[0001] 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.
[0002] Various formats for color, integral transfer elements are described in the prior
art, such as U.S. Patents 3,415,644; 3,415,645; 3,415,646; 3,647,437; 3,635,707; 3,756,815,
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 proportion 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 imagewise distribution of diffusible
dyes diffuses to the dye image-receiving layer to form an image of the original subject.
The user does not have to time this process.
[0003] 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.
[0004] Peel-apart formats for color diffusion transfer assemblages have previously been
described, for example, in U.S. Patents 2,983,606, 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.
[0005] U.S. Patent 3,730,718 relates to diffusion transfer assemblages wherein a stripping
layer is employed so that an image-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. However, assemblages wherein
particulate material is present in layers on both sides of a stripping layer exhibit
nonuniform fracture of the stripping layer upon separation, with the dis- advantages
as described below.
[0006] U.S. 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 the stripping layer and the silver halide emulsion layer and
which contains particulate material as described herein.
[0007] A problem has developed with the use of stripping layers in assemblages such as described
above. While it is highly desirable to have the stripping layer be removed in one
uniform piece and remain with the separated portion that is to be discarded, in practice
it has been found that the stripping layer itself fractures. This results in portions
of the stripping layer randomly adhering to the two separated surfaces. A very blotchy
appearance thus results on the back of the separated image-receiving layer which is
undesirable in a commercial product. This blotchy appearance is particularly noticeable
in D
min areas of a transparency format.
[0008] The object of the present invention is to provide 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.
[0009] This object is achieved with a photographic assemblage as described above which is
characterized in that each side of the stripping layer has a hydrophilic layer immediately
adjacent thereto, other than a photosensitive silver halide emulsion layer or an image-receiving
layer, and only one of the hydrophilic layers contains particulate material substantially
insensitive to light and in a volume percentage of 5 to 75 percent of the hydrophilic
material-particulate material mixture in that layer, 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.
[0010] In a preferred embodiment of the invention, the hydrophilic layer which contains
the particulate material is located between the stripping layer and the silver halide
emulsion layer so that upon separation, substantially all of the stripping layer will
remain with the portion of the assemblage containing the silver halide emulsion layer.
[0011] In forming a black-and-white image, the exposed photosensitive element is developed.
In the unexposed areas, a silver halide complexing agent dissolves the silver halide
and transfers it to the image-receiving layer. Silver precipitating nuclei in the
image-receiving layer then cause the transferred 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
U.S. Patents 3,220,835 and 3,820,999.
[0012] In a preferred embodiment of the invention, the silver halide emulsion layer has
associated therewith a dye image-providing material.
[0013] Any material may be employed as the stripping layer in the invention provided it
has the required properties. Such materials are disclosed, for example, in U.S. Patents
3,220,835, 3,730,718 and 3,820,999 and include gum arabic, sodium alginate, pectin,
polyvinyl alcohol and hydroxyethyl cellulose. In a preferred embodiment of this invention,
hydroxyethyl cellulose is employed.
[0014] The stripping layer materials employed in this invention can be employed in any amount
which is effective for the intended purpose. Good results have been obtaiqed at a
concentration of from 5 to 2000 mg/m
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.
[0015] 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,
acrylamide 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. Good results have been obtained at coverages ranging from
0.1 to 2.0 g/m
2 of element.
[0016] 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. Good results have been obtained with carbon black,
such as Cabot Regal 400
* carbon black, average particle diameter 0.07pm and CITGO (Columbia) Carbon Raven
410°, average particle diameter 0.07 pm; titanium dioxide, such as Gulf and Western
Horsehead° Rutile, average particle diameter 0.25 pm; colloidal silica such as DuPont
Ludox° AM, average particle diameter 0.012 pm; and poly(methyl methacrylate) beads,
average particle diameter 0.5 um. In a preferred embodiment, carbon black is employed.
[0017] The particle size of the particulate material employed in the invention can vary
widely, as evidenced by the range of particle sizes shown above. In general, the particle
size will range from 0.01 um to 0.5 um. The amount of particulate material to be coated
can also vary widely, as long as the volume percentage of particulate material in
the hydrophilic material-particulate material mixture in that layer is from 5 to 75
percent. Where less than 5 percent, or more than 75 percent, of particulate material
is employed the desirable improvements in layer separation will not be realized. This
percentage is commonly referred to in the art as a PVC percentage (pigment volume
content). A preferred range of PVC percentages for the invention is from 10 to 50
percent. The amount of particulate material to be coated in the hydrophilic layer
is a function of its density.
[0018] Particulate material has been employed in photographic elements for a number of reasons.
For example, in U.S. Patent 4,259,518, discussed above, it is disclosed in column
4 that 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 been expected, therefore, that such material in a layer would
decrease the adhesion of that layer to an adjacent layer. It was unexpectedly found
in accordance 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 stripping 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 reverse side thereof.
[0019] The employment of particulate material in one of the hydrophilic layers adjacent
to the stripping layer in the assemblages described herein is the means whereby the
bond between these two layers can be strengthened. This ensures that stripping will
take place at the opposite side of the stripping layer. The hydrophilic layer on the
opposite side of the stripping layer should be substantially free of particulate material
since any appreciable amount of particulate material in that layer would tend undesirably
to strengthen the bond between that layer and the stripping layer.
[0020] 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 invention combines the handling
and storage characteristics of conventional photographs with the convenience and benefits
of instant photography. Transparencies can also be obtained in 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 subsequent removal of residual image dye, silver halide and opacifying
layers. In that embodiment, it would be desirable to have the stripping layer remain
with the portion 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-receiving
layer. Clean separation would then occur on the other side of the stripping layer
where it is desired.
[0021] 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.
[0022] A process for producing a photographic image in color according to this invention
comprises:
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 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:
(a). an imagewise 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 imagewise 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.
[0023] The photographic element in the above- described process can be treated with an alkaline
processing composition to effect or initiate development in any manner. A preferred
method for applying processing composition is by use of a rupturable container or
pod,which contains the composition.
[0024] 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;
b) a transparent cover sheet located over the layer outermost from the support of
the photosensitive element;
c) 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 between
the photosensitive element and the transparent cover sheet;
and wherein the assemblage contains a stripping layer and adjacent hydrophilic layers
as described above.
[0025] In a preferred embodiment of the invention, the means containing the alkaline processing
composition is a rupturable container or pod which is adapted to be positioned during
processing of the assemblage so that a compressive force applied to the container
by pressure-applying members, such as would be found in a camera designed for in-camera
processing, will effect a discharge of the container's contents within the assemblage.
[0026] The dye image-providing material useful in this invention is either positive- or
negative-working, and is either initially mobile or immobile in the photographic element
during processing with an alkaline composition.
[0027] A format for integral negative-receiver photographic elements in which the present
invention is useful is disclosed in Canadian Patent 928,559. In this embodiment, the
support for the photographic element is transparent and is coated with the image-receiving
layer, a substantially opaque, light- reflective layer, the stripping layer and adjacent
hydrophilic layers described above, and the photosensitive layer or layers described
above. A rupturable container, containing an alkaline processing composition including
a developing agent and an opacifier, is positioned between the top layer and a transparent
cover sheet which has thereon, in sequence, a neutralizing layer, and a timing 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 opacifier 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 development, diffuse to the image-receiving
layer to provide a positive, right-reading image which is viewed through the transparent
support on the opaque reflecting layer background.
[0028] Still other useful integral formats in which this invention can be employed are described
in U.S. Patents 3,415,644; 3,415,645; 3,415,646; 3,647,437 and 3,635,707.
[0029] The assemblage of the present invention is used to produce positive images in single
or multicolors. In a three-color system, each silver halide emulsion layer of the
film assembly will have associated therewith 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. The dye image-providing-material
associated with each silver halide emulsion layer is contained either in the silver
halide emulsion layer itself or in a layer contiguous to the silver halide emulsion
layer.
[0030] 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, catechol and 3-pyrazolidinone compounds. A combination of different
ETA's, such as those disclosed in U.S. Patent 3,039,869, can also be employed.
[0031] Use of a neutralizing material in the described assemblages increases the stability
of the transferred image. The neutralizing material will effect a reduction in the
pH of the image layer from about 13 or 14 to at least 11 and preferably 5 to 8 within
a short time after imbibition. Suitable materials and their functioning are disclosed
on pages 22 and 23 of the July 1974 edition of Research Disclosure, and pages 35 through
37 of the July 1975 edition of Research Disclosure.--
[0032] A timing or inert spacer layer can be employed over the neutralizing layer which
"times" or controls the pH 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 disclosed in the Research Disclosure articles mentioned in the paragraph above
concerning neutralizing layers.
[0033] 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 colloid layers, such as gelatin, in the photographic elements
of the invention in an alkaline medium and preferably when processed in a medium having
a pH 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 colloid layers of the photographic elements in an alkaline medium. "Mobile" has
the same meaning as "diffusible".
[0034] The term "associated therewith" as used herein is intended to mean that the materials
can be in either the same or different layers, so long as the materials are accessible
to one another.
[0035] The following examples are provided to further illustrate the invention.
Example 1
[0036] A) A control integral imaging-receiver (IIR) element was prepared by coating the
following layers in the order recited on a transparent poly(ethylene terephthalate)
film support. Quantities are parenthetically 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) (50:40:10 mole ratio) (1.6) and gelatin (0.75);
(3) Reflecting layer of titanium dioxide (17) and gelatin (2.6);
(4) Opaque layer of carbon black (0.95) and gelatin (0.65);
(5) Gelatin interlayer (0.54);
(6) Stripping layer of Natrosol° GXR-250 hydroxyethyl cellulose (0.81);
(7) Gelatin interlayer (0.65);
(8) Cyan dye releaser B of U.S. Patent 4,356,250 (0.37) and gelatin (0.54); and
(9) Gelatin overcoat (0.43).
[0037] It should be noted that layers 8 and 9 represent the top and bottom layers of a complete
IIR such as described in Example 1 of U.S. Patent 4,356,250. For purposes of this
test, it was not necessary to have a complete light-sensitive element.
[0038] B) An IIR similar to A) was prepared except that layer 7 also contained poly(methylmethacrylate)
beads (0.56), average particle diameter 0.5 µm, 47X PVC (pigment volume content).
[0039] C) An IIR similar to A) was prepared except that layer 7 also contained poly(methylmethacrylate)
beads (0.18), average particle diameter 0.5 µm, PVC 22%.
[0040] D) An IIR similar to A) was prepared except that layer 7 also contained DuPont Ludox°
AM colloidal silica (0.95), average particle diameter 0.012 pm, PVC 471.
[0041] E) An IIR similar to A) was prepared except that layer 7 also contained DuPont Ludox°
AM colloidal silica (0.32), average particle diameter 0.012 pm, PVC 23%.
[0042] F) An IIR similar to A) was prepared except that layer 7 also contained Cabot Regal
400 carbon black (0.95), average particle diameter 0.07 µm, PVC 50%.
[0043] G) An IIR similar to A) was prepared except that layer 7 also contained Cabot Regal
400 carbon black (0.32), average particle diameter 0.07 pm, PVC 25%.
[0044] H) An IIR similar to A) was prepared except that layer 7 also contained Gulf and
Western Horsehead Rutile titanium dioxide (1.8), average particle diameter 0.25 pm,
PVC 48%.
[0045] I) An IIR similar to A) was prepared except that layer 7 also contained Gulf and
Western Horsehead Rutile titanium dioxide (0.59), average particle diameter 0.25 pm,
PVC 24%.
[0046] The above coatings were prepared with nearly constant PVC percentages of particulate
material, thus the actual coated weights vary.
[0047] A "tape test" was run on the above IIR's. This test has a high correlation with actual
stripping performances in actual photographic coatings. The test consists of firmly
applying a short strip of 3M Scotch° 810 Magic Transparent Tape on the top of layer
9 of the IIR to be tested and then rapidly pulling on the tape.
[0048] IIR's B through I thus tested stripped at the point between layers 6 and 5, thus
indicating the weakest bond in the element. In control IIR A, a random discontinuous
stripping occurred.
[0049] 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 none-the-less stronger
than the bond between layers 6 and 5).
[0050] The following results were obtained:

[0051] The above results indicate that in all instances, 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 IIR elements B, D, F and H, a strong bond was obtained between layers 6
and 7 due to the higher concentration of particulate material employed.
Example 2
[0052] A) An IIR similar to that of A) in Example 1 was prepared except that after layer
7, the following layers were employed:
(8) Cyan redox dye-releaser layer,
(9) Gelatin interlayer,
(10) Red-sensitive silver halide emulsion layer,
(11) Gelatin interlayer,
(12) Magenta redox dye-releaser layer,
(13) Green-sensitive silver halide emulsion layer,
(14) Gelatin interlayer,
(15) Yellow redox dye-releaser layer,
(16) Blue-sensitive silver halide emulsion layer, and
(17) Gelatin overcoat layer.
[0053] Layers 8-17 are similar to those described in Example 1 of U.S. Patent 4,356,250
of Irani et al.
[0054] B) An IIR similar to A) was prepared except that layer 7 also contained DuPont Ludox°
AM colloidal silica (0.11), average particle diameter 0.012 µm, PVC of 9.
[0055] C) An IIR similar to A) was prepared except that layer 7 also contained DuPont Ludox°
AM colloidal silica (0.32), average particle diameter 0.012 pm, PVC of 23.
[0056] D) An IIR similar to A) was prepared except that layer 7 also contained DuPont Ludox°
AM colloidal silica (0.65), average particle diameter 0.012 µm, PVC of 38.
[0057] E) An IIR similar to A) was prepared except that layer 7 also contained DuPont Ludox°
AM colloidal silica (0.95), average particle diameter 0.012 µm, PVC of 48.
[0058] F) An IIR similar to A) was prepared except that layer 7 also contained CITGO (Columbia)
Carbon Raven 410° carbon black (0.11), average particle diameter 0.07 µm, PVC of 10.
[0059] G) An IIR similar to A) was prepared except that layer 7 also contained CITGO (Columbia)
Carbon Raven 410
0 carbon black (0.32), average particle diameter 0.07 µm, PVC of 25.
[0060] H) An IIR similar to A) was prepared except that layer 7 also contained CITGO (Columbia)
Carbon Raven 410° carbon black (0.65), average particle diameter 0.07 µm, PVC of 40.
[0061] I) An IIR similar to A) was prepared except that layer 7 also contained CITGO (Columbia)
Carbon Raven 410° carbon black (0.95), average particle diameter 0.07 µm, PVC of 52.
[0062] A cover sheet and processing pod were also prepared similar to those in Example 1
of U.S. Patent 4,356,250, and assembled into film assemblages.
[0063] The above film assemblages were exposed to a graduated density color test object
(to verify that the stripping layer and adjacent hydrophilic layer had no sensitimetric
effect). The assemblages were then processed by spreading the contents of the processing
pod between the cover sheet and IIR by using a pair of juxtaposed rollers. The film
assemblages, as assembled, were then incubated for 1 week at room temperature, 3 weeks
at room temperature, and 3 weeks at 32°C/15% RH. Each assemblage was then manually
peeled apart to separate the receiver portion from the upper silver halide emulsion
layers.
[0064] Ideally, separation should occur between layers 5 and 6 (designated as location 1).
Sometimes the separation occurred between layers 6 and 7 (designated as location 2).
This leaves objectionably visible irregular shaped areas of the stripping layer on
the back of the peeled receiver. In other instances, separation occurred in various
locations from layer 8 upward (designated as location 3). This is the least desirable
point of separation as the emulsion layer(s) and dye releaser layer(s) are retained
on the element with the image and may cause stain problems in addition to being visually
objectionable.
[0065] The data below show the stripping behavior for the different particulate materials
in layer 7, coated adjacent to stripping layer 6. The area percent separation is tabulated
by locations 1/2/3. Ideal separation would thus be 100/0/0; 100 area percent separation
between layers 5 and 6 for both wet (center) and dry (edge) areas. Very poor separation,
such as 30/60/10, indicates that less than one-third of the area separated between
layers 5 and 6, almost two-thirds of the stripping layer was retained on the back
of the separated receiver, and significant portions of the emulsion layers were fractured.
[0066] Separation is initiated in the dry outer mask area of the assemblage and continues
through the initially wet center image area. Thus, clean separation is desirable within
both the dry and wet areas of the assemblage as well as at the interface. The following
results were obtained:

[0067] The above results indicate that the addition of particulate material to layer 7 improved
both wet and dry stripping. In most cases, improved separation between layers 5 and
6 was obtained as the quantity of silica or carbon black was increased. Very high
levels should be avoided, however, as problems will arise with poor layer integrity
(spontaneous separation) and brittleness.