CA1213458A - Hydrophilic layers adjacent a stripping layer for diffusion transfer assemblages - Google Patents
Hydrophilic layers adjacent a stripping layer for diffusion transfer assemblagesInfo
- Publication number
- CA1213458A CA1213458A CA000446598A CA446598A CA1213458A CA 1213458 A CA1213458 A CA 1213458A CA 000446598 A CA000446598 A CA 000446598A CA 446598 A CA446598 A CA 446598A CA 1213458 A CA1213458 A CA 1213458A
- Authority
- CA
- Canada
- Prior art keywords
- layer
- assemblage
- silver halide
- halide emulsion
- stripping
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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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
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- Engineering & Computer Science (AREA)
- Architecture (AREA)
- Structural Engineering (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
- Steroid Compounds (AREA)
Abstract
HYDROPHILIC LAYERS ADJACENT A STRIPPING LAYER
FOR DIFFUSION TRANSFER ASSEMBLAGES
Abstract of the Disclosure Photographic assemblages and processes are described wherein a stripping layer is employed to enable an image-receiving layer to be separated from the rest of the assemblage after processing. Each side of the stripping layer has a hydrophilic layer immediately adjacent thereto, one of which contains particulate material substantially insensitive to light and in a volume ratio of particulate material to hydrophilic material of at least 0.5, so that upon separation, substantially all of the stripping layer will remain with the portion of the assemblage having the hydrophilic layer containing the particulate material.
FOR DIFFUSION TRANSFER ASSEMBLAGES
Abstract of the Disclosure Photographic assemblages and processes are described wherein a stripping layer is employed to enable an image-receiving layer to be separated from the rest of the assemblage after processing. Each side of the stripping layer has a hydrophilic layer immediately adjacent thereto, one of which contains particulate material substantially insensitive to light and in a volume ratio of particulate material to hydrophilic material of at least 0.5, so that upon separation, substantially all of the stripping layer will remain with the portion of the assemblage having the hydrophilic layer containing the particulate material.
Description
HYDROPHILIC LAYERS ADJACENT A STRIPPING LAYER
FOR DIFFUSION TRANSFER ASSEMBLAGES
This invention relates to photography, and more particularly to black-and-white and color diffusion transfer photography wherein a stripping layer with adjacent hydrophilic layers, one of which contains particulate material in a certain amount, is employed to enable an image-receiving layer to be cleanly separated from the rest of the assemblage after processing. In a preferred embodiment, the separated image-receiving layer has substantially none of the stripping layer adhered thereto.
Transparencies or prints which are lest bulky can thereby be obtainer from integral assemblages.
Various formats for color, integral transfer elements are described in the prior art, such as US.
Patents 3,415,644; 3,415,545; 3,4159646; 3,647,437;
3,635,7~7; 3 9 756,815, and Canadian Patents 928,559 and 674,082. In these formats, the image-receiving layer containing the photographic image for viewing remains permanently attached and integral with the image generating and ancillary layers present in the structure when a transparent support is employed on the viewing side of the assemblage. The image is formed by dyes, produced in the image generating units, diffusing through the layers of the structure to the dye image-receiving layer. After exposure of the assemblage, an alkaline processing composition permeates the various layers to initiate development of the exposed photosensitive silver halide emulsion layers. The emulsion layers are developed in proper-lion to the extent of the respective exposures, and the image dyes which are formed or released in the respective image generating layers begin to diffuse throughout the structure. At least a portion of the images distribution of diffusible dyes diffuse to the dye image-receivlng layer to form an image of the ., original subject The user does not have to time this process.
A problem with the integral assemblages described above is that the silver halide and other imaging layers, the spent pod which originally contained processing fluid, and the trap which retains excess processing fluid remain with the print after processing. The resulting prints are bulky and are somewhat difficult to stock or store in albums.
Peel-apart formats for color diffusion transfer assemblages have previously been described, for example, in US. Patents 2,g83,606, 3,362,819 and 3,362,821. In these formats, the image-receiving element must be separated from the photosensitive element after a certain amount of time has elapsed, usually about one minute This requires the customer to time the process which may be a disadvantage if a clock is not available. Also the portion of the assemblage to be discarded is wet with caustic processing fluid and care must be taken with its handling.
It would be desirable to provide a diffusion transfer assemblage in which a print can be obtained without the spent imaging layers, pod and trap, as in the peel-apart format described above, but with the elimination of the necessity for timing the process and the handling of wet discarded materials, as in the integral format described above. Such a print would comprise the support, dye image-receiving layer and reflecting layers only, and would more closely resemble conventional prints in appearance and handling.
Research Disclosure, Vol. 176, December _ 1478, Item 17622 discloses image transfer formats and concepts for removal of expended processing materials from image transfer units after processing No 3L2~3~S~3 specific materials are disclosed in this reference, however US. Patent 4,459,346 relates Jo per-fluorinated stripping agents for diffusion transfer assemblages. The use of hydrophilic layers on both sides of the stripping layer, one of which contains particulate material, is not disclosed in this reference, however.
A problem has developed with the use ox stripping layers in the assemblages described above.
While it is highly desirable to have the stripping layer be removed in one uniform piece and remain with the separated portion what is to be discarded, in practice it has been found thaw the stripping layer itself fractures. This results in portions of the stripping layer randomly adhering to the two supporting surfaces. A very blotchy appearance thus results on the back of the separated image-receiving layer which it undesirable in a commercial product.
This blotchy appearance is particularly noticeable in Din areas of a if nsparency format.
It would be desirable to find a way to eliminate the nonuniform fracturing of a tripping layer in diffusion transfer assemblages as described above 80 that substantially ~11 of the stripping layer will remain with the portion of the assemblage to be discarded. These and other advantages are provided by this invention.
US. Patent 2,977~226 relates to diffusion transfer assemblages whereon stripping layers are employed to separate two image-receiving layers from photosensitive layers. That patent, however, does not disclose the use of hydrophilic layers on either side of the stripping layer, one of which contain particulate material as described herein.
it jig US. Patent 3,730,718 relates to diffusion transfer assemblages wherein a stripping layer is employed in a diffusion transfer assemblage Jo that an l~age-receiving layer may be separated from a light-sensitive element during development. In the example in that patent a stripping layer is employed between layers, both of which contain particulate material. We have found however, that assemblages wherein particulate material is present in layers on both sides of a stripping layer also exhibit nonuni-form fracture of the stripping layer upon separation, with the disadvantages as described above.
US. Patent 4,359,518 also relates to diffusion transfer assemblages wherein a stripping sheet is employed in conjunction with a release layer to effect stripping a photosensitive layer from a film unit after processing. Particulate material such as silica particles are employed in a timing layer of the stripping sheet to prevent blocking and to function as an antistatic agent. In Example A of that patent, a release layer is employed between a silver halide emulsion layer and a "protective layer", the composition of which appears to be unknown. This patent, however, does not disclose the use of a hydrophilic layer located between to stripping layer and the silver halide emulsion layer and which contains particulate material as described herein.
US. Patent 4,377,632 relates to the use of a strippable layer between an image-receiving layer and an anti-halation layer. In Example 1 of that patent, the annihilation layer comprises carbon black dispersed in gelatin at a coverage of about 15 mg/ft2 of carbon black and about 30 mg/ft2 of gelatin. Such a volume ratio of particulate material to hydrophilic material in that anti-halation layer (about 0.26) is substantially below the volume ratio 3~5~
s -of particulate material to hydrophilic material in one of the hydrophilic layers adjacent to the strip-ping layer according to this invention. As will be shown by comparative tests hereinafter, a low level of particulate material in the hydrophilic layer does not provide a strong enough bond to the adjacent stripping layer to prevent the discontinuous trip-ping problem discussed above.
A photographic assemblage in accordance with the invention comprises:
a a photosensitive element comprising a support having thereon at least one photosensitive silver halide emulsion layer;
by an image-receiving layer; and c) a stropping layer located between the silver halide emulsion layer and the image-receiving layer so that the image-receiving layer may be separated, after processing, from the portion of the assemblage containing the silver halide emulsion layer;
and wherein each side of the stripping layer has a hydrophilic layer immediately Addison thereto, and one of the hydrophilic layers contains portico-late material substantially insensitive to light and in a volume ratio of particulate material to hydra-Philip material in that layer of at least OWE so that upon separation, substantially all of the stripping layer will remain with the portion of the assemblage having the hydrophilic layer containing the particulate material.
In a preferred embodiment of the invention, the hydrophilic layer which contains the particulate material it located between the stripping layer and the silver halide emulsion layer so that upon swooper-lion, substantially all of the stripping layer will remain with the portion of the assemblage containing the silver halide emulsion layer In forming a black-and-white image, the exposed photosensitive element is developed. In the unexposed ureas, a silver halide comp'Lexlng agent dissolves the silver halide and transfers it to the image-receiving layer. Silver precipitating nuclei in the image-receiving layer then cause the wryness furred silver halide complex to be reduced to silver, thereby forming an image pattern corresponding to the original. Details of the process are well known to those skilled in the art as shown, for example, by US. Patents 3,220,835 and 3,820,999.
In a preferred embodiment of the invention, the solver halide emulsion layer has associated therewith a dye image-providing material Any material may be employed as the strip-ping layer in the invention provided it has the required properties. Such materials are disclosed, for example, Lo US. Patents 3,220,835, 3,730,718 and 3,820,999 and include gum Arabic sodium allegiant, pectin, polyvinyl alcohol and hydroxyethyl cell-lose. In a preferred embodiment of this invention, hydroxyethyl cellulose is employed.
The stripping layer materials employed in this invention can be employed in any amount which is effective for the intended purpose. In general, good results have been obtained at a concentration of from about 5 to about 2000 mum 2 of element. The particular amount to be employed will vary, of course, depending on the particular stripping layer material employed and the particular diffusion transfer element selected.
The materials employed in the hydrophilic layers on each side of the stripping layer in this invention include any of the well known materials commonly used in the photographic art for such use.
These materials include, for example, gelatin, polysaccharides, a~rylamide polymers and other polymeric materials such as those disclosed in Research Disclosure, Vol. 176, December 1978, Item _ 17643, page 26. In a preferred embodiment of the invention, gelatin is employed. The coverage of the hydrophilic layer can be widely varied, as desired.
In general, good results have been obtained at coverage ranging from about 0.1 to about 2.0 g/m2 of element.
lo The particulate material employed in the hydrophilic layers of the invention described above can be any material provided it produces the desired results of tightly bonding that layer to the adjacent stripping layer. Such material should not be light-sensitive since it would interfere with the imaging chemistry in the light-sensitive portion of the photosensitive element. In general, good results have been obtained with carbon black, such as Cabot Regal 400 carbon black, average particle diameter 0.07 em; titanium dioxide, such as Gulf and Western Horsehide Utile, average particle diameter 0.25 em; colloidal silica such as Dupont Ludox0 AM, average particle diameter 0.22 em; and poly~methyl me~hacrylate) beads, average particle diameter 0.5 em. In a preferred embodiment, carbon black is employed.
The particle size of the particulate maternal employed in the invention can vary widely, as evidenced by the range of particle sizes shown above. The amount of particulate material to be coated can Allah vary widely, as long as the volume ratio of particulate material to hydrophilic material in that layer is at least about 0.5. A preferred range of volume ratios is from about 0.5 to about 20.
For example a volume ratio of 0.5 means that one unit on a volume basis of particulate , Jo I
material is Jo be employed with two units on a volume basis of hydrophilic material. The weigh of the material to be employed is a function of its density. For example, if carbon is to be employed in a 0.65 g/m' hydrophilic layer of gelatin a volume ratio of 0.5 between the two would correspond to a coverage of carbon at 0.6 gym Particulate material has been employed in photographic elements for a number of reasons. For lo example, in ITS Patent 4,259,518 discussed above, it is disclosed in column 4 what silica particles in the outermost layer prevents blocking when the stripping layer is wound upon itself. Such materials are known in the art as "anti-blocking" agents. It would have lo been thought, therefore, that such material in a layer would decrease the adhesion of that layer to an adjacent layer. It was unexpectedly found in accord-ante with this invention, however, that just the opposite occurred. It was found that the hydrophilic layer adjacent the stripping layer which contains the particulate material has a stronger bond to the stripping layer than does the hydrophilic layer on the other side thereof. Since stripping occurs at the weakest interface bond, this enables the strip-I ping layer to remain, after separation, with the portion of the assemblage to be discarded, usually the portion containing the silver halide emulsion layer or layers. Thus the stripped image-receiving layer in that case will have a clean appearance on the back side thereof.
The employment of particulate material in one of the hydrophilic layers adjacent to the strip-ping layer in the assemblages described herein is thus the means whereby that bond between those two layers can be strengthened, thus ensuring that stripping will take place at the opposite side of the stripping layer. The hydrophilic layer on the I
opposite side of the stripping layer should prefer-ably be free, or substantially free 9 of particulate material since any appreciable amount of particulate material in that layer would tend Jo strengthen the bond between that 'layer and the stripping layer, which is undesirable.
This invention can be used in diffusion transfer assemblages where a reflection print is obtained without the bulkiness of silver halide and other layers, the spent pod and trap. In other words, the assemblages of this combines the handling and storage characteristics of conventional photo-graphs with the convenience and benefits of instant photography. Transparencies can also be obtained in lo the same manner. In addition, transparency elements can also be obtained in accordance with the invention by employing a transparent support and utilizing the retained image in the element along with the subset quint removal of residual image dye, silver halide and pacifying layers. In that embodim nut, it would be desirable to have the stripping layer remain with the petition of the assemblage containing the dye image receiving layer, since that portion is the one to be discarded. In that case, the particulate material would be located in the hydrophilic layer between the stripping layer and the dye image-receiv-in layer. Clean separation would then occur on the other side of the stripping layer where it is desired.
By removing the silver halide and dye image-providing material layers from the assemblage, there is also provided the option of recovery of these expensive materials from the discarded portion of the assemblage, if it is economically feasible to do so.
A process for producing a photographic image in color according to this invention comprises:
. .
I
I) exposing a photosensitive element comprising a support having whereon a least one photosensitive silver halide emulsion layer having associated therewith a dye image-providing material;
II) treating the element with an alkaline processing composition in the presence of a silver halide developing agent to effect development of each exposed silver halide emulsion layer whereby:
pa) an images distribution of the dye image-providing material is formed as a function of the development of the silver halide emulsion layer;
and (b) at least a portion of the images distribution of the dye image-providing material diffuses to a dye image-receiving layer; and III) separating the dye image-receiving layer from the rest of the photosensitive element by means of a stripping layer and adjacent hydrophilic layers as described above, so that substantially all of said stripping layer will remain with the portion of the element having the hydrophilic layer containing the particulate material as described above.
The photographic element in the above-described process can be treated with an alkaline processing composition to effect or initiate develop-mint in any manner. A preferred method for applying processing composition is by use of a rupturable container or pod which contains the composition.
In a preferred embodiment of the invention the photographic assemblage comprises:
a) a photosensitive element comprising a support having thereon at least one silver halide emulsion layer having associated therewith a dye image providing material;
by a transparent cover sheet located over the layer outermost from the support of the photosensi-live element;
34LS~
I a dye image-receiving layer located either in the photosensitive element or on the transparent cover sheet; and d) an alkaline processing composition and means containing same for discharge bottle the photosensi-live element and the transparent cover sheet;
and wherein the assemblage conchs stripping layer and adjacent hydroph:Llic layers as described above.
I In a preferred embodiment of the invention, the means containing the alkaline processing compost-lion is a rupturable container or pod which is adapted to be positioned during processing of the film unit so that a compressive force applied Jo the container by pressure applying members, such as would be found in a camera designed for in-camera process sing, will effect a discharge of the container's contents within the film unit. In general, the processing composition employed in this invention contains the developing agent for development although the composition could also just be an alkaline solution where the developer is incorporated in the photographic element or cover sheet, in which case the alkaline solution serves to activate the incorporated developer.
The dye image-providing material useful in this invention is either positive- or negati~e-work-in, and is either initially mobile or immobile in the photographic element during processing with an alkaline composition. examples of initially mobile, positive-working dye image-providing materials useful in this invention are described in US. Patents 29983,606; 39536,739; 3,705,1~4; 3,482,972;
FOR DIFFUSION TRANSFER ASSEMBLAGES
This invention relates to photography, and more particularly to black-and-white and color diffusion transfer photography wherein a stripping layer with adjacent hydrophilic layers, one of which contains particulate material in a certain amount, is employed to enable an image-receiving layer to be cleanly separated from the rest of the assemblage after processing. In a preferred embodiment, the separated image-receiving layer has substantially none of the stripping layer adhered thereto.
Transparencies or prints which are lest bulky can thereby be obtainer from integral assemblages.
Various formats for color, integral transfer elements are described in the prior art, such as US.
Patents 3,415,644; 3,415,545; 3,4159646; 3,647,437;
3,635,7~7; 3 9 756,815, and Canadian Patents 928,559 and 674,082. In these formats, the image-receiving layer containing the photographic image for viewing remains permanently attached and integral with the image generating and ancillary layers present in the structure when a transparent support is employed on the viewing side of the assemblage. The image is formed by dyes, produced in the image generating units, diffusing through the layers of the structure to the dye image-receiving layer. After exposure of the assemblage, an alkaline processing composition permeates the various layers to initiate development of the exposed photosensitive silver halide emulsion layers. The emulsion layers are developed in proper-lion to the extent of the respective exposures, and the image dyes which are formed or released in the respective image generating layers begin to diffuse throughout the structure. At least a portion of the images distribution of diffusible dyes diffuse to the dye image-receivlng layer to form an image of the ., original subject The user does not have to time this process.
A problem with the integral assemblages described above is that the silver halide and other imaging layers, the spent pod which originally contained processing fluid, and the trap which retains excess processing fluid remain with the print after processing. The resulting prints are bulky and are somewhat difficult to stock or store in albums.
Peel-apart formats for color diffusion transfer assemblages have previously been described, for example, in US. Patents 2,g83,606, 3,362,819 and 3,362,821. In these formats, the image-receiving element must be separated from the photosensitive element after a certain amount of time has elapsed, usually about one minute This requires the customer to time the process which may be a disadvantage if a clock is not available. Also the portion of the assemblage to be discarded is wet with caustic processing fluid and care must be taken with its handling.
It would be desirable to provide a diffusion transfer assemblage in which a print can be obtained without the spent imaging layers, pod and trap, as in the peel-apart format described above, but with the elimination of the necessity for timing the process and the handling of wet discarded materials, as in the integral format described above. Such a print would comprise the support, dye image-receiving layer and reflecting layers only, and would more closely resemble conventional prints in appearance and handling.
Research Disclosure, Vol. 176, December _ 1478, Item 17622 discloses image transfer formats and concepts for removal of expended processing materials from image transfer units after processing No 3L2~3~S~3 specific materials are disclosed in this reference, however US. Patent 4,459,346 relates Jo per-fluorinated stripping agents for diffusion transfer assemblages. The use of hydrophilic layers on both sides of the stripping layer, one of which contains particulate material, is not disclosed in this reference, however.
A problem has developed with the use ox stripping layers in the assemblages described above.
While it is highly desirable to have the stripping layer be removed in one uniform piece and remain with the separated portion what is to be discarded, in practice it has been found thaw the stripping layer itself fractures. This results in portions of the stripping layer randomly adhering to the two supporting surfaces. A very blotchy appearance thus results on the back of the separated image-receiving layer which it undesirable in a commercial product.
This blotchy appearance is particularly noticeable in Din areas of a if nsparency format.
It would be desirable to find a way to eliminate the nonuniform fracturing of a tripping layer in diffusion transfer assemblages as described above 80 that substantially ~11 of the stripping layer will remain with the portion of the assemblage to be discarded. These and other advantages are provided by this invention.
US. Patent 2,977~226 relates to diffusion transfer assemblages whereon stripping layers are employed to separate two image-receiving layers from photosensitive layers. That patent, however, does not disclose the use of hydrophilic layers on either side of the stripping layer, one of which contain particulate material as described herein.
it jig US. Patent 3,730,718 relates to diffusion transfer assemblages wherein a stripping layer is employed in a diffusion transfer assemblage Jo that an l~age-receiving layer may be separated from a light-sensitive element during development. In the example in that patent a stripping layer is employed between layers, both of which contain particulate material. We have found however, that assemblages wherein particulate material is present in layers on both sides of a stripping layer also exhibit nonuni-form fracture of the stripping layer upon separation, with the disadvantages as described above.
US. Patent 4,359,518 also relates to diffusion transfer assemblages wherein a stripping sheet is employed in conjunction with a release layer to effect stripping a photosensitive layer from a film unit after processing. Particulate material such as silica particles are employed in a timing layer of the stripping sheet to prevent blocking and to function as an antistatic agent. In Example A of that patent, a release layer is employed between a silver halide emulsion layer and a "protective layer", the composition of which appears to be unknown. This patent, however, does not disclose the use of a hydrophilic layer located between to stripping layer and the silver halide emulsion layer and which contains particulate material as described herein.
US. Patent 4,377,632 relates to the use of a strippable layer between an image-receiving layer and an anti-halation layer. In Example 1 of that patent, the annihilation layer comprises carbon black dispersed in gelatin at a coverage of about 15 mg/ft2 of carbon black and about 30 mg/ft2 of gelatin. Such a volume ratio of particulate material to hydrophilic material in that anti-halation layer (about 0.26) is substantially below the volume ratio 3~5~
s -of particulate material to hydrophilic material in one of the hydrophilic layers adjacent to the strip-ping layer according to this invention. As will be shown by comparative tests hereinafter, a low level of particulate material in the hydrophilic layer does not provide a strong enough bond to the adjacent stripping layer to prevent the discontinuous trip-ping problem discussed above.
A photographic assemblage in accordance with the invention comprises:
a a photosensitive element comprising a support having thereon at least one photosensitive silver halide emulsion layer;
by an image-receiving layer; and c) a stropping layer located between the silver halide emulsion layer and the image-receiving layer so that the image-receiving layer may be separated, after processing, from the portion of the assemblage containing the silver halide emulsion layer;
and wherein each side of the stripping layer has a hydrophilic layer immediately Addison thereto, and one of the hydrophilic layers contains portico-late material substantially insensitive to light and in a volume ratio of particulate material to hydra-Philip material in that layer of at least OWE so that upon separation, substantially all of the stripping layer will remain with the portion of the assemblage having the hydrophilic layer containing the particulate material.
In a preferred embodiment of the invention, the hydrophilic layer which contains the particulate material it located between the stripping layer and the silver halide emulsion layer so that upon swooper-lion, substantially all of the stripping layer will remain with the portion of the assemblage containing the silver halide emulsion layer In forming a black-and-white image, the exposed photosensitive element is developed. In the unexposed ureas, a silver halide comp'Lexlng agent dissolves the silver halide and transfers it to the image-receiving layer. Silver precipitating nuclei in the image-receiving layer then cause the wryness furred silver halide complex to be reduced to silver, thereby forming an image pattern corresponding to the original. Details of the process are well known to those skilled in the art as shown, for example, by US. Patents 3,220,835 and 3,820,999.
In a preferred embodiment of the invention, the solver halide emulsion layer has associated therewith a dye image-providing material Any material may be employed as the strip-ping layer in the invention provided it has the required properties. Such materials are disclosed, for example, Lo US. Patents 3,220,835, 3,730,718 and 3,820,999 and include gum Arabic sodium allegiant, pectin, polyvinyl alcohol and hydroxyethyl cell-lose. In a preferred embodiment of this invention, hydroxyethyl cellulose is employed.
The stripping layer materials employed in this invention can be employed in any amount which is effective for the intended purpose. In general, good results have been obtained at a concentration of from about 5 to about 2000 mum 2 of element. The particular amount to be employed will vary, of course, depending on the particular stripping layer material employed and the particular diffusion transfer element selected.
The materials employed in the hydrophilic layers on each side of the stripping layer in this invention include any of the well known materials commonly used in the photographic art for such use.
These materials include, for example, gelatin, polysaccharides, a~rylamide polymers and other polymeric materials such as those disclosed in Research Disclosure, Vol. 176, December 1978, Item _ 17643, page 26. In a preferred embodiment of the invention, gelatin is employed. The coverage of the hydrophilic layer can be widely varied, as desired.
In general, good results have been obtained at coverage ranging from about 0.1 to about 2.0 g/m2 of element.
lo The particulate material employed in the hydrophilic layers of the invention described above can be any material provided it produces the desired results of tightly bonding that layer to the adjacent stripping layer. Such material should not be light-sensitive since it would interfere with the imaging chemistry in the light-sensitive portion of the photosensitive element. In general, good results have been obtained with carbon black, such as Cabot Regal 400 carbon black, average particle diameter 0.07 em; titanium dioxide, such as Gulf and Western Horsehide Utile, average particle diameter 0.25 em; colloidal silica such as Dupont Ludox0 AM, average particle diameter 0.22 em; and poly~methyl me~hacrylate) beads, average particle diameter 0.5 em. In a preferred embodiment, carbon black is employed.
The particle size of the particulate maternal employed in the invention can vary widely, as evidenced by the range of particle sizes shown above. The amount of particulate material to be coated can Allah vary widely, as long as the volume ratio of particulate material to hydrophilic material in that layer is at least about 0.5. A preferred range of volume ratios is from about 0.5 to about 20.
For example a volume ratio of 0.5 means that one unit on a volume basis of particulate , Jo I
material is Jo be employed with two units on a volume basis of hydrophilic material. The weigh of the material to be employed is a function of its density. For example, if carbon is to be employed in a 0.65 g/m' hydrophilic layer of gelatin a volume ratio of 0.5 between the two would correspond to a coverage of carbon at 0.6 gym Particulate material has been employed in photographic elements for a number of reasons. For lo example, in ITS Patent 4,259,518 discussed above, it is disclosed in column 4 what silica particles in the outermost layer prevents blocking when the stripping layer is wound upon itself. Such materials are known in the art as "anti-blocking" agents. It would have lo been thought, therefore, that such material in a layer would decrease the adhesion of that layer to an adjacent layer. It was unexpectedly found in accord-ante with this invention, however, that just the opposite occurred. It was found that the hydrophilic layer adjacent the stripping layer which contains the particulate material has a stronger bond to the stripping layer than does the hydrophilic layer on the other side thereof. Since stripping occurs at the weakest interface bond, this enables the strip-I ping layer to remain, after separation, with the portion of the assemblage to be discarded, usually the portion containing the silver halide emulsion layer or layers. Thus the stripped image-receiving layer in that case will have a clean appearance on the back side thereof.
The employment of particulate material in one of the hydrophilic layers adjacent to the strip-ping layer in the assemblages described herein is thus the means whereby that bond between those two layers can be strengthened, thus ensuring that stripping will take place at the opposite side of the stripping layer. The hydrophilic layer on the I
opposite side of the stripping layer should prefer-ably be free, or substantially free 9 of particulate material since any appreciable amount of particulate material in that layer would tend Jo strengthen the bond between that 'layer and the stripping layer, which is undesirable.
This invention can be used in diffusion transfer assemblages where a reflection print is obtained without the bulkiness of silver halide and other layers, the spent pod and trap. In other words, the assemblages of this combines the handling and storage characteristics of conventional photo-graphs with the convenience and benefits of instant photography. Transparencies can also be obtained in lo the same manner. In addition, transparency elements can also be obtained in accordance with the invention by employing a transparent support and utilizing the retained image in the element along with the subset quint removal of residual image dye, silver halide and pacifying layers. In that embodim nut, it would be desirable to have the stripping layer remain with the petition of the assemblage containing the dye image receiving layer, since that portion is the one to be discarded. In that case, the particulate material would be located in the hydrophilic layer between the stripping layer and the dye image-receiv-in layer. Clean separation would then occur on the other side of the stripping layer where it is desired.
By removing the silver halide and dye image-providing material layers from the assemblage, there is also provided the option of recovery of these expensive materials from the discarded portion of the assemblage, if it is economically feasible to do so.
A process for producing a photographic image in color according to this invention comprises:
. .
I
I) exposing a photosensitive element comprising a support having whereon a least one photosensitive silver halide emulsion layer having associated therewith a dye image-providing material;
II) treating the element with an alkaline processing composition in the presence of a silver halide developing agent to effect development of each exposed silver halide emulsion layer whereby:
pa) an images distribution of the dye image-providing material is formed as a function of the development of the silver halide emulsion layer;
and (b) at least a portion of the images distribution of the dye image-providing material diffuses to a dye image-receiving layer; and III) separating the dye image-receiving layer from the rest of the photosensitive element by means of a stripping layer and adjacent hydrophilic layers as described above, so that substantially all of said stripping layer will remain with the portion of the element having the hydrophilic layer containing the particulate material as described above.
The photographic element in the above-described process can be treated with an alkaline processing composition to effect or initiate develop-mint in any manner. A preferred method for applying processing composition is by use of a rupturable container or pod which contains the composition.
In a preferred embodiment of the invention the photographic assemblage comprises:
a) a photosensitive element comprising a support having thereon at least one silver halide emulsion layer having associated therewith a dye image providing material;
by a transparent cover sheet located over the layer outermost from the support of the photosensi-live element;
34LS~
I a dye image-receiving layer located either in the photosensitive element or on the transparent cover sheet; and d) an alkaline processing composition and means containing same for discharge bottle the photosensi-live element and the transparent cover sheet;
and wherein the assemblage conchs stripping layer and adjacent hydroph:Llic layers as described above.
I In a preferred embodiment of the invention, the means containing the alkaline processing compost-lion is a rupturable container or pod which is adapted to be positioned during processing of the film unit so that a compressive force applied Jo the container by pressure applying members, such as would be found in a camera designed for in-camera process sing, will effect a discharge of the container's contents within the film unit. In general, the processing composition employed in this invention contains the developing agent for development although the composition could also just be an alkaline solution where the developer is incorporated in the photographic element or cover sheet, in which case the alkaline solution serves to activate the incorporated developer.
The dye image-providing material useful in this invention is either positive- or negati~e-work-in, and is either initially mobile or immobile in the photographic element during processing with an alkaline composition. examples of initially mobile, positive-working dye image-providing materials useful in this invention are described in US. Patents 29983,606; 39536,739; 3,705,1~4; 3,482,972;
2,756,142i 3,880,65S and 3,854,985. Examples of negative-working dye image-providing materials useful in this invention include conventional couplers which react with oxidized aromatic primary amino color I
I
developing agents to produce or release a dye such as those described, for example in US. Patent
I
developing agents to produce or release a dye such as those described, for example in US. Patent
3,227,550 and Canadian Patent 602,607. In a preferred embodiment of this invention, the dye image-providing material is a ballasted, redo dye-releasing (RDR) compound. Such compounds are well known to those skilled in the art and are, generally speaking, compounds which will react with oxidized or unoxidized developing agent or electron transfer agent to release a dye. Such nondiffusible RDR's include negative-working compounds, as described in US. Patents 39728,113 of Beaker et at;
3~7259062 ox Anderson and Lump 3,698,897 of Gompf and Lump 3,628,952 of Poshly et at; 3,443,939 and 3,443,940 of Bloom et at; 47053,312 of Fleckenstein;
3~7259062 ox Anderson and Lump 3,698,897 of Gompf and Lump 3,628,952 of Poshly et at; 3,443,939 and 3,443,940 of Bloom et at; 47053,312 of Fleckenstein;
4,076,529 of Fleckenstein et at; 4,055,428 of Comma et at; 4,149,892 of Deguchi et at; 41198,235 and 4,179,291 of Vetted et at; Research slicer 15157, November, 1976 and Research Disclosure 15654, April, 1977. Such nondiffusible RDR's also include positive-working compounds, as described in US.
Patents 3,980,479; 4,139~379; Lowe 4,199,354;
4,232,107; 4,199,355 and German Patent 2~854,946.
In a preferred embodiment of the invention, RDRIs such as those in the Fleckenstein et at patent referred to above are employed. Such compounds are ballasted sulfonamide compounds which are alkali-cleavable upon oxidation to release a diffusible dye from the nucleus and have the formula:
Jo G
I
atlas tam_ l i .
NHS02-Col I`
wherein:
(a) Cot is a dye or dye precursor moiety;
(b) Ballast is an organic ballasting radical of such molecular size and configuration (e.g., simple organic groups or polymeric groups) as to render the compound nondiffusible in the photosensitive element during development in an alkaline processing compost-lion;
(c) G is OR or NHRl wherein R is hydrogen or a hydrolyzable moiety and R' is hydrogen or a subset-tuned or unsubstitutPd alkyd group of 1 to 22 carbon atoms, such as methyl, Ethyl, hydroxyethyl, propel, Boyle, secondary bottle, tertiary bottle, cyclopropyl, 4-chlorobutyl, cyclobutyl, 4 nitroamyl, Huxley, cyclohexyl, octal, decal, octadecyl, docosyl, bouncily or phenethyl when Al is an alkyd group of greater than 6 carbon atoms 9 it can serve as a partial or sole Ballast group);
(d) Y represents the atoms necessary to complete a Bunsen nucleus, a naphthalene nucleus or a 5- to 7-membered heterocyclic ring such as porcelain or pyrimidine; and (e) m is a positive integer or 1 to 2 and is 2 when G is OR or when Al is a hydrogen or an alkyd group of less than 8 carbon atoms.
For further details concerning the above-described sulfonamide compounds and specific examples of same, reference is made Jo the above mentioned Fleckens~ein et at US. Patent 4,076,529.
In another preferred embodiment of the invention, positive-workin2, nondiffusible RDR's of the type disclosed in US. Patents 4,139,379 and 49139,389 are employed. In this embodiment, an immobile compound is employed which as incorporated in a photographic element is incapable of releasing a diffusible dye. However, during photographic process sing under alkaline conditions the compound is capable of accepting at least one electron (i.e., being reduced) and thereafter releases a diffusible dye. These immobile compounds are ballasted electron accepting nucleophilic displacement compounds.
S A format for integral nega~ive-receiver photographic elements in which the pronto invention is useful is disclosed in Canadian Patent 928,559.
In this embodiment, the support for the photographic element is transparent and us coaxed with the image-receiving layer, a substantially opaque, light-reflective layer, the stripping layer and adjacent hydrophilic layers described above, and the photo-sensitive layer or layers described above. A rupture able container, containing an alkaline processing lo composition including a developing agent and an pacifier, is positioned between the top layer end a transparent cover sheet which has thereon, in sequence, a neutralizing layer, and a tying layer.
The film unit is placed in a camera, exposed through the transparent cover sheet and then passed through a pair of pressure-applying members in the camera as it is being removed therefrom. The pressure-applying members rupture the container and spread processing composition and pacifier over the negative portion of the film unit to render it light-insensitive. The processing composition develops each silver halide layer and dye images, formed as a result of develop-mint 9 diffuse to the image-receiving layer Jo provide a positive, right-reading image which is viewed through the transparent support on the opaque reflecting layer background. For further details concerning the format of this particular integral film unit, reference is made Jo the above-mentioned Canadian Patent 928,559.
Still other useful integral formats in which this invention can be employed are described in US.
Puns 3,415,644; 3,415,645; 3,415,646, 3,647,437 . ,;
and aye In most of these formats, a photo-sensitive silver halide emulsion is coated on an opaque support and a dye image-receivlng layer is located on a separate transparent support superposed over the layer outermost from the opaque support. In addition, this transparent support also contains a neutralizing layer and a timing layer underneath the dye image-receiving layer.
In another embodiment of the invention, the neutralizing layer and timing layer are located underneath the photosensitive layer or layers. In that embodiment, the photosensitive element would comprise a support having thereon, in sequence, a neutralizing layer, a timing layer and at least one photosensitive silver halide emulsion layer having associated therewith a dye tmage-providing material.
The dye image-receiving layer would be provided on transparent cover sheet with the processing compost-lion being applied there between.
The film unit or assemblage of the present invention is used to produce positive images in single or multicolors. In a three-color system, etch silver halide emulsion layer of the film assembly will have associated earth a dye image-providing material which possesses a predominant spectral absorption within the region of the visible spectrum to which said silver halide emulsion is sensitive, i.e., the blue-sensltive silver halide emulsion layer will have a yellow dye image-provi~ing material associated earth the green-sensitive silver halide emulsion layer will have a magenta dye image-providing material associated therewith and the red-sensitive silver halide emulsion layer will have a cyan dye image-providing material associated therewith. The dye image-providing material also elated with each silver halide emulsion layer is contained either in the silver halide emulsion layer "i itself or in a layer contiguous Jo the silver halide emulsion layer, i.e. 9 the dye image providing Metro-at can be coated in a separate layer underneath the silver halide emulsion layer with respect to the exposure direction.
The concentration of the dye image-providing material that is employed in the present invention can be varied over a wide range, depending upon the particular compound employed and the results lo desired. For example, the dye lmage-providîng material coated in a layer at a concentration of 0.1 to 3 gym has been found to be useful. The dye image-providing material is usually dispersed in a hydrophilic film forming natural material or sync Thetis polymer, such as gelatin, polyvinyl alcohol,etc, which is adapted to be permeated by aqueous alkaline processing composition.
A variety of silver halide developing agents are useful in this invention. Specific examples of developers or electron transfer agents (ETA's) useful in this invention include hydroquinone compounds, catcall compounds, and 3-pyrazolidinone compounds as disclosed in column 16 of US. Patent 4,358,527, issued November 9, OWE A combination of different ETA's, such as those disclosed in US. Patent 3,039,869, can also be employed. These ETA's are employed on the liquid processing composition or contained, at least in part, in any layer or layers of the photographic element or film assemblage to be activated by the alkaline processing composition, such as in the silver halide emulsion layers, the dye image-providing material layers, lnterlayers, image-receiving layer, etc.
In this invention, in which dye image-providing material can be used which produce dip-fusible dye images as a function of development, either conventional negative-working or dlrect-posi-I
live silver halide emulsions can be employed. If the silver halide emulsion employed is a clirect-positive silver halide emulsion, such as an internal image emulsion designed for use in the internal image reversal process, or a fogged, direct-positive emulsion such as a sol~rizlng emulsion, which is developable in unexposed areas 9 a positive image can be obtained on the dye image-receiving layer by using ballasted dye image-providing materials. After lo exposure of the film assemblage or unit, the alkaline processing composition permeates the various layers to initiate development of the exposed photosensitive silver halide emulsion layers. The developing agent present in the film unit develops each of the silver halide emulsion layers in the unexposed areas since the silver halide emulsions are direct-positive ones), thus causing the developing agent to become oxidized images corresponding to the unexposed areas of the direc~-positive silver halide emulsion layers. The oxidized developing agent then cross-oxidizes the dye image-providing material compounds and the oxidized form of the compounds then undergoes a base-initiated reaction Jo release the dyes image-wise as a function of the images exposure of each of the silver halide emulsion layers. At least a portion of the images distributions of diffusible dyes diffuse to the image-receivlng layer to form a positive image of the original subject. After being contacted by the alkaline processing composition a neutralizing layer in the film unit or image-receiv-in unit lowers the pi of the film unit or image receiver Jo stabilize the image.
Internal image silver halide emulsions useful in this invention are described more fully on the November, 1976 edition of Research Disclosure, pages 76 through 79.
';, The various silver halide emulsion layers of a color film assembly employed in this invention are disposed in the usual order, i.e., the blue sensitive silver halide emulsion layer first with respect to the exposure side, followed by the green-sensitive and red-sensitive silver halide emulsion layers. If desired, a yellow dye layer or a yellow colloidal silver layer can be present between the blazons live and green-sensitive silver halide emulsion layers for absorbing or filtering blue radiation that is transmitted through the blue-sensitive layer. If desired, the selectively sensitized silver halide emulsion layers can be disposed in a different order, e.g., the blue-sensitive layer first with respect to the exposure side 9 followed by the red-sensitive and green-sensltive layers The rupturable container employed in certain embodiments of this invention is disclosed in US.
Patents 2,543,181; 2,643,886; 2,653,732; 2,723,051;
3J056~492; 3~056,491 and 3,152,515. In general, such containers comprise a rectangular sheet of fluid- and air-impervious material folded longitudinally upon itself to form two walls which are sealed to one another along their longitudinal and end margins to form a cavity in which processing solution is con-twined.
Generally speaking, except where noted otherwise, the silver halide emulsion layers employed in the invention comprise photosensitive silver halide dispersed in gelatin and are about 0.6 to 6 microns in thickness; the dye image providing Motorola-awls are dispersed in an aqueous alkaline solution-permeable polymeric binder, such as gelatin, as a separate layer about 0.2 to 7 microns in thickness;
and the alkaline solutlon-p~rmeable polymeric inter-layers, e.g., gelatin, are about 0.2 to 5 microns in thickness. Of course these thicknesses are approxi-I
~19-mate only and can be modified according to the product desired Scavengers for oxidized developing agent can be employed in various inter layers of the photogra-phi elements of the invention. Suitable materializer disclosed on page 83 of the November 1976 edition of Research Disclosure.
.
Any material is useful as the dye image receiving layer in this invention as long as the lo desired function of mordan~ing or otherwise fixing the dye images is obtained, The particular material chosen will, of course, depend upon the dye to be mordant Ed Suitable materials are disclosed on pages 80 through 82 of the November 1976 edition of Research Disclosure.
Use of a neutralizing malarial in the film units employed in this invention will usually increase the stability of the transferred image.
Generally, the neutralizing material will effect a reduction in the pi of the image layer from about 13 or 14 Jo at least 11 and preferably 5 to 8 within a short time after ~mbibition. Suitable materials and their functioning are disclosed on pages 22 and 23 of the July 1974 edition of Research Do schoolhouses and pages 35 through 37 of the July 1975 edition of Research Disclosure.
A timing or inert spacer layer can be employed in the practice of this invention over the neutralizing layer which "times" or controls the pi reduction as a function of the rate at which alkali diffuses through the inert spacer layer. Examples of such timing layers and their functioning are disk closed in the Research Disclosure articles mentioned in the paragraph above concerning neutralizing layers.
The alkaline processing composition employed in this invention is the conventional aqueous soul-lion of an alkaline material, ego alkali metal hydroxides or carbonates such as sodium hydroxide, sodium carbonate or an mine such as diethylamine, preferably possessing a pi in excess of 11 7 and preferably containing a developing agent as described previously. Suitable materials and addenda frequent-lye added to such compositions are disclosed Oh pages lo 79 and 80 of the November, 1976 edition of Research Disclosure.
The alkaline solution permeable, Susan tidally opaque llght-reflective layer employed in certain embodiments of photographic film units used I in this invention is described more fully in the November, 1976 edition of Research Disclosure page 82.
The supports for the photographic elements used in this invention can be any material, as long as it does not deleteriously affect the photographic properties ox the film unit and is dimensionally stable. Typical flexible sheet materials are dyes cried on page 85 of the November, 1976 edition of Research Disclosure.
While the invention has been described with reference TV layers of silver halide emulsions and dye image-providing materials, Dallas coating, such as would be obtained using a Grover printing tech-unique, Gould Allah be employed. In this technique, small dots of blue-9 green- and red-sensitive Emil-sons have associated therewith, respectively, dots of yellow, magenta end cyan color-providing sub-stances. After development, the ~ransfPrred dyes would tend to fuse together into continuous tone 3~5~3 In an alternative embodiment, ho emulsions sensitive to each of the three primary regions of the spectrum can be disposed as a single segmented layer, e.g., as by the use of micro vessels, as described in Whit more US. Patent 4,362,806, issued December 7, 1982.
The silver halide emulsions useful in this Invention, both negative-working and direct-positive ones, are well known to those skilled in the art and are described in Research Disclosure, Volume 176, December 1978, Item 17643, pages 22 and 233 Emil soon preparation and types"; they are usually comma-gaily and spectrally sensitized as described on page comical sensitigationl', and "Spectral sunsuit-ration and desenæitizatlon", of the above article;
they are optionally protected against the production of fog and stabilized against loss of sensitivity during keeping by employing the materials described on pages 24 and 25, "Antifoggants and stabilizers" 9 of the above article; they usually contain hardeners and coating aids us described on pave 26, 'harden-ens", and pages 26 and 279 kowtowing aids", of the above article; they and other layers in the photogra-phi elements used in this lnven~ion usually contain plasticizers, vehicles and filter dyes described on 25 page 27, "Plasticizers and lubricants"; page 26, "Vehicles and vehicle extenders"; and pages 25 and 269 "Absorbing and scattering materials", of the above article; they and other layers in the photogra-phi elements use in this invention can contain addenda which are incorporated by using the pro-seeders described on page 27, "Methods of addition", of the above article; and they are usually coated and dried by using the various techniques described on pages 27 and 28~ "Coating and drying procedures of the above article.
,~, ~3~5~
The term "nondiffusing" used herein has the meaning commonly applied to the term in photography and denotes materials that for all practical purposes do not migrate or wander through organic killed S layers 9 such as gelatin, in the photographic element of the invention in an alkaline medium and preferably when processed in a medium having a pi of 11 or greater. The same meaning is to be attached to the term "immobile". The term "diffusible" as applied to the materials of this invention has the converse meaning and denotes materials having the property of diffusing effectively through the killed layers of the photographic element in an alkaline medium.
"Mobile" has the same meaning as "diffusible".
The term "associated wherewith" as used herein is intended to mean what the materials can be in either the same or different layers, so long as the materials are accessible to one another The following examples are provided Jo further illustrate the invention Example 1 A) A control integral imaging-receiver (SIR) element Web prepared by coating the following layers in the order recited on a transparent polyethylene terephthalate) film support. Quantities are parent thetically given in grams per square meter, unless otherwise stated.
(1) Image-receiving layer of poly(styrene-co-N-benzyl-N,N-dimethyl-N-vinylbenzylammonium chloride co-divinylbenzene)(molar ratio 49/49/2) (1.1) and gelatin (1.2);
(2) Image-receiving layer of poly~styrene-co-l-vinylimidazole-co-3-benzyl-1-vinylimidazolium chloride mole ratio) (1.6) and gelatin (0.75);
(3) Reflecting layer of titanium dioxide (17) and gelatin (2.6);
I Opaque layer of carbon black (0.95) and gelatin (0.65);
Patents 3,980,479; 4,139~379; Lowe 4,199,354;
4,232,107; 4,199,355 and German Patent 2~854,946.
In a preferred embodiment of the invention, RDRIs such as those in the Fleckenstein et at patent referred to above are employed. Such compounds are ballasted sulfonamide compounds which are alkali-cleavable upon oxidation to release a diffusible dye from the nucleus and have the formula:
Jo G
I
atlas tam_ l i .
NHS02-Col I`
wherein:
(a) Cot is a dye or dye precursor moiety;
(b) Ballast is an organic ballasting radical of such molecular size and configuration (e.g., simple organic groups or polymeric groups) as to render the compound nondiffusible in the photosensitive element during development in an alkaline processing compost-lion;
(c) G is OR or NHRl wherein R is hydrogen or a hydrolyzable moiety and R' is hydrogen or a subset-tuned or unsubstitutPd alkyd group of 1 to 22 carbon atoms, such as methyl, Ethyl, hydroxyethyl, propel, Boyle, secondary bottle, tertiary bottle, cyclopropyl, 4-chlorobutyl, cyclobutyl, 4 nitroamyl, Huxley, cyclohexyl, octal, decal, octadecyl, docosyl, bouncily or phenethyl when Al is an alkyd group of greater than 6 carbon atoms 9 it can serve as a partial or sole Ballast group);
(d) Y represents the atoms necessary to complete a Bunsen nucleus, a naphthalene nucleus or a 5- to 7-membered heterocyclic ring such as porcelain or pyrimidine; and (e) m is a positive integer or 1 to 2 and is 2 when G is OR or when Al is a hydrogen or an alkyd group of less than 8 carbon atoms.
For further details concerning the above-described sulfonamide compounds and specific examples of same, reference is made Jo the above mentioned Fleckens~ein et at US. Patent 4,076,529.
In another preferred embodiment of the invention, positive-workin2, nondiffusible RDR's of the type disclosed in US. Patents 4,139,379 and 49139,389 are employed. In this embodiment, an immobile compound is employed which as incorporated in a photographic element is incapable of releasing a diffusible dye. However, during photographic process sing under alkaline conditions the compound is capable of accepting at least one electron (i.e., being reduced) and thereafter releases a diffusible dye. These immobile compounds are ballasted electron accepting nucleophilic displacement compounds.
S A format for integral nega~ive-receiver photographic elements in which the pronto invention is useful is disclosed in Canadian Patent 928,559.
In this embodiment, the support for the photographic element is transparent and us coaxed with the image-receiving layer, a substantially opaque, light-reflective layer, the stripping layer and adjacent hydrophilic layers described above, and the photo-sensitive layer or layers described above. A rupture able container, containing an alkaline processing lo composition including a developing agent and an pacifier, is positioned between the top layer end a transparent cover sheet which has thereon, in sequence, a neutralizing layer, and a tying layer.
The film unit is placed in a camera, exposed through the transparent cover sheet and then passed through a pair of pressure-applying members in the camera as it is being removed therefrom. The pressure-applying members rupture the container and spread processing composition and pacifier over the negative portion of the film unit to render it light-insensitive. The processing composition develops each silver halide layer and dye images, formed as a result of develop-mint 9 diffuse to the image-receiving layer Jo provide a positive, right-reading image which is viewed through the transparent support on the opaque reflecting layer background. For further details concerning the format of this particular integral film unit, reference is made Jo the above-mentioned Canadian Patent 928,559.
Still other useful integral formats in which this invention can be employed are described in US.
Puns 3,415,644; 3,415,645; 3,415,646, 3,647,437 . ,;
and aye In most of these formats, a photo-sensitive silver halide emulsion is coated on an opaque support and a dye image-receivlng layer is located on a separate transparent support superposed over the layer outermost from the opaque support. In addition, this transparent support also contains a neutralizing layer and a timing layer underneath the dye image-receiving layer.
In another embodiment of the invention, the neutralizing layer and timing layer are located underneath the photosensitive layer or layers. In that embodiment, the photosensitive element would comprise a support having thereon, in sequence, a neutralizing layer, a timing layer and at least one photosensitive silver halide emulsion layer having associated therewith a dye tmage-providing material.
The dye image-receiving layer would be provided on transparent cover sheet with the processing compost-lion being applied there between.
The film unit or assemblage of the present invention is used to produce positive images in single or multicolors. In a three-color system, etch silver halide emulsion layer of the film assembly will have associated earth a dye image-providing material which possesses a predominant spectral absorption within the region of the visible spectrum to which said silver halide emulsion is sensitive, i.e., the blue-sensltive silver halide emulsion layer will have a yellow dye image-provi~ing material associated earth the green-sensitive silver halide emulsion layer will have a magenta dye image-providing material associated therewith and the red-sensitive silver halide emulsion layer will have a cyan dye image-providing material associated therewith. The dye image-providing material also elated with each silver halide emulsion layer is contained either in the silver halide emulsion layer "i itself or in a layer contiguous Jo the silver halide emulsion layer, i.e. 9 the dye image providing Metro-at can be coated in a separate layer underneath the silver halide emulsion layer with respect to the exposure direction.
The concentration of the dye image-providing material that is employed in the present invention can be varied over a wide range, depending upon the particular compound employed and the results lo desired. For example, the dye lmage-providîng material coated in a layer at a concentration of 0.1 to 3 gym has been found to be useful. The dye image-providing material is usually dispersed in a hydrophilic film forming natural material or sync Thetis polymer, such as gelatin, polyvinyl alcohol,etc, which is adapted to be permeated by aqueous alkaline processing composition.
A variety of silver halide developing agents are useful in this invention. Specific examples of developers or electron transfer agents (ETA's) useful in this invention include hydroquinone compounds, catcall compounds, and 3-pyrazolidinone compounds as disclosed in column 16 of US. Patent 4,358,527, issued November 9, OWE A combination of different ETA's, such as those disclosed in US. Patent 3,039,869, can also be employed. These ETA's are employed on the liquid processing composition or contained, at least in part, in any layer or layers of the photographic element or film assemblage to be activated by the alkaline processing composition, such as in the silver halide emulsion layers, the dye image-providing material layers, lnterlayers, image-receiving layer, etc.
In this invention, in which dye image-providing material can be used which produce dip-fusible dye images as a function of development, either conventional negative-working or dlrect-posi-I
live silver halide emulsions can be employed. If the silver halide emulsion employed is a clirect-positive silver halide emulsion, such as an internal image emulsion designed for use in the internal image reversal process, or a fogged, direct-positive emulsion such as a sol~rizlng emulsion, which is developable in unexposed areas 9 a positive image can be obtained on the dye image-receiving layer by using ballasted dye image-providing materials. After lo exposure of the film assemblage or unit, the alkaline processing composition permeates the various layers to initiate development of the exposed photosensitive silver halide emulsion layers. The developing agent present in the film unit develops each of the silver halide emulsion layers in the unexposed areas since the silver halide emulsions are direct-positive ones), thus causing the developing agent to become oxidized images corresponding to the unexposed areas of the direc~-positive silver halide emulsion layers. The oxidized developing agent then cross-oxidizes the dye image-providing material compounds and the oxidized form of the compounds then undergoes a base-initiated reaction Jo release the dyes image-wise as a function of the images exposure of each of the silver halide emulsion layers. At least a portion of the images distributions of diffusible dyes diffuse to the image-receivlng layer to form a positive image of the original subject. After being contacted by the alkaline processing composition a neutralizing layer in the film unit or image-receiv-in unit lowers the pi of the film unit or image receiver Jo stabilize the image.
Internal image silver halide emulsions useful in this invention are described more fully on the November, 1976 edition of Research Disclosure, pages 76 through 79.
';, The various silver halide emulsion layers of a color film assembly employed in this invention are disposed in the usual order, i.e., the blue sensitive silver halide emulsion layer first with respect to the exposure side, followed by the green-sensitive and red-sensitive silver halide emulsion layers. If desired, a yellow dye layer or a yellow colloidal silver layer can be present between the blazons live and green-sensitive silver halide emulsion layers for absorbing or filtering blue radiation that is transmitted through the blue-sensitive layer. If desired, the selectively sensitized silver halide emulsion layers can be disposed in a different order, e.g., the blue-sensitive layer first with respect to the exposure side 9 followed by the red-sensitive and green-sensltive layers The rupturable container employed in certain embodiments of this invention is disclosed in US.
Patents 2,543,181; 2,643,886; 2,653,732; 2,723,051;
3J056~492; 3~056,491 and 3,152,515. In general, such containers comprise a rectangular sheet of fluid- and air-impervious material folded longitudinally upon itself to form two walls which are sealed to one another along their longitudinal and end margins to form a cavity in which processing solution is con-twined.
Generally speaking, except where noted otherwise, the silver halide emulsion layers employed in the invention comprise photosensitive silver halide dispersed in gelatin and are about 0.6 to 6 microns in thickness; the dye image providing Motorola-awls are dispersed in an aqueous alkaline solution-permeable polymeric binder, such as gelatin, as a separate layer about 0.2 to 7 microns in thickness;
and the alkaline solutlon-p~rmeable polymeric inter-layers, e.g., gelatin, are about 0.2 to 5 microns in thickness. Of course these thicknesses are approxi-I
~19-mate only and can be modified according to the product desired Scavengers for oxidized developing agent can be employed in various inter layers of the photogra-phi elements of the invention. Suitable materializer disclosed on page 83 of the November 1976 edition of Research Disclosure.
.
Any material is useful as the dye image receiving layer in this invention as long as the lo desired function of mordan~ing or otherwise fixing the dye images is obtained, The particular material chosen will, of course, depend upon the dye to be mordant Ed Suitable materials are disclosed on pages 80 through 82 of the November 1976 edition of Research Disclosure.
Use of a neutralizing malarial in the film units employed in this invention will usually increase the stability of the transferred image.
Generally, the neutralizing material will effect a reduction in the pi of the image layer from about 13 or 14 Jo at least 11 and preferably 5 to 8 within a short time after ~mbibition. Suitable materials and their functioning are disclosed on pages 22 and 23 of the July 1974 edition of Research Do schoolhouses and pages 35 through 37 of the July 1975 edition of Research Disclosure.
A timing or inert spacer layer can be employed in the practice of this invention over the neutralizing layer which "times" or controls the pi reduction as a function of the rate at which alkali diffuses through the inert spacer layer. Examples of such timing layers and their functioning are disk closed in the Research Disclosure articles mentioned in the paragraph above concerning neutralizing layers.
The alkaline processing composition employed in this invention is the conventional aqueous soul-lion of an alkaline material, ego alkali metal hydroxides or carbonates such as sodium hydroxide, sodium carbonate or an mine such as diethylamine, preferably possessing a pi in excess of 11 7 and preferably containing a developing agent as described previously. Suitable materials and addenda frequent-lye added to such compositions are disclosed Oh pages lo 79 and 80 of the November, 1976 edition of Research Disclosure.
The alkaline solution permeable, Susan tidally opaque llght-reflective layer employed in certain embodiments of photographic film units used I in this invention is described more fully in the November, 1976 edition of Research Disclosure page 82.
The supports for the photographic elements used in this invention can be any material, as long as it does not deleteriously affect the photographic properties ox the film unit and is dimensionally stable. Typical flexible sheet materials are dyes cried on page 85 of the November, 1976 edition of Research Disclosure.
While the invention has been described with reference TV layers of silver halide emulsions and dye image-providing materials, Dallas coating, such as would be obtained using a Grover printing tech-unique, Gould Allah be employed. In this technique, small dots of blue-9 green- and red-sensitive Emil-sons have associated therewith, respectively, dots of yellow, magenta end cyan color-providing sub-stances. After development, the ~ransfPrred dyes would tend to fuse together into continuous tone 3~5~3 In an alternative embodiment, ho emulsions sensitive to each of the three primary regions of the spectrum can be disposed as a single segmented layer, e.g., as by the use of micro vessels, as described in Whit more US. Patent 4,362,806, issued December 7, 1982.
The silver halide emulsions useful in this Invention, both negative-working and direct-positive ones, are well known to those skilled in the art and are described in Research Disclosure, Volume 176, December 1978, Item 17643, pages 22 and 233 Emil soon preparation and types"; they are usually comma-gaily and spectrally sensitized as described on page comical sensitigationl', and "Spectral sunsuit-ration and desenæitizatlon", of the above article;
they are optionally protected against the production of fog and stabilized against loss of sensitivity during keeping by employing the materials described on pages 24 and 25, "Antifoggants and stabilizers" 9 of the above article; they usually contain hardeners and coating aids us described on pave 26, 'harden-ens", and pages 26 and 279 kowtowing aids", of the above article; they and other layers in the photogra-phi elements used in this lnven~ion usually contain plasticizers, vehicles and filter dyes described on 25 page 27, "Plasticizers and lubricants"; page 26, "Vehicles and vehicle extenders"; and pages 25 and 269 "Absorbing and scattering materials", of the above article; they and other layers in the photogra-phi elements use in this invention can contain addenda which are incorporated by using the pro-seeders described on page 27, "Methods of addition", of the above article; and they are usually coated and dried by using the various techniques described on pages 27 and 28~ "Coating and drying procedures of the above article.
,~, ~3~5~
The term "nondiffusing" used herein has the meaning commonly applied to the term in photography and denotes materials that for all practical purposes do not migrate or wander through organic killed S layers 9 such as gelatin, in the photographic element of the invention in an alkaline medium and preferably when processed in a medium having a pi of 11 or greater. The same meaning is to be attached to the term "immobile". The term "diffusible" as applied to the materials of this invention has the converse meaning and denotes materials having the property of diffusing effectively through the killed layers of the photographic element in an alkaline medium.
"Mobile" has the same meaning as "diffusible".
The term "associated wherewith" as used herein is intended to mean what the materials can be in either the same or different layers, so long as the materials are accessible to one another The following examples are provided Jo further illustrate the invention Example 1 A) A control integral imaging-receiver (SIR) element Web prepared by coating the following layers in the order recited on a transparent polyethylene terephthalate) film support. Quantities are parent thetically given in grams per square meter, unless otherwise stated.
(1) Image-receiving layer of poly(styrene-co-N-benzyl-N,N-dimethyl-N-vinylbenzylammonium chloride co-divinylbenzene)(molar ratio 49/49/2) (1.1) and gelatin (1.2);
(2) Image-receiving layer of poly~styrene-co-l-vinylimidazole-co-3-benzyl-1-vinylimidazolium chloride mole ratio) (1.6) and gelatin (0.75);
(3) Reflecting layer of titanium dioxide (17) and gelatin (2.6);
I Opaque layer of carbon black (0.95) and gelatin (0.65);
(5) Gelatin inter layer (0.54);
(6) Stripping layer of Notoriously GXR-2S0 hydroxy-ethyl cellulose (0.81);
(7) Gelatin inter layer ~0.65);
(8) Cyan dye releaser B of US. Patient 4,356,250 (0.37) and gelatin (0.54); and I gelatin overcoat (0.43).
It should be noted that layers 8 and 9 represent the top and bottom layers of a complete SIR
such as described in Example 1 of US. Patent 15 4,356,250. For purposes of this test, it was not necessary Jo have a complete llght-sensitive element.
B) An SIR similar to A) was prepared except that layer 7 also contained poly(methylmethacrylate) beads (0.56).
C) An SIR similar to A) was prepared except that layer 7 also contained poly(methylmethacrylate) beads (0.18).
D) An SIR similar to A) was prepared except that layer 7 also contained Dupont Ludox~ AM
colloidal silica (0.95).
E) An SIR similar to A) was prepared except that layer 7 Also contained Dupont Ludox6 AM
colloidal silica (0.32).
F) An SIR similar to A) was prepared except that layer 7 also contained Cabot Regal 400 carbon black (0.g5).
G) An SIR similar to A) was prepared except that layer 7 also contained Cabot Regal 400 carbon black (0.32).
H) An SIR similar to A) was prepared except that layer 7 also contained Gulf and Western Horse-head Utile titanium dioxide (1.8).
:~, I) An SIR similar to A) was prepared except that layer 7 also contained Gulf and Western Horse-head Utile titanium dioxide (0.59).
The above coatings were prepared with S constant volumes of particulate material, thus the actual coated weights vary. Each material was coated at a lo and 3X level corresponding to a volume ratio of particulate material to hydrophilic material of 0.26 and 0.79.
A "tape test" was run on the above Iris.
This test has a high correlation with actual strip-ping performances in actual photographic coatings.
m e test consists of firmly applying a short strip of EM Scotch 810 Magic Transparent Tape on the top of layer 9 of the SIR to be tested and then rapidly put 1 in on the tape.
All of the Iris thus tested stripped at the point between layers 6 and 5, thus indicating the weakest bond in the element In control element A, a random discontinuous stripping occurred.
A second tape test was run On the residual element on top of layer 6 to determine the next weakest bond. If layer 6 was not removed by this second test, then the bond between layers 7 and 6 was considered to be strong. If layer 6 was removed by the second tape test, then the bond was considered to be weak (but Nina less stronger than the bond between layers 6 and 5).
The following results were obtained:
~3~5~3 Bond Bond Particulate Between Between Volume Material in Layers Layers SIR Ratio* Layer 7 ~g/m2~ 5 and 6 6 and 7 A -I none Weak Weak (Con- (discontinuous stripping Rowley) B 0.79 poly~methylmeth- Weakest Strong acrylate) beads (0.563 C 0.26 poly(methylmeth- Weakest Weak acryla~e) beads (0.18~
D 0.79 silica (0.95) Weakest Strong E 0.26 silica (0.32) Weakest Weak lo F 0.79 carbon black (0.95) Weakest Strong G 0.26 carbon black (0.32) Weakest Weak H 0.79 titanium dioxide Weakest Strong (1.8) I 0.26 titanium dioxide Weakest Weak (0.59) * Of particulate material to hydrophilic material in layer 7.
The above result indicate what employing particulate material in a hydrophilic layer adjacent a stripping layer improves the adhesion between those two layers, thus causing stripping to occur on the opposite side of the stripping layer. In SIR eye-mints B, D, F and H, a strong bond was obtained between layers 6 and 7 since the volume ratio of particulate material to hydrophilic material was above the minimum ratio of 0.5 as described herein.
In SIR elements C, E, G and I, a weak bond was obtained between layers 6 and 7 since the volume ratio of particulate material to hydrophilic material was below Q.5. Other photographic tests have shown a 'I"
I
correlation between: I a weak bond between layers 6 and 7 and 2) discontinuous stripping when such materials are incorporated into complete photographic assemblages. After processing a photographic asset-blaze but before stripping, the adhesive bonding between various layers may change since the alkaline processing composition may affect their adhesive characteristics. A strong bond is thus needed between layers 6 and 7 in order to minimize the possibility of discontinuous stripping in a photogra-phi assemblage.
The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention.
It should be noted that layers 8 and 9 represent the top and bottom layers of a complete SIR
such as described in Example 1 of US. Patent 15 4,356,250. For purposes of this test, it was not necessary Jo have a complete llght-sensitive element.
B) An SIR similar to A) was prepared except that layer 7 also contained poly(methylmethacrylate) beads (0.56).
C) An SIR similar to A) was prepared except that layer 7 also contained poly(methylmethacrylate) beads (0.18).
D) An SIR similar to A) was prepared except that layer 7 also contained Dupont Ludox~ AM
colloidal silica (0.95).
E) An SIR similar to A) was prepared except that layer 7 Also contained Dupont Ludox6 AM
colloidal silica (0.32).
F) An SIR similar to A) was prepared except that layer 7 also contained Cabot Regal 400 carbon black (0.g5).
G) An SIR similar to A) was prepared except that layer 7 also contained Cabot Regal 400 carbon black (0.32).
H) An SIR similar to A) was prepared except that layer 7 also contained Gulf and Western Horse-head Utile titanium dioxide (1.8).
:~, I) An SIR similar to A) was prepared except that layer 7 also contained Gulf and Western Horse-head Utile titanium dioxide (0.59).
The above coatings were prepared with S constant volumes of particulate material, thus the actual coated weights vary. Each material was coated at a lo and 3X level corresponding to a volume ratio of particulate material to hydrophilic material of 0.26 and 0.79.
A "tape test" was run on the above Iris.
This test has a high correlation with actual strip-ping performances in actual photographic coatings.
m e test consists of firmly applying a short strip of EM Scotch 810 Magic Transparent Tape on the top of layer 9 of the SIR to be tested and then rapidly put 1 in on the tape.
All of the Iris thus tested stripped at the point between layers 6 and 5, thus indicating the weakest bond in the element In control element A, a random discontinuous stripping occurred.
A second tape test was run On the residual element on top of layer 6 to determine the next weakest bond. If layer 6 was not removed by this second test, then the bond between layers 7 and 6 was considered to be strong. If layer 6 was removed by the second tape test, then the bond was considered to be weak (but Nina less stronger than the bond between layers 6 and 5).
The following results were obtained:
~3~5~3 Bond Bond Particulate Between Between Volume Material in Layers Layers SIR Ratio* Layer 7 ~g/m2~ 5 and 6 6 and 7 A -I none Weak Weak (Con- (discontinuous stripping Rowley) B 0.79 poly~methylmeth- Weakest Strong acrylate) beads (0.563 C 0.26 poly(methylmeth- Weakest Weak acryla~e) beads (0.18~
D 0.79 silica (0.95) Weakest Strong E 0.26 silica (0.32) Weakest Weak lo F 0.79 carbon black (0.95) Weakest Strong G 0.26 carbon black (0.32) Weakest Weak H 0.79 titanium dioxide Weakest Strong (1.8) I 0.26 titanium dioxide Weakest Weak (0.59) * Of particulate material to hydrophilic material in layer 7.
The above result indicate what employing particulate material in a hydrophilic layer adjacent a stripping layer improves the adhesion between those two layers, thus causing stripping to occur on the opposite side of the stripping layer. In SIR eye-mints B, D, F and H, a strong bond was obtained between layers 6 and 7 since the volume ratio of particulate material to hydrophilic material was above the minimum ratio of 0.5 as described herein.
In SIR elements C, E, G and I, a weak bond was obtained between layers 6 and 7 since the volume ratio of particulate material to hydrophilic material was below Q.5. Other photographic tests have shown a 'I"
I
correlation between: I a weak bond between layers 6 and 7 and 2) discontinuous stripping when such materials are incorporated into complete photographic assemblages. After processing a photographic asset-blaze but before stripping, the adhesive bonding between various layers may change since the alkaline processing composition may affect their adhesive characteristics. A strong bond is thus needed between layers 6 and 7 in order to minimize the possibility of discontinuous stripping in a photogra-phi assemblage.
The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention.
Claims (34)
1. In a photographic assemblage comprising:
a) a photosensitive element comprising a support having thereon at least one photosensitive silver halide emulsion layer;
b) an image-receiving layer; and c) a stripping layer located between said silver halide emulsion layer and said image-receiving layer so that said image-receiving layer may be separated, after processing, from the portion of said assemblage containing said silver halide emulsion layer;
the improvement wherein each side of said stripping layer has a hydrophilic layer immediately adjacent thereto, and one of said hydrophilic layers contains particulate material substantially insensi-tive to light and in a volume ratio of particulate material to hydrophilic material in that layer of at least 0.5, so that upon separation, substantially all of said stripping layer will remain with the portion of said assemblage having said hydrophilic layer containing said particulate material.
a) a photosensitive element comprising a support having thereon at least one photosensitive silver halide emulsion layer;
b) an image-receiving layer; and c) a stripping layer located between said silver halide emulsion layer and said image-receiving layer so that said image-receiving layer may be separated, after processing, from the portion of said assemblage containing said silver halide emulsion layer;
the improvement wherein each side of said stripping layer has a hydrophilic layer immediately adjacent thereto, and one of said hydrophilic layers contains particulate material substantially insensi-tive to light and in a volume ratio of particulate material to hydrophilic material in that layer of at least 0.5, so that upon separation, substantially all of said stripping layer will remain with the portion of said assemblage having said hydrophilic layer containing said particulate material.
2. The assemblage of claim 1 wherein said hydrophilic layer which contains said particulate material is located between said stripping layer and said silver halide emulsion layer so that upon separation, substantially all of said stripping layer will remain with said portion of said assemblage containing said silver halide emulsion layer.
3. The assemblage of claim 2 which also contains an alkaline processing composition and means containing same for discharge within said assemblage.
4. The assemblage of claim 3 wherein said image-receiving layer contains silver precipitating nuclei.
5. The assemblage of claim 3 wherein said silver halide emulsion layer has associated therewith a dye image-providing material.
6. The assemblage of claim 5 wherein said stripping layer comprises hydroxyethyl cellulose.
7. The assemblage of claim 5 wherein said particulate material comprises carbon black, titanium dioxide, silica or poly(methyl methacrylate) beads.
8. The assemblage of claim 5 wherein each said hydrophilic layer comprises gelatin.
9. The assemblage of claim 8 wherein said particulate material is carbon black.
10. The assemblage of claim 9 wherein said stripping layer comprises hydroxyethyl cellulose.
11. The assemblage of claim 5 wherein said photosensitive element comprises a support having thereon a red-sensitive silver halide emulsion layer having a cyan dye image-providing material associated therewith, a green-sensitive silver halide emulsion layer having a magenta dye image-providing material associated wherewith, and a blue-sensitive silver halide emulsion layer having a yellow dye image-providing material associated therewith.
12. The assemblage of claim 5 wherein said dye image-providing material is a ballasted sulfon-amido compound which is alkali-cleavable upon oxida-tion to release a diffusible color-providing moiety, said compound having the formula:
wherein:
(a) Col is a dye or dye precursor moiety;
(b) Ballast is an organic ballasting radical of such molecular size and configuration as to render said compound nondiffusible in said photosensitive element during development in an alkaline processing composition;
(c) G is OR or NHR1 wherein R is hydrogen or a hydrolyzable moiety and R1 is hydrogen or an alkyl group of 1 to 22 carbon atoms;
(d) Y represents the atoms necessary to complete a benzene nucleus, a naphthalene nucleus or a 5- to 7-membered heterocyclic ring; and (e) m is a positive integer of 1 to 2 and is 2 when G is OR or when R1 is hydrogen or an alkyl group of less than 8 carbon atoms.
wherein:
(a) Col is a dye or dye precursor moiety;
(b) Ballast is an organic ballasting radical of such molecular size and configuration as to render said compound nondiffusible in said photosensitive element during development in an alkaline processing composition;
(c) G is OR or NHR1 wherein R is hydrogen or a hydrolyzable moiety and R1 is hydrogen or an alkyl group of 1 to 22 carbon atoms;
(d) Y represents the atoms necessary to complete a benzene nucleus, a naphthalene nucleus or a 5- to 7-membered heterocyclic ring; and (e) m is a positive integer of 1 to 2 and is 2 when G is OR or when R1 is hydrogen or an alkyl group of less than 8 carbon atoms.
13. The assemblage of claim 5 wherein:
(a) said image-receiving layer is located in said photosensitive element between said support and said silver halide emulsion layer; and (b) said assemblage also includes a transparent cover sheet over the layer outermost from said support.
(a) said image-receiving layer is located in said photosensitive element between said support and said silver halide emulsion layer; and (b) said assemblage also includes a transparent cover sheet over the layer outermost from said support.
14. The assemblage of claim 13 wherein said transparent cover sheet is coated with, in sequence, a neutralizing layer and a timing layer.
15. The assemblage of claim 14 wherein said discharging means is a rupturable container contain-ing said alkaline processing composition and an opacifying agent, said container being so positioned during processing of said assemblage that a compres-sive force applied to said container will effect a discharge of the container's contents between said transparent sheet and the layer outermost from said support.
16. The assemblage of claim 5 wherein said support of said photosensitive element is opaque, and said image-receiving layer is located on a separate transparent support superposed on the layer outermost from said opaque support.
17. The assemblage of claim 16 wherein said transparent support has thereon, in sequence, a neutralizing layer, a timing layer and said image-receiving layer.
18. The assemblage of claim 16 wherein said opaque support has thereon, in sequence, a neutraliz-ing layer, a timing layer and said silver halide emulsion layer.
19. The assemblage of claim 5 wherein said support of said photosensitive element is transparent.
20. An integral photographic assemblage comprising:
(a) a photosensitive element comprising a transparent support having thereon the following layers in sequence: a dye image-receiving layer; an alkaline solution-permeable, light-reflective layer;
an alkaline solution-permeable, opaque layer; a hydrophilic layer; a stripping layer which enables said dye image-receiving layer to be separated, after processing, from the rest of said assemblage; a hydrophilic layer; a red-sensitive silver halide emulsion layer having a cyan dye image-providing material associated therewith; a green-sensitive silver halide emulsion layer having a magenta dye image-providing material associated therewith; and a blue-sensitive, silver halide emulsion layer having a yellow dye image-providing material associated therewith;
(b) a transparent cover sheet superposed over said blue-sensitive silver halide emulsion layer and comprising a transparent support having therein, in sequence, a neutralizing layer and a timing layer; and (c) a rupturable container containing an alka-line processing composition and an opacifying agent, said container being so positioned during processing of said assemblage that a compressive force applied to said container will effect a discharge of the container's contents between said transparent cover sheet and said blue-sensitive silver halide emulsion layer;
and wherein said hydrophilic layer which is located between said stripping layer and said red-sensitive silver halide emulsion layer contains particulate material substantially insensitive to light and in a volume ratio of particulate material to hydrophilic material in that layer of at least 0.5, so that upon separation, substantially all of said stripping layer will remain with the portion of said assemblage containing said silver halide emul-sion layers.
(a) a photosensitive element comprising a transparent support having thereon the following layers in sequence: a dye image-receiving layer; an alkaline solution-permeable, light-reflective layer;
an alkaline solution-permeable, opaque layer; a hydrophilic layer; a stripping layer which enables said dye image-receiving layer to be separated, after processing, from the rest of said assemblage; a hydrophilic layer; a red-sensitive silver halide emulsion layer having a cyan dye image-providing material associated therewith; a green-sensitive silver halide emulsion layer having a magenta dye image-providing material associated therewith; and a blue-sensitive, silver halide emulsion layer having a yellow dye image-providing material associated therewith;
(b) a transparent cover sheet superposed over said blue-sensitive silver halide emulsion layer and comprising a transparent support having therein, in sequence, a neutralizing layer and a timing layer; and (c) a rupturable container containing an alka-line processing composition and an opacifying agent, said container being so positioned during processing of said assemblage that a compressive force applied to said container will effect a discharge of the container's contents between said transparent cover sheet and said blue-sensitive silver halide emulsion layer;
and wherein said hydrophilic layer which is located between said stripping layer and said red-sensitive silver halide emulsion layer contains particulate material substantially insensitive to light and in a volume ratio of particulate material to hydrophilic material in that layer of at least 0.5, so that upon separation, substantially all of said stripping layer will remain with the portion of said assemblage containing said silver halide emul-sion layers.
21. The assemblage of claim 20 wherein said stripping layer comprises hydroxyethyl cellulose.
22. The assemblage of claim 20 wherein said particulate material comprises carbon black, titanium dioxide, silica or poly(methyl methacrylate) beads.
23. The assemblage of claim 22 wherein said particulate material is present at a volume ratio of about 0.5 to about 20.
24. The assemblage of claim 20 wherein each said hydrophilic layer comprises gelatin.
25. The assemblage of claim 24 wherein said particulate material is carbon black.
26. The assemblage of claim 25 wherein said stripping layer comprises hydroxyethyl cellulose.
27. A process for producing a photographic image in color comprising:
I) exposing a photosensitive element comprising a support having thereon at least one photosensitive silver halide emulsion layer having associated therewith a dye image-providing material;
II) treating said element with an alkaline processing composition in the presence of a silver halide developing agent to effect development of each said exposed silver halide emulsion layer, whereby:
(a) an imagewise distribution of said dye image-providing material is formed as a function of said development of said silver halide emulsion layer; and (b) at least a portion of said imagewise distribution of said dye image-providing material diffuses to a dye image-receiving layer; and III) separating said dye image-receiving layer from the rest of said photosensitive element, said separation being facilitated by means of a stripping layer located between said silver halide emulsion layer and said dye image-receiving layer, and wherein each side of said stripping layer has a hydrophilic layer immediately adjacent thereto, and one of said hydrophilic layers contains particulate material substantially insensitive to light and in a volume ratio of particulate material to hydrophilic material in that layer of at least 0.5, so that substantially all of said stripping layer will remain with the portion of said element having said hydrophilic layer containing said particulate material.
I) exposing a photosensitive element comprising a support having thereon at least one photosensitive silver halide emulsion layer having associated therewith a dye image-providing material;
II) treating said element with an alkaline processing composition in the presence of a silver halide developing agent to effect development of each said exposed silver halide emulsion layer, whereby:
(a) an imagewise distribution of said dye image-providing material is formed as a function of said development of said silver halide emulsion layer; and (b) at least a portion of said imagewise distribution of said dye image-providing material diffuses to a dye image-receiving layer; and III) separating said dye image-receiving layer from the rest of said photosensitive element, said separation being facilitated by means of a stripping layer located between said silver halide emulsion layer and said dye image-receiving layer, and wherein each side of said stripping layer has a hydrophilic layer immediately adjacent thereto, and one of said hydrophilic layers contains particulate material substantially insensitive to light and in a volume ratio of particulate material to hydrophilic material in that layer of at least 0.5, so that substantially all of said stripping layer will remain with the portion of said element having said hydrophilic layer containing said particulate material.
28. The process of claim 27 wherein said hydrophilic layer which contains said particulate material is located between said stripping layer and said silver halide emulsion layer so that upon separation, substantially all of said stripping layer will remain with said portion of said element con-taining said silver halide emulsion layer.
29. The process of claim 28 wherein said stripping layer comprises hydroxyethyl cellulose.
30. The process of claim 28 wherein said particulate material comprises carbon black, titanium dioxide, silica or poly(methyl methacrylate) beads.
31. The process of claim 30 wherein said particulate material is present at a volume ratio of about 0.5 to about 20.
32. The process of claim 28 wherein each said hydrophilic layer comprises gelatin.
33. The process of claim 32 wherein said particulate material is carbon black.
34. The process of claim 33 wherein said stripping layer comprises hydroxyethyl cellulose.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US49747283A | 1983-05-23 | 1983-05-23 | |
| US497,472 | 1990-03-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1213458A true CA1213458A (en) | 1986-11-04 |
Family
ID=23977025
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000446598A Expired CA1213458A (en) | 1983-05-23 | 1984-02-02 | Hydrophilic layers adjacent a stripping layer for diffusion transfer assemblages |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0127431B1 (en) |
| JP (1) | JPS59220727A (en) |
| CA (1) | CA1213458A (en) |
| DE (1) | DE3474220D1 (en) |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3674482A (en) * | 1970-07-13 | 1972-07-04 | Polaroid Corp | Novel photographic products and processes |
| DE2049688C3 (en) * | 1970-10-09 | 1981-02-12 | Agfa-Gevaert Ag, 5090 Leverkusen | Photographic material and process for producing colored photographic images |
| US4298682A (en) * | 1980-08-01 | 1981-11-03 | Eastman Kodak Company | Photographic element having overcoating of ionic polyester in hydrophilic colloid |
| US4359518A (en) * | 1981-06-26 | 1982-11-16 | Polaroid Corporation | Stripping sheet for use with diffusion transfer film unit |
-
1984
- 1984-02-02 CA CA000446598A patent/CA1213458A/en not_active Expired
- 1984-05-23 DE DE8484303481T patent/DE3474220D1/en not_active Expired
- 1984-05-23 JP JP10276184A patent/JPS59220727A/en active Granted
- 1984-05-23 EP EP19840303481 patent/EP0127431B1/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| DE3474220D1 (en) | 1988-10-27 |
| EP0127431A3 (en) | 1986-07-30 |
| JPS633300B2 (en) | 1988-01-22 |
| EP0127431A2 (en) | 1984-12-05 |
| EP0127431B1 (en) | 1988-09-21 |
| JPS59220727A (en) | 1984-12-12 |
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