U.S. patent number 3,734,726 [Application Number 05/186,394] was granted by the patent office on 1973-05-22 for diffusible color coupler moieties are released from nondiffusible m-sulfoamidoanilines or m-sulfoamidophenols in diffusion transfer photographic products and processes.
This patent grant is currently assigned to Eastman Kodak Company. Invention is credited to John Figueras, Max H. Stern.
United States Patent |
3,734,726 |
Figueras , et al. |
May 22, 1973 |
DIFFUSIBLE COLOR COUPLER MOIETIES ARE RELEASED FROM NONDIFFUSIBLE
M-SULFOAMIDOANILINES OR M-SULFOAMIDOPHENOLS IN DIFFUSION TRANSFER
PHOTOGRAPHIC PRODUCTS AND PROCESSES
Abstract
Color, diffusion transfer photographic elements, film units and
processes are described which employ a nondiffusible, substantially
colorless m-sulfonamidoaniline or m-sulfonamidophenol which reacts
with oxidized color developing agent to release a coupler moiety
which couples with oxidized color developing agent to produce a
diffusible dye which diffuses to a dye image-receiving layer.
Inventors: |
Figueras; John (Rochester,
NY), Stern; Max H. (Rochester, NY) |
Assignee: |
Eastman Kodak Company
(Rochester, NY)
|
Family
ID: |
22684782 |
Appl.
No.: |
05/186,394 |
Filed: |
October 4, 1971 |
Current U.S.
Class: |
430/223; 430/543;
430/242; 430/552 |
Current CPC
Class: |
G03C
8/10 (20130101) |
Current International
Class: |
G03C
8/10 (20060101); G03C 8/02 (20060101); G03c
001/40 (); G03c 005/54 (); G03c 007/00 () |
Field of
Search: |
;96/3,22,29D,54,55,77,74,99,100 |
References Cited
[Referenced By]
U.S. Patent Documents
|
|
|
2543338 |
February 1951 |
Schmidt et al. |
|
Primary Examiner: Brown; J. Travis
Assistant Examiner: Suro Pico; Alfonso T.
Claims
We claim:
1. A photosensitive element comprising a support having thereon at
least one photosensitive silver halide emulsion layer, each said
silver halide emulsion layer having associated therewith a
nondiffusible m-sulfonamidoaniline or m-sulfonamidophenol which is
capable of reacting with oxidized, aromatic, primary amino color
developing agent to release a coupler moiety which is capable of
reacting with oxidized, aromatic, primary amino color developing
agent to produce a diffusible dye.
2. The photosensitive element of claim 1 wherein said sulfonamido
compound has the formula:
wherein:
1. COUP is a photographic coupler capable of reacting with
oxidized, aromatic, primary amino color developing agent to produce
a diffusible dye;
2. Ballast is an organic ballasting radical of such molecular size
and configuration as to render said alkali-cleavable compound
nondiffusible during development in an alkaline processing
composition; and
3. G is OR or NR.sub.1 R.sub.2 wherein R is hydrogen or a
hydrolyzable moiety and R.sub.1 and R.sub.2 are each hydrogen or an
alkyl group.
3. The photosensitive element of claim 2 wherein G is NR.sub.1
R.sub.2 wherein R.sub.1 and R.sub.2 are alkyl groups having eight
to 22 carbon atoms.
4. The photosensitive element of claim 1 wherein said sulfonamido
compound is present in said silver halide emulsion layer.
5. A photosensitive element comprising a support having thereon a
red-sensitive silver halide emulsion layer having associated
therewith a cyan dye image-providing material, a green-sensitive
silver halide emulsion layer having associated therewith a magenta
dye image-providing material, and a blue-sensitive silver halide
emulsion layer having associated therewith a yellow dye
image-providing material, at least one of said dye image-providing
materials being a nondiffusible m-sulfonamidoaniline or
m-sulfonamidophenol which is capable of reacting with oxidized,
aromatic, primary amino color developing agent to release a coupler
moiety which is capable of reacting with oxidized, aromatic,
primary amino color developing agent to produce a diffusible
dye.
6. The photosensitive element of claim 5 wherein said sulfonamido
compound has the formula:
wherein:
1. COUP is a photographic coupler capable of reacting with
oxidized, aromatic, primary amino color developing agent to produce
a diffusible dye;
2. Ballast is an organic ballasting radical of such molecular size
and configuration as to render said alkali-cleavable compound
nondiffusible during development in an alkaline processing
composition; and
3. G is OR or NR.sub.1 R.sub.2 wherein R is hydrogen or a
hydrolyzable moiety and R.sub.1 and R.sub.2 are each hydrogen or an
alkyl group.
7. A photographic film unit which is adapted to be processing by
passing said unit between a pair of juxtaposed pressure-applying
members comprising:
a. a photosensitive element comprising a support having thereon at
least one photosensitive silver halide emulsion layer, each said
silver halide emulsion layer having associated therewith a
nondiffusible m-sulfonamidoaniline or m-sulfonamidophenol which is
capable of reacting with oxidized, aromatic, primary amino color
developing agent to release a coupler moiety which is capable of
reacting with oxidized, aromatic, primary amino color developing
agent to produce a diffusible dye;
b. a dye image-receiving layer; and
c. means for discharging an alkaline processing composition within
said film unit;
said film unit containing an aromatic primary amino color
developing agent.
8. The film unit of claim 7 wherein said sulfonamido compound has
the formula:
wherein:
1. COUP is a photographic coupler capable of reacting with
oxidized, aromatic, primary amino color developing agent to produce
a diffusible dye;
2. Ballast is an organic ballasting radical of such molecular size
and configuration as to render said alkali-cleavable compound
nondiffusible during development in an alkaline processing
composition; and
3. G is OR or NR.sub.1 R.sub.2 wherein R is hydrogen or a
hydrolyzable moiety and R.sub.1 and R.sub.2 are each hydrogen or an
alkyl group.
9. The film unit of claim 8 wherein G is NR.sub.1 R.sub.2 wherein
R.sub.1 and R.sub.2 are alkyl groups having eight to 22 carbon
atoms.
10. The film unit of claim 7 wherein said sulfonamido compound is
present in said silver halide emulsion layer.
11. The film unit of claim 7 wherein said dye image-receiving layer
is located in said photosensitive element between said support and
the lowermost photosensitive silver halide emulsion layer.
12. The film unit of claim 7 wherein said dye image-receiving layer
is coated on a separate support and is adapted to be superposed on
said photosensitive element after exposure thereof.
13. The film unit of claim 12 wherein said discharging means is a
rupturable container and is so positioned during processing of said
film unit that a compressive force applied to said container by
said pressure-applying members will effect a discharge of the
container's contents between said dye image-receiving layer and the
outermost layer of said photosensitive element.
14. A photographic film unit which is adapted to be processed by
passing said unit between a pair of juxtaposed pressure-applying
members comprising:
a. a photosensitive element comprising a support having thereon a
red-sensitive silver halide emulsion layer having associated
therewith a cyan dye image-providing material, a green-sensitive
silver halide emulsion layer having associated therewith a magenta
dye image-providing material, and a blue-sensitive silver halide
emulsion layer having associated therewith a yellow dye
image-providing material;
b. a dye image-receiving layer; and
c. a rupturable container containing an alkaline processing
composition, said rupturable container being adapted to be
positioned during processing of said film unit so that a
compressive force applied to said container by said
pressure-applying members will effect a discharge of the
container's contents within said film unit;
said film unit containing an aromatic, primary amino color
developing agent; at least one of said dye image-providing
materials being a nondiffusible m-sulfonamidoaniline or
m-sulfonamidophenol which is capable of reacting with oxidized,
aromatic, primary amino color developing agent to release a coupler
moiety which is capable of reacting with oxidized, aromatic,
primary amino color developing agent to produce a diffusible
dye.
15. The film unit of claim 14 wherein said sulfonamido compound has
the formula:
wherein:
1. COUP is a photographic coupler capable of reacting with
oxidized, aromatic, primary amino color developing agent to produce
a diffusible dye;
2. Ballast is an organic ballasting radical of such molecular size
and configuration as to render said alkali-cleavable compound
nondiffusible during development in an alkaline processing
composition; and
3. G is OR or NR.sub.1 R.sub.2 wherein R is hydrogen or a
hydrolyzable moiety and R.sub.1 and R.sub.2 are each hydrogen or an
alkyl group.
16. A process for producing a photographic transfer image in color
comprising:
A. imagewise-exposing a photosensitive element comprising a support
having thereon at least one photosensitive silver halide emulsion
layer, each said silver halide emulsion layer having associated
therewith a dye image-providing material comprising a nondiffusible
m-sulfonamidoaniline or m-sulfonamidophenol which is capable of
reacting with oxidized, aromatic, primary amino color developing
agent to release a coupler moiety which is capable of reacting with
oxidized, aromatic, primary amino color developing agent to produce
a diffusible dye;
B. treating said photosensitive element with an alkaline processing
composition in the presence of an aromatic, primary amino color
developing agent to effect development of each of said exposed
silver halide emulsion layers, thereby oxidizing said developing
agent;
C. said oxidized developing agent thereby reacting with said
sulfonamido compound to release said coupler moiety which couples
with oxidized, aromatic, primary amino color developing agent to
form an imagewise distribution of diffusible dye as a function of
said imagewise exposure of each of said silver halide emulsion
layers; and
D. at least a portion of each of said imagewise distributions of
diffusible dye diffusing to a dye image-receiving layer to provide
a positive image.
17. The process of claim 16 wherein said treatment step B) is
effected by:
A. superposing over the layer most remote from the support of said
photosensitive element said dye image-receiving layer coated on a
support;
B. positioning a rupturable container containing an alkaline
processing composition between said exposed photosensitive element
and said dye image-receiving layer, said alkaline processing
composition containing said developing agent; and
C. applying a compressive force to said container to effect a
discharge of the container's contents between said most remote
layer of said exposed photosensitive element and said dye
image-receiving layer.
18. The process of claim 16 wherein said sulfonamido compound has
the formula:
wherein:
1. COUP is a photographic coupler capable of reacting with
oxidized, aromatic, primary amino color developing agent to produce
a diffusible dye;
2. Ballast is an organic ballasting radical of such molecular size
and configuration as to render said alkali-cleavable compound
nondiffusible during development in an alkaline processing
composition; and
3. G is OR or NR.sub.1 R.sub.2 wherein R is hydrogen or a
hydrolyzable moiety and R.sub.1 and R.sub.2 are each hydrogen or an
alkyl group.
19. The process of claim 18 wherein G is NR.sub.1 R.sub.2 wherein
R.sub.1 and R.sub.2 are alkyl groups having eight to 22 carbon
atoms.
20. The process of claim 16 wherein said sulfonamido compound is
present in said silver halide emulsion layer.
Description
This invention relates to photography and more particularly to
color, diffusion transfer photography employing dye image-providing
materials which are m-sulfonamidoanilines or m-sulfonamidophenols
which produce a diffusible dye upon reaction with a color
developing agent.
Color, diffusion transfer processes of the prior art such as U.S.
Pat. No. 2,983,606 generally involve the use of a photographic
element comprising a support, at least one silver halide emulsion
layer, and contained therein or contiguous thereto, a dye
developer. A liquid processing composition is applied to the
photosensitive element and permeates the emulsion to provide a
solution of the dye developer substantially uniformly distributed
therein. As the exposed silver halide emulsion is developed, the
oxidation product of the dye developer is immobilized or
precipitated in situ with the developed silver, thereby providing
an imagewise distribution of unoxidized dye developer dissolved in
the liquid processing composition. This immobilization is
apparently due, at least in part, to a change in the solubility
characteristics of the dye developer upon oxidation, and
particularly as regards its solubility in alkaline solutions. At
least part of this imagewise distribution of unoxidized
dye-developer is transferred to a superposed image-receiving layer
to provide the transfer image.
In these prior art systems, the developer moiety of the dye
developer is transferred with the dye to the image-receiving layer.
In the absence of some further treatment, such as pH reduction with
an acid, the developer moiety can undergo aerial oxidation which
will have a substantial effect upon the stability to light of the
resulting dye developer image. Accordingly, it would be highly
desirable to provide a transfer system in which only the desired
chemical entity, i.e., the dye, is transferred to the receiver.
U.S. Pat. No. 2,543,338 describes how an azine dye image may be
obtained by coupling oxidized color developing agent with
m-sulfonamidoaniline derivatives. These compounds do not contain a
second coupler moiety, however, which is capable of producing a
diffusible dye imagewise.
In U.S. Pats. Nos. 3,443,939, 3,443,940, 3,443,943, and 3,498,785
and Belgian Patent 718,505, "splittable" ring-closing compounds
such as dye developers are described wherein a diffusible dye
moiety is split off the compound and transferred to provide the
desired image while the remainder of the compound undergoes an
internal cyclization or ring-closing reaction. Since a preformed
dye is employed in these compounds, however, the location of these
compounds in a photographic element is restricted in order to avoid
speed loss. Thus, they must be placed in a layer underneath, with
respect to exposure direction, the emulsion layer with which they
are associated. It would be desirable to provide compounds which
could be incorporated anywhere in the photographic element such as
in the emulsion layer, as desired, in order to take advantage of
quicker access time to the developer, fewer number of layers to be
coated, etc.
It is therefore an object of this invention to provide photographic
elements, film units and processes for producing a photographic
transfer image in color wherein a substantially colorless dye
image-providing material is employed.
It is another object of this invention to provide a photographic
system wherein the dye image-providing material can be located in
or above its associated emulsion layer with respect to the exposure
direction.
It is still a further object of this invention to provide
photographic systems for producing photographic transfer images in
color in which the dye image-receiving layer can either be located
on a separate support or can be located integral with the
photosensitive element.
These and other objects are achieved by our invention which is
described hereinafter.
A photographic film unit according to our invention which is
adapted to be processed by passing the unit between a pair of
juxtaposed pressure-applying members comprises:
a. a photosensitive element comprising a support having thereon at
least one photosensitive silver halide emulsion layer, each silver
halide emulsion layer having associated therewith a nondiffusible
m-sulfonamidoaniline or m-sulfonamidophenol which is capable of
reacting with oxidized, aromatic, primary amino color developing
agent to release a coupler moiety which is capable of coupling with
oxidized, aromatic, primary amino color developing agent to produce
a diffusible dye;
b. a dye image-receiving layer; and
c. means for discharging an alkaline processing composition within
said film unit, preferably a rupturable container which is adapted
to be positioned during processing of said film unit so that a
compressive force applied to said container by the
pressure-applying members will effect a discharge of the
container's contents within said film unit;
the film unit containing an aromatic, primary amino color
developing agent.
A photosensitive element according to our invention is set forth in
a) in the film unit described above.
The above-described sulfonamido compounds may be represented by the
following formula:
wherein:
1. COUP is a photographic coupler capable of reacting with oxidized
aromatic primary amino color developing agent to produce a
diffusible dye,
2. Ballast is an organic ballasting radical of such molecular size
and configuration as to render the compound nondiffusible during
development in an alkaline processing composition; and
3. G is OR or NR.sub.1 R.sub.2 wherein R is hydrogen or a
hydrolyzable moiety and R.sub.1 and R.sub.2 are each hydrogen or an
alkyl group.
A process for producing a photographic transfer image in color
according to our invention comprises:
a. treating the above-described photosensitive element with an
alkaline processing composition in the presence of said silver
halide developing agent to effect development of each of the
exposed silver halide emulsion layers, thereby oxidizing the
developing agent;
b. the oxidized developing agent thereby reacting with each
sulfonamido compound to release the coupler moiety, which couples
with oxidized color developing agent to form an image-wise
distribution of diffusible dye as a function of the imagewise
exposure of each of the silver halide emulsion layers; and
c. at least a portion of each of the imagewise distributions of
diffusible dye diffusing to a dye image-receiving layer to provide
a positive image.
The photosensitive 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. In general, the processing
composition employed in our system contains the developing agent
for development although the composition could also just be an
alkaline solution where the developer is incorporated in the
photosensitive element, in which case the alkaline solution serves
to activate the incorporated developer.
The dye image-receiving layer in the above-described film unit can
be located on a separate support adapted to be superposed on the
photosensitive element after exposure thereof. Such image-receiving
elements are generally disclosed, for example, in U.S. Pat. No.
3,362,819. A rupturable container is employed and is positioned in
relation to the photosensitive element and the image-receiving
element so that a compressive force applied to the container by
pressure-applying members, such as would be found in a typical
camera used for in-camera processing, will effect a discharge of
the container's contents between the image-receiving element and
the outermost layer of the photosensitive element. After
processing, the dye image-receiving element is separated from the
photosensitive element.
The dye image-receiving layer in the above-described film unit can
also be located integral with the photosensitive element between
the support and the lowermost photosensitive silver halide emulsion
layer. A general format for integral receiver-negative
photosensitive elements is disclosed in copending U.S. application
Ser. No. 115,459 of Barr, Bush and Thomas filed Feb. 16, 1971 and
now abandoned. In such an embodiment, the support for the
photosensitive element is transparent and is coated with an
image-receiving layer, a substantially opaque light-reflective
layer, e.g., TiO.sub.2, and then the photosensitive layer or layers
described above. After exposure of the photosensitive element, a
rupturable container containing an alkaline processing composition
and an opaque process sheet are brought into superposed position.
Pressure-applying members in the camera rupture the container and
spread processing composition over the photosensitive element as
the film unit is withdrawn from the camera. The processing
composition develops each exposed silver halide emulsion layer and
dye images are formed as a function of development which 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. For other details concerning the
format of this particular integral film unit, reference is made to
the above-mentioned Barr, Bush and Thomas U.S. application Ser. No.
115,459.
Another format for integral negative-receiver photo-sensitive
elements in which the present invention can be employed is
disclosed in Cole U.S. application Ser. No. 115,552 filed Feb. 16,
1971 and now abandoned. In this embodiment, the support for the
photosensitive element is transparent and is coated with the
image-receiving layer, a substantially opaque, light-reflective
layer, the photosensitive layer or layers described above, and a
top transparent sheet. A rupturable container containing an
alkaline processing composition and an opacifier is positioned
adjacent to the top layer and sheet. The film unit is placed in a
camera, exposed through the top transparent 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-sensitive. The
processing composition develops each silver halide layer and dye
images are formed as a result of development which 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. For further details concerning the
format of this particular integral film unit, reference is made to
the above-mentioned Cole U.S. application Ser. No. 115,552.
In the formula listed above for our compounds which are
alkali-cleavable upon oxidation, R is preferably hydrogen, although
it could be any hydrolyzable entity well known to those skilled in
the art, e.g., acetyl, mono-, di- or trichloroacetyl radicals,
perfluoracyl, pyruvyl, alkoxyacyl, nitrobenzoyl, cyanobenzoyl,
sulfonyl, sulfinyl, etc.
In the above formula describing our compounds, R.sub.1 and R.sub.2
are each preferably hydrogen although one or both could be an alkyl
group of from one to 22 carbon atoms which could serve as the
Ballast group indirectly attached to the ring as defined below.
The nature of the ballast group in the formula for the compounds
described above (Ballast) is not critical as long as it confers
nondiffusibility to the compounds. Typical ballast groups include
long-chain alkyl radicals linked directly or indirectly to the
compound as well as aromatic radicals of the benzene and
naphthalene series indirectly attached or fused directly to the
benzene nucleus, etc. Useful ballast groups generally have at least
8 carbon atoms.
In addition to Ballast, the benzene nucleus in the above formula
may have groups attached thereto such as the halogens, alkyl, aryl,
alkoxy, aryloxy, nitro, amino, alkylamino, arylamino, amido, cyano,
alkylmercapto, keto, carboalkoxy, etc. In addition, such groups may
combine together with the carbon atoms to which they are attached
on the ring to form another ring which may be saturated or
unsaturated including a carbocyclic ring, a heterocyclic ring,
etc.
As previously mentioned, Coup in the above formula represents a
photographic coupler. Coupler compounds are well known to those
skilled in the art and include a phenol, naphthol, indazolone,
open-chain benzoyl acetanilide, pivalylacetanilide, malonamide,
malonanilide, cyanoacetyl, coumarone, pyrazolone, compounds
described in U.S. Patent 2,756,142, etc. These compounds may
contain a solubilizing group if desired.
Compounds within the scope of our invention include the
following:
Compounds No. 1 Yellow dye-forming compounds
Compound No. 2 Yellow dye-forming compound
Compound No. 3 Magenta dye-forming compound ##SPC1##
Compound No. 4 Cyan dye-forming compound ##SPC2##
Compound No. 5 Cyan dye-forming compound ##SPC3##
Compound No. 6 Cyan dye-forming compound ##SPC4##
Of the above compounds, especially good results are obtained with
Compound Nos. 1, 2 and 3.
The film unit or assembly of the present invention may be 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 possessing
a spectral absorption range substantially complementary to the
predominant sensitivity range of its associated emulsion, i.e., the
blue-sensitive silver halide emulsion layer will have a yellow dye
image-providing material associated therewith, 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 associated with each silver halide
emulsion layer may be contained either in the silver halide
emulsion layer itself or in a layer contiguous to the silver halide
emulsion layer. Since our dye image-providing materials are
substantially colorless, they are preferably located in the silver
halide emulsion itself without loss of photographic speed. This is
advantageous since a separate layer for the dye image-providing
material is not required.
The concentration of the dye image-providing compounds that are
employed in the present invention may be varied over a wide range
depending upon the particular compound employed and the results
which are desired. For example, the compounds of the present
invention may be coated in layers by using coating solutions
containing between about 0.5 and about 8 percent by weight, of the
dye image-providing compound distributed in a hydrophilic
film-forming natural material or synthetic polymer, such as
gelatin, polyvinyl alcohol, etc., which is adapted to be permeated
by aqueous alkaline processing composition.
As previously mentioned, the aromatic primary amino color
developing agent employed in our invention is preferably present in
the alkaline processing composition in the rupturable pod. The
color developing agent can also be incorporated into the
photosensitive element as a separate layer, e.g., by employing a
Schiff base derivative of an aromatic primary amino color
developing agent such as that formed by reacting
o-sulfobenzaldehyde and N,N-diethyl-3-methyl-4-aminoaniline. Such
incorporated developing agent will be activated by the alkaline
processing composition. While the incorporated developing agent can
be positioned in any layer of the photosensitive element from which
it can be readily made available for development upon activation
with alkaline processing composition, it is generally either
incorporated in the light-sensitive silver halide emulsion layers
or in layers contiguous thereto. The aromatic primary amino color
developing agents employed in this invention are preferably
p-phenylenediamine or p-aminophenol color developing agents. These
developing agents are well known to those skilled in the art.
Although it is not intended to limit the present invention to any
particular theory or reaction mechanism, it is believed that the
following chemical reactions take place according to a particular
process of the invention: ##SPC5##
In using the dye image-providing compounds according to our
invention, the production of diffusible dye images is a function of
the reduction of developable silver halide images which may involve
direct or reversal development of the silver halide emulsions with
a silver halide developing agent. If the silver halide emulsion
employed is a direct-positive silver halide emulsion, such as an
internal-image emulsion or a solarizing emulsion, which is
developable in unexposed areas, a positive image can be obtained on
the dye image-receiving layer. After exposure of the film 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 imagewise
corresponding to the unexposed areas of the direct-positive silver
halide emulsion layers. The oxidized developing agent then reacts
with the dye image-providing compounds to release a coupler moiety
which in turn couples with oxidized color developing agent to form
diffusible dyes imagewise as a function of the imagewise exposure
of each of the silver halide emulsion layers. At least a portion of
the imagewise distributions of diffusible dyes diffuses to the
image-receiving layer to form a positive image of the original
subject. After being contacted by the alkaline processing
composition, a pH-lowering layer in the film unit or
image-receiving unit (if such a layer is needed) lowers the pH of
the film unit or image-receiver to stabilize the image.
Internal image silver halide emulsions useful in the
above-described embodiment are direct positive emulsions that form
latent images predominantly inside the silver halide grains, as
distinguished from silver halide grains that form latent images
predominantly on the surface thereof. Such internal image emulsions
were described by Davey et al in U.S. Pat. No. 2,592,250 issued
Apr. 8, 1952, and elsewhere in the literature. Internal image
silver halide emulsions can be defined in terms of the increased
maximum density obtained when developed with "internal-type"
developers over that obtained when developed with "surface-type"
developers. Suitable internal image emulsions are those which, when
measured according to normal photographic techniques by coating a
test portion of the silver halide emulsion on a transparent
support, exposing to a light intensity scale having a fixed time
between 0.01 and 1 second, and developing for 3 minutes at
20.degree.C. in Developer A below (internal-type developer), have a
maximum density at least five times the maximum density obtained
when an equally exposed silver halide emulsion is developed for 4
minutes at 20.degree.C. in Developer B described below
(surface-type developer). Preferably, the maximum density in
Developer A is at least 0.5 density unit greater than the maximum
density in Developer B.
DEVELOPER A
Hydroquinone 15 g. Monomethyl-p-aminophenol sulfate 15 g. Sodium
sulfite (desiccated) 50 g. Potassium bromide 10 g. Sodium hydroxide
25 g. Sodium thiosulfate 20 g. Water to make one liter.
DEVELOPER B
P-hydroxyphenylglycine 10 g. Sodium carbonate 100 g. Water to make
1 liter
The solarizing direct positive silver halide emulsions useful in
the above-described embodiment are well-known silver halide
emulsions which have been effectively fogged either chemically or
by radiation to a point which corresponds approximately to the
maximum density of the reversal curve as shown by Mees, The Theory
of the Photographic Process, published by the Macmillan Co., New
York, New York, 1942, pages 261-297. Typical methods for the
preparation of solarizing emulsions are shown by Groves British
Patent 443,245, Feb. 25, 1936, who subjected emulsions to Roentgen
rays "until an emulsion layer formed therefrom, when developed
without preliminary exposure, is blackened up to the apex of its
graduation curve;" Szaz British Patent 462,730, Mar. 15, 1937, the
use of either light or chemicals such as silver nitrate, organic
sulfur compounds and dyes to convert ordinary silver halide
emulsions to solarizing direct positive emulsions; and Arens U.S.
Pat. No. 2,005,837, June 25, 1935, the use of silver nitrate and
other compounds in conjunction with heat to effect solarization.
Kendall and Hill U.S. Pat. No. 2,541,472, Feb. 13, 1951, shows
useful solarized emulsions particularly susceptible to exposure
with long wavelength light and initial development to produce the
Herschel effect described by Mees above, produced by adding
benzothiazoles and other compounds to the emulsions which are
fogged either chemically or with white light. In using the
emulsions a sufficient reversal image exposure is employed using
minus blue light of from about 500-700 m.mu. wavelength preferably
520-554 m.mu., to substantially destroy the latent image in the
silver halide grains in the region of the image exposure.
Particularly useful are the fogged direct-positive emulsions of
Berriman U.S. Pat. No. 3,367,778; Illingsworth U.S. Pats. Nos.
3,501,305, 3,501,306 and 3,501,307; and combinations thereof.
Internal image silver halide emulsions which contain or which are
processed in the presence of fogging or nucleating agents are
particularly useful in the above-described embodiment since the use
of fogging agents is a convenient way to inject electrons into the
silver halide grains. Suitable fogging agents include the
hydrazines disclosed in Ives U.S. Pats. Nos. 2,588,982 issued Mar.
11, 1952 and 2,563,785 issued Aug. 7, 1951; the hydrazides and
hydrazones disclosed in Whitmore U.S. Pat. No. 3,227,552 issued
Jan. 4, 1966; hydrazone quaternary salts described in Lincoln and
Heseltine application Ser. No. 828,064 filed Apr. 28, 1969; or
mixtures thereof. The quantity of fogging agent employed can be
widely varied depending upon the results desired. Generally, the
concentration of fogging agent is from about 1 to about 20 mg. per
square foot of photosensitive layer in the photosensitive element
or from about 0.1 to about 2 grams per liter of developer it it is
located in the developer.
Other embodiments in which our imaging chemistry can be employed
include the techniques described in U.S. Pats. Nos. 3,227,550;
3,227,551; 3,227,552; and in British Patent 904,364, p. 19, lines
1-41, wherein our dye image-providing materials are substituted for
the nondiffusible couplers described therein. For example, a film
unit using development inhibitor-releasing couplers as described in
U.S. Pat. No. 3,227,551 may be employed in conjunction with the dye
image-providing materials described herein.
Another embodiment of our invention uses the image-reversing
technique disclosed in British Patent 904,364, page 19, lines 1-41.
In this system our alkali-cleavable compounds are used in
combination with physical development nuclei in a nuclei layer
contiguous to the photosensitive silver halide emulsion layer. The
film unit contains a silver halide solvent, preferably in a
rupturable container with the alkaline processing composition, and
the photosensitive element contains an immobilizing coupler, which
is capable of reacting with oxidized developer to form an immobile
product.
Spectral sensitizing dyes can be used conveniently to confer
additional sensitivity to the light sensitive silver halide
emulsion of the multilayer photographic elements of the invention.
For instance, additional spectral sensitization can be obtained by
treating the emulsion with a solution of a sensitizing dye in an
organic solvent or the dye may be added in the form of a dispersion
as described in Owens et al British Patent 1,154,781 issued June
11, 1969. For optimum results, the dye can either be added to the
emulsion as a final step or at some earlier stage.
Sensitizing dyes useful in sensitizing such emulsions are
described, for example, in Brooker et al, U.S. Pat. No. 2,526,632,
issued Oct. 24, 1950; Sprague U.S. Pat. No. 2,503,776, issued Apr.
11, 1950; Brooker et al U.S. Pat. No. 2,493,748, issued Jan. 10,
1950; and Taber et al, U.S. Pat. No. 3,384,486 issued May 21, 1968.
Spectral sensitizers which can be used include the cyanines,
merocyanines, complex (tri or tetranuclear) merocyanines, complex
(tri or tetranuclear) cyanines, holopolar cyanines, styryls,
hemicyanines (e.g. enamine hemicyanines), oxonols and hemioxonols.
Dyes of the cyanine classes can contain such basic nuclei as the
thiazolines, oxazolines, pyrrolines, pyridines, oxazoles,
thiazoles, selenazoles and imidazoles. Such nuclei can contain
alkyl, alkylene, hydroxyalkyl, sulfoalkyl, carboxyalkyl, aminoalkyl
and enamine groups and can be fused to carbocyclic or hetrocyclic
ring systems either unsubstituted or substituted with halogen,
phenyl, alkyl, haloalkyl, cyano, or alkoxy groups. The dyes can be
symmetrical or unsymmetrical and can contain alkyl, phenyl, enamine
or heterocyclic substituents on the methine or polymethine chain.
The merocyanine dyes can contain the basic nuclei mentioned above
as well as acid nuclei such as thiohydantoins, rhodanines,
oxazolidenediones, thiazolidenediones, barbituric acids,
thiazolineones, and malononitrile. These acid nuclei can be
substituted with alkyl, alkylene, phenyl, carboxyalkyl, sulfoalkyl,
hydroxyalkyl, alkoxyalkyl, alkylamino groups, or heterocyclic
nuclei. Combinations of these dyes can be used, if desired. In
addition, supersensitizing addenda which do not absorb visible
light can be included, for instance, ascorbic acid derivatives,
azaindenes, cadmium salts, and organic sulfonic acids as described
in McFall et al U.S. Pat. No. 2,933,390 issued Apr. 19, 1960 and
Jones et al U.S. Pat. No. 2,937,089 issued May 17, 1960.
The various silver halide emulsion layers of a color film assembly
of the invention can be 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 Carey Lea silver layer can be present between the
blue-sensitive and green-sensitive silver halide emulsion layer for
absorbing or filtering blue radiation that may be 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, followed by the red-sensitive and
green-sensitive layers.
The silver halide emulsions used in this invention can comprise,
for example, silver chloride, silver bromide, silver chlorobromide,
silver bromoiodide, silver chlorobromoiodide or mixtures thereof.
The emulsions can be coarse or fine grain and can be prepared by
any of the well-known procedures, e.g., single jet emulsions such
as those described in Trivelli and Smith, The Photographic Journal,
Vol. LXXIX, May, 1939 (pp 330-338), double jet emulsions, such as
Lippmann emulsions, ammoniacal emulsions, thiocyanate or thioether
ripened emulsions such as those described in Nietz et al U.S. Pat.
No. 2,222,264 issued Nov. 19, 1940; Illingsworth U.S. Pat. No.
3,320,069 issued May 16, 1967; and McBride U.S. Pat. No. 3,271,157
issued Sept. 6, 1966. Surface image emulsions can be used or
internal image emulsions can be used such as those described in
Davey et al U.S. Pat. No. 2,592,250 issued May 8, 1952; Porter et
al U.S. Pat. No. 3,206,313 issued Sept. 14, 1965; Berriman U.S.
Pat. No. 3,367,778 issued Feb. 6, 1968; and Bacon et al U.S. Pat.
No. 3,447,927 issued June 3, 1969. The emulsions may be regular
grain emulsions such as the type described in Klein and Moisar, J.
Phot. Sci., Vol. 12, No. 5, Sept./Oct., 1964, (pp. 242-251).
Negative type emulsions may be used or direct positive emulsions
may be used such as those described in Leermakers U.S. Pat. No.
2,184,013 issued Dec. 19, 1939; Kendall et al U.S. Pat. No.
2,541,472 issued Feb. 13, 1951; Berriman U.S. Pat. No. 3,367,778
issued Feb. 6, 1968; Schouwenaars British Patent 723,019 issued
Feb. 2, 1955; Illingsworth et al French Patent 1,520,821 issued
Mar. 4, 1968; Illingsworth U.S. Pat. No. 3,501,307 issued Mar. 17,
1970; Ives U.S. Pat. No. 2,563,785 issued Aug. 7, 1951; Knott et al
U.S. Pat. No. 2,456,953 issued Dec. 21, 1948; and Land U.S. Pat.
No. 2,861,885 issued Nov. 25, 1958.
The emulsions used with this invention may be sensitized with
chemical sensitizers, such as with reducing agents; sulfur,
selenium or tellurium compounds; gold, platinum or palladium
compounds; or combinations of these. Suitable procedures are
described in Sheppard et al U.S. Pat. No. 1,623,499 issued Apr. 5,
1927; Waller et al U.S. Pat. No. 2,399,083 issued Apr. 23, 1946;
McVeigh U.S. Pat. No. 3,297,447 issued Jan. 10, 1967; and Dunn U.S.
Pat. No. 3,297,446 issued Jan. 10, 1967.
The silver halide emulsions used with this invention may contain
speed increasing compounds such as polyalkylene glycols, cationic
surface active agents and thioethers or combinations of these as
described in Piper U.S. Pat. No. 2,886,437 issued May 12, 1959;
Dann et al U.S. Pat. No. 3,046,134 issued July 24, 1962; Carroll et
al U.S. Pat. No. 2,944,900 issued July 12, 1960; and Goffe U.S.
Pat. No. 3,294,540 issued Dec. 27, 1966.
The silver halide emulsions used in the practice of this invention
can be protected against the production of fog and can be
stabilized against loss of sensitivity during keeping. Suitable
antifoggants and stabilizers each used alone or in combination
include thiazolium salts described in Brooker et al U.S. Pat. No.
2,131,038 issued Sept. 27, 1938; and Allen et al U.S. Pat. No.
2,694,716 issued Nov. 16, 1954; the azaindenes described in Piper
U.S. Pat. No. 2,886,437 issued May 12, 1959; and Heimbach et al
U.S. Pat. No. 2,444,605 issued July 6, 1948; the mercury salts as
described in Allen et al U.S. Pat. No. 2,728,663 issued Dec. 27,
1955; the urazoles described in Anderson et al U.S. Pat. No.
3,287,135 issued Nov. 22, 1966; the sulfocatechols described in
Kennard et al U.S. Pat. No. 3,236,652 issued Feb. 22, 1966; the
oximes described in Carroll et al British Patent 623,448 issued May
18, 1949; nitron; nitroindazoles; the mercaptotetrazoles described
in Kendall et al U.S. Pat. No. 2,403,927 issued July 16, 1946;
Kennard et al U.S. Pat. No. 3,266,897 issued Aug. 16, 1966; and
Luckey et al U.S. Pat. No. 3,397,987 issued Aug. 20, 1968; the
polyvalent metal salts described in Jones U.S. Pat. No. 2,839,405
issued June 17, 1958; the thiuronium salts described in Herz et al
U.S. Pat. No. 3,220,839 issued Nov. 30, 1965; the palladium,
platinum and gold salts described in Trivelli et al U.S. Pat. No.
2,566,263 issued Aug. 28, 1951; and Yutzy et al U.S. Pat. No.
2,597,915 issued May 27, 1952.
The rupturable container employed in this invention can be of the
type disclosed in U.S. Pat. Nos. 2,543,181; 2,643,886; 2,653,732;
2,723,051; 3,056,492; 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 contained.
In a color film unit according to this invention, each silver
halide emulsion layer containing a dye image-providing material or
having the dye image-providing material present in a contiguous
layer may be separated from the other silver halide emulsion layers
in the negative portion of the film unit by materials including
gelatin, calcium alginate, or any of those disclosed in U.S. Pat.
No. 3,384,483, polymeric materials such as polyvinylamides as
disclosed in U.S. Pat. No. 3,421,892, or any of those disclosed in
French Patent 2,028,236 or U.S. Pat. Nos. 2,992,104; 3,043,692;
3,044,873; 3,061,428; 3,069,263; 3,069,264; 3,121,011; and
3,427,158.
Generally speaking, except where noted otherwise, the silver halide
emulsion layers in the invention comprise photosensitive silver
halide dispersed in gelatin and are about 0.6 to 6 microns in
thickness and the alkaline solution-permeable polymeric
interlayers, e.g., gelatin, are about 1 to 5 microns in thickness.
Of course these thicknesses are approximate only and can be
modified according to the product desired. In addition to gelatin,
other suitable hydrophilic materials which can be employed include
both naturallyoccurring substances such as proteins, e.g., gelatin
derivatives, cellulose derivatives, polysaccharides such as
dextran, gum arabic and the like; and synthetic polymeric
substances such as water soluble polyvinyl compounds like
poly(vinylpyrrolidone), acrylamide polymers and the like.
The photographic emulsion layers and other layers of a photographic
element employed in the practice of this invention can also contain
alone or in combination with hydrophilic, water-permeable colloids,
other synthetic polymeric compounds such as dispersed vinyl
compounds such as in latex form and particularly those which
increase the dimensional stability of the photographic materials.
Suitable synthetic polymers include those described for example, in
Nottorf U.S. Pat. No. 3,142,568 issued July 28, 1964; White U.S.
Pat. No. 3,193,386 issued July 6, 1965; Houck et al U.S. Pat. No.
3,062,674 issued Nov. 6, 1962; Houck et al U.S. Pat. No. 3,220,844
issued Nov. 30, 1965; Ream et al U.S. Pat. No. 3,287,289 issued
Nov. 22, 1966; and Dykstra U.S. Pat. No. 3,411,911 issued Nov. 19,
1968. Particularly effective are those water-insoluble polymers of
alkyl acrylates and methacrylates, acrylic acid, sulfoalkyl
acrylates or methacrylates, those which have cross-linking sites
which facilitate hardening or curing described in Smith U.S. Pat.
No. 3,488,708 issued Jan. 6, 1970, and those having recurring
sulfobetaine units as described in Dykstra Canadian Patent
774,054.
Any material can be employed as the image-receiving layer in this
invention as long as the desired function of mordanting or
otherwise fixing the dye images will be obtained. The particular
material chosen will, of course, depend upon the dye to be
mordanted. If acid dyes are to be mordanted, the image-receiving
layer can contain basic polymeric mordants such as polymers of
amino guanidine derivatives of vinyl methyl ketone such as
described in Minsk U.S. Pat. No. 2,882,156 issued Apr. 14, 1959,
and basic polymeric mordants such as described in copending U.S.
application Ser. No. 100,491 of Cohen et al filed Dec. 21, 1970.
Other mordants useful in our invention include poly4-vinylpyridine,
the 2-vinyl pyridine polymer metho-p-toluene sulfonate and similar
compounds described in Sprague et al U.S. Pat. No. 2,484,430 issued
Oct. 11, 1949, and cetyl trimethylammonium bromide, etc. Effective
mordanting compositions are also described in Whitmore U.S. Pat.
No. 3,271,148 and Bush U.S. Pat. No. 3,271,147, both issued Sept.
6, 1966.
Furthermore, the image-receiving layer can be sufficient by itself
to mordant the dye as in the case of use of an alkaline
solution-permeable polymeric layer such as N-methoxymethyl
polyhexylmethylene adipamide; partially hydrolyzed polyvinyl
acetate; polyvinyl alcohol with or without plasticizers; cellulose
acetate; gelatin; and other materials of a similar nature.
Generally, good results are obtained when the image-receiving
layer, preferably alkaline solution-permeable, is transparent and
about 0.25 to about 0.40 mil in thickness. This thickness, of
course, can be modified depending upon the result desired. The
image-receiving layer can also contain ultraviolet absorbing
materials to protect the mordanted dye images from fading due to
ultraviolet light, brightening agents such as the stilbenes,
coumarins, triazines, oxazoles, dye stabilizers such as the
chromanols, alkylphenols, etc.
Use of a pH-lowering material in the dye image-receiving element of
a film unit according to the invention will usually increase the
stability of the transferred image. Generally, the pH-lowering
material will effect a reduction in the pH of the image layer from
about 13 or 14 to at least 11 and preferably 5-8 within a short
time after imbibition. For example, polymeric acids as disclosed in
U.S. Pat. No. 3,362,819 or solid acids or metallic salts, e.g.,
zinc acetate, zinc sulfate, magnesium acetate, etc., as disclosed
in U.S. Pat. No. 2,584,030 may be employed with good results. Such
pH-lowering materials reduce the pH of the film unit after
development to terminate development and substantially reduce
further dye transfer and thus stabilize the dye image.
An inert timing or spacer layer can be employed in the practice of
our invention over the pH-lowering 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
include gelatin, polyvinyl alcohol or any of those disclosed in
U.S. Pat. No. 3,455,686. The timing layer is also effective in
evening out the various reaction rates over a wide range of
temperatures, e.g., premature pH reduction is prevented when
imbibition is effected at temperatures above room temperature, for
example, at 95.degree. to 100.degree.F. The timing layer is usually
about 0.1 to about 0.7 mil in thickness. Especially good results
are obtained when the timing layer comprises a hydrolyzable polymer
or a mixture of such polymers which are slowly hydrolyzed by the
processing composition. Examples of such hydrolyzable polymers
include polyvinyl acetate, polyamides, cellulose esters, etc.
The alkaline processing composition employed in this invention is
the conventional aqueous solution of an alkaline material, e.g.,
sodium hydroxide, sodium carbonate or an amine such as
diethylamine, preferably possessing a pH in excess of 11, and
preferably containing a developing agent as described previously.
The solution also preferably contains a viscosity-increasing
compound such as a high-molecular-weight polymer, e.g., a
water-soluble ether inert to alkaline solutions such as
hydroxyethyl cellulose or alkali metal salts of carboxymethyl
cellulose such as sodium carboxymethyl cellulose. A concentration
of viscosity-increasing compound of about 1 to about 5 percent by
weight of the processing composition is preferred which will impart
thereto a viscosity of about 100 cps. to about 200,000 cps. In
certain embodiments of our invention, an opacifying agent, e.g.,
TiO.sub.2, carbon black, etc., may be added to the processing
composition.
While the alkaline processing composition used in this invention
can be employed in a rupturable container, as described previously,
to conveniently facilitate the introduction of processing
composition into the film unit, other methods of inserting
processing composition into the film unit could also be employed,
e.g., interjecting processing solution with communicating members
similar to hypodermic syringes which are attached either to a
camera or camera cartridge.
The alkaline solution-permeable, substantially opaque,
light-reflective layer employed in certain embodiments of
photographic film units of our invention can generally comprise any
opacifier dispersed in a binder as long as it has the desired
properties. Particularly desirable are white light-reflective
layers since they would be esthetically pleasing backgrounds on
which to view a transferred dye image and would also possess the
optical properties desired for reflection of incident radiation.
Suitable opacifying agents include titanium dioxide, barium
sulfate, zinc oxide, barium stearate, silver flake, silicates,
alumina, zirconium oxide, zirconium acetyl acetate, sodium
zirconium sulfate, kaolin, mica, or mixtures thereof in widely
varying amounts depending upon the degree of opacity desired. The
opacifying agents may be dispersed in any binder such as an
alkaline solution-permeable polymeric matrix such as, for example,
gelatin, polyvinyl alcohol, and the like. Brightening agents such
as the stilbenes, coumarins, triazines and oxazoles can also be
added to the light-reflective layer, if desired. When it is desired
to increase the opacifying capacity of the light-reflective layer,
dark-colored opacifying agents, e.g., carbon black, nigrosine dyes,
etc., may be added to it, or coated in a separate layer adjacent to
the light-reflective layer.
The supports for the photographic elements of this invention can be
any material as long as it does not deleteriously effect the
photographic properties of the film unit and is dimensionally
stable. Typical flexible sheet materials include cellulose nitrate
film, cellulose acetate film, poly(vinyl acetal) film, polystyrene
film, poly(ethyleneterephthalate) film, polycarbonate film,
poly-.alpha.-olefins such as polyethylene and polypropylene film,
and related films or resinous materials as well as glass, paper,
metal, etc. The support is usually about 2 to 6 mils in
thickness.
While the invention has been described with reference to layers of
silver halide emulsions and dye image-providing materials, dotwise
coating, such as would be obtained using a gravure printing
technique, could also be employed. In this technique, small dots of
blue, green and red-sensitive emulsions have associated therewith,
respectively, dots of yellow, magenta and cyan color-providing
substances. After development, the transferred dyes would tend to
fuse together into a continuous tone.
The photographic layers employed in the practice of this invention
may contain surfactants such as saponin; anionic compounds such as
the alkyl aryl sulfonates described in Baldsiefen, U.S. Pat. No.
2,600,831 issued June 17, 1952; amphoteric compounds such as those
described in Ben-Ezra, U.S. Pat. No. 3,133,816 issued May 19, 1964;
and water-soluble adducts of glycidol and an alkyl phenol such as
those described in Olin Mathieson, British Patent 1,022,878 issued
Mar. 16, 1966; and Knox, U.S. Pat. No. 3,514,293 issued May 26,
1970.
The various layers, including the photographic layers, employed in
the practice of this invention can contain light-absorbing
materials and filter dyes such as those described in Sawdey, U.S.
Pat. No. 3,253,921 issued May 31, 1966; Gaspar, U.S. Pat. No.
2,274,782 issued Mar. 3, 1942; Silberstein et al, U.S. Pat. No.
2,527,583 issued Oct. 31, 1950; and VanCampen, U.S. Pat. No.
2,956,879 issued Oct. 18, 1960.
The sensitizing dyes and other addenda used in the practice of this
invention can be added from water solutions or suitable organic
solvent solutions may be used. The compounds can be added during
various procedures including those described in Collins et al U.S.
Pat. No. 2,912,343 issued Nov. 10, 1959; McCrossen et al U.S. Pat.
No. 3,342,605 issued Sept. 19, 1967; Audran U.S. Pat. No. 2,996,287
issued Aug. 15, 1961 and Johnson et al U.S. Pat. No. 3,425,835
issued Feb. 4, 1969.
The photographic layers used in the practice of this invention may
be coated by various coating procedures including dip coating, air
knife coating, curtain coating, or extrusion coating using hoppers
of the type described in Beguin U.S. Pat. No. 2,681,294 issued June
15, 1954. If desired, two or more layers may be coated
simultaneously by the procedures described in Russell U.S. Pat. No.
2,761,791 issued Sept. 4, 1956; Hughes U.S. Pat. No. 3,508,947
issued Apr. 28, 1970; and Wynn British Patent 837,095 issued June
9, 1960. This invention also can be used for silver halide layers
coated by vacuum evaporation as described in British Patent 968,453
issued Sept. 2, 1964 and LuValle et al U.S. Pat. No. 3,219,451
issued Nov. 23, 1965.
The photographic and other hardenable layers used in the practice
of this invention can be hardened by various organic or inorganic
hardeners, alone or in combination, such as the aldehydes, and
blocked aldehydes as described in Allen et al U.S. Pat. No.
3,232,764 issued Feb. 1, 1966; ketones, carboxylic and carbonic
acid derivatives, sulfonate esters, sulfonyl halides and vinyl
sulfonyl ethers as described in Burness et al U.S. Pat. No.
3,539,644 issued Nov. 10, 1970; active halogen compounds, epoxy
compounds, aziridines, active olefins, isocyanates, carbodiimides,
polymeric hardeners such as oxidized polysaccharides like
dialdehyde starch and oxyguargum and the like.
The following examples further illustrate the invention.
EXAMPLE 1
A single layer supported gelatinous silver halide (cubic bromide)
emulsion coating is prepared which contains per square foot of
coating 82 mg of Compound No. 2, 82 mg of di-n-butylphthalate, 150
mg of silver and 500 mg of gelatin. A sample of the photosensitive
element is exposed to a graduated-density multicolor test object. A
processing composition comprising:
Na.sub.2 CO.sub.3 --H.sub.2 O 22.0 g 4-Amino-N-ethyl-N-.beta.-
hydroxyethylaniline Sulfate 11.0 g Ascorbic acid 0.385 g KBr 0.825
g Na.sub.2 SO.sub.3 2.0 g Water to 1 liter 2.0 g
is employed in a pod and is spread between the exposed surface of
the photosensitive element and a superposed dye image-receiving
element comprising a support coated with 700 mg/ft.sup.2 of gelatin
and 230 mg/ft.sup.2 of the mordant
N-N-dimethyl-N-.beta.-hydroxyethyl-N-.gamma.-stearamidopropyl-ammonium
dihydrogen phosphate, by passing the transfer "sandwich" between a
pair of juxtaposed pressure rollers.
After 7 minutes at about 27.degree.C, the film unit is separated. A
negative yellow dye image is observed on the dye image-receiving
sheet.
EXAMPLE 2
Example 1 is repeated except that the coating contains per square
foot of coating 82 mg of Compound No. 1. A negative yellow dye
image is again obtained on the dye image-receiving sheet.
EXAMPLE 3
The procedure of Example 1 is repeated with a sample of a coating
containing 82 mg of Compound No. 3 per square foot of coating
dissolved in tricresyl phosphate. A negative magenta dye image is
obtained on the dye image-receiving sheet.
The invention has been described with particular reference to
certain preferred embodiments thereof, but it will be understood
that variations and modifications can be effected within the spirit
and scope of the invention.
* * * * *