Dye free, spectrally sensitive silver halide layers in diffusion transfer films

Claim 2

A composite photographic diffusion transfer process film unit which comprises a plurality of sequential layers including, in combination, a first dimentionally stable transparent layer; a first dyeable layer adapted to receive diffusion transfer process dye image-forming material diffusing thereto; an opaque layer; a first photosensitive silver halide layer comprising a dispersion of silver halide grains possessing a first mean particle size, having associated therewith a diffusion transfer process dye image-forming material possessing spectral absorption within the spectral range to which the silver halide grains are sensitive; a second photosensitive silver halide layer substantially free of diffusion transfer process dye image-forming material comprising a dispersion of silver halide grains possessing a second mean particle size and substantially spectrally sensitive within said spectral range; said second mean particle size being less than said first particle size; a second dimensionally stable transparent layer; means for providing a processing composition intermediate the second dimensionally stable transparent layer and the next adjacent silver halide layer; means for providing opacifying agent intermediate the second dimensionally stable layer and the next adjacent silver halide layer in a quantity effective to prevent exposure of the photosensitive silver halide layers during processing of the film unit in the presence of radiation actinic to the photosensitive layers and incident on said second dimensionally stable transparent layer and the opaque layer is effective to prevent exposure of said photosensitive layers during processing of said film unit in the presence of radiation actinic to the photosensitive layer and incident on said first dimensionally stable layer; means for maintaining the composite unit intact subsequent to diffusion transfer processing; said second silver halide layer possessing a sensitivity to incident radiation at wavelengths to which it has been sensitized greater than the sensitivity exhibited by said first photosensitive silver halide layer to said radiation at said wavelengths; said layers arranged in substantially parallel planar relationship; and said dimensionally stable layers being externally disposed with respect to the other of said layers.

Claim 3

A composite photographic diffusion transfer color process film unit as defined in claim 1 wherein said processing composition possesses a first processing pH and said film unit includes means for converting, subsequent to substantial dye transfer image formation in said dyeable layer, said processing composition from said first processing pH to a second pH at which each of said dye transfer images exhibit increased stability.

Claim 4

A composite photographic diffusion transfer process film unit as defined in claim 2 wherein said first processing pH is an alkaline pH and said second pH is lower than said first pH.

Claim 5

A composite photographic diffusion transfer process film unit as defined in claim 3 wherein said second pH is > one pH unit less than said first pH.

Claim 6

A composite photographic diffusion transfer process film unit as defined in claim 2 wherein said means for converting said processing composition from said first to said second pH subsequent to substantial dye transfer image formation in said first dyeable layer comprises a polymeric neutralizing layer positioned intermediate at least one of said first dimensionally stable transparent layer and said dyeable layer, and said second dimensionally stable transparent layer and said next adjacent silver halide layer.

Claim 7

A composite photographic diffusion transfer process film unit as defined in claim 1 wherein said opaque layer is actinic radiation reflective.

Claim 8

A composite photographic diffusion transfer process film unit as defined in claim 6 wherein said opaque layer comprises titanium dioxide dispersed in a processing composition permeable polymeric binder.

Claim 9

A composite photographic diffusion transfer process film unit as defined in claim 7 wherein said opaque layer comprises a composite including a layer containing carbon black dispersed in a processing composition permeable polymeric binder positioned intermediate said opaque layer comprising titanium dioxide and the photosensitive silver halide layer next adjacent thereto.

Claim 10

A composite photographic diffusion transfer process film unit as defined in claim 1 wherein said opacifying agent is actinic radiation absorptive.

Claim 11

A composite photographic diffusion transfer process film unit as defined in claim 9 wherein said opacifying agent comprises an inorganic pigment.

Claim 12

A composite photographic diffusion transfer process film unit as defined in claim 10 wherein said opacifying agent including said inorganic reflecting pigment is disposed in said processing composition.

Claim 13

A composite photographic diffusion transfer process film unit as defined in claim 1 wherein said means for providing said processing composition comprises rupturable container means retaining said processing composition extending transverse an edge of said film unit to effect, upon application of compressive pressure to the container means, discharge of said container means processing composition contents intermediate said second dimensionally stable transparent layer and the next adjacent silver halide layer.

Claim 14

A composite photographic diffusion transfer process film unit as defined in claim 1 wherein said diffusion transfer process dye image-forming material is a dye which is a silver halide developing agent.

Claim 15

A composite photographic diffusion transfer process film unit as defined in claim 13 wherein said dye is soluble and diffusible at a first pH and substantially nondiffusible at a second pH.

Claim 16

A composite photographic diffusion transfer process film unit as defined in claim 1 wherein said second photosensitive silver halide layer comprises a particulate dispersion of photosensitive silver iodochlorobromide, silver iodochloride or silver iodobromide grains.

Claim 17

A composite photographic diffusion transfer process film unit as defined in claim 15 wherein said dispersion comprising said photosensitive silver iodochlorobromide, silver iodochloride or silver iodobromide dispersion possesses a mean grain size within the range of about 0.2 to 3.0 μ.

Claim 18

A composite photographic diffusion transfer process film unit as defined in claim 16 wherein each of said first and second photosensitive silver halide layers comprises photosensitive silver iodochlorobromide, silver iodochloride or silver iodobromide grains.

Claim 19

A process for providing a composite photographic diffusion transfer process dye image which comprises, in combination, the steps of: a. exposing to incident actinic radiation a photographic diffusion transfer process film unit which comprises, a plurality of sequential layers including in combination, a dimensionally stable transparent layer; a dyeable layer adapted to receive diffusion transfer process dye image-forming material diffusing thereto; an opaque layer; a first photosensitive silver halide layer comprising a dispersion of silver halide grains possessing a first mean particle size and having associated therewith a diffusion transfer process dye image-forming material possessing spectral absorption within the spectral range to which the silver halide layer is sensitive; a second photosensitive silver halide layer comprising a dispersion of silver halide grains possessing a mean particle size less than said first mean particle size, substantially spectrally sensitive within said spectral range, and substantially free of diffusion transfer process dye image-forming material; a second dimensionally stable transparent layer; said second silver halide layer possessing a sensitivity to incident radiation at wavelengths to which it has been sensitized in excess of the sensitivity exhibited by said first photosensitive silver halide layer to said radiation at said wavelengths; said layers arranged in substantially parallel planar relationship; and said dimensionally stable layers being externally disposed with respect to the other of said layers; b. contacting the silver halide layers with a processing composition and effecting development of the photoexposed silver halide layers and formation of an imagewise distribution of mobile dye image-forming material as a function of the point-to-point degree of silver halide layer photoexposure; and c. transferring, by diffusion, at least a portion of said imagewise distribution of mobile dye image-forming material to said dyeable layer adapted to receive dye image-forming material diffusing thereto to thereby provide to said dyeable layer a dye image in terms of said imagewise distribution.

Claim 20

A process for providing a composite photographic diffusion transfer process dye image which comprises, in combination, the steps of: a. exposing to incident actinic radiation a photographic diffusion transfer process film unit which comprises, a plurality of sequential layers including in combination, a dimensionally stable transparent layer; a dyeable layer adapted to receive diffusion transfer process dye image-forming material diffusing thereto; an opaque layer; a first photosensitive silver halide layer comprising a dispersion of silver halide grains possessing a first mean particle size and having associated therewith a diffusion transfer process dye image-forming material possessing spectral absorption within the spectral range to which the silver halide layer is sensitive; a second photosensitive silver halide layer comprising a dispersion of silver halide grains possessing a mean particle size less than said first mean particle size, substantially spectrally sensitive within said spectral range, and substantially free of diffusion transfer process dye image-forming material; a second dimensionally stable transparent layer; said second silver halide layer possessing a sensitivity to incident radiation at wavelengths to which it has been sensitized in excess of the sensitivity exhibited by said first photosensitive silver halide layer to said radiation at said wavelengths; said layers arranged in substantially parallel planar relationship; and said dimensionally stable layers being externally disposed with respect to the other of said layers; b. contacting the silver halide layers with a processing composition and effecting development of the photoexposed silver halide layers and formation of an imagewise distribution of mobile dye image-forming material as a function of the point-to-point degree of silver halide layer photoexposure; and c. transferring, by diffusion, at least a portion of said imagewise distribution of mobile dye image-forming material to said dyeable layer adapted to receive dye image-forming material diffusing thereto to thereby provide to said dyeable layer a dye image in terms of said imagewise distribution.

Claim 21

A process for providing a photographic diffusion transfer process dye image as defined in claim 18 including the step of converting the pH of said film unit, subsequent to substantial dye image formation in said dyeable layer, from a first processing pH provided by said processing composition to a second pH at which said dye images exhibit increased stability.

Claim 22

A process for providing a photographic diffusion transfer process dye image as defined in claim 19 wherein said dye image-forming material comprises a dye which is a silver halide developing agent and is soluble and diffusible in said processing composition at said first pH as a function of the photoexposure of said film unit and is substantially nondiffusible at said second pH.

Claim 23

A process for providing a photographic diffusion transfer process dye image as defined in claim 18 wherein said first processing pH is an alkaline pH and said second pH is > about one pH unit lower than said first pH.

Claim 24

A process for providing a photographic diffusion transfer process dye image as defined in claim 18 including the step of providing opacifying agent continguous the surface of said silver halide layer next adjacent said second dimensionally stable transparent layer.

Claim 25

A process of forming transfer images in color as defined in claim 18 wherein said second photosensitive silver halide layer comprises a particulate dispersion of photosensitive silver iodochlorobromide, silver iodochloride or silver iodobromide grains.

Claim 26

A process of forming transfer images in color as defined in claim 23 wherein said dispersion comprising said photosensitive silver halide iodochlorobromide, silver iodochloride or silver iodobromide dispersion possesses a mean grain size within the range of about 0.2 to 3.0 μ.

Claim 27

A process of forming transfer images in color as defined in claim 24 wherein each of said first and second photosensitive silver halide layers comprises photosensitive silver iodochlorobromide, silver iodochloride or silver iodobromide grains.

Claim 28

A process of forming transfer images in color as defined in claim 18 wherein said dye image-providing material is a dye which is a silver halide developing agent.

Claim 29

A process for providing a photographic diffusion transfer process dye image as defined in claim 18 which comprises, in combination, the steps of: a. exposing to incident actinic radiation a composite photographic film unit which comprises a plurality of sequential layers including a first dimensionally stable layer transparent to incident actinic radiation; a dyeable layer; an opaque layer; at least two selectively sensitized silver halide units at least one of said selectively sensitized units including a said first photosensitive silver halide layer comprising a particulate dispersion of photosentitive silver iodochlorobromide, silver iodochloride or silver iodobromide grains which possesses said first mean particle size and in contiguous parallel planar relationship thereto a said second photosensitive silver halide layer comprising a particulate dispersion of photosensitive silver halide grains which possess a mean particle size less than said first mean particle size wherein said second photosensitive silver halide layer of said composite unit is positioned intermediate the exposure surface of said film unit and said first photosensitive silver halide layer and possesses a sensitivity to incident radiation at wavelengths to which it has been selectively sensitized in excess of the sensitivity exhibited by said first photosensitive silver halide layer to said radiation at said wavelengths, and said first photosensitive silver halide layer has disposed therein said diffusion transfer process dye image-forming material; a second dimensionally stable layer transparent to incident actinic radiation; and means for securing the layers in substantially fixed relationship; a rupturable container retaining a processing composition possessing substantially uniformly dispersed therein opacifying agent present in a quantity sufficient, upon distribution of the processing composition as a layer intermediate the second dimensionally stable transparent layer and next adjacent selectively sensitized silver halide emulsion layer, to substantially prevent transmission therethrough of incident exposure radiation actinic to the silver halide emulsion layers and the rupturable container is positioned and extends transverse an edge of the photosensitive element to effect discharge of the container's said processing composition intermediate the second dimensionally stable transparent layer and the next adjacent selectively sensitized silver halide emulsion layer; b. effecting discharge of the container's processing composition intermediate the second dimensionally stable transparent layer and the next adjacent selectively sensitized silver halide layer; c. effecting thereby development of each of the selectively sensitized silver halide emulsions; d. forming thereby imagewise distributions of mobile dye as a function of development; e. transferring, by diffusion, at least a portion of each of the imagewise distributions of mobile dye to said dyeable layer to provide a dye image in terms of the imagewise distribution; and f. maintaining the composite structure intact subsequent to processing.

Claim 30

A process for providing composite photographic diffusion transfer process dye images as defined in claim 27 which comprises, in combination, the steps of: a. exposing to incident actinic radiation a photographic film unit which comprises a composite structure containing, as essential layers, in sequence, a first dimensionally stable alkaline solution impermeable transparent layer; an alkaline solution dyeable polymeric layer; an alkaline solution permeable inorganic light-reflecting pigment layer comprising titanium dioxide; an alkaline solution permeable opaque layer comprising carbon black; a red-sensitive silver halide emulsion unit having associated therewith cyan dye; a green-sensitive silver halide emulsion unit having associated therewith magenta dye; a blue-sensitive silver halide emulsion unit having associated therewith yellow dye, each of said cyan, magenta and yellow dyes being a silver halide developing agent and at least one of said red-, green- and blue-sensitive silver halide emulsion units comprising a composite unit including said first and second photosensitive silver halide layers each comprising a particulate dispersion of photosensitive silver iodochlorobromide, iodochloride or iodobromide grains, the dispersion comprising said first photosensitive silver halide layer possessing a mean particle size in excess of the mean particle size of the dispersion comprising said second photosensitive silver halide layer and said second photosensitive silver halide layer is positioned intermediate the exposure surface of said film unit and said first photosensitive silver halide layer and possesses a sensitivity to incident radiation at wavelengths to which it is sensitive in excess of the sensitivity exhibited by first photosensitive silver halide layer to said radiation at said wavelengths, and the cyan, magenta and yellow dye associated with a said composite unit disposed within said first photosensitive silver halide layer, each of the cyan, magenta and yellow dyes being soluble and diffusible, in alkali, at a first pH; a second dimensionally stable alkaline solution impermeable transparent layer; a polymeric layer containing sufficient acidifying capacity to effect reduction of a processing composition having the first pH at which the cyan, magenta and yellow dyes are soluble and diffusible to a second pH at which the dyes are substantially nondiffusible positioned intermediate at least one of said dimensionally stable transparent layers and next adjacent layer; and means securing said layers in substantially fixed relationship; and a rupturable container retaining an aqueous alkaline processing composition having the first pH and containing substantially uniformly disposed therein opacifying agent substantially nondiffusible from said processing composition and present in a quantity sufficient, upon distribution of the aqueous alkaline processing composition possessing the first pH as a layer intermediate the second dimensionally stable transparent layer and the blue-sensitive silver halide emulsion unit, to provide a layer possessing an optical transmission density > about six density units with respect to incident radiation actinic to the silver halide emulsion layers, and the container is fixedly positioned and extends transverse a leading edge of the photosensitive element to effect upon application of compressive force unidirectional discharge of the container's aqueous alkaline processing composition possessing the first pH intermediate the second dimensionally stable transparent layer and the blue-sensitive silver halide emulsion unit; b. applying compressive force to the rupturable container to effect unidirectional discharge of the container's aqueous alkaline processing composition intermediate the second dimensionally stable transparent layer and the blue-sensitive silver halide emulsion unit; c. effecting thereby development of the red-, green- and blue-sensitive silver halide emulsion layers; d. immobilizing the cyan, magenta and yellow dyes as a result of development of their associated silver halide emulsion layers; e. forming thereby an imagewise distribution of mobile cyan, magenta and yellow dye as a function of the point-to-point degree of exposure of their associated silver halide emulsion layers; f. transferring, by diffusion, at least a portion of each of the imagewise distributions of mobile cyan, magenta and yellow dye to said alkaline solution permeable polymeric layer dyeable by said dyes to provide thereto a multicolor dye image; g. transferring, by diffusion, subsequent to substantial dye transfer, a sufficient portion of the ions of the aqueous alkaline processing solution to the polymeric acid layer to thereby reduce the alkalinity of the film unit from the first pH, at which the cyan, magenta and yellow image dyes are soluble and diffusible to a second pH, at which the cyan, magenta and yellow image dyes are substantially nondiffusible; and h. maintaining the composite structure intact subsequent to processing.

Claim 31

A composite photographic diffusion transfer process film unit which comprises a plurality of sequential layers including, in combination, a first dimensionally stable transparent layer; a first dyeable layer adapted to receive diffusion transfer process dye image-forming material diffusing thereto; an opaque layer; at least two selectively sensitized silver halide units at least one of said selectively sensitized units including a first photosensitive silver halide layer comprising a particulate dispersion of photosensitive silver iodochlorobromide, silver iodochloride or silver iodobromide grains which possesses a first mean particle size, said first layer having disposed therewithin a diffusion transfer process dye image-forming material possessing spectral absorption within the spectral range to which said grains are sensitive and in contiguous relationship thereto a second photosensitive silver halide layer substantially free of diffusion transfer process dye image-forming material, comprising a particulate dispersion of photosensitive silver halide grains which possess a second mean particle size less than said first mean particle size wherein said second photosensitive silver halide layer of said composite unit is positioned intermediate the exposure surface of said film unit and said first photosensitive silver halide layer, is substantially spectrally sensitive within said spectral range and possesses a sensitivity to incident radiation at wavelengths to which it has been selectively sensitized greater than the sensitivity exhibited by said first photosensitive silver halide layer to said radiation at said wavelengths; a second dimensionally stable transparent layer; means for providing a processing composition intermediate the second dimensionally stable transparent layer and the next adjacent silver halide layer; means for providing opacifying agent intermediate the second dimensionally stable layer and the next adjacent silver halide layer in a quantity effective to prevent exposure of the photosensitive silver halide layers during processing of the film unit in the presence of radiation actinic to the photosensitive layers and incident on said second dimensionally stable transparent layer and the opaque layer is effective to prevent exposure of said photosensitive layers during processing of said film unit in the presence of radiation actinic to the photosensitive layers and incident on said first dimensionally stable layer; means for maintaining the composite unit intact subsequent to diffusion transfer processing; said layers arranged in substantially parallel planar relationship; and said dimensionally stable layers being externally disposed with respect to the other of said layers.

Claim 32

A composite photographic diffusion transfer process film unit which comprises a plurality of sequential layers including, in combination, a first dimensionally stable transparent layer; a first dyeable layer adapted to receive diffusion transfer process dye image-forming material diffusing thereto; an opaque layer; at least two selectively sensitized silver halide units at least one of said selectively sensitized units including a first photosensitive silver halide layer comprising a particulate dispersion of photosensitive silver iodochlorobromide, silver iodochloride or silver iodobromide grains which possesses a first mean particle size, said first layer having disposed therewithin a diffusion transfer process dye image-forming material possessing spectral absorption within the spectral range to which said grains are sensitive and in contiguous relationship thereto a second photosensitive silver halide layer substantially free of diffusion transfer process dye image-forming material, comprising a particulate dispersion of photosensitive silver halide grains which possess a second mean particle size less than said first mean particle size wherein said second photosensitive silver halide layer of said composite unit is positioned intermediate the exposure surface of said film unit and said first photosensitive silver halide layer, is substantially spectrally sensitive within said spectral range and possesses a sensitivity to incident radiation at wavelengths to which it has been selectively sensitized greater than the sensitivity exhibited by said first photosensitive silver halide layer to said radiation at said wavelengths; a second dimensionally stable transparent layer; means for providing a processing composition intermediate the second dimensionally stable transparent layer and the next adjacent silver halide layer; means for providing opacifying agent intermediate the second dimensionally stable layer and the next adjacent silver halide layer in a quantity effective to prevent exposure of the photosensitive silver halide layers during processing of the film unit in the presence of radiation actinic to the photosensitive layers and incident on said second dimensionally stable transparent layer and the opaque layer is effective to prevent exposure of said photosensitive layers during processing of said film unit in the presence of radiation actinic to the photosensitive layers and incident on said first dimensionally stable layer; means for maintaining the composite unit intact subsequent to diffusion transfer processing; said layers arranged in substantially parallel planar relationship; and said dimensionally stable layers being externally disposed with respect to the other of said layers.

Claim 33

A photographic diffusion transfer color process film unit as defined in claim 29 wherein each of the selectively sensitized silver halide units possesses predominant spectral sensitivity to separate regions of the spectrum and the dye image-forming material associated with each of said silver halide layers possesses a spectral absorption range subsequent to processing substantially complementary to the predominant sensitivity range of its associated silver halide layer.

Claim 34

A photographic diffusion transfer color process film unit as defined in claim 30 wherein said selectively sensitized silver halide layers of said composite unit each comprise silver iodochlorobromide, iodochloride or iodobromide grains possessing a mean grain size within the range of about 0.2 to 3.0 μ.

Claim 35

A photographic diffusion transfer color process film unit as defined in claim 31 wherein said photosensitive silver halide of said composite unit is present at a coverage of 40 to 200 mgs./ft. 2 silver halide and said dye image-forming material is present in a ratio of 1.5 to 0.4 dye to silver halide.

Claim 36

A composite photographic diffusion transfer process film unit as defined in claim 29 wherein said color film unit includes means for converting the pH of said processing composition, subsequent to substantial diffusion dye image-forming materials to said dyeable layer, from a first alkaline processing pH to a second pH less than said first pH at which the dye transfer image provided by said dye image-forming materials exhibits increased stability.

Claim 37

A composite photographic diffusion transfer process film unit as defined in claim 29 wherein said selectively sensitized silver halide units include, as essential layers, a red-sensitive silver halide emulsion layer having associated therewith a diffusion transfer process cyan dye image-forming material, a green-sensitive silver halide emulsion layer having associated therewith a diffusion transfer process magenta dye image-forming material and a blue-sensitive silver halide emulsion layer having associated therewith a diffusion transfer process yellow dye image-forming material.