US3806342A - Composite diffusion transfer photographic product and process - Google Patents

Composite diffusion transfer photographic product and process Download PDF

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Publication number
US3806342A
US3806342A US00101902A US10190270A US3806342A US 3806342 A US3806342 A US 3806342A US 00101902 A US00101902 A US 00101902A US 10190270 A US10190270 A US 10190270A US 3806342 A US3806342 A US 3806342A
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United States
Prior art keywords
layer
silver
silver halide
product
opacifying
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Expired - Lifetime
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US00101902A
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English (en)
Inventor
L Farney
C Groncki
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Polaroid Corp
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Polaroid Corp
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Priority to US00101902A priority Critical patent/US3806342A/en
Priority to BE777399A priority patent/BE777399A/fr
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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
    • G03C8/42—Structural details
    • G03C8/44—Integral units, i.e. the image-forming section not being separated from the image-receiving section
    • 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 photographic prodnot including a layer containing an opacifying system may be exposed to a light source and then processed to form a negative image and a positive transfer image in a layer situated above the layer containing the opacifying system.
  • the opacifying system is capable of effectively masking the negative image but does not prevent photoexposure of the light-sensitive material in the photographic product. Accordingly, the product provides a composite print which contains both a negative and a positive image pattern and the positive pattern is viewable by reflection as a positive reproduction of the original subject matter.
  • any of the aforementioned photographic products may contain an outer layer comprising a silver receptive layer, ie., a layer containing at least one silver precipitating agent, or the silver precipitating agent may be present initially in the processing composition.
  • the photosensitive system of photographic products of the type mentioned above may contain a silver halide emulsion and preferably a mixed silver halide emulsion, having a relatively high film speed. Also, excellent results have been obtained employing emulsions containing a relatively small amount of silver.
  • application Ser. No. 519,995 discloses that the silver halide in the photographic products described and claimed therein may be present in an amount sufficient to provide a silver coverage on the order of from about 0.02 to about 0.1 g. per sq. ft. surface area.
  • the silver halide present in the single layer film units ie., the film units containing no second or additional layer of opacity-providing material
  • the silver halide is previously present in an amount sufficient to provide a silver coverage of at least 0.01 g. per sq. ft.
  • development of the exposed film unit may be effected by impregnation with a non-alkaline processing composition and the alkalinity required to initiate development may be generated in situ electrolytically at some time subsequent to impregnation.
  • the processing composition may also contain other reagents such as a viscosity-increasing, film-forming material, for example, sodium carboxymethyl cellulose, hydroxyethyl cellulose, etc., preservatives, antifoggants, and the like.
  • the processing composition may also contain silver precipitating nuclei.
  • silver precipitating nuclei may be generated in situ electrolytically according to the procedure described and claimed in the commonly assigned copending application of Ronald F. Cieciuch, Ser. No. 519,886, filed Jan. 11, 1966, or a soluble fogging agent may be contained in the processing composition according to the procedures described and claimed in the commonly assigned copending application of Leonard C. Farney, Ser. No. 519,967, filed Jan. 11, 1966.
  • Additional patent applications relating to photographic products of the type to which the present invention pertains include commonly assigned applications Ser. Nos. 519,955 and 526,673, both filed by Leonard C. Farney on Jan. 11, 1966.
  • Application Ser. No. 519,955 relates to photographic products wherein a siliceous material preferably a finely granulated colloidal silica is incorporated in a layer containing the opacifying system. The presence of the siliceous material enhances the covering power of the opacifying system and increases the effectiveness of the silver in the transfer process by which the positive'image is obtained.
  • the present invention is directed to novel photographic products which present certain improvements over' the photographic pro-ducts heretofore known to the art such as those described and claimed in the above-mentioned patent applications.
  • pellucid layer 12 comprises an opacifying system which may be an opacifying material such as finely divided titanium dioxide, calcium carbonate, magnesium oxide, barium sulfate, etc., or a mixture of such materials, dispersed in a suitable permeable colloidal carrier or'in'atrii such as gelatin.
  • the opacifying material is present in an amount sufficient to effectively mask the negative silver image formed after development in light-sensitive layer 11 but the amount of opacifying materiallis insufficient to preclude photoexposure of the light-sensitive layer from a light source on the same side ofthe supportas,v the two layers (e.g., in the manner shown-in the figure).
  • the opacifying material further serves to provide a background, preferably a white background, for viewing the composite print, .without separation, by reflected light as a positive silver image.
  • the term effectively masking denotes the ability'of the opacifying material to sufiiciently mask or obscure the negative image so that the composite print is viewable as a posi; tive image
  • layer 12 need not contain an opacifying system and, in, some products, an opacifying system need notbepresent.
  • the opacifying system can be' included in light sensitive layer 11,
  • a moisture activatable developer system of the type described inmo r -e detail hereinafter can be integrated in photographic'struc tures such as those described in the aforementioned US. Pat. 2,861,885 in lieu of the processing compositions shown therein to provide photographic products for producing diffusion transfer image patterns developable by moisture and which can be viewed without separation.
  • Pellucid, image-receiving layer 13 comprises one of the known vigorous silver precipitating environments containing silver-precipitating nuclei, e.g., at least one silverprecipitating agent dispersed in a microscopically continuous vehicle.
  • a dispersion of such nuclei in a colloidal material such as colloidal silica or gelatin can provide suitable pellucid image-receiving layers for products of the present invention.
  • pellucid, image-receving layer 13 preferably comprises an ingredient whichcan selectively prevent diffusion thereto or deposition therein of any substantial amount of visible sliver from, the exposed and developed portions of light sensitive.- layer 11.
  • the subject matter .14 e.g., a document having areas which are opaque, e.g., printing and areas which will transmit visible light
  • a suitable light source 15 e.g., a document having areas which are opaque, e.g., printing and areas which will transmit visible light
  • support 10' is transparent, light sensitive layer 11 can be exposed thcrethrough to provide an image pattern in layer 13 which can be viewed by pro-. jection.
  • the photographic product is confined in a camera or other suitable device," so that light-sensitive layer 11 is photoexposed for the requisite time only to light transmitted through or refiected from subject matter 14, thereby to form a'developable image in terms of the light-transmittant areas of .the subject matter. 1 1
  • photographic products of the present invention can be developed by moisture preferably in the form of steam.
  • This development is achieved by integrating a moisture activatablesystem including a silver halide developing agent and a silver halide transfer agent with the elements of the photographic products.
  • the integration is such that in the presence of moisture, e.g., steam, the silver halide developing agent can reduce exposed silver halide while at least part of the imagewise distribu-v tion of soluble silver complex formed from unreducecf silver halide can be transferred to layer 13 by the silver halide transfer agent.
  • the manners in which the moisture activatable system is integrated with the essential elements of the photographic products of the present invention can varyl-For' example, the silver halide developing agent amdjor the silver halide transfer agent can be included separately or together in any of the layers mentioned before. However, in the preferred embodiment of the present invention, at least the developing agent is included in light sensitive layer 11 and in the especially preferred embodiment, both the developing agent and the transfer agent are included in light sensitive layer 11.
  • Silver halide developing agents are known to the art and include among others, hydroquinone and derivatives of hydroquinones such as 4-methylphenyl hydroquinone etc., catechol and derivatives of catechol, such as 4-phenyl catechol etc., derivatives of naphthol, such as 4-methoxyl-naphthol, derivatives of phenol such as methyl paraaminophenol etc., the 3-pyrazolidones, such as l-phenyl- 3 pyrazolidone.
  • the especially preferred silver halide developing agents in the practice of the present invention are metol, phenidone, pyrocatechol, methyl hydroquinone and toluyl hydroquinone.
  • the compounds which function as silver halide transfer agents of the present invention are suceinimide, the alkali metal sulfites or combinations thereof.
  • the transfer agents of the present invention are surprisingly compatable with silver halide developing agents and they can be included in silver halide emulsion layers in combination with such developing agents.
  • silver halide transfer agents e.g., silver halide solvents or silver halide complexing agents heretofore employed in the diffusion transfer art are not conveniently included in silver halide emulsion layers containing silver halide developing agents.
  • transfer agents such as thiocyanates, thioureas, thiosulfates and mercapto containing compounds in emulsion layers containing developing agents can desensitize, fog, spot or otherwise adversely affect the quality of the diffusion transfer image pattern obtained on exposure and development of such emulsions.
  • succinimide and alkali metal sulfites have not been regarded in the art as eifective transfer agents in silver halide diffusion transfer systems.
  • the silver halide developing agent can be employed in amounts between about .01 to about .1 g./ft. and the silver halide transfer agent can be employed in amounts between about 0.04 to about 0.4 g./ft.
  • the silver halide developing agent as well as the silver halide transfer agent are included in light sensitive layer 11.
  • layer 11 contains an opacifying material which can be the same material providing the opacifying system of translucent layer 12.
  • An especially suitable opacifying material for inclusion in layer 11 is titanium dioxide with the preferred amount involved being sufiicient to provide between about 800 to about 2000 rngms/ft. of titanium dioxide in layer 11.
  • the photographic product of the figure is contacted with moisture, preferably steam to activate the aforementioned processing system.
  • moisture preferably steam to activate the aforementioned processing system.
  • the system reduces exposed silver halide in. layer 11 while substantially simultaneously forming an imagewise distribution of soluble silver complex from unreduced silver halide.
  • At least part of the complex is transferred through pellucid layer 12 to image-receiving layer 13 where it is reduced to image silver to provide a positive silver transfer image pattern.
  • transparent image-receiving layer 13 preferably comprises an ingredient which can selectively prevent diffusion thereto or deposition therein of any substantial amounts of visible silver from the exposed and developed portions of light sensitive layer 11.
  • the soluble complex providing the positive image pattern is transferred to layer 13 initially but apparently silver from exposed portions of layer 11 can also be transferred to or deposited in layer 13.
  • This transfer of silver from exposed portions of layer 11 can ultimately prevent effective discrimination between the positive and negative patterns.
  • the effect of this unwanted visible silver in layer 13 is not especially apparent when succinimide is employed as a transfer agent but is especially apparent when the alleali metal sulfites alone are so employed.
  • layer 13 comprises an ingredient which can effectively prevent this unwanted silver from being diffused thereto or otherwise deposited therein.
  • R can be hydrogen, hydroxyl, amino, lower alkyl of from 1-4 carbon atoms, lower alkoxy of from 1-4 carbon atoms, an aryl radical, e.g., phenyl, tolyl or a heterocyclic radical, e.g., pyridyl, provided that only one R of Formula 1 can be hydrogen and the other is as defined; R is R can be hydrogen, halogen, lower alkyl, aryl or lower alkoxy group.
  • the amount of the above described compounds employed in products of the present invention can vary and amounts between about 0.5 to about 3.0 mg. per sq. ft. are suitable.
  • the silver halide in layer 11 should be present in an amount sufiicient to provide a silver coverage on the order of from about 0.02 to about 0.1 gm. per sq. ft. of surface area, although good results have been obtained with as little as 0.006 gm. per sq. ft.
  • gelatin e.g., gelatin
  • silver is preferably from about 5:1 to
  • a photographically innocuous humectant such as u-methyl glucoside materially lowers the processing time and/or the amount of processing composition necessary. This is apparently due to the ability of the humectant to retain water in the emulsion matrix which in turn minimizes shrinkage or, stated another way, minimizes the swelling needed for processing, thus lowering the induction time and/or the time required for the soluble silver complex to transfer to the layer where it is reduced to image silver.
  • This concept of providing a humectant in the emulsion layer is described with more particularity, and claimed in the aforementioned copending application of Leonard C. Farney. Ser. No. 526,673.
  • the opacifying material in pellucid layer 12 is present in an amount suificient to mask effectively the negative image formed in layer 11 and to provide the background for viewing the composite print as a positive refiection print.
  • the amount of opacifying material is insuflicient to preclude photoexposure, and most preferably, insufficient to effect adversely, i.e., to lower the film speed of the product, at least to any appreciable extent.
  • ranges on the order of at least 0.1, e.g., from about 0.1 to about 2.0 gm. of opacifying material per sq. ft. of surface area have been found to be desirable with from about 0.8 to about 1.5 gm. per sq. ft. providing particularly satisfactory results in terms of density, contrast and stability.
  • the ratio of opacifying material per sq. ft. in layer 12 to silver per sq. ft. in layer 11 is preferably on the order of from about 30:1 to about 50:1.
  • the present invention thus makes it possible for one to obtain positive silver transfer images of good density and resolution from photographic products containing a relatively small amount of silver.
  • Ludox (30% soln.) mls 50 Water ls 50 AgNOg (0.5 N) ml 1 Sodium sulfide (1 N) mls 0.5 2 thiouracil gm 0.05 Succinimide gms 8 Wetting agent (25 Triton X-100) cc .5
  • EXAMPLE 2 Prepare a titanium dioxide slurry by mixing together the following ingredients:
  • Ludox (30% soln.) mls 50 Water mls 50 A No 0.5 N) ml 1 Sodium sulfide (l N) ml 0.5 2 thiouracil gm 0.05 Succinimide arm. 8 Wetting agent (25% Triton X-100) cc .5
  • EXAMPLE 3 Repeat the procedure of Example 2 but substitute 0.5 gm. of 2-thiobarbituric acid for the 0.05 gm. of 2-thiouracil in the mixture for preparing the receptive layer.
  • the product is processed in steam for 3 minutes, a positive image pattern having a Dm of 1.38 and a D of 0.08 is obtained.
  • EXAMPLE 6 Repeat the procedure of Example 2 but add 1.2 gms. succinimide to the emulsion mixture and leave out the 8 grns. of succinimide in the mixture for preparing the receptive layer.
  • EXAMPLE 7 Repeat the procedure of Example 2 but substitute 1 ml. 0.5 N Ni(NO for the AgNO in the diffusion transfer layer of Example 2.
  • EXAMPLE 8 Repeat the procedure of Example 2 but do not coat the titanium dioxide slurry on the silver halide emulsion layer and instead coat the diffusion transfer layer mixture directly on the emulsion layer to provide a product having the opacifying system distributed in the emulsion layer.
  • EXAMPLE 9 Repeat the procedure of Example 1 but coat the slurry of Example 2 on the emulsion layer of Example 1 to provide a product having the opacifying system interposed between the emulsion layer and receptive layer.
  • the present invention provides novel film products comprising a layer of opacifying material superposed on a light-sensitive layer, which film product is exposed through the translucent layer and then processed by moisture, preferably steam, to form a composite print containing a visible transfer image which may be viewed by reflection or projection as a positive image.
  • a diffusion transfer photographic product for forming a composite print wherein a positive image is formed in an image-receiving layer arranged in combination with a light sensitive layer containing a negative image so that said positive image is viewable by reflection or projection without separation; said product comprising as essential elements thereof a light sensitive silver halide emulsion layer, a receiving layer which can receive a diffusion transfer positive image pattern and comprises an ingredient which can selectively prevent diffusion thereto of any substantial amounts of silver from exposed portions of the light sensitive layer and a moisture activatable system comprising a silver halide developing agent and a silver halide transfer agent chosen from the group consisting of succinimide, an alkali metal sulfite or mixtures thereof integrated with said elements so that the product can be developed by moisture.
  • a photographic product of claim 1 further including an opacifying system.
  • a photographic product of claim 1 including a layer comprising an opacifying system interposed between said receptive layer and said light sensitive layer.
  • a photographic product for forming a composite print wherein a positive image is formed over a negative image and said positive image is viewable by reflection or projection without separation and said product comprising as essential elements thereof a support, a first layer on the support containing a light sensitive silver halide emulsion, a second layer on said first layer containing an opacifying system which can effectively mask a developed negative image pattern in the first layer and a silver receptive layer which can receive a positive diffusion transfer image pattern from the light sensitive layer and comprising a material which can selectively prevent diffusion thereto of any substantial amounts of silver from exposed and developed portions of the light sensitive layer and a moisture activatable processing system comprising a silver halide transfer agent chosen from the group consisting of succinimide, an alkali metal sulfite or mixtures thereof integrated with said elements so that the product can be developed by moisture.
  • a silver halide transfer agent chosen from the group consisting of succinimide, an alkali metal sulfite or mixtures thereof integrated with said elements
  • a product of claim 8 wherein said transfer agent comprises sodium sulfite.
  • a product of claim 11 wherein said transfer agent comprises sodium sulfite.
  • a product of claim 5 wherein said opacifying system comprises a white pigment as an opacifying material.
  • a product of claim 5 wherein said opacifying system comprises titanium dioxide as an opacifying material.
  • a product of claim 5 wherein said emulsion comprises a mixed silver halide emulsion and said opacifying system is present in an amount insufiicient to lower, at least to any appreciable extent, the film speed of said product.
  • said opacifying system comprises a white pigment material in an amount sufficient to provide from about 0.1 to about 2.0 gm. of opacifying material per sq. ft. of surface area.
  • said opacifying system comprises a white pigment material in an amount sufiicient to provide a ratio of opacifying material per square foot in said second layer to silver per square foot in said first layer of from about 30:1 to about 50:1.
  • a product of claim 5 wherein the silver receptive layer comprises a compound conforming to the following tautomeric formulae:
  • a photographic process comprising the steps of exposing a photographic product of claim 1 to a source of activating radiation and contacting the exposed produce with moisture.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US00101902A 1970-12-28 1970-12-28 Composite diffusion transfer photographic product and process Expired - Lifetime US3806342A (en)

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US00101902A US3806342A (en) 1970-12-28 1970-12-28 Composite diffusion transfer photographic product and process
BE777399A BE777399A (fr) 1970-12-28 1971-12-28 Separateur impermeable electriquement conducteur, destine a un accumulateur electrique

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3985561A (en) * 1973-06-22 1976-10-12 Agfa-Gevaert N.V. Diffusion transfer process using silver halide emulsions with 90% chloride and high binder to silver halide ratios
US4359397A (en) * 1980-12-31 1982-11-16 Polaroid Corporation Benzotriazole complexes and film units employing same
US4418139A (en) * 1980-12-31 1983-11-29 Polaroid Corporation Film units containing thermally induced water-releasing benzotriazole complex

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3985561A (en) * 1973-06-22 1976-10-12 Agfa-Gevaert N.V. Diffusion transfer process using silver halide emulsions with 90% chloride and high binder to silver halide ratios
US4359397A (en) * 1980-12-31 1982-11-16 Polaroid Corporation Benzotriazole complexes and film units employing same
US4418139A (en) * 1980-12-31 1983-11-29 Polaroid Corporation Film units containing thermally induced water-releasing benzotriazole complex

Also Published As

Publication number Publication date
BE777399A (fr) 1972-06-28

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