Classifications

• • 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
  • G03C8/52—Bases or auxiliary layers; Substances therefor

Definitions

• transfer image formation is obtained by exposing a photosensitive element or negative component comprising at least one light-sensitive silver halide layer having associated therewith a dye imageproviding material (which may be a complete dye or a dye intermediate, e.g., hourly spacer) to form a developable image; thereafter developing this image by applying an aqueous alkaline processing fluid; forming, as a function of this development, an imagewise distribution of soluble and diffusible dye image-providing material; and transferring this imagewise distribution, at least in part, by diffusion, to a superposed imagereceiving element or positive component including a dyeable stratum to impart thereto a color transfer image, usually a positive image.
• the dye image-providing materials which may be employed in such processes generally may be characterized as being (1) either initially soluble or diffusible in the processing composition but which are selectively rendered non-diffusible in an imagewise pattern as a function of development; or (2) initially insoluble or non-diffusible in the processing composition but which are selectively rendered diffusible in an imagewise pattern as a function of development.
• image-providing materials Numerous examples of both types of image-providing materials are recited in the patent literature.
• a particularly useful class of such materials are dye developers (dyes which are also silver halide developing agents) described in U.S. Pat. No. 2,983,606 and many other patents.
• multicolor images may be obtained by employing a photosensitive element or negative component including at least two selectively sensitized silver halide layers, each having associated therewith a dye image-providing material exhibiting desired spectral absorption characteristics.
• a photosensitive element or negative component including at least two selectively sensitized silver halide layers, each having associated therewith a dye image-providing material exhibiting desired spectral absorption characteristics.
• the most commonly employed elements of this type are the so-called tripack structures employing a blue-, a greenand a red-sensitive silver halide layer having associated therewith, respectively, a yellow, a magenta and a cyan dye image-providing material.
• the negative and positive components may be ini-' tially separate elements which are brought into superposition during development and thereafter retained together or separated to provide the desired transfer image (e.g., as described in the aforementioned U.S. Pat. No. 2,983,606); or they may be contained together as a unitary structure, e.g., the so-called integral negative-positive film units wherein the respective components are retained together prior to exposure and following image-formation.
• a reflecting layer usually a white pigment such as titanium dioxide
• the respective components in such integral film units may be contained on a single dimensionally stable layer or support or they may be confined between a pair of such supports. Of course, any support associated with the positive component should be transparent to permit viewing of the transfer image.
• timing layers comprising, as a continuous phase, the coalesced essence of an aqueous film-forming synthetic polymer dispersion which is substantially impermeable to the aqueous alkaline processing fluid, e.g., a latex, and a discontinuous phase comprising a material sometimes referred to as a permeator which is permeable to the processing fluid.
• Preferred latices disclosed in that application include a 60-38-2 copolymer of methylmethacrylate, butylacrylate and acrylic acid, respectively; a 60-30-4-6 copolymer of butylacrylate, diacetone acrylamide, styrene and methacrylic acid, respectively; and a 60-30-4-6-l.5-0.5 copolymer of butylacrylate, diacetone acrylamide, styrene, methacrylic acid, 2- sulfoethyl methacrylate and diviniyl benzene, respectively, all proportion designations being on a dry weight basis.
• latices Among other useful latices, mentionmay be made of polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, acrylic polymers and copolymers as, for example, a terpolymer of butylacrylate, methylmethacrylate and small amounts of acrylic acid or methacrylic acid, and innumerable other latices which will readily come to mind to one of ordinary skill in polymer chemistry. An extensive compilation of appropriate latices which may be utilized herein will be found in U.S. Pat. No. 2,795,564.
• Useful permeators disclosed in that application include isopropyl cellulose, preferably containing about 1.3 isopropyl groups per cellulosic monomer unit, hydroxypropyl cellulose, acrylonitrile acrylic acid copolymers, methacrylate acrylic acid copolymers, preferably containing about 3% by weight acrylic acid, poly-N- ethyl acrylamide, polyacrylamide, polyethylene oxide, terpolymers of N-ethylacrylamide, methylacrylamide and acrylamide, copolymers of N-ethylacrylamide and 2-vinyl pyridine, copolymers of N-isopropyl acrylamide and N-vinyl pyrrolidone, copolymers of N-isopropyl acrylamide and dimethylaminoethyl acrylate, etc.
• Other useful permeators include graft copolymers of the type disclosed in the aforementioned U.S. Pat. No. 3,575,701 and which are disclosed in this patent
• the coalesced latex portion of the timing layer is denoted as the continuous phase
• the permeator component is denoted as the discontinuous phase.
• Such'terminology connotes an admixture of the two components with the former component being present in greater concentration than the latter which may, if desired, be present in the form of continuous channels, etc., throughout the coalesced latex.
• the ratio of latex .to permeator employed may vary in accordance with the particular rate or degree of diffusibility desired in the photographic system in which it is employed. It will be appreciated that as the concentration of permeator increases, the permeability of the layer also increases.
• a typical latex/permeator timing layer of this invention may contain a ratio of latex to permeator on the order of from about 19:1 to about 99:1, a typical ratio being on the order of about 40:1.
• a ratio of latex to permeator on the order of from about 19:1 to about 99:1, a typical ratio being on the order of about 40:1.
• the timing layers of this invention possess a total thickness such that, if the layer consisted only of the coalesced latex, it would be impermeable to the alkaline processing fluid. It may, for example, be on the order of 0.1 to 0.7 mil thick and may, for example, contain on the order of 300-1700 mgs. of solids/sq. ft. of surface area. Where employed in systems wherein the photosensitive strata are to be exposed and/or the resulting image is to be viewed through this layer, it is desirable that the layer, like any other layers through which exposure is to be made and/or the image viewed, should be as thin as possible. In such instances, it will also be appreciated that the timing layer of this invention should also be as clear or transparent to visible light as possible.
• the latex and permeator be compatible, since incompatibility will result in a film which may not be as transparent or clear as desired and is not macroscopically homogenous.
• various degrees of compatibility may be achieved. The indicativeness of such compatibility may be appreciated by the clarity of the ultimate film produced light scatter being a concomitant result of the absence of compatibility between the latex and the permeator used therewith, and being further indicative of the degree of macromolecular nonhomogeneity.
• the layer may be considered to be homogeneous if the coalesced latex contains a permeator which is distributed compatibly throughout the coalesced latex film so as not to produce scattering of incident light. In absolute terms, that is, on the microscopic level, the layer will generally consist essentially of the coalesced latex with a multiplicity of small localized areas comprising the permeator.
• the present invention is directed to timing layers of the type described in the aforementioned copending application Ser. No. 246,779 and photographic systems of the type previously described employing such timing layers, the essence of the invention being employing polyvinyl alcohol as the permeator to achieve certain advantages to be described hereinafter.
• this component or image-receiving element generally comprises a suitable support which may be opaque or transparent, e.g., a paper base support having the desired neutralizing layer, e.g., an acid layer of the type described in U.S. Pat. No. 3,362,819, a timing layer comprising a latex of the type described in the aforementioned copending application Ser. No. 246,779 with polyvinyl alcohol as the permeator; and a dyeable stratum such as any of those heretofore known, e.g., of the type described in U.S. Pat.
• No. 3,148,061 comprising polyvinyl alcohol and poly-4- vinyl pyridine.
• Other reagents such as stabilizers, development restrainers, UV light absorbers and the like may be and frequently are also present and the presence or absence of such additional reagents performing specific desired functions per se comprises no part of this invention.
• a typical image-receiving element of the foregoing description may, for example, comprise a paper base support having thereon, in order, a layer about 0.8 mil thick comprising the partial butyl ester of polyethylene/maleic anhydride copolymer prepared in accordance with Example 10 of U.S. Pat. No. 3,362,819; a timing layer about 0.3 mil thick containing about a :1 ratio of a 60-30-4-6 copolymer of butylacrylate,
• polyvinyl alcohol e.g., Elvanol 72-60" (trade name of E. I. duPont de Nemours & Co. for high viscosity, hydrolyzedpolyvinyl alcohol); and a dyeable stratum or receiving layer about 0.4 mil thick comprising a 2:1 mixture, by weight, of polyvinyl alcohol and poly-4-vinylpyridine.
• neutralizing and timing layers associated with the positive component may be disposed in the negative component, as disclosed in U.S. Pat. No. 3,362,821, or in both.
• the preferred integral negative-positive film units contemplated by this invention are of the type disclosed in U.S. Pat. No. 3,415,644 wherein the essential layers of the negative and positive components are confined between a pair of support members, the one associated with the negative component being opaque and the one associated with the positive component being transparent for exposure of the film unit and subsequent viewing of the resulting color image by reflected light.
• such a configuration for forming multi-color images may comprise, in order, a transparent support, a neutralizing layer, a timing layer of this invention, a dyeable stratum, a blue-sensitive silver halide emulsion layer having a yellow dye image-providing material associated therewith in the same or in an adjacent layer, a green-sensitive silver halide emulsion layer having a magenta dye image-providing material associ ated therewith in the same or in an adjacent layer, a red-sensitive silver halide emulsion layer having a cyan dye image-providing material associated therewith in the same or in an adjacent layer, and an opaque support.
• an interlayer or spacer layer is disposed between each set of silver halide and associated dye image-providing material, e.g., an interlayer of the type described in U.S. Pat. No. 3,625,685 comprising a latex and a permeator.
• the permeator so employed in these negative interlayers may be polyvinyl alcohol as in the timing layers of this invention.
• the negative and positive components are preferably prelaminated in accordance with the precedures described and claimed in US. Pat. Nos.
• the processing composition also contains a reflecting agent, e.g., a dispersion of titanium dioxide, so that the thus applied layer masks effectively the negative component (including developed silver and any associated dye image-providing material) and provides the requisite background for viewing the color transfer image by reflected light, without separation, through the transparent support.
• a reflecting agent e.g., a dispersion of titanium dioxide
• the processing composition also contains additional opacifying agent which in combination with the opaque support provides a lighttight envelope sandwiching the negative component so that the film unit may be developed in the light.
• additional opacifying agent which in combination with the opaque support provides a lighttight envelope sandwiching the negative component so that the film unit may be developed in the light.
• An illustrative integral negative-positive fllm unit of this description may be prepared, for example, by coating, in succession, on a gelatin subbed 4 mil. opaque polyethylene terephthalate film base, the following layers:
• a blue-sensitive gelatino silver iodobromide emulsion layer including the auxiliary developer 4'- methylphenyl hydroquinone coated at a coverage of about mgs./ft. ofsilver, about 60 mgs./ft. of gelatin and about 30 mgs./ft. of auxiliary developer; and
• the three dye developers employed above may be the following:
• a transparent 4 mil. polyethylene terephthalate film base may be coated, in succession, with the following illustrative layers:
• timing layer containing about a 40:1 ratio of a 60-30-4 -6 copolymer of butylacrylate, diacetone acrylamide, styrene and methacrylic acid and polyvinyl alcohol at a coverage of about 500 mgs./ft. and
• the two components may then be laminated together to provide the desired integral film unit.
• a rupturable container comprising an outer layer of lead foil and an inner liner or layer of polyvinyl chloride retaining an aqueous alkaline processing solution may than be fixedly mounted on the leading edge of each of the laminates, by pressure-sensitive tapes,,interconnecting the respective container and laminates so that, upon application of compressive pressure to the container to rupture the containers marginal seal, its contents may be distributed between the dyeable stratum (layer 3 of the positive component) and the gelatin layer (layer 9) of the negative component.
• An illustrative processing composition to be employed in the rupturable container may comprise the following properties of ingredients:
• This film unit may then be exposed in known manner to form a developable image and the thus exposed element may then be developed by applying compressive pressure to the rupturable container in order to distribute the aqueous alkaline processing composition, thereby forming a multicolor transfer image which is viewable through the transparent polyethylene terephthalate film base as a positive reflection print.
• the layers of this invention may be prepared simply and efficiently by admixing the polyvinyl alcohol, latex and any other solids together in the desired amounts in a single pot process.
• permeators such as polyacrylamide can not be so admixed and the polyacrylamide must first be put into solution. This takes up to 24 hours and requires storage in drums for subsequent use in commercial production.
• polyvinyl alcohol has given evidence of improved photographic results. Specifically, it gives evidence of better performance during development at cold temperatures while maintaining the same performance at room temperatures and higher. Thus, polyvinyl alcohol gives evidence of better performance over the temperature scale from hot to cold in terms of time controlling the diffusion of alkali and subsequent pH reduction within the prescribed time sequence in the development process.
• the permeator and latex forming the layer should be com patible in the sense that they do not interact to absorb and/or reflect light. It has been found that polyvinyl alcohol will so interact when alkali is added to adjust the pH, e.g., at pH 7, to produce a haze. In systems such as the illustrative integral negative-positive film unit wherein viewing is effected through this layer, this of course is undesirable and this neutralization step heretofore suggested should be obviated. For example, without neutralization, e.g., at pH 4.5, the layer is perfectly clear and performs its desired function in the prescribed manner.
• the haze resulting from neutralization of course is not a problem in systems wherein the timing and neutralizing layers are so disposed in the product, e.g., in the negative component, that they are not in the path of viewing light. Moreover, it doesvnot appear to be a problem in those systems wherein the layers are so disposed in the image-receiving element which is sepa rated after image formation. While the exact reason is not entirely clear, the haze problem appears to be a surface phenomenon which is obviated in these systems.
• the spacer layer of this invention may, if desired, include alkali to adjust the pH, it being understood that if this pH adjustment causes undesirable haze, it should not be done. In either case, the spacer layers of this invention will provide the advantages noted above.
• a photographic product comprising a photosensitive element including at least one light-sensitive silver halide layer having a dye image-providing material associated therewith and an image receiving element including a dyeable stratum adapted for receiving a dye image pattern and a neutralizing system integrated with said photosensitive system or said image receiving element for lowering the pH of an aqueous alkaline processing composition; said neutralizing system including a neutralizing layer and a spacer layer arranged on a support and wherein said spacer layer is disposed with respect to said neutralizing layer so that said processing fluid must first diffuse through the spacer layer before contacting the neutralizing layer;
• said spacer layer com-' prises as a continuous phase a coalesced aqueous film-forming synthetic polymer dispersion which is substantially impervious to said processing fluid and a discontinuous phase comprising polyvinyl alcohol.
• an integral negative-positive film unit including a negative component comprising at least one lightsensitive silver halide layer having a dye imageproviding material associated therewith, a positive .component including at least a dyeable stratum, means for applying a reflecting layer between said positive and negative components in an amount sufficient upon development of said film unit to mask effectively said negative component and toprovide a background for viewing a color image imparted to said dyeable stratum of said positive component by reflected light by applying an aqueous alkaline processing fluid to said film unit after exposure thereof, said film unit further including a neutralizing layer for lowering the environmental pH subsequent to application of said alkaline processing fluid and a spacer layer so disposed with respect to said neutralizing layer that said processing fluid must first diffuse through said spacer layer before contacting said neutralizing layer;
• said spacer layer comprises as a continuous phasea coalesced aqueous film-forming synthetic polymer dispersion which is substantially impermeable to said processing fluid and a discontinuous phase comprising polyvinyl alcohol.
• a film unit as defined in claim 5 including means for applying said aqueous alkaline processing fluid to develop said film unit.
• a film unit as defined in claim 5 wherein said means for applying a reflecting layer comprises a layer of a white pigment disposed in a layer between said positive and negative components.
• a film unit as defined in claim 5 including at least two selectively sensitized silver halide layers, each hav' in g asso ciated therewith a dye image-providing material, a nd a layer intermedia t e saidsilver halide layers comprising as a continuous phase: the coalesced essence of an aqueous film-forming synthetic polymer dispersion which is substantially impermeable to said processing fluid and a discontinuous phase comprising polyvinyl alcohol.
• a red-sensitive silver halide layer having associated therewith, respectively, a yellow, magenta and a cyan dye image-providing material, a neutralizing 1 layer for lowering the environmental pH after application of an aqueous alkaline processing fluid to develop said film unit, and a spacer layer so disposed in said film unit with respect to said neutralizing layer that said alkaline processing fluid must diffuse through said spacer layer before contacting said neutralizing layer;
• said spacer layer comprises as a continuous phase a coalesced aqueous film-forming synthetic polymer dispersion which is substantially impermeable to said processing fluid and a discontinuous phase comprising polyvinyl alcohol.
• said spacer layer comprises as a continuous phase a coalesced aqueous film-forming synthetic polymer dispersion which is substantially impermeable to said processing fluid and a discontinuous phase comprising polyvinyl alcohol. 14.
• a photosensitive element which comprises, in
• a layer intermediate said silver halide layers comprising, as a continuous phase, a coalesced aqueous film-forming synthetic polymer dispersion adapted to provide a dye image-forming material imperme layer and associated dye image-providing material being'separated from the next adjacent silver halide layer and associated dye image-providing material by one of said intermediate layers.
• a photographic product comprising a photosensitive element including at least one light-sensitive silver halide layer having a dye image-providing material associated therewith is exposed to form a developable image and thereafter an aqueous alkaline processing fluid is applied between the thus exposed photosensitive element and a superposed image-receiving element to develop said image and to impart to said receiving element a color diffusion transfer image and said photographic product includes a neutralizing system integrated with said photosensitive elementor said image receiving element; said neutralizing system including a neutralizing layer and a spacer layer arranged on a support and wherein said spacer layer is disposed with respect to said neutralizing layer so that said processing fluid must first diffuse through the spacer layer before contacting the neutralizing layer;
• said spacer layer comprises as a continuous phase a coalesced aqueous film-forming synthetic polymer dispersion which is substantially impervious to said processing fluid and a discontinuous phase comprising polyvinyl alcohol.
• the improvement comprising employing as said film unit a film unit as defined in claim 5.

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Citations (7)

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• 1972
  • 1972-12-26 US US00318402A patent/US3856522A/en not_active Expired - Lifetime
• 1973
  • 1973-12-07 JP JP48137241A patent/JPS4991642A/ja active Pending
  • 1973-12-07 GB GB5684773A patent/GB1453844A/en not_active Expired
  • 1973-12-07 CA CA187,675A patent/CA1014785A/en not_active Expired
  • 1973-12-21 FR FR7346130A patent/FR2279132A2/fr active Granted
  • 1973-12-21 DE DE2364137A patent/DE2364137C2/de not_active Expired
• 1979
  • 1979-11-26 JP JP15213079A patent/JPS55111943A/ja active Granted

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