinone, which will develop a latent photographic image within the photosensitive layer II.
  • the liquid composition also preferably includes a substance such as sodium thiosulfate, which will react with the unexposed silver halide in the photosensitive layer H to form therewith soluble, positive, image-forming complexes.
  • the hinge Hi is formed of a suitable substance such as cellulose acetate, cellophane, paper or metal foil, and is attached to the respective layers as by an adhesive.
  • the novel composite film unit shown in Fig. 1 it is placed within a camera, and the base layer iii, along with the photosensitive layer H, is moved to approximately the position shown in Fig. 1. It is equally possible for the image-carrying layer 1 2 to be moved with respect to the base layer iii and the photosensitive layer H. This relative movement of the two portions of the film unit permits the exposure of the photosensitive layer il. After the exposure of the photosensitive layer Ii to actinic light, the film A preferred way of applying this stress is to pass the composite film through a pair of pressure rollers, the container end entering first.
  • This applica tion of pressure to the film unit will rupture the container l3 and spread the liquid composition released from the container in a uniform film throughout the area between the photosensitive layer H and the image-carrying layer l2.
  • the developer contained in the liquid composition will develop the latent photographic image and the substance, such as sodium thiosulfate, will form, with the unexposed silver halide, soluble positive image-forming complexes. While this process is underway, the film-forming material in the liquid composition will be forming a dimensionally stable image-receiving layer between the image-carrying layer l2 and the photosensitive layer II.
  • the positive image-forming complexes mentioned above will transfer from the photosensitive layer to the formed image-receiving layer and will form therein a positive image of the subject matter of the latent image.
  • the film-forming material acts as an adhesive to hold the image-carrying layer l2 to the photosensitive layer, and will thus create a light-tight unit which may be handled in the daylight without danger of interfering with the photographic process.
  • the photosensitive layer II and the base layer ill are stripped from the image-carrying layer l2 which has on its surface the imagereceiving layer, to reveal the final positive image contained in said image-receiving layer. Since the image-receiving layer has a greater affinity for the image-carrying layer than it has for the photosensitive layer, it will adhere'to the former layer.
  • a composite photographic film having light-impervious outer surfaces which permit handling of the film in daylight without affecting the photosensitive material.
  • This construction permits the film unit to be loaded in a camera and discharged therefrom in daylight.
  • the photosensitive layer can be exposed to actinic light by separating the image-carrying layer therefrom when the film is in the camera due to the hinged connection of the several parts of the film.
  • This novel construction affords advantages of ease of handling and allows the immediate ejection of the film from a camera after exposure.
  • a substance such as sodium thiosulfate creates soluble positive image-forming complexes with the unexposed silver halide and transfers these image-forming complexes from the photosensitive layer to the image-carrying layer l2, and the image is formed on and within the surface of the image-carrying layer 52.
  • no image-receiving layer, as such, is formed during the processing of the film.
  • this image area would be that portion of the area of the image-carrying layer which is adapted to receivethe positive image, including a sufficient area to constitute a frame for the final positive image.
  • the photosensitive layer H is smaller than the image-carrying layer 12, the image area will ordinarily be approximately the size of the photosensitive layer.
  • the photosensitive layer H is of the same size as the photosensitive layer ll, depending upon the desired image and frame in the final positive image.
  • Fig. 2 there is shown another embodiment of the present invention wherein there is provided a base layer 20 of paper or a dyed cellulosic film base similar to that described in connection with Fig. 1. .
  • comprising a silver halide emulsion.
  • an image-carrying layer 22 preferably formed of a porous sub,- stance such as blotting paper, a container 23 for a liquid composition, and a hinge 24.
  • Container 23 and hinge 24 are preferably made of the same materials as mentioned in connection with corresponding elements described more completely in the discussion of Fig. 1 above
  • Fig. 2 includes, in addition to the elements recited above, an image area sheet 25.
  • the image area sheet 25 is preferably formed of ,a relatively liquid-absorbent, liquid-permeable material, such as paper, in-
  • the liquid composition in the container 23 is preferably of the same type as that described in connection with the liquid composition used with the embodiment of the invention shown in Fig. 1.
  • is exposed to actinic light after relative separation of the photosensitive layer El and the image area sheet 25 has been accomplished.
  • the film unit is then run through pressure applying means which releases the liquid composition from the container 23 and spreads it between the photosensitive layer 2
  • the soluble, positive image-forming complexes are transferred onto and within the surface of the image area sheet 25 and the final positive image is formed on and within the surface of said image area sheet 25 in those cases where the image-carrying layer is not made of glass.
  • the excess liquid composition which is not used in the development, image-forming and film-forming processes mentioned above flows over the edges of the image area sheet 25 where it adheres to and is absorbed within the surface of the blotter-like image-carrying layer 22.
  • the base layer 23, along with the photosensitive layer 2 is stripped from the image area sheet 25, which in turn, may preferably be stripped from the image-carrying layer 22.
  • a base layer of a cellulosic film base or similar material like that described in connection with the base layer I0 shown in Fig. 1.
  • comprising a silver halide emulsion.
  • An image-carrying layer 32 of paper such as baryta paper or alpha paper, hardened gelatin or glass is also provided.
  • a hinge 34 Connecting the photosensitive layer assembly (i. e. the base layer 30 and the photosensitive layer 3
  • a container 33 for the liquid composition is positioned between the photosensitive layer assembly and the image-carrying layer there is positioned a container 33 for the liquid composition.
  • the container and the hinge are at opposite ends of the film unit. are also shown as having substantially the same thickness. It is also desirable for these twoele- 'ments to have substantially the same compres- .bility.
  • the container 33 is preferably made of a substance similar to that described in connection with the, container
  • the liquid composition within the container is preferably of the same type as that described in connection with Fig. 1.
  • the hinge 34 can be made of paper, a synthetic high polymer or a cellulosic film base such as cellulose acetate.
  • is moved away from the image-carrying layer to permit direct exposure of the photosensitive layer 3
  • pressure applying means such as a pair, of rollers
  • the liquid composition is released by the pressure from the container and is spread uniformly and unidirectionally between the photosensitive layer 3
  • the liquid composition contains a film-forming substance such as sodium carboxymethyl cellulose, this substance forms an image-receiving layer between the photosensitive layer 3
  • the film-forming substance additionally serves a temporary adhesive function, as discussed in connection with Fig. 1. If the liquid composition does not contain a film-forming substance, the positive image is formed on and within the surface of the imagecarrying layer 32.
  • the liquid composition may have included therein a nonfilm-forming substance which increases its adhesive qualities.
  • the image area on the image-carrying layer is roughly that portion of the layer defined by the edges thereof, the corgtainer at one end, and the hinge at the other en
  • the various hinges shown therein have been referred to as being attached to the image-carrying layer or the base layer. It is obvious that this attachment can be accomplished by forming the hinge of a thermoDlastic composition, or by using a suitable adhesive, or by mechanical means such as stitching or stapling.
  • the photosensitive layer has been shown as being smaller than the base layer in each instance. This is a preferred form of the invention, since it results in a saving of the photosensitive material. However, the phototensive in area.
  • the hinge can be made by extending the adjacent ends of the base layer and image-carrying layer and suitab-ly joining them together.
  • photosensitive layer II is a silver halide emulsion or the like, that is, an emulsion of a heavy metal salt capable of having a latent image formed therein upon exposure, which latent image may be rendered visible by suitable silver halide developing agents.
  • the liquid released from container 13 cooperates with the emulsion and with image-carrying layer l2 to carry out a transfer process.
  • This transfer process involves the development of a latent image in the photosensitive emulsion and, in one preferred form, the removal from that emulsion of part at least of the undeveloped silver halide as a soluble complex, which soluble complex is transported from the photosensitive layer to form the positive print.
  • the treatment of the photosensitive diazonium may be accomplished by applying thereto a liquid containing certain developing reagents.
  • a liquid containing certain developing reagents L. P. Clerc, Photography Theory and Practice, second edition, published 1937 by Pitman Publishing Company, page 444, paragraph 693.
  • the products of the present invention may be used in conjunction with, or may comprise as elements thereof, diazonium photosensitive layers.
  • the photographic product may be formed by having any of the aforementioned physical structures and the photosensitive layer ll of said product may have as itsphotosensitiVe 8 substance a diazonium compoundsuch as that sold by the Boston Blue Print Company under the name Blackline #202, and the liquid reagent in the container l3then preferably comprises, by weight, 4 parts of medium visosity sodium carboxymethyl cellulose, parts of water and 8 parts of Blackline Developer #203 sold by Boston Blue Print company and manufactured by Frederick Post Company, Chicago).
  • the photosensitive layer ll may be obtained by applying to one side of a suitable sheet material a sensitizing solution which consists of 20 grams of chlorostannate of paradiazo-di N butyl-aniline, 0.4 gram of Pontacyl Brilliant Blue 2R, and 1 liter of water.
  • the liquid developing reagent in the container 13 then preferably comprises, by weight, 4 parts of medium viscosity sodium carboxymethyl cellulose, 100 parts of water, 5.8 parts of sodium carbonate (monohydrate) and 2.3 parts of phloroglucinol.
  • the diazonium photosensitive layer may also be obtained by dipping a sheet of paper in a solution of Du Pont Naphthanil Diazo Black B, and the developing solution in container I3 may comprise 1500 parts, by weight, of a 5% water solution of sodium carboxymethyl cellulose, 10 parts of resorcinal and 1 part of sodium hydroxide.
  • ferric salts of organic acids for example, the oxalates, tartrates, and citrates are reduced to ferrous salts when exposed to light.
  • L. P. Clerc Photography Theory and- Practice, second edition, published 1937 by Pitman Publishing Company, page 402, paragraph 621 et seq.; Crowley Patents Nos. 2,093,421, 2,113,423,- 2,130,070, 2,130,071, 2,137,015.
  • a considerable number of photographic processes depend-for their functioning on this photochemical phenomenon. It is known in connection with these iron salts that any reagent that will differentiate between ferric and ferrous salts can be used to develop the barely visible image formed by the photochemical reduction of the ferric salt into an image which is very easily visible.
  • Examples of such developing reagents are potassium ferricyanide, potassium ferrocyanide, tannins, gallic acid, B-naphthoquinone-sulphonic acid. silver salts, platinum and palladium salts. It is believed to be now apparent to one skilled in the art that the photoresponsive ferrous salts may constitute the photosensitive material of the photosensitive layer H, and the liquid in the container I3 may include or dissolve in its travel to the photosensitive layer any one of the aforementioned developing reagents for distinguishing between the ferric and ferrous salts and producing the easily visible image from the very light image that is originally obtained by the photoexposure of the iron salts.
  • the products of the present invention may comprise, or may be used with, any photographic, photosensitive material for the purpose of developing the same. It is to be understood that the invention is not limited to materials sensitive to visible radiation but includes photographic, photosensitive materials sensitive to such other radiation as X-ray, ultraviolet, infrared or gamma radiation.
  • 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 sufficient to effect said transformation
  • said product comprising a liquid-confining layer, includingat least a photographic photosensitive portion capable of having an image formed therein upon photoexposure, another liquid-confining layer, an opaque stratum associated with each of said liquid-confining layers, and a rupturable container holding a viscous liquid, said liquid'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 layers and container being attached together by means of a hinge, said liquid-confining layers being normally superposed with said photosensitive portion positioned between said opaque strata so as to exclude actinic light from said photosensitive portion, saidhinge permitting said layers to be separated so as to allow exposure of said photosensitive portion and then permitting said layers to be superposed again, with said liquid being held by said container so as not to
  • 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 sufficient to effect said transformation, said product comprising a liquid-confining layer, including at least a photographic photosensitive portion capable of having an image formed therein upon photoexposure, another liquid-confining layer, an opaque stratum associated with each of said liquid-confining layers, and a rupturable container holding a viscous liquid, said liquid 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 layers and container being attached together by means of a hinge, said liquid confining layers being normally superposed with said photosensitive portion positioned between said opaque strata so as to exclude actinic light from said photosensitive portion, said hinge permitting said layers to be separated so as to allow exposure of said photosensitive portion and then permitting said layers to be superposed again, with said liquid being held by said container so as not to wet said layers
  • a photographicproduct containing material including a photographic reagent, for producing a transformation of an image in said product, said reagent being present in .an amount sufficient to effect said transformation, said product comprising a liquid-confining layer, including at least a photographic photosensitive portion capable of having an image formed therein upon photoexposure, another liquidconfining layer, an opaque stratum associated with each of said liquid-confining layers, and a rupturable container holding a viscous liquid, said liquid being in an amount sufiicient 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 layers and container being attached together by means of a hinge, said liquid-confining layers being normally superposed with said photosensitive portion positioned between said opaque strata so as to exclude actinic light from said photosensitive portion, said hinge permitting said layers to be separated so as to allow exposure of said photosensitive portion and then permitting said layers to be superposed again, with said liquid being held by said container so as
  • said second liquid-confining layer comprises'the double layer and the inner layer thereof comprises animagearea sheet separably secured to the outer layer, said outer layer beingblotterlike.

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  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
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Description

Aug. 21, 1951 E. H. LAND 2,565,377
HINGED PHOTOGRAPHIC FILM UNIT CONTAINING A LIQUID Filed June 13, 1950 Phoosensiflve Layer FIG.
Base Layer Con'lainer lrnage Cai-rying Layer Hinge FlG. 2
Layer Image Carrying Laycb lmag-Area Shed 25 F IG. 3
Coniainer 31 Bang Layer 3O Hinge 33 32 Image Carrying Layer hobseasifive Layer Patented Aug. 21, 1951 HINGEID FHOTOGRAPHIC FILM UNIT CONTAINING A LIQUID Edwin H. Land, Cambridge, Mass., assignor to Polaroid Corporation, Cambridge, Mass., a corporation of Delaware Application June 13, 1950, Serial No. 167,832
9 Claims.
This invention relates to photography and more particularly to novel, composite photographic film units and materials.
This application is acontinuation-in-part 01 my copending application, Serial No. 651,124. filed March 1, 1946 for Hinged Photographic Film Unit Containing a Liquid, now abandoned.
One object of the present invention is to provide a novel, composite photographic film unit comprising a photosensitive layer and a base layer forming a, photosensitive layer assembly, another layer, and a liquid container, said other layer and said assembly being hinged together for separation during exposure of the photosensitive layer and rejoinder after exposure.
Still another object of the invention is to provide a composite photographic film unit comprising a photosensitive layer assembly, an image-carrying layer and a container for a liquid composition positioned betweensaid assembly and said image-carrying layer, said image-carrying layer and said photosensitive layer assembly being hinged for separation during exposure and rejoinder after exposure.
Another object is to provide a novel, composite photographic film of the above type wherein the to prevent the layers from separating while allowing manual separation thereof.
Another object of the present invention is to provide a novel, composite photographic film unit having a photosensitive layer assembly connected to an image-carrying layer by a hinge, and having a, container between said assembly and said image-carrying layer, the thickness and compressibility of the composite film in that portion including said container being the same as the thickness and compressibility of the composite film in that portion including said hinge.
These and other objects of the invention will in part be obvious and will in part appear hereinafter.
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 7 wherein Figure l is a partially schematic perspective view of one form of the present invention;
Fig. 2 is a cross-sectional view of a, novel, composite photographic material showing another feature of the present invention; and
Fig. 3 is a cross-sectional view of another modification of the present invention.
Referring now to Fig. '1, which is similar. to one of the film units described in my copending application mentioned above, there is shown one form of the present invention. As shown in Fig. 1 of the instant application, there is provided a base layer In carrying thereon a photosensitive layer ll, these two layers comprising a photosensitive assembly. There is also provided an image-carrying layer I2 and a container or pod l3 mounted on said image-carrying layer and having therein. a liquid composition or reagent.
Connecting the image-carrying layer with the photosensitive layer assembly, i. e., the photosensitive layer. II and the base I0, there is provided a hinge ll. As can be seen from Fig. 1, this hinge allows the base layer l0, along with the photosensitive layer H, to be moved relative to the image-carrying layer l2, so that, when the composite film unit is positioned within a camera, the inner surface of the photosensitive layer H may be exposed to actinic light.
In a preferred form of the present invention, the base layer In comprises paper or other opaque substance. It may be a cellulosic film base such as a sheet of cellulose acetate, cellulose nitrate or cellulose acetate butyrate where the cellulosic film base has been treated to make it opaque to light. Photosensitive layer II is preferably of the type which is rendered developable by exposure to light, e. g., an emulsion of silver halide or of a mixture of silver halides or of a mixed silver halide. The image-carrying layer [2 is preferably formed of a substance such as paper, including alpha and barytapaper, or a substance like hardened opaque gelatin, although it may be formed of a material such as opaque glass.
Container I3 of the liquid composition is preferably formed of an elongated, water-vapor-impervious and oxygen-impervious material such as a wax coated metal foil. This container is so formed that the application of a suitable mechanical stress thereto as, for example, the squeezing together of the faces of the composite film unit will release the liquid composition in said container in only one direction, longitudinally of the film unit, so as to spread said liquid composition between the photosensitive layer ii and the layer l2.
unit is subjected to mechanical stress.
The iiquid composition is preferably viscous and preferably contains therein a water-soluble film-forming material such as a high molecular weight polymer or protein as, for example, gelatin or a polymeric water-soluble ether, inert to an alkali solution, such as hydroxy-methyl cellulose, or a metal salt of carboxymethyl cellulose, for example, sodium or aluminum carboxymethyl cellulose. This film-forming substance, such as sodium carboxymethyl cellulose, when spread between the photosensitive layer I l and the image carrying layer 52, quickly forms a dimensionally stable, firm film, which is known as, and hereafter referred to as, an image-receiving layer.
This film-forming substance, as it forms the film, and after the film is formed, acts as an adhesive to hold the image-carrying layer to the photosensitive layer assembly, so that the two will not be separated after the film unit has been processed.
The liquid composition in the container 13 also preferably has included therein a developer such as hydroquinone, which will develop a latent photographic image within the photosensitive layer II. The liquid composition also preferably includes a substance such as sodium thiosulfate, which will react with the unexposed silver halide in the photosensitive layer H to form therewith soluble, positive, image-forming complexes.
The hinge Hi is formed of a suitable substance such as cellulose acetate, cellophane, paper or metal foil, and is attached to the respective layers as by an adhesive.
In the use of the novel composite film unit shown in Fig. 1, it is placed within a camera, and the base layer iii, along with the photosensitive layer H, is moved to approximately the position shown in Fig. 1. It is equally possible for the image-carrying layer 1 2 to be moved with respect to the base layer iii and the photosensitive layer H. This relative movement of the two portions of the film unit permits the exposure of the photosensitive layer il. After the exposure of the photosensitive layer Ii to actinic light, the film A preferred way of applying this stress is to pass the composite film through a pair of pressure rollers, the container end entering first. This applica tion of pressure to the film unit will rupture the container l3 and spread the liquid composition released from the container in a uniform film throughout the area between the photosensitive layer H and the image-carrying layer l2. The developer contained in the liquid composition will develop the latent photographic image and the substance, such as sodium thiosulfate, will form, with the unexposed silver halide, soluble positive image-forming complexes. While this process is underway, the film-forming material in the liquid composition will be forming a dimensionally stable image-receiving layer between the image-carrying layer l2 and the photosensitive layer II. The positive image-forming complexes mentioned above will transfer from the photosensitive layer to the formed image-receiving layer and will form therein a positive image of the subject matter of the latent image.
As mentioned above, the film-forming material acts as an adhesive to hold the image-carrying layer l2 to the photosensitive layer, and will thus create a light-tight unit which may be handled in the daylight without danger of interfering with the photographic process.
In a preferred form of the embodiment of the present invention, after a sufiicienttime for development, the photosensitive layer II and the base layer ill are stripped from the image-carrying layer l2 which has on its surface the imagereceiving layer, to reveal the final positive image contained in said image-receiving layer. Since the image-receiving layer has a greater affinity for the image-carrying layer than it has for the photosensitive layer, it will adhere'to the former layer.
By the use of the present invention there is v provided a composite photographic film having light-impervious outer surfaces which permit handling of the film in daylight without affecting the photosensitive material. This construction permits the film unit to be loaded in a camera and discharged therefrom in daylight. The photosensitive layer can be exposed to actinic light by separating the image-carrying layer therefrom when the film is in the camera due to the hinged connection of the several parts of the film. 1
This novel constructionaffords advantages of ease of handling and allows the immediate ejection of the film from a camera after exposure.
The above discussion of the present invention as embodied in Fig. 1 has been limited to the use of the presentnovel composite film in such a manner that the photosensitive layer is exposed directly to actinic light. It is apparent, however, that if the base layer [0 be transparent, such as may be the case with a number of materials mentioned=above, the photosensitive layer may be exposed through the base layer ll]. In this embodiment of the invention, it is not necessary to separate the photosensitive layer assembly, 1. e., the base layer Ill. and the photosensitive layer H, from the image-carrying layer during exposure of the photosensitive layer. The hinge in this modification. of the invention serves primarily to hold the various portions of the film unit together duringexposure and subsequent processing, and permits easy separation thereof after processing.
It is. also possible to practice the invention as described above without the use of a film-forming substance in the liquid composition. In this embodiment of the invention a substance such as sodium thiosulfate creates soluble positive image-forming complexes with the unexposed silver halide and transfers these image-forming complexes from the photosensitive layer to the image-carrying layer l2, and the image is formed on and within the surface of the image-carrying layer 52. In this case, no image-receiving layer, as such, is formed during the processing of the film.
Throughout the specification and claims, reference is madc to an image area. In Fig. 1, this image area would be that portion of the area of the image-carrying layer which is adapted to receivethe positive image, including a sufficient area to constitute a frame for the final positive image. Where the photosensitive layer H is smaller than the image-carrying layer 12, the image area will ordinarily be approximately the size of the photosensitive layer. Where the photosensitive layer H is of the same size as the photosensitive layer ll, depending upon the desired image and frame in the final positive image.
r Referring now to Fig. 2, there is shown another embodiment of the present invention wherein there is provided a base layer 20 of paper or a dyed cellulosic film base similar to that described in connection with Fig. 1. .There is also provided a photosensitive layer 2| comprising a silver halide emulsion. There is shown an image-carrying layer 22, preferably formed of a porous sub,- stance such as blotting paper, a container 23 for a liquid composition, and a hinge 24. Container 23 and hinge 24 are preferably made of the same materials as mentioned in connection with corresponding elements described more completely in the discussion of Fig. 1 above, Fig. 2 includes, in addition to the elements recited above, an image area sheet 25. The image area sheet 25 is preferably formed of ,a relatively liquid-absorbent, liquid-permeable material, such as paper, in-
cluding alpha and baryta paper, or a substance like hardened gelatin. It may, however, be made of a material such as glass. The liquid composition in the container 23 is preferably of the same type as that described in connection with the liquid composition used with the embodiment of the invention shown in Fig. 1.
In the use of the composite film unit shown in Fig. 2, photosensitive layer 2| is exposed to actinic light after relative separation of the photosensitive layer El and the image area sheet 25 has been accomplished. The film unit is then run through pressure applying means which releases the liquid composition from the container 23 and spreads it between the photosensitive layer 2| and the image area sheet 25. If a film-forming material is included in the liquid composition, a positive image will be produced in the film formed by this film-forming material between the photosensitive layer and the image area sheet 25. If no film-forming material is included in the liquid composition, the soluble, positive image-forming complexes are transferred onto and within the surface of the image area sheet 25 and the final positive image is formed on and within the surface of said image area sheet 25 in those cases where the image-carrying layer is not made of glass. The excess liquid composition which is not used in the development, image-forming and film-forming processes mentioned above flows over the edges of the image area sheet 25 where it adheres to and is absorbed within the surface of the blotter-like image-carrying layer 22.
When the above process has been completed, the base layer 23, along with the photosensitive layer 2 is stripped from the image area sheet 25, which in turn, may preferably be stripped from the image-carrying layer 22.
As discussed in connection with Fig. 1, it is possible to expose the photosensitive layer 2| through the base layer 20.
Referring now to Fig. 3, there is shown still another modification of the present invention, wherein there is provided a base layer of a cellulosic film base or similar material, like that described in connection with the base layer I0 shown in Fig. 1. There is also provided a photosensitive layer 3|, comprising a silver halide emulsion. An image-carrying layer 32 of paper such as baryta paper or alpha paper, hardened gelatin or glass is also provided. Connecting the photosensitive layer assembly (i. e. the base layer 30 and the photosensitive layer 3|) with the image-carrying layer 32, there is provided a hinge 34. Between the photosensitive layer assembly and the image-carrying layer there is positioned a container 33 for the liquid composition. It should be noted in connection with Fig. 3 that the container and the hinge are at opposite ends of the film unit. are also shown as having substantially the same thickness. It is also desirable for these twoele- 'ments to have substantially the same compres- .bility.
The container 33 is preferably made of a substance similar to that described in connection with the, container |3 of Fig. 1, e. g. a Water- .vaporand oxygen-impervious material such as ,a wax coated metal foil. The liquid composition within the container is preferably of the same type as that described in connection with Fig. 1. The hinge 34 can be made of paper, a synthetic high polymer or a cellulosic film base such as cellulose acetate.
In the use of the modification of the present invention described in Fig. 3, the photosensitive layer 3| is moved away from the image-carrying layer to permit direct exposure of the photosensitive layer 3|. It is also possible, of course, to expose the photosensitive layer 3| through the baselayer 3|] if the latter be made of a transparent material. After exposure of the photosensitive layer 3| to actinic light, the photosensitive layer assemly is folded down upon the image-carrying layer, if it has been separated The hinge and the container therefrom during exposure. The film unit is then run through pressure applying means such as a pair, of rollers, the container end going first. As
described in connection with Fig. 1, the liquid composition is released by the pressure from the container and is spread uniformly and unidirectionally between the photosensitive layer 3| and the image-carrying layer 32. If the liquid composition contains a film-forming substance such as sodium carboxymethyl cellulose, this substance forms an image-receiving layer between the photosensitive layer 3| and the image-carrying layer 32, and the final positive image is formed within this image-receiving layer. The film-forming substance additionally serves a temporary adhesive function, as discussed in connection with Fig. 1. If the liquid composition does not contain a film-forming substance, the positive image is formed on and within the surface of the imagecarrying layer 32. The liquid composition may have included therein a nonfilm-forming substance which increases its adhesive qualities.
In connection with Fig. 3, the image area on the image-carrying layer is roughly that portion of the layer defined by the edges thereof, the corgtainer at one end, and the hinge at the other en In connection with all of the figures of the above-described drawings, the various hinges shown therein have been referred to as being attached to the image-carrying layer or the base layer. It is obvious that this attachment can be accomplished by forming the hinge of a thermoDlastic composition, or by using a suitable adhesive, or by mechanical means such as stitching or stapling.
In the drawings, the photosensitive layer has been shown as being smaller than the base layer in each instance. This is a preferred form of the invention, since it results in a saving of the photosensitive material. However, the phototensive in area.
In the drawings, various hinges have been shown as being made of one piece of material folded upon itself. It is apparent, however, that these hinges couldbe made of two or more pieces attached together.
It is also apparent that the hinge can be made by extending the adjacent ends of the base layer and image-carrying layer and suitab-ly joining them together.
In the various figures of the drawings, the components of the photographic material of the present invention have been shown as separate, distinct, and relatively thick layers. It should be understood that the relative thickness of these layers is shown only for illustrative purposes to clarify the invention. In actual practice, some of these layers are extremely thin.
In the products hereinbefore described there is provided a container 13 for carrying a liquid in such condition that the liquid may be readily released for the purpose of processing photosensitive layer H. In the preferred embodiment of the product, photosensitive layer II is a silver halide emulsion or the like, that is, an emulsion of a heavy metal salt capable of having a latent image formed therein upon exposure, which latent image may be rendered visible by suitable silver halide developing agents. The liquid released from container 13 cooperates with the emulsion and with image-carrying layer l2 to carry out a transfer process. This transfer process involves the development of a latent image in the photosensitive emulsion and, in one preferred form, the removal from that emulsion of part at least of the undeveloped silver halide as a soluble complex, which soluble complex is transported from the photosensitive layer to form the positive print.
By so forming the products described hereinbefore as to omit therefrom the substance for forming the soluble complex, it becomes possible to only develop the photosensitive silver halide emulsion. Similarly, by eliminating the developer and, if necessary, increasing the concentration of the sodium thiosulfate or other substance for forming the soluble complex, it becomes possible to predeterminedly fix out a developed negative by means of the aforementioned liquid-containing products. It is believed to be also evident now that other developable photographic products may constitute the photosensitive layer I l which Certain diazonium compounds are destroyed by light, and photographic processes involving such compounds as their photographic materials have been used commercially. There are several known ways in which a diazonium salt layer may be exposed and developed to produce a relatively stable image. In each of these processes the treatment of the photosensitive diazonium may be accomplished by applying thereto a liquid containing certain developing reagents. (L. P. Clerc, Photography Theory and Practice, second edition, published 1937 by Pitman Publishing Company, page 444, paragraph 693.)
The products of the present invention may be used in conjunction with, or may comprise as elements thereof, diazonium photosensitive layers. For example, the photographic product may be formed by having any of the aforementioned physical structures and the photosensitive layer ll of said product may have as itsphotosensitiVe 8 substance a diazonium compoundsuch as that sold by the Boston Blue Print Company under the name Blackline #202, and the liquid reagent in the container l3then preferably comprises, by weight, 4 parts of medium visosity sodium carboxymethyl cellulose, parts of water and 8 parts of Blackline Developer #203 sold by Boston Blue Print company and manufactured by Frederick Post Company, Chicago). In the alternative, the photosensitive layer ll may be obtained by applying to one side of a suitable sheet material a sensitizing solution which consists of 20 grams of chlorostannate of paradiazo-di N butyl-aniline, 0.4 gram of Pontacyl Brilliant Blue 2R, and 1 liter of water. The liquid developing reagent in the container 13 then preferably comprises, by weight, 4 parts of medium viscosity sodium carboxymethyl cellulose, 100 parts of water, 5.8 parts of sodium carbonate (monohydrate) and 2.3 parts of phloroglucinol.
The diazonium photosensitive layer may also be obtained by dipping a sheet of paper in a solution of Du Pont Naphthanil Diazo Black B, and the developing solution in container I3 may comprise 1500 parts, by weight, of a 5% water solution of sodium carboxymethyl cellulose, 10 parts of resorcinal and 1 part of sodium hydroxide.
It is also well known that certain ferric salts of organic acids, for example, the oxalates, tartrates, and citrates are reduced to ferrous salts when exposed to light. (L. P. Clerc, Photography Theory and- Practice, second edition, published 1937 by Pitman Publishing Company, page 402, paragraph 621 et seq.; Crowley Patents Nos. 2,093,421, 2,113,423,- 2,130,070, 2,130,071, 2,137,015.) A considerable number of photographic processes depend-for their functioning on this photochemical phenomenon. It is known in connection with these iron salts that any reagent that will differentiate between ferric and ferrous salts can be used to develop the barely visible image formed by the photochemical reduction of the ferric salt into an image which is very easily visible. Examples of such developing reagents are potassium ferricyanide, potassium ferrocyanide, tannins, gallic acid, B-naphthoquinone-sulphonic acid. silver salts, platinum and palladium salts. It is believed to be now apparent to one skilled in the art that the photoresponsive ferrous salts may constitute the photosensitive material of the photosensitive layer H, and the liquid in the container I3 may include or dissolve in its travel to the photosensitive layer any one of the aforementioned developing reagents for distinguishing between the ferric and ferrous salts and producing the easily visible image from the very light image that is originally obtained by the photoexposure of the iron salts.
Broadly, the products of the present invention may comprise, or may be used with, any photographic, photosensitive material for the purpose of developing the same. It is to be understood that the invention is not limited to materials sensitive to visible radiation but includes photographic, photosensitive materials sensitive to such other radiation as X-ray, ultraviolet, infrared or gamma radiation.
Since certain changes may be made in the above product and different embodiments of the invention could be made without departing from the scope thereof, 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. 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 sufficient to effect said transformation, said product comprising a liquid-confining layer, includingat least a photographic photosensitive portion capable of having an image formed therein upon photoexposure, another liquid-confining layer, an opaque stratum associated with each of said liquid-confining layers, and a rupturable container holding a viscous liquid, said liquid'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 layers and container being attached together by means of a hinge, said liquid-confining layers being normally superposed with said photosensitive portion positioned between said opaque strata so as to exclude actinic light from said photosensitive portion, saidhinge permitting said layers to be separated so as to allow exposure of said photosensitive portion and then permitting said layers to be superposed again, with said liquid being held by said container so as not to wet said layers and with said container being positioned for releasing said liquid between said layers, said photosensitive portion comprising a single frame for producing a single photographic image, said hinge being positioned adjacent a marginal edge of the frame, said container being also positioned adjacent a marginal edge of said frame so that liquid released from said container may be spread between said layers across said frame, said liquid being sufiicientl adhesive to maintain said two layers in light-excluding relationship to said photosensitive portion when said liquid is spread between said layers.
2. 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 sufficient to effect said transformation, said product comprising a liquid-confining layer, including at least a photographic photosensitive portion capable of having an image formed therein upon photoexposure, another liquid-confining layer, an opaque stratum associated with each of said liquid-confining layers, and a rupturable container holding a viscous liquid, said liquid 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 layers and container being attached together by means of a hinge, said liquid confining layers being normally superposed with said photosensitive portion positioned between said opaque strata so as to exclude actinic light from said photosensitive portion, said hinge permitting said layers to be separated so as to allow exposure of said photosensitive portion and then permitting said layers to be superposed again, with said liquid being held by said container so as not to wet said layers and with said container being positoned for releasing said liquid between said layers, one of said two liquid-confining layers comprising a double layer, the inner layer thereof being secured to the outer layer and being smaller than both the outer layer thereof and the other liquid-confining layer, said container being positioned, when said two liquid-confining layersaresuperposed, so as to release its liquid adjacent one edge of said smaller inner layer, the other edges of said smaller inner layer being spaced inwardly of the corresponding edges of said outer layer, themarginal facing surfaces of saidtwo liquid-confining layers being spaced farther apart than the central portions thereof when said liquid-confining layers are superposed, said photosensitive portion comprising a single frame for producing a single photographic image, said hinge being positioned adjacent a marginal edge of the frame, said container being also positioned adjacent a marginal edge of said frame so that liquid released=from said container may be spread-between" said liquid-confining layers across said frame, said liquid being sufficiently adhesive to maintain saidtwo liquid-confining layers in light-excluding relationship to said photosensitive portion when said liquid is spread between said liquid-confining layers.
3. A photographicproduct containing material, including a photographic reagent, for producing a transformation of an image in said product, said reagent being present in .an amount sufficient to effect said transformation, said product comprising a liquid-confining layer, including at least a photographic photosensitive portion capable of having an image formed therein upon photoexposure, another liquidconfining layer, an opaque stratum associated with each of said liquid-confining layers, and a rupturable container holding a viscous liquid, said liquid being in an amount sufiicient 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 layers and container being attached together by means of a hinge, said liquid-confining layers being normally superposed with said photosensitive portion positioned between said opaque strata so as to exclude actinic light from said photosensitive portion, said hinge permitting said layers to be separated so as to allow exposure of said photosensitive portion and then permitting said layers to be superposed again, with said liquid being held by said container so as not to wet said layers and with said container being positioned for releasing said liquid between said layers, one of said two liquid-confining layers comprising a double layer, the inner layer thereof being secured to the outer layer and being smaller than both the outer layer thereof and the other liquid-confining layer, said container being positioned, when said two liquid-confining layers are superposed, so as to release its liquid adjacent one edge of said smaller inner layer, the other edges of said smaller inner layer being spaced inwardly of the corresponding edges of said outer layer, the marginal facing surfaces of said two liquid-confining layers being spaced farther apart than the central portions thereof when said liquidconfining layers are superposed, said photosensitive portion comprising a single frame for producing a single photographic image, said hinge being positioned adjacent a marginal edge of the frame, said container bein also positioned adjacent a marginal edge of said frame so that liquid released from said container may be spread between said liquid-confining layers across said frame, said liquid being sufliciently adhesive to maintain said two liquid-confining layers in light-excluding relationship to said photosensitive portion when said liquid is spread between easemen- 11.. said liquid-confining layers, said photosensitive portion comprising a silver halide, said product including a developer for exposed silver halide and a silver halide solvent.
4. The product of claim 3 whereinsaid hinge and said container are positioned adjacent the same edge of said frame and said container .is between said edge and said hinge.
5. The product of claim 3 wherein said'hinge and said container are positioned adjacent opposite edges ofsaid frame.
'6. The product ofclaim 73 wherein said hinge and said container are positioned adjacent opposite edges of said frame andhaving substantially the same thickness and compressibility up to-the rupture point ofthe container.
'7. The product of claim 3 wherein said outer layer of said double liquid-confining layer comprises a paper absorbent to said liquid.
8. The product of claim 3 :wherein said first liquid-confining layer comprises the double layer and the inner layer thereof is a photosensitive silver halide layer.
9. The product of claim '3 wherein said second liquid-confining layer comprises'the double layer and the inner layer thereof comprises animagearea sheet separably secured to the outer layer, said outer layer beingblotterlike.
EDWIN H. LAND.
REFERENCES CITED The following references areof record in the flleof'this patent:
UNITEDSTATES PATENTS Number Name Date 1,972,424 Mediger Sept. 4, 1934 1,976,152 Thornton Oct. 9, 1934 2,053,115 Snyder Sept. 1, 1936 2,071,136 Meinzinger Feb. 16, 1937 2,315,373 Land. .Mar. 30, 1943 2,322,005 Fierke June 15, 1943 2,322,006 'Fierke June 15, 1943 2,322,027 Jelley June 15, 194.3 2,346,774 Mahler Apr. '18, 1944 2,352,014 Rott Jun .20, 1944 2,435,718 Land Feb. '10, 1948 FOREIGN PATENTS Number Country Date 370,821 Germany .May 25, 1921 328,762 Great Britain May 8, 1930

Claims (1)

1. A PHOTOGRAPHIC PRODUCT CONTANING MATERIAL, INCLUDING A PHOTOGRAPHIC REAGENT, FOR PRODUCING A TRANSFORMATION OF AN IMAGE IN SAID PRODUCT, SAID REAGENT BEING PRESENT IN AN AMOUNT SUFFICIENT TO EFFECT SAID TRANSFORMATION, SAID PRODUCT COMPRISING A LIQUID-CONFINING LAYER, INCLUDING AT LEAST A PHOTOGRAPHIC PHOTOSENSITIVE PORTION CAPABLE OF HAVING AN IMAGE FORMED THEREIN UPON PHOTOEXPOSURE, ANOTHER LIQUID-CONFINING LAYER, AN OPAQUE STRATUM ASSOCIATED WITH EACH OF SAID LIQUID-CONFINING LAYERS, AND A RUPTURABLE CONTAINER HOLDING A VISCOUS LIQUID, SAID LIQUID BEING IN AN AMOUNT SUFFICIENT FOR TRANSFORMING SAID IMAGE IN SAID PHOTOSENSITIVE PORTION, SAID LIQUID, UPON PERMEATION OF SAID PHOTOSENSITVE PORTION, RENDERING SAID TRANSFORMING MATERIAL EFFECTIVE TO TRANSFORM SAID IMAGE, SAID LAYERS AND CONTAINER BEING ATTACHED TOGETHER BY MEANS OF A HINGE, SAID LIQUID-CONFINING LAYERS BEING NORMALLY SUPERPOSED WITH SAID PHOTOSENSITIVE PORTION POSITIONED BETWEEN SAID OPAQUE STRATA SO AS TO EXCLUDE ACTINIC LIGHT FROM SAID PHOTOSENSITIVE PORTION, SAID HINGE PERMITTING SAID LAYERS TO BE SEPARATED SO AS TO ALLOW EXPOSURE OF SAID PHOTOSENSITIVE PORTION AND THEN PERMITTING SAID LAYERS TO BE SUPERPOSED AGAIN, WITH SAID LIQUID BEING HELD UP SAID CONTAINER SO AS NOT TO WET SAID LAYERS AND WITH SAID CONTAINER BEING POSITIONED FOR RELEASING SAID LIQUID BETWEEN SAID LAYERS, SAID PHOTOSENSITIVE PORTION COMPRISING A SINGLE FRAME FOR PRODUCING A SINGLE PHOTOGRAPHIC IMAGE, SAID HINGE BEING POSITIONED ADJACENT A MARGINAL EDGE OF THE FRAME, SAID CONTAINER BEING ALSO POSITINED ADJACENT A MARGINAL EDGE OF SAID FRAME SO THAT LIQUID RELEASED FROM SAID CONTAINER MAY BE SPREAD BETWEEN SAID LAYERS ACROSS SAID FRAME, SAID LIQUID BEING SUFFICIENTLY ADHESIVE TO MAINTAIN SAID TWO LAYER IN LIGHT-EXCLUDING RELATIONSHIP TO SAID PHOTOSENSITIVE PORTION WHEN SAID LIQUID IS SPREAD BETWEEN SAID LAYERS.
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US2698798A (en) * 1949-05-21 1955-01-04 Polaroid Corp Color photographic process and product
US2725298A (en) * 1952-05-03 1955-11-29 Eastman Kodak Co Transfer process of photographic printing
US2740717A (en) * 1952-05-03 1956-04-03 Eastman Kodak Co Photographic transfer process
US2740714A (en) * 1951-06-19 1956-04-03 Polaroid Corp Photographic film assembly
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