Photographic products and processes utilizing a polyvalent metal ion-cross-linked polymeric layer

Claim 2

A photographic film unit as defined in claim 1 wherein said metal ion cross-linked polymeric layer is impermeable to dye image-forming material and means for interposing said dye image-forming material impermeable polymeric layer comprises disposing a polymeric layer permeable to processing composition solubilized dye image-forming material and adapted to be cross-linked by contact with metal ion capable of cross-linking its polymeric component between said dyeable polymeric layer and the photosensitive silver halide emulsion layer next adjacent and disposing metal ion adapter to Cross-link said dye image-forming material permeable polymeric layer to provide said dye image-forming material impermeable metal ion cross-linked polymeric layer in said processing composition as retained in said rupturable container and adapted to be discharged in functional contact with said dye image-forming material permeable polymeric layer in a concentration effective, subsequent to substantial dye image-forming material transfer to said dyeable polymeric layer from said associated silver halide emulsion layer as a function of exposure of said emulsion layer, to provide said dye image-forming material impermeable metal ion cross-linked polymeric layer.

Claim 3

A photographic film unit as defined in claim 1 wherein said means for interposing said polymeric layer comprises disposing a film-forming polymer adapted to be cross-linked by contact with metal ion capable of cross-linking its polymeric component in said processing composition retained in said rupturable container and adapted upon distribution of said processing composition between said dyeable polymeric layer and the photosensitive silver halide emulsion layer next adjacent thereto to provide a substantially continuous dye image-forming material permeable polymeric layer, and said metal ion disposed as a metallic salt in a processing composition permeable layer of said photosensitive element and adapted to be solubilized by contact with distributed processing composition and to diffuse, subsequent to substantial dye image-forming material transfer to said dyeable polymeric layer from said associated silver halide emulsion layer as a function of exposure of said emulsion layer, to said dye image-forming material permeable polymeric layer in a concentration effective to provide a dye image-forming material impermeable metal ion cross-linked polymeric layer.

Claim 4

A photographic film unit as defined in claim 4 wherein said film-forming polymeric material comprises carboxymethyl cellulose.

Claim 5

A photographic film unit as defined in claim 5 wherein said metallic salt comprises cadmium acetate.

Claim 6

A photographic film unit as defined in claim 6 wherein said metallic salt is disposed in said dyeable polymeric layer.

Claim 7

A photographic film unit as defined in claim 4 wherein said film-forming polymeric material comprises carboxymethyl hydroxyethyl cellulose.

Claim 8

A photographic film unit as defined in claim 1 wherein said metal ion is polyvalent.

Claim 9

A photographic film unit as defined in claim 1 wherein said metal ion is selected from the group consisting of: cadmium, magnesium, calcium, zinc, zirconium, aluminum, chromium, and nickel metal ions.

Claim 10

A photographic film unit as defined in claim 1 wherein said first dimensionally stable layer layer is transparent to incident actinic radiation.

Claim 11

A photographic film unit as defined in claim 10 wherein said opacifying agent is initially present intermediate said dyeable polymeric layer and the photosensitive silver halide emulsion layer next adjacent thereto in a quantity sufficient to mask said dye image-providing material.

Claim 12

A photographic film unit as defined in claim 1 wherein said processing composition is an aqueous alkaline composition.

Claim 13

A photographic film unit as defined in claim 13 wherein said dye image-providing material is a dye which is a silver halide developing agent.

Claim 14

A photographic film unit as defined in claim 1 wherein said opacifying agent is present in a quantity sufficient to prevent exposure of said silver halide emulsion during processing in the presence of radiation actinic thereto and incident on said distributed processing solution.

Claim 15

A photographic film unit as defined in claim 1 wherein said opacifying agent is actinic radiation reflective.

Claim 16

A photographic film unit as defined in claim 16 wherein said opacifying agent is titanium dioxide.

Claim 17

A photographic film unit as defined in claim 14 wherein said photosensitive element comprises at least two selectively sensitized silver halide emulsion layers eAch having a dye which dye is a silver halide developing agent of a predetermined color associated therewith, each of said dyes soluble and diffusible in processing composition as a function of the point-to-point degree of exposure of the respective emulsion associated therewith.

Claim 18

A photographic film unit as defined in claim 18 wherein each of said selectively sensitized photosensitive silver halide emulsions has predominant spectral sensitivity to separate regions of the spectrum and the dye associated with each of said silver halide emulsion layers possesses a spectral absorption range subsequent processing substantially complementary to the predominant sensitivity range of its associated emulsion layer.

Claim 19

A photographic film unit as defined in claim 19 wherein each of said silver halide emulsion layers and its associated dye is separated from the next adjacent silver halide emulsion layer and its associated dye by an alkaline solution permeable polymeric interlayer.

Claim 20

A photographic film unit as defined in claim 14 including at least one polymeric acid layer positioned intermediate at least one of said first dimensionally stable layers and the photosensitive silver halide emulsion layer next adjacent thereto, and said second dimensionally stable layer and the dyeable polymeric layer adjacent thereto, said processing composition comprises an aqueous alkaline processing composition possessing a first pH at which said dye is soluble and diffusible and said polymeric acid layers possess sufficient acid capacity to reduce said processing composition from said first pH to a second pH at which said dye is substantially nondiffusible subsequent to substantial dye image diffusion to said dyeable polymeric layer from said silver halide emulsion layer as a function of exposure of said emulsion layer.

Claim 21

A photographic film unit as defined in claim 21 which is adapted to be processed by passing said unit between a pair of juxtaposed pressure-applying members and which comprises, in combination: a photosensitive element including a composite structure containing, as essential layers, in sequence, a dimensionally stable liquid impermeable opaque layer; a red-sensitive silver halide emulsion layer having associated therewith cyan dye; a green-sensitive silver halide emulsion layer having associated therewith magenta dye; a blue-sensitive silver halide emulsion layer having associated therewith yellow dye, each of said cyan, magenta and yellow dyes being silver halide developing agents and being soluble and diffusible in aqueous alkaline processing composition at a first pH; an alkaline solution permeable transparent polymeric layer dyeable by said dyes; an alkaline solution permeable transparent polymeric acid layer containing sufficient acidifying capacity to effect reduction of an aqueous alkaline processing composition having said first pH to a second pH at which said dyes are substantially nondiffusible; a dimensionally stable liquid impermeable transparent layer; and means securing said layers in substantially fixed relationship; a rupturable container retaining an aqueous alkaline processing composition fixedly positioned and extending transverse a leading edge of said photosensitive element to effect unidirectional discharge of said container''s processing composition between said dyeable polymeric layer and said blue-sensitive silver halide emulsion layer upon application of compressive pressure to said container, said aqueous alkaline processing composition possessing said first pH, opacifying agent in a quantity sufficient to mask said cyan, magenta and yellow dyes associated with said red-, green- and blue-sensitive silver halide emulsion layers and a film-forming polymer adapted to be cross-linked by contact with metal ion capable of cross-linking its polymeric component in a quantity sufficient to provide a substantially continuous, alkaline processing composition solubilized cyan, magenta and yellow dye permeable polymeric layer upon dIstribution of said aqueous alkaline processing composition intermediate said dyeable polymeric layer and said blue-sensitive silver halide emulsion layer; and said metal ion adapted to cross-link said polymeric layer at said second pH disposed as a metallic salt in a processing composition permeable layer of said photosensitive element and adapted to be solubilized by contact with said distributed processing composition and to coact with said cross-linkable polymeric layer in a concentration effective at said second pH to provide an alkaline processing composition solubilized cyan, magenta and yellow dye impermeable metal ion cross-linked polymeric layer intermediate said dyeable polymeric layer and said blue-sensitive silver halide emulsion.

Claim 22

A photographic film unit as defined in claim 22 wherein said first pH is above 9 and said second pH is below 9.

Claim 23

A photographic film unit as defined in claim 22 wherein said metallic salt is cadmium acetate.

Claim 24

A photographic film unit as defined in claim 22 wherein said metal ion adapted to cross-link said film-forming polymer at said second pH is disposed in said aqueous alkaline processing composition possessing said first pH as retained in said rupturable container.

Claim 25

A photographic film unit in defined in claim 25 wherein said metal ion is nickel ion.

Claim 26

A photographic film unit as defined in claim 26 including said metal ion is disposed in a processing composition permeable layer.

Claim 27

A photographic film unit as defined in claim 27 wherein said metallic salt is cadmium acetate.

Claim 28

A photographic film unit as defined in claim 24 wherein said film-forming polymer is carboxymethyl cellulose.

Claim 29

A process for forming transfer images in color which comprises, in combination, the steps of: a. exposing a photographic film unit which is adapted to be precessed by passing the unit between a pair of juxtaposed pressure-applying members and which includes, in combination, a composite structure comprising a first dimensionally stable layer opaque to incident actinic radiation; a photosensitive silver halide layer having associated therewith a dye image-forming material which is processing composition soluble and diffusible as a function of exposure of the photosensitive silver halide layer to incident actinic radiation; a polymeric layer dyeable by said dye image-forming material; a second dimensionally stable layer transparent to incident actinic radiation; and means securing said layers in substantially fixed relationship; and a rupturable container retaining a processing composition containing an opacifying agent in a quantity sufficient to mask said dye image-forming material fixedly positioned and extending transverse a leading edge of said photosensitive element to effect unidirectional discharge of said container''s alkaline processing composition between said dyeable polymeric layer and the photosensitive silver halide layer next adjacent thereto; b. applying compressive force to said rupturable container to effect unidirectional discharge of said container''s processing composition between said dyeable polymeric layer and the photosensitive silver halide layer next adjacent thereto; c. effecting thereby development of imagewise halide layer; image-forming forming thereby an imagewise distribution of mobile dye image-formng material as a function of the point-to-point degree of silver halide layer exposure; e. transferring, by diffusion, at least a portion of said imagewise distribution of said mobile dye image-providing material to said polymeric layer dyeable by said dye image-forming material to provide a dye image thereto in terms of said distribution; f. interposing, subsequent to substantial dye transfer image formation and preceding substantial environmental dye transfer image degradation, a polymeric layer intermediate said dyeable polymeric layer and said silver halide layer next adjacent; said polymeric layer comprising a polymeric material having a metal ion capable of cross-linking its polymeric component associated therewith; and g. maintaining said composite structure intact subsequent to said processing.

Claim 30

A process as defined in claim 30 which includes the step of disposing a polymeric layer permeable to processing composition solubilized dye image-forming material and adapted to be cross-linked by contact with said metal ion between said dyeable polymeric layer and the photosensitive silver halide emulsion layer next adjacent and disposing metal ion adapted to cross-link said dye image-forming material permeable polymeric layer to provide a dye image-forming material impermeable metal ion cross-linked polymeric layer in a processing composition permeable layer of said photosensitive element as a metallic salt adapted to be solubilized by contact with distributed processing composition and to diffuse into contact with said dye image-forming material permeable polymeric layer in a concentration effective, subsequent to substantial dye image-forming material transfer to said dyeable polymeric layer from said associated silver halide emulsion layer as a function of exposure of said emulsion layer, to provide said dye image-forming material impermeable metal ion cross-linked polymeric layer.

Claim 31

A process as defined in claim 30 which includes the step of disposing a polymeric material permeable to processing composition solubilized dye image-forming material and adapted to be cross-linked by contact with said metal ion between said dyeable polymeric layer and the photosensitive silver halide emulsion layer next adjacent and disposing said metal ion adapted to cross-link said dye image-forming material permeable polymeric layer to provide a dye image-forming material impermeable metal ion cross-linked polymeric layer in said processing composition as retained in said rupturable container and adapted to be discharged in functional contact with said dye image-forming material permeable polymeric material in a concentration effective, subsequent to substantial dye image-forming material transfer to said dyeable polymeric layer from said associated silver halide emulsion layer as a function of exposure of said emulsion layer, to provide said dye image-forming material impermeable metal ion cross-linked polymeric layer.

Claim 32

A process as defined in claim 30 which includes the step of disposing a film-forming polymer adapted to be cross-linked by contact with said metal ion in said processing composition retained in said rupturable container and adapted upon distribution of said processing composition between said dyeable polymeric layer and the photosensitive silver halide emulsion layer next adjacent thereto to provide a substantially continuous dye image-forming material permeable polymeric layer, and said metal ion disposed as a metallic salt in a processing composition permeable layer of said photosensitive element and adapted to be solubilized by contact with distributed processing composition and to diffuse, subsequent to substantial dye image-forming material transfer to said dyeable polymeric layer from said associated silver halide emulsion layer as a function of exposure of said emulsion layer, to said dye image-forming material permeable polymeric layer in a concentration effective to proved a dye image-forming material impermeable metal ion cross-linked polymeric layer.

Claim 33

A process as defined in claim 33 wherein said film-forming polymeric material comprises carboxymethyl cellulose.

Claim 34

A process as defined in claim 34 wherein said metallic salt comprises cadmium acetate.

Claim 35

A process as defined in claim 35 wherein said metallic salt is disposed in said dyeable polymeric layer.

Claim 36

A process as defined in claim 33 wherein said film-forming polymeric material comprises carboxymethyl hydroxyethyl cellulose.

Claim 37

A process as defined in claim 30 wherein said metal ion is polyvalent.

Claim 38

A process as defined in claim 38 wherein said metal ion is selecteD from the group consisting of: cadmium, magnesium, calcium, zinc, zirconium, aluminum, chromium, and nickel metal ions.

Claim 39

A process as defined in claim 30 wherein said first dimensionally stable layer is transparent to incident actinic radiation.

Claim 40

A process as defined in claim 40 wherein said opacifying agent is initially present intermediate said dyeable polymeric layer and the photosensitive silver halide emulsion layer next adjacent thereto in a quantity sufficient to mask said dye image-forming material.

Claim 41

A process as defined in claim 30 wherein said dye image-forming material is a dye which is a silver halide developing agent.

Claim 42

A process as defined in claim 42 wherein said photographic film unit includes at least two selectively sensitized silver halide emulsion layers, each of said silver halide emulsions having associated therewith a dye, which is a silver halide developing agent, of predetermined color.

Claim 43

A process as defined in claim 43 wherein each of said selectively sensitized silver halide emulsion layers possesses predominant spectral sensitivity to a separate region of the spectrum and the dye associated with each of said emulsion layers possesses a spectral absorption range subsequent to processing substantially complementary to the predominant sensitivity range of its associated emulsion.

Claim 44

A process as defined in claim 42 wherein said composition is an aqueous alkaline composition.

Claim 45

A process as defined in claim 45 wherein said composite structure includes at least one polymeric acid layer positioned intermediate at least one of said first dimensionally stable layers and the next adjacent photosensitive silver halide layer, and said second dimensionally stable layer and the next adjacent dyeable polymeric layer and said polymeric acid layers containing sufficient acidifying groups to effect reduction of an aqueous alkaline processing composition possessing a first pH at which said dyes are substantially soluble and diffusible to a second pH at which said dyes are substantially nondiffusible and including the step of transferring, by diffusion, subsequent to substantial transfer image formation, a sufficient portion of the ions of said alkaline processing solution to said polymeric acid layers to thereby reduce the alkalinity of said solution from said first pH to said second pH.

Claim 46

A process as defined in claim 46 wherein said metal ion is adapted to cross-link said polymeric layer intermediate said dyeable polymeric layer and said silver halide layer at said second pH.

Claim 47

A process as defined in claim 47 wherein said metal ion is disposed in said aqueous alkaline processing composition possessing said first pH as contained in said rupturable container.

Claim 48

A process as defined in claim 48 wherein said aqueous alkaline processing composition additionally contains a film-forming polymeric material adapted to be cross-linked by contact with said metal ion at said second pH in a quantity sufficient to provide said polymeric layer intermediate said said dyeable polymeric layer and said silver halide layer upon said distribution of said processing composition.

Claim 49

A process as defined in claim 49 wherein said metal ion is zirconia and said film-forming polymeric material is carboxymethyl cellulose and hydroxyethyl cellulose.

Claim 50

A process as defined in claim 30 wherein a metallic salt providing first metal ion is disposed in said polymeric layer dyeable by said dye image-forming material and second metal ion is disposed in said processing composition.

Claim 51

A process as defined in claim 51 wherein said metallic salt is cadmium acetate and said second metal ion is nickel.

Claim 52

A process as defined in claim 30 wherein said opacifying agent is titanium dioxide.

Claim 53

A process as defined in claim 30 including the step of separating said container from said composite structure subsequent to substantial transfer image formation.