US2653872A - Photographic product comprising a rupturable container carrying a liquid for processing said product - Google Patents

Photographic product comprising a rupturable container carrying a liquid for processing said product Download PDF

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Publication number
US2653872A
US2653872A US724784A US72478447A US2653872A US 2653872 A US2653872 A US 2653872A US 724784 A US724784 A US 724784A US 72478447 A US72478447 A US 72478447A US 2653872 A US2653872 A US 2653872A
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United States
Prior art keywords
layer
image
photosensitive
developer
product
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Expired - Lifetime
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US724784A
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English (en)
Inventor
Edwin H Land
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Polaroid Corp
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Polaroid Corp
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Publication date
Priority to FR960188D priority Critical patent/FR960188A/fr
Application filed by Polaroid Corp filed Critical Polaroid Corp
Priority to US724784A priority patent/US2653872A/en
Priority to GB1722/48A priority patent/GB684594A/en
Application granted granted Critical
Publication of US2653872A publication Critical patent/US2653872A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
    • G03C8/02—Photosensitive materials characterised by the image-forming section
    • G03C8/04—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of inorganic or organo-metallic compounds derived from photosensitive noble metals
    • G03C8/06—Silver salt diffusion transfer

Definitions

  • a principal object of the present invention is to provide photographic iilm units of the type described in my above-mentioned copending applications wherein a photographic film unit comprising a base layer, a photosensitive layer and another layer is exposed to actinic light through said base layer, and said iilm unit is developed to produce therein a final positive image by creating in said nlm unit a layer of liquid composition nearest the surface of said photosensitive layer which is farthest from said base layer, and improving on the products described in my said copending applications so as to permit the formation of a positive image having characteristics equal to those products where exposure of the photosensitive layer is made directly through the side of said photosensitive layer which is rst contacted by said liquid composition.
  • Another object of this invention is to provide a photographic lm unit comprising a layer of photosensitive material, a base for said layer, and another layer, said unit being arranged for exposure oi said photosensitive material through said base layer and production of a positive image of a subject image on or in said other layer, said photosensitive layer having such optical characteristics as to substantially prevent scattering of light passing therethrough.
  • Another object of the present invention is to provide a composite photographic nlm unit containing a material capable of reacting with a liquid composition used for developing said photosensitive material to prevent the existence of any developer in stain-forming condition in the highlights of a positive image when an amount of developer is used which is in excess of the amount required to fully develop a fully developable portion of said photosensitive material.
  • Another object of the present invention is to provide in a product of the above type an amount of developer in excess of that required to fully develop a fully developable portion of said latent image and to react said liquid composition with a material capable of preventing the existence of any developer in a stain-forming condition in the highlights of the positive image.
  • the invention accordingly comprises the product possessing the features, properties, and the relation of elements which are exemplified in the following detailed disclosure, and the scope of the application of which will be indicated in the claim.
  • Figure 1 is an exaggerated sectional schematic view of the invention as applied to a film unit of the type shown in my above-mentioned copending application Serial No. 578,379;
  • Fig. 2 is an exaggerated schematic, diagrammatic view of a modification of the invention.
  • Fig. 3 is an exaggerated schematic, diagrammatic view of another modification of the invention.
  • the present invention therefore, relates to the provision of photographic products wherein a photographic l'm'unit may be exposed through n Ji the base layer with the resulting simplification of camera structure and manufacture of the lm unit.
  • a base layer I0 adapted to carry on one surface thereof a photosensitive layer I2.
  • another layer I4 hereinafter referred to as an image-carrying layer, which may be joined to the base layer or the photosensitive layer on the edge portions thereof.
  • a container I6 adapted to have therein a liquid composition. This container can be attached to either the photosensitive layer I2 or the image-carrying layer I4. Films of this general character are described in my above-mentioned copending application Serial No. 578,379.
  • the base layer I0 is preferably made of a suitable iilm base material such as a cellulosic ester or mixed esters such as cellulose nitrate, cellulose acetate, cellulose acetate propionate or other transparent materials capable of supporting a photosensitive emulsion.
  • the photosensitive layer is preferably of the type rendered developable by exposure to light, such as a noble metal halide. and is preferably an emulsion of a silver halide or of a mixture of silver halides or of a mixed silver halide.
  • the image-carrying layer I4 in a preferred embodiment of the invention is formed of a photographic material known in the art as baryta paper, although it can be made of other substances.
  • This layer is preferably permeable to a substance contained in the liquid composition and may also be manufactured from t adapted to form from a latent photographic image a positive image-forming component.
  • This latter substance in a preferred form of the invention is sodium thiosulfate.
  • liquid compositions may be produced as shown in the following nonlimiting example:
  • Example 1 The following substances are put in a beaker and stirred with a plastic rod until dissolved:
  • the above mixture is stirred in a closed mixer having a nitrogen atmosphere over the liquid therein, and the temperature is raised to 178 F.
  • the mixture is maintained at this temperature for approximately 31/2 hours.
  • 10 grams of sodium thiosulfate are added to the above mixture.
  • 18 grams of hydroquinone are added to the mixture.
  • 249 cc. of water are then added to the mixture some time before the completion of the 31/2 hour heating period.
  • the container IE is preferably formed of a substance such as an oxygen and water-vapor impervious material, such, for example, as a sheet of wax impregnated, metal coated paper or wax coated metal foil, or a metal foil coated with a resin, such as polyvinyl butyral, which is inert to alkali.
  • a substance such as an oxygen and water-vapor impervious material, such, for example, as a sheet of wax impregnated, metal coated paper or wax coated metal foil, or a metal foil coated with a resin, such as polyvinyl butyral, which is inert to alkali.
  • the photosensitive layer I2 is exposed to actinic light through the base layer I0 and, Without further exposure to light, the whole assembly is subjected to a mechanical stress such as by passing through a wringer, not shown, starting with the container end. As the film is squeezed through the wringer, the container I6 is ruptured and the liquid composition is uniformly spread between the photosensitive layer I2 and the image-carrying layer I4.
  • the developer develops the latent photographic imade and the sodium thiosulfate forms silver complexes with the unexposed silver halide grains and carries these complexes into the image-receiving layer, being formed by the solidication of the film-forming substance contained in the liquid composition.
  • These complexes are then developed and formed into a positive image. While this process is in operation, as stated above, the film-forming substance, i. e., the sodium carboxymethyl cellulose is being solidified into a dimensionally stable film.
  • the photosensitive layer in this modification of the invention is preferably made of a very finegrained emulsion, so as to prevent scattering of light during its passage through the emulsion layer.
  • the latent image which is formed on the lower surface of the photosensitive layer is substantially as sharp as the latent image formed on the upper surface of the photosensitive layer.
  • the developer composition shown in the example is quite a contrasty developed. It therefore accentuates the contrast and compensates somewhat for any scattering or diffusion of the image caused by the scattering or diffusion of light passing through the photosensitive layer. There is thus produced an image which has substantially the same detail as an image produced by exposing first the side of the photosensitive material which is first contacted by the liquid composition.
  • Another modification of the invention includes the additional provision in the film unit of a layer of a material which is capable of reacting with the liquid composition to prevent the existence of any developer in stain-forming condition in the highlights of the positive image.
  • a material may take the form of an oxidizing agent associated with the photosensitive layer, which oxidizes the developer and renders the developer relatively immobile, thereby trapping the developer in the place where it is oxidized.
  • an oxidizing agent may be a layer of very fine-grained, pre-exposed photosensitive emulsion, or it may be an oxidizing agent such as sodium perborate.
  • such a material prefferably be a substance such as lead acetate or an acid which has the ability of lowering the pH of the liquid composition, at least in the highlights of the positive image, to a point Where staining by the developer cannot take place.
  • a developer which, when oxidized, is capable of coupling with a dye-coupler to form an immobile dye. If this be the case, a dye-coupler should be incorporated in the layer with the oxidizing agent and thus, as the excess developer becomes oxidized, it couples to form an immobile dye and is thereby kept from the highlights of the positive image.
  • a modication of the invention wherein a very thin, relatively large-grained photosensitive layer is provided.
  • a base layer l0 which corresponds to the basel layer i@ of Fig. l.
  • a layer 24 of a very fine-grained pho-tosensitive emulsion which has been uniformly exposed to actinic light to make it developable.
  • a very thin layer 22 of a relatively large-grained photosensitive emulsion adapted to be exposed in a camera to a subject image.
  • the base layer vIll is preferably formed of a suitable cellulosic lm base, such as cellulose acetate, cellulosev layer 22 comprises a relatively large-grained sil-j ver halide emulsion.
  • the layer 24 may however comprise a nonphotosensitive silver salt or a slightly photosensitive silver salt of an organic linear high polymer.
  • the liquid composition carried by the container I6 may be of the type described in the example above, although it preferably contains about half the amount of hydroquinone and sodium thiosulfate listed in that example.
  • Other suitable developers may be used in the practice of the present invention.
  • the image-carrying layer I4 is preferably formed of a sheet of bartya-coated paper, and, in a preferred example, the baryta paper has coated thereon a material, or materials, which will insolubilize the film-forming material, increase the contrast, and reduce the alkalinity in the highlights of the positive image.
  • a material or materials, which will insolubilize the film-forming material, increase the contrast, and reduce the alkalinity in the highlights of the positive image.
  • a preferred example of such a material is lead acetate.
  • the photosensitive layer 22 is exposed to actinic light from the subject image, through the base layer l0 and the fine-grained pre-exposed photosensitive layer 24. Due to the extremely fine grains in the layer 24, there is substantially no scattering or diffusion of the light passing therethrough, and the latent image formed in the photosensitive layer 22 has a sharpness comparable with that obtained by exposing this layer from the side thereof which, is rst contacted with the liquid composition.
  • the film unit is processed, in a preferred example, by passing it through a pair of pressure rollers, the kcontainer end going first. 'This releases the liquid composition from the container and spreads it in a uniform layer between the image-carrying layer I4 andthe photosensitive layer 22.
  • the developer develops the latent image in the photosensitive layer 22. rlhe sodium thiosulfate forms soluble silver complexes with the unexposed silver halide, and these silver complexes are developed by the developer into a positive image on and within the film formed by the film-forming material of the liquid composition.
  • the amount of developer available for reacting with any portion of the photosensitive layer 22 may be such that it will be completely exhausted by developing a fully developable portion thereof.
  • a material other than a mie-grained pre-exposed photosensitive material', and'- such materials may be a nonph-otosensitive oxidizing agent such as sodium perbcrate.
  • the layer 24 might be formed of anemulsion of very small crystals of sodium perborate coated on-to base i0 prior to the casting ⁇ thereon of the photosensitive layer 22.
  • the oxidizing agent may be placedon the surface of theV base layer by anyother suitable means suchask by evaporating or precipitating from a concentrated solution thereof.
  • a color-forming developer such as diethylparaphenylenediamne hydrochloride.
  • a color former adapted to ⁇ couple with the oxidized developer may be incorporated in layer 24 along with the oxidizing agent.
  • a color former may be p-nitrophenylacetonitrile or 2,4 dichloro-lr-naphthol. It is obvious, from the above discussion, that the immobile dye-forming materials may be used either with a pre-exposed photcsensitive layer or with an oxidiaing agent layer.
  • thelayer 24? of material capable of preventing stainV due to'- excessdeveloper may be placed' in a position other than between the base layer and the photosensitive layer.
  • This layer is preferably positioned' so that its reaction with the liquid composition is somewhat delayed so that it does not interfere' with either the development of the latent image or the production of the positive image.
  • This layer can, therefore, be placed beneath the imagecarrying layer. If such be the case, the position of this layer will depend upon the color of the reaction product of the liquid therewith.
  • this reaction product is a colored substance this layer is preferably covered by a coating, such as baryta, which will hide the colored product.
  • this layer may 1be coincident with the surfacel of the image-carrying layer.
  • a nonhai'a'- tion layer which has such permeability as not to interfere withy the ionicl transfer of image-forming components and' also' one which is' not dissolved by the liquid composition utilized in developing the' photosensitive layer andv creating the finall positive image.
  • Such a layer should also be so formed that the materials thereof are' non-migratory and' do not enter into the photo'- sensitive layer to any considerable extent, since otherwise they might reduce the sensitivity of the' photosensitive layer'.
  • This particular feature is of cor'isid'e'rabie importance in those cases' where an extremely thin photosensitive layer is utilized.
  • Fig. 3 there is shown one modification of the present invention having incorporated therein a nonna-lation layer.
  • a very thin layer 22 of a large grain photosensitive' material Coated on this photosens'ltive layer 22 there is a nonhalation layer 30.
  • the usual container I6 for a liquid composition is provided and there is also included an imagecarrying layer I4'.
  • the layer 30' is formed by coating on the photosensitive layer 22 an emulsion ofgelatin and' very finely comminuted carbony such as carbon black or a lamp black. Such a layer is permeable to' the liquid composition and does not appear to' interfere with the ionic transfer of the image-forming components.
  • This nonhalation' layer may, however, be made of other permeable materials having incorporated therein immobile, insoluble dyes'.
  • This layer 30 should' be formedl of a nlm-forming material in which silver will not form as readily as in the nlm-forming material from container I6.
  • the photosensltive layer' is ⁇ exposed: to actinic light through layers l'0 ⁇ and 'f 2li,r and is then processed, such as by passing through a pair of pressure rollers, the container end going rst.
  • The-developer developsstable, positive imagev b-'y meansV of some of the- It-is either usedV up by oxidizing' 1.
  • the invention When incorporated in this embodiment o! the invention it will act in the same manner. That is, it prevents halation in the photosensitive layer and does not interfere with the photographic process.
  • a composite lm unit having a photosensitive element which comprises a transparent base layer on one side of which two silver halide layers are superposed and through the second side of which actinic light is transmitted for exposing said photosensitive element, a rst of said silver halide layers comprising a pre-exposed fine grain silver halide emulsion supported upon the first-mentioned side of said transparent base, and a second of said silver halide layers constituting an unexposed thin, large grain silver halide emulsion in which a latent image is adapted to be formed upon exposure of said photosensitive ele.- ment, said second silver halide layer being supported upon the outer surface of said first silver halide layer, an image-carrying l-ayer for a transfer image secured to said photosensitive element in superposed relation thereto on the same side thereof as said second silver halide layer, and a rupturable container holding a liquid composition comprising a silver halide developer and a silver halide solvent rendered effective upon rupture of

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US724784A 1947-01-28 1947-01-28 Photographic product comprising a rupturable container carrying a liquid for processing said product Expired - Lifetime US2653872A (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
FR960188D FR960188A (en(2012)) 1947-01-28
US724784A US2653872A (en) 1947-01-28 1947-01-28 Photographic product comprising a rupturable container carrying a liquid for processing said product
GB1722/48A GB684594A (en) 1947-01-28 1948-01-20 Improvements in or relating to photographic film units and processes

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US724784A US2653872A (en) 1947-01-28 1947-01-28 Photographic product comprising a rupturable container carrying a liquid for processing said product

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US2653872A true US2653872A (en) 1953-09-29

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2798021A (en) * 1953-09-25 1957-07-02 Polarold Corp Method of protectively treating and mounting photographic prints
US3020155A (en) * 1956-05-23 1962-02-06 Eastman Kodak Co Photographic diffusion transfer process

Citations (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US742405A (en) * 1901-12-17 1903-10-27 Farbenfabriken Elberfeld Co Photographic plate and process of making same.
US1173429A (en) * 1912-12-05 1916-02-29 Frederic E Ives Color photography.
US1306904A (en) * 1919-06-17 Cojgor bhotogbaphy
US1320760A (en) * 1919-11-04 Motion-picture in colors
US1447759A (en) * 1918-10-01 1923-03-06 Christensen Jens Herman Sensitized photographic element
US1597727A (en) * 1922-10-20 1926-08-31 Ig Farbenindustrie Ag Film
GB324394A (en) * 1928-10-25 1930-01-27 Thomas Thorne Baker Improvements in or relating to photography in natural colours
GB326559A (en) * 1928-11-20 1930-03-20 Adrian Bernard Klein Improvements in or relating to colour-photography
GB328336A (en) * 1928-11-01 1930-05-01 Thomas Thorne Baker Improvements in or relating to bi-packs for two-colour photography
US1841653A (en) * 1927-08-22 1932-01-19 Frans Van Der Grinten Process for developing positive diazo prints
US1956230A (en) * 1928-12-31 1934-04-24 Agfa Ansco Corp Process for obtaining different gradations in developing silver halide emulsion layers
GB511180A (en) * 1937-12-09 1939-08-09 Kodak Ltd Improvements in photographic anti-halation, filter layers and other non-sensitised layers
FR879995A (fr) * 1941-01-24 1943-03-10 Ig Farbenindustrie Ag Procédé pour la constitution d'images photographiques positives
US2315966A (en) * 1940-04-15 1943-04-06 Eastman Kodak Co Photographic emulsion
US2327828A (en) * 1941-03-26 1943-08-24 Eastman Kodak Co Colloidal carbon antihalation layer
US2352014A (en) * 1941-07-21 1944-06-20 Rott Andre Photomechanical printing process and printing material for carrying out the same
US2415666A (en) * 1943-07-10 1947-02-11 Eastman Kodak Co Ascorbic acid in photographic developing solutions
US2500421A (en) * 1944-11-03 1950-03-14 Polaroid Corp Photographic silver halide transfer process
US2543181A (en) * 1947-01-15 1951-02-27 Polaroid Corp Photographic product comprising a rupturable container carrying a photographic processing liquid

Patent Citations (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1306904A (en) * 1919-06-17 Cojgor bhotogbaphy
US1320760A (en) * 1919-11-04 Motion-picture in colors
US742405A (en) * 1901-12-17 1903-10-27 Farbenfabriken Elberfeld Co Photographic plate and process of making same.
US1173429A (en) * 1912-12-05 1916-02-29 Frederic E Ives Color photography.
US1447759A (en) * 1918-10-01 1923-03-06 Christensen Jens Herman Sensitized photographic element
US1597727A (en) * 1922-10-20 1926-08-31 Ig Farbenindustrie Ag Film
US1841653A (en) * 1927-08-22 1932-01-19 Frans Van Der Grinten Process for developing positive diazo prints
GB324394A (en) * 1928-10-25 1930-01-27 Thomas Thorne Baker Improvements in or relating to photography in natural colours
GB328336A (en) * 1928-11-01 1930-05-01 Thomas Thorne Baker Improvements in or relating to bi-packs for two-colour photography
GB326559A (en) * 1928-11-20 1930-03-20 Adrian Bernard Klein Improvements in or relating to colour-photography
US1956230A (en) * 1928-12-31 1934-04-24 Agfa Ansco Corp Process for obtaining different gradations in developing silver halide emulsion layers
GB511180A (en) * 1937-12-09 1939-08-09 Kodak Ltd Improvements in photographic anti-halation, filter layers and other non-sensitised layers
US2315966A (en) * 1940-04-15 1943-04-06 Eastman Kodak Co Photographic emulsion
FR879995A (fr) * 1941-01-24 1943-03-10 Ig Farbenindustrie Ag Procédé pour la constitution d'images photographiques positives
US2327828A (en) * 1941-03-26 1943-08-24 Eastman Kodak Co Colloidal carbon antihalation layer
US2352014A (en) * 1941-07-21 1944-06-20 Rott Andre Photomechanical printing process and printing material for carrying out the same
US2415666A (en) * 1943-07-10 1947-02-11 Eastman Kodak Co Ascorbic acid in photographic developing solutions
US2500421A (en) * 1944-11-03 1950-03-14 Polaroid Corp Photographic silver halide transfer process
US2543181A (en) * 1947-01-15 1951-02-27 Polaroid Corp Photographic product comprising a rupturable container carrying a photographic processing liquid

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2798021A (en) * 1953-09-25 1957-07-02 Polarold Corp Method of protectively treating and mounting photographic prints
US3020155A (en) * 1956-05-23 1962-02-06 Eastman Kodak Co Photographic diffusion transfer process

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FR960188A (en(2012)) 1950-04-14
GB684594A (en) 1952-12-24

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