U.S. patent number 3,854,945 [Application Number 05/227,113] was granted by the patent office on 1974-12-17 for shifted indophenol dye developers.
This patent grant is currently assigned to Eastman Kodak Company. Invention is credited to Walter Monroe Bush, Daniel Francis Reardon.
United States Patent |
3,854,945 |
Bush , et al. |
December 17, 1974 |
**Please see images for:
( Certificate of Correction ) ** |
SHIFTED INDOPHENOL DYE DEVELOPERS
Abstract
Dye developers and processes for making said dye developers are
disclosed, along with photographic compositions and photographic
elements containing said dye developers wherein the dye developer
comprises a silver halide developing moiety connected to an
indophenol moiety. In one aspect, the light-absorption
characteristics of dye developers comprising the indophenol moiety
when incorporated in a photographic element can be shifted to
provide for exposure of a photosensitive material without
substantial absorption competition and then can be shifted by
contact with an 'onium compound to provide a good image dye. In
another aspect, photographic elements are disclosed which contain a
photosensitive composition having associated therewith a shifted
indophenol dye developer; preferably, the photographic elements are
used in image transfer film units.
Inventors: |
Bush; Walter Monroe (Victor,
NY), Reardon; Daniel Francis (Rochester, NY) |
Assignee: |
Eastman Kodak Company
(Rochester, NY)
|
Family
ID: |
22851791 |
Appl.
No.: |
05/227,113 |
Filed: |
February 17, 1972 |
Current U.S.
Class: |
430/224; 430/505;
430/243; 430/559 |
Current CPC
Class: |
C07D
231/52 (20130101); G03C 8/18 (20130101) |
Current International
Class: |
C07D
231/52 (20060101); C07D 231/00 (20060101); G03C
8/18 (20060101); G03C 8/02 (20060101); G03c
007/00 (); G03c 005/54 (); G03c 001/40 (); G03c
001/10 () |
Field of
Search: |
;96/29D,99,3,77 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Torchin; Norman G.
Assistant Examiner: Schilling; Richard L.
Attorney, Agent or Firm: Battist; G. E.
Claims
We claim:
1. A photographic element comprising a support and at least one
layer thereon containing a photographic silver halide having
associated therewith a dye developer which is diffusible in an
alkaline processing medium and has the general formula:
D-(SID)
wherein D- is an aromatic nucleus polysubstituted with hydroxy
groups, amino groups or alkylamino groups to provide a group which
is capable of developing silver halide, and (SID) is an indophenol
dye moiety.
2. A photographic element according to claim 1 wherein (SID) is a
group having the formula:
(COUP)=N--Ar--OH
wherein (COUP) is a color coupler connected to the nitrogen atom at
its coupling position and Ar is an arylene group containing from 6
to 20 carbon atoms.
3. A photographic element according to claim 2 wherein Ar is a
phenylene group.
4. A photographic element according to claim 1 which comprises at
least one layer containing an 'onium salt in water-permeable
association with said dye developer.
5. A photographic element according to claim 1 wherein D comprises
an aromatic nucleus which contains at least two substituents
thereon from the class of hydroxy groups, primary amino groups or
alkylamino groups.
6. A photographic element according to claim 1 wherein D- is a
hydroquinone group.
7. A photographic element according to claim 1 wherein said element
comprises at least two separate layers containing a silver halide
emulsion, each having a separate dye developer of said formula
associated therewith.
8. A photographic element according to claim 1 wherein said element
comprises a blue-sensitive silver halide emulsion layer having
associated therewith a yellow-forming indophenol dye developer, a
green-sensitive silver halide emulsion layer having associated
therewith a magenta-forming indophenol dye developer, and a
red-sensitive silver halide emulsion layer having associated
therewith a cyan-forming indophenol dye developer.
9. A photographic element according to claim 8 wherein said
cyan-forming dye developer, said magenta-forming dye developer and
said yellow-forming dye developer are each of said formula:
D-(SID)
and said element contains an image-receiving layer.
10. A photographic element according to claim 2 wherein Ar is a
phenylene group and said OH group is para to said nitrogen
atom.
11. A photographic element according to claim 1 wherein said dye
developer has the formula:
D-(PYZ)=N--Ar--OH
wherein D- is an aromatic nucleus polysubstituted with hydroxy
groups, primary amino groups or alkylamino groups to provide a
group which is capable of developing silver halide, Ar is a
phenylene group, and (PYZ) is a pyrazolone coupler radical or a
pyrazolotriazole coupler connected at its coupling position to said
nitrogen atom.
12. A photographic element according to claim 1 wherein said dye
developer has the formula:
D-(KMC)=N--Ar--OH
wherein D- is an aromatic nucleus polysubstituted with hydroxy
groups, primary amino groups or alkylamino groups to provide a
group which is capable of developing silver halide, Ar is a
phenylene group, and (KMC) is an open-chain ketomethylene coupler
radical connected at its coupling position to said nitrogen
atom.
13. A photographic element according to claim 1 wherein said dye
developer has the formula:
D-(PhC)=N--Ar--OH
wherein D- is an aromatic nucleus polysubstituted with hydroxy
groups, primary amino groups or alkylamino groups to provide a
group which is capable of developing silver halide, Ar is a
phenylene group, and (PhC) is a phenolic coupler radical connected
at its coupling position to said nitrogen atom.
14. A photographic film unit comprising:
a. a photosensitive element comprising a support having thereon a
layer containing a silver halide composition having associated
therewith a dye developer which is diffusible in an alkaline
processing medium and has the formula:
D-(SID)
wherein D- is an aromatic nucleus polysubstituted with hydroxy
groups, primary amino groups or alkylamino groups to provide a
group which is capable of developing silver halide, and (SID) is an
indophenol dye moiety;
b. a dye image-receiving layer; and
c. means for discharging an alkaline processing composition within
said film unit.
15. The film unit of claim 14 wherein said image-receiving layer is
located in said photosensitive element between said support and any
said silver halide composition layer.
16. A film unit according to claim 14 containing an 'onium salt in
liquid-permeable association with said dye developer and which is
sequestered from said dye developer until contact with said liquid
processing composition.
17. The film unit of claim 14 wherein said photosensitive element
comprises a support having thereon:
a. a red-sensitive silver halide emulsion layer having associated
therewith a cyan-forming dye developer;
b. a green-sensitive silver halide emulsion layer having associated
therewith a magenta-forming dye developer; and
c. a blue-sensitive silver halide emulsion layer having associated
therewith a yellow-forming dye developer.
18. A film unit according to claim 14 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.
19. A film unit according to claim 14 wherein said image-receiving
layer is coated adjacent said silver halide emulsion layers with an
opaque layer between said silver halide emulsion layers and said
image-receiving layer.
20. A film unit according to claim 14 wherein said discharging
means comprises a rupturable container and is so positioned during
processing of said film unit that a compressive force applied to
said container by pressure-applying members will effect a discharge
of the container's contents between said dye image-receiving layer
and the layer most remote from the support of said photosensitive
element.
21. A film unit according to claim 14 wherein said discharging
means comprises a rupturable container and is so positioned during
processing of said film unit that a compressive force applied to
said container by pressure-applying members will effect a discharge
of the container's contents between the layer most remote from the
support of said photosensitive element and a cover sheet superposed
on said photosensitive element.
22. A photographic film unit according to claim 14 wherein said dye
developer has the formula: ##SPC24##
23. A photographic film unit according to claim 14 wherein said dye
developer has the formula: ##SPC25##
24. A photographic film unit according to claim 14 wherein said dye
developer has the formula: ##SPC26##
25. A process for producing a photographic transfer image
comprising:
a. imagewise-exposing a photosensitive element comprising a support
having thereon a layer containing a silver halide composition
having associated therewith a dye developer which is diffusible in
an alkaline processing medium and has the formula:
D-(SID)
wherein D- is an aromatic nucleus polysubstituted with hydroxy
groups, amino groups or alkylamino groups to provide a group which
is capable of developing silver halide, and (SID) is an indophenol
dye moiety;
b. treating said photosensitive element with an alkaline processing
composition to effect development of said exposed silver halide
composition layer;
c. forming an imagewise distribution of said dye developer as a
function of development of said silver halide composition
layer;
d. at least a portion of said imagewise distribution of diffusible
dye developer diffusing to an image-receiving layer; and
e. contacting said dye developer with an 'onium compound at some
point after imagewise exposure.
26. A process according to claim 25 wherein said image-receiving
layer contains an 'onium compound.
27. The process of claim 25 wherein said treatment step b) is
effected by:
a. superposing over the layer outermost from the support of said
photosensitive element said image-receiving layer coated on a
support;
b. positioning a rupturable container containing said alkaline
processing composition between said exposed photosensitive element
and said image-receiving layer; and
c. applying a compressive force to said container to effect a
discharge of the container's contents between said outermost layer
of said exposed photosensitive element and said image-receiving
layer.
28. The process of claim 25 wherein said support is transparent and
said image-receiving layer is located between said support and said
silver halide composition layer, and said treatment is effected by
applying a compressive force to a rupturable container located
between the outermost layer of said photosensitive element and a
transparent superposed cover sheet, and wherein said container
contains an alkaline processing composition which is discharged by
said compressive force.
29. A process according to claim 25 wherein development of said
exposed silver halide composition layer is carried out with an
auxiliary developer present in said layer.
30. A photographic product comprising a support having thereon an
image receiving layer which contains an imagewise distribution of
an 'onium indophenoxide of the formula:
D-(SID) .sup.- .sup.+M
wherein D- is an aromatic nucleus polysubstituted with hydroxy
groups, amino groups or alkylamino groups to provide a group which
is capable of developing silver halide, (SID) is an indophenol dye
moiety, and M is an 'onium group.
31. A photographic product according to claim 30 wherein M is a
quaternary ammonium group.
32. A photographic product according to claim 30 wherein said
'onium indophenoxide has the formula:
D-(COUP)=N--Ar--O.sup.- .sup.+ M
wherein D- is an aromatic nucleus polysubstituted with hydroxy
groups, amino groups or alkylamino groups to provide a group which
is capable of developing silver halide, (COUP) is a photographic
color coupler, Ar is an arylene group containing from about 6 to
about 20 carbon atoms, and M is an 'onium group.
33. A photographic product according to claim 32 wherein (COUP) is
an open-chain ketomethylene color coupler group connected at its
coupling position to said nitrogen atom.
34. A photographic product according to claim 32 wherein (COUP) is
a pyrazolone or pyrazolotriazole color coupler group connected at
its coupling position to said nitrogen atom.
35. A photographic product according to claim 32 wherein (COUP) is
a phenolic color coupler connected at its coupling position to said
nitrogen atom.
36. A photographic product according to claim 30 which contains 1)
an 'onium indophenoxide of said formula wherein (SID) comprises a
phenolic color coupler, 2) an 'onium indophenoxide of said formula
wherein (SID) comprises an open-chain ketomethylene color coupler
and 3) an 'onium indophenoxide of said formula wherein (SID)
comprises a pyrazolone or pyrazolotriazole color coupler.
37. A photographic product according to claim 30 wherein said
image-receiving layer comprises a polymer with 'onium groups
thereon.
38. A photographic product according to claim 30 wherein said M
represents an immobile 'onium compound which is present in said
image-receiving layer at concentrations of about 25 mg. to 1000 mg.
per square foot.
39. A photographic product according to claim 30 wherein D- is a
hydroquinone group or an oxidized hydroquinone group.
Description
This invention relates to compositions of matter, processes for
preparing compositions of matter, photographic elements containing
these compositions of matter and processes for forming photographic
image records. In one aspect, this invention relates to shifted dye
developers wherein the dye is an indophenol moiety. In another
aspect, this invention relates to photographic elements for
recording an imagewise exposure, which elements contain shifted
indophenol dye developers and to photographic image records
containing a dye developer wherein the dye is an 'onium
indophenoxide. In still another aspect, this invention relates to
improved image transfer film units and processes for forming image
records in image transfer film units.
It is known in the prior art to use dye developers in photographic
elements such as image transfer systems as disclosed in U.S. Pat.
Nos. 2,983,606, 3,225,001, etc., where most of the dyes of said dye
developers are anthraquinone dyes or azo dyes. It is also known in
the art to use shifted dye developers in image transfer systems
such as disclosed in U.S. Pat. No. 3,336,287 issued Aug. 15, 1967,
3,307,947 issued Mar. 7, 1967, and the like. Several references
also disclose the use of hydrolyzable groups attached to an
anthraquinone or azo dye to shift the color of the dye temporarily
toward lower wavelengths whereby their use in a photosensitive
element will result in a reduced absorption of light available for
exposure of the associated silver halide emulsion or an inner
silver halide emulsion with respect to the direction of exposure --
U.S. Pat. Nos. 3,230,082 issued Jan. 18, 1966, 3,230,085 issued
Jan. 18, 1966, 3,146,102 (column 12) by Weyerts et al issued Aug.
25, 1964, etc. However, improved classes of dye developers are
desired which would substantially obviate the absorption
competition with the associated photosensitive emulsion and
underlying photosensitive emulsion layers and at the same time
provide short image transfer times and good image quality in the
image record after transfer.
We have now discovered a new class of compounds which can be used
in photographic elements, and especially in image transfer film
units, to provide improved transfer systems and improved image
properties. Generally, the compounds are dye developers wherein the
dye is an indophenol, referred to herein as a shifted indophenol
dye developer. These compounds can be coated in the photosensitive
element with low color absorption, and after exposure of the
photosensitive element can be brought into contact with a
positively charged compound which is preferably an 'onium compound
to produce an image dye having very good image characteristics
including stability, density and the like.
In one preferred embodiment, this invention relates to a
photographic element comprising a support and at least one layer
thereon containing a photosensitive, image-recordng material having
associated therewith a dye developer of the general formula:
D--(SID)
wherein D-is an aromatic group which is a silver halide developer
and (SID) is an indophenol dye moiety.
In another embodiment, this invention relates to an image transfer
film unit comprising a photosensitive element containing a
blue-sensitive silver halide emulsion layer having associated
therewith a yellow-forming indophenol dye developer, a
green-sensitive silver halide emulsion layer having associated
therewith a magenta-forming indophenol dye developer, and a
redsensitive silver halide emulsion having associated therewith a
cyan-forming indophenol dye developer.
In another embodiment, this invention relates to a photographic
film unit comprising:
1. a photosensitive element comprising a support having thereon a
layer containing a silver halide composition having associated
therewith a dye developer having the formula:
D-(SID)
wherein D-is an aromatic group which is a silver halide developer
and (SID) is an indophenol dye moiety;
2. a dye image-receiving layer; and
3. means for discharging an alkaline processing composition within
said film unit.
Preferably, the image-receiving layer comprises an 'onium compound
which can be a mordant for the indophenol dye developer.
In still another embodiment, this invention relates to 'onium
indophenoxides and photographic elements containing indophenoxides
which have the formula:
D-(SID).sup.-.sup.+M
wherein D-is a silver halide developing group, either in the
oxidized or unoxidized state, (SID) is an indophenol moiety, and M
is an 'onium group.
In another highly preferred embodiment, this invention relates to
image transfer elements comprising the combination of a shifted
indophenol dye developer and an incorporated auxiliary silver
halide developer which is a reducing agent.
In the drawings, FIG. 1 shows a representative absorption shift
which is obtained with a yellow indophenol based on an open-chain
ketomethylene coupler (line Y), a magenta indophenol based on a
pyrazolone color coupler (line M), and a cyan indophenol based on a
phenolic color coupler (line C), wherein the absorption
characteristics of the indophenols as incorporated in the
photographic element are shown, respectively, as lines SY, SM and
SC and the absorption characteristics after contact with an 'onium
compound are shown as lines Y, M and C. Further details of the
absorption shift are described in Bush et al, U.S. Ser. No. 169,706
filed Aug. 6, 1971, now U.S. Pat. No. 3,791,827, which is
incorporated herein by reference. FIGS. 2 and 3 show representative
absorption characteristics of the dye developers of Examples 2
(Compound I) and 8 (Compound IV).
In FIGS. 4-6, a preferred film unit is described which is based on
the shifted indophenol dye developers.
The shifted dye developers of this invention are generally those
which comprise a silver halide developing agent moiety linked to an
indophenol dye moiety. Generally, the shifted dye developers can be
represented by the formula:
D-(SID)
wherein D-is a moiety of a silver halide developing agent including
those having hydrolyzable groups thereon, and preferably is a
disubstituted aromatic group such as a naphthalene or, more
preferably, a phenylene group wherein the disubstituted groups are
hydroxy groups, primary amino groups or alkylamino groups,
including substituted alkylamino groups, wherein the second
substituent is preferably in the ortho or para position; and (SID)
is a shifted indophenol dye moiety including, of course, the
desired linking groups between the dye moiety and the developing
agent moiety, especially where chromophore insulating groups are
desired. In one preferred embodiment, (SID) can be represented by
the formula:
(COUP)=N--Ar--OH
wherein Ar is an arylene group comprising from 6 to 20 carbon atoms
including substituted and unsubstituted arylene groups, fused-ring
substituents and the like, and is preferably a phenylene group
which is preferably substituted with halogen atoms or groups
containing halogen atoms in the ortho or meta positions of the
ring; and (COUP) is a color-forming coupler including the linking
group to D--, such as phenolic couplers, pyrazolone couplers,
pyrazolotriazole couplers, couplers having openchain methylene
groups and the like, wherein said coupler is linked to said
nitrogen atom through a carbon atom at the coupling position.
Generally, when the above shifted dye developers are utilized in an
image transfer film unit, the shifted dye developer is diffusible
and will migrate to an image-receiving layer upon contact with an
alkaline processing solution unless the developer group is oxidized
by reaction with developable silver halide or oxidized with a redox
agent; the image-receiving layer preferably has an 'onium compound
associated therewith to provide the 'onium indophenoxide image
dye.
The compounds or groups referred to herein as couplers contain a
"coupling position" which is generally known to those skilled in
the art as being the position on the coupler molecule that reacts
or couples with oxidized color developing agents. Typical useful
couplers include phenolic couplers, including .alpha.-naphthols
which couple at the 4-position, open-chain ketomethylene couplers
which couple at the carbon atom forming the methylene moiety (e.g.,
##SPC1##
wherein * denotes the coupling position), 5-pyrazolone couplers
which couple at the carbon atom in the 4-position, and the like.
Typical specific coupler compounds which can be reacted with
p-aminophenols to form the indophenol moiety according to this
invention are disclosed in U.S. Pat. Nos. 2,407,210 by Weissberger
et al issued Sept. 3, 1946; 2,298,443 by Weissberger issued Oct.
13, 1942; 2,875,057 by McCrossen et al issued Feb. 24, 1959;
3,265,506 by Weissberger et al issued Aug. 9, 1966; 3,408,194 by
Loria Issued Oct. 29, 1968; 3,447,928 by Loria issued June 3, 1969;
2,369,489 by Porter et al issued Feb. 13, 1945; 2,600,788 by Loria
et al issued June 17, 1952; 2,908,573 by Bush et al issued Oct. 13,
1959; 3,062,653 by Weissberger et al issued Nov. 6, 1962; 3,419,391
by Young issued Dec. 31, 1968; 3,519,429 by Lestina issued July 7,
1970; 3,152,896 by Tuite issued Oct. 13, 1964; 2,423,730 by
Salminen et al issued July 8, 1947; 2,474,293 by Weissberger et al
issued June 28, 1949; 3,476,563 by Loria issued Nov. 4, 1969;
2,772,162 by Salminen et al issued Nov. 27, 1956; and 3,002,836 by
Vittum et al issued Oct. 3, 1961; and U.S. Ser. No. 778,333 by
Bailey et al filed Nov. 22, 1968, now abandoned; which are all
incorporated herein by reference.
The group defined as Ar above is preferably the residue of an
aromatic color developing agent such as an aminophenol, a
phenylenediamine and the like and, of course, including the various
substituents on the aromatic group which are known in the art for
the respective color developing agent. In one preferred embodiment
where Ar is the nucleus of an aminophenol developing agent, the
aromatic compound can contain the substituents as disclosed, for
example, in Bush et al, U.S. Ser. No. 169,706 filed Aug. 6, 1971
now U.S. Pat. No. 3,791,827, which is incorporated herein by
reference.
In the shifted indophenol dye developers, the indophenol moiety
preferably contains an insulating linkage connecting it to the
developing agent moiety (D-). Insulating linkages of this type,
sometimes referred to as achromophoric groups or bonds, are known
in the art, for example, as disclosed in U.S. Pat. No. 3,255,001
issued June 7, 1966. The insulating group does not contribute a
color-producing group to the indophenol dye chromophore, but acts
to prevent or interrupt any system of conjugation or resonance
extending from the azomethine groups of the indophenol moiety to
the developing group, i.e., such as a hydroquinone group. Thus, any
influence of the developer group on the color characteristics of
the azomethine linkage is substantially excluded. The insulating
linkage which preferably forms a part of the indophenol moiety as
defined herein can be any group which will break up the resonance
system, for example, those groups listed in U.S. Pat. No. 3,255,001
issued June 7, 1966, and the like.
The term "azomethine linkage" as used herein is understood to mean
the grouping: ##SPC2##
Preferably, the azomethine compounds of this invention are further
defined as being indophenols, which is understood to refer to
compounds having the general structure:
(COUP)=N--Ar--OH
wherein (COUP) is a color coupler such as a pyrazolone color
coupler, a pyrazolotriazole coupler, an open-chain ketomethylene
color coupler, a phenolic color coupler and the like, which is
connected to the nitrogen atom in the coupling position of said
coupler; and Ar is as defined above.
The term "nondiffusing" used herein has the meaning commonly
applied to the term in color photography and denotes materials
which for all practical purposes do not migrate or wander through
organic colloid layers, such as gelatin, comprising the sensitive
elements of the invention. The same meaning is to be attached to
the term "immobile".
The term "diffusible" as applied to the color-providing materials
of this invention has the converse meaning and denotes materials
having the property of diffusing effectively through the colloid
layers of the sensitive elements in the presence of the
nondiffusing materials. "Mobile" has the same meaning.
The shifted indophenols are reacted with 'onium salts at
appropriate times in photographic processes to provide a
bathochromic absorption shift, thus forming an 'onium
indophenoxide. The 'onium indophenoxides can generally be
represented by the formula:
D-(SID).sup.-.sup.+M
and more preferably by:
D-(COUP)=N--Ar--O.sup.- .sup.+M
wherein D-, (SID), (COUP) and Ar are as defined above, and M is an
'onium group including sulfonium, phosphonium and, preferably,
quaternary ammonium groups. When the 'onium indophenoxide is formed
in or has transferred to the desired image-receiving layer, the
developer group can be in the oxidized or unoxidized state.
The 'onium salts used to form the 'onium indophenoxides are
generally quaternary ammonium salts, quaternary phosphonium salts,
tertiary sulfonium salts and the like, and are generally used in
concentrations necessary to form an 'onium indophenoxide with all
of the indophenol present in the photographic element. When the
'onium compound is immobile or ballasted and present in an image
layer, it is generally utilized in concentrations of about 25 mg.
to about 1,000 mg. per square foot, and preferably about 50 to
about 500 mg. per square foot, depending, of course, on the ratio
of ' onium atoms to molecular weight of the compound employed. When
the 'onium salt is supplied by a solution such as in the processing
solution, typical useful concentrations range from 0.01% by weight
to about 5% by weight of the 'onium compound to provide complete
reaction, again depending on the concentration of the dye in the
photographic element and the ratio of 'onium groups to molecular
weight of the 'onium compound.
In one embodiment of this invention, color image transfer systems
are prepared by using an appropriate shifted indophenol dye in each
of three differently sensitized emulsion layers of a photographic
element.
One layer of the element comprises a blue-sensitive silver halide
emulsion which has associated therewith a shifted yellow indophenol
dye developer. Typical shifted yellow dye developers have the
formula:
D-(KMC)=N--Ar--OH
wherein D-and Ar are as defined above and (KMC) is an open-chain
ketomethylene color coupler connected to said nitrogen atom at its
coupling position. A typical specific compound of this type is:
Compound I ##SPC3##
Another layer of the element comprises a greensensitive silver
halide emulsion having associated therewith a shifted magenta
indophenol dye developer. Typical shifted magenta dye developers
have the formula:
D-(PYZ)=N--Ar--OH
wherein D-and Ar are as defined above and PYZ is a pyrazolone or
pyrazolotriazole color coupler, and preferably a color coupler
which contains either the moieties: ##SPC4##
or ##SPC5##
wherein the 4-position in said ring is directly bonded to the
nitrogen atom in the above dye developer formula. Typical specific
compounds of this type are:
Compound II ##SPC6##
and
Compound V ##SPC7##
Another layer of the element comprises a red-sensitive silver
halide emulsion having associated therewith a shifted cyan
indophenol dye developer. Typical shifted cyan dye developers have
the formula:
D-(PhC)=N--Ar--OH
wherein D--and Ar are as defined above and PhC is a phenolic color
coupler connected to said nitrogen atom at its coupling position.
Typical specific compounds of this type are:
Compound III ##SPC8##
and ##SPC9##
Compound IV
The shifted indophenol dye developers can be prepared by several
techniques. In one embodiment, oxichromic developers are prepared
as described in Lestina and Bush, U.S. Ser. No. 206,949 entitled
"Oxichromic Compounds, Stabilized Oxichromic Compounds and
Processes for Preparing Same" filed Dec. 10, 1971, and the
oxichromic developers are then chromogenically oxidized by aerial
oxidation, electrochemical oxidation and the like to provide
indophenol dye developers. In another embodiment, the indophenol
dye developers are prepared by 1) reacting a masked silver halide
developing compound with a color coupler by a condensation
reaction, 2) reacting the condensation product with an aminophenol
and 3) then removing the masking groups from the moiety which was
the silver halide developing compound. In certain variations, the
aminophenol can be reacted with the color coupler before
condensation with the masked silver halide developing compound. The
color coupler can be reacted with an oxidized aminophenol to form
the dye or, in certain embodiments, the couplers when halogenated
on the active methylene group can be reacted with unoxidized
aminophenols, as disclosed in U.S. Ser. Nos. 206,924 by Machiele or
206,927, now abandoned, by Reardon, both filed Dec. 10, 1971.
Generally, it is known in the prior art to make dye developers by
reacting a masked developer with a dye moiety by a condensation
reaction, for example, as disclosed in Journal of Chemical and
Engineering Data, Vol. 9, No. 2, 1964, pp. 232-238. After
condensation, the masking groups protecting the silver halide
developing functions can be readily removed since dyes used in the
past, such as azo dyes, anthraquinone dyes and the like, are
relatively stable to conditions necessary to remove the masking
groups. In one embodiment, we have now found that dye developers
comprising dye moieties containing an azomethine linkage, such as
indophenol dyes, can be prepared by condensation reactions with
masked developers when precautions are taken to use mild hydrolysis
conditions wherein the pH is maintained between pH of about 7 to
about 10 and the masking groups are groups which will readily
hydrolyze under these conditions such as, for example, masking
groups forming carbonates, oxalates, trifluoroacetates and the like
with the silver halide developing moiety. When masking groups such
as acetoxy groups are used on the silver halide developing moiety,
hydrolysis of the masking group is generally accompanied by
substantial destruction of the indophenol.
The hydrolysis reaction is preferably carried out with a mild
hydrolyzing agent such as weak alkali, methylamine, thiourea, zinc
and acetic acid and the like. Generally, the hydrolysis procedure
is dependent on the groups on the dye moiety and the specific group
to be removed. However, the above hydrolyzing agents can generally
be used to achieve removal of carbonate, oxalate, trifluoroacetate
groups and the like.
In certain preparations of the dye developers of this invention,
the masking groups are attached to a developing moiety which is
preferably a polyhydroxybenzene compound such as hydroquinone, and
the masking groups are carbonate-containing masking groups such as
carboalkoxy groups, carbobenzoxy groups and the like which can
contain from 2-20 carbon atoms.
The shifted indophenol dye developers are especially useful in
image transfer systems since they can be incorporated in the silver
halide image-recording layer without substantial detrimental
adsorption of light in any of the recording layers, i.e., the
yellow, green and red recording layers, During development, the
indophenol dye developers are insolubilized in those areas where
silver halide development occurs and the unreacted indophenol dye
developer is free to diffuse or migrate to a receiver layer such as
a mordant layer. At some point after imagewise exposure of the
silver halide layer, the indophenol dye developer can be contacted
with an 'onium compound to convert the indophenol moiety to an
'onium indophenoxide which will provide a desired shift in color
adsorption providing highly useful dyes for color systems.
A particularly preferred embodiment of the present invention
involves a photographic film unit comprising:
1. a photosensitive element comprising a support having thereon a
silver halide emulsion layer having associated therewith an
indophenol dye developer,
2. a dye image-receiving layer having associated therewith an
'onium compound, and
3. a container means for discharging an alkaline processing
composition within said unit. Preferably, said container means is a
rupturable container which is positioned during processing of said
film unit so that a compressive force applied to the container by
pressure-applying members will effect a discharge of the
container's contents into the film unit.
The dye image-receiving layer of the 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
disclosed, for example, in U.S. Pat. No. 3,362,819. The rupturable
container is usually positioned during processing of said film unit
so that a compressive force applied to the container by
pressure-applying members in a camera will effect a discharge of
the container's contents between the image-receiving element and
the outermost layer of the photosensitive element. The dye
image-receiving layer can also be located integral with the
photosensitive element between the support and the lowermost
photosensitive silver halide emulsion layer. Such integral
receiver-negative photosensitive elements are disclosed, for
example, in U.S. Pat. No. 3,415,644 and are useful in camera
apparatus of the type disclosed in Belgian pat. Nos. 718,553 and
718,554. The processing composition for such integral elements
wherein the receiver is permanently laminated to the negative
contains opacifying agents such as titanium dioxide or carbon
black. Barrier layers such as those described in subsequent
paragraphs may be used to advantage in such integral elements
between the various emulsion and dye-developer layers.
In one highly preferred embodiment according to this invention,
which is shown in FIG. 5 in detail, the shifted indophenol dye
developers are used in an integral image transfer system wherein
the image-receiving layer is separated from the image-recording
layers, i.e., photosensitive layers containing silver halide
emulsions, by a processing composition and dye developer-permeable
opaque layer. The image-recording silver halide emulsions have
associated therewith respectively a dye image-providing material
which is a dye developer. The processing composition is uniformly
applied to the image-recording layers on the side opposite the
opaque layer, which can be accomplished by inserting an alkaline
composition between the image-recording layers and a cover sheet.
The processing composition permeates the image-recording layers,
rendering the dye developer nondiffusible in the developed areas,
and initiates diffusion in the nondeveloped areas wherein the dye
developer can diffuse through the opaque layer to the
image-receiving layer and upon treatment with an 'onium compound
will provide the desired image dye. Since the element cannot be
exposed through the opaque layer, it must, of course, be exposed
from the opposite side. In this system, the present shifted
indophenol developers permit exposure through the required side and
still obtain effective contact with the silver halide emulsion to
render the dye developer nondiffusing in the developed areas, thus
avoiding severe color contamination; since the shifted indophenol
dye developers can be incorporated in the emulsion layer or
positioned between the emulsion layer and the exposure source
without substantial competitive light absorption, a high-speed
photographic system with this format based on negative emulsions
and diffusible dye image-providing substances can now be made. In
highly preferred embodiments, image transfer elements of this type
are made with a support having an image-receiving layer thereon and
in sequence an opaque layer and at least one image-recording layer
with a cover sheet superposed on the image-recording layer to
permit uniform application of a processing liquid to the side of
the image-recording layer opposite the opaque layer. After
processing, the cover sheet can remain laminated with the support
having said layers coated thereon.
The color film assembly of the present invention may contain
various silver halide emulsion layers 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 of a Carey Lea silver layer may 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 may be disposed in a
different order, e.g., the red-sensitive layer first with respect
to the exposure side, followed by the green-sensitive and
blue-sensitive layers, since many of the dye developers of this
invention which are in association with the sensitive layers do not
absorb substantial radiation in the visible region of the radiation
spectrum.
Our novel indophenol dye developers may be employed for all colors
or in combination with suitable additional dye developers in a
three-color photosensitive element of the invention. Dye
developers, i.e., compounds which contain in the same molecule both
the chromophoric system of a dye and also a silver halide
developing function, and their functioning in color diffusion
transfer systems in general are well-known in the art as shown, for
example, by U.S. Pat. Nos. 2,983,606, 2,992,106, 3,047,386,
3,076,808, 3,076,820, 3,077,402, 3,126,280, 3,131,061, 3,134,762,
3,134,765, 3,135,604, 3,135,605, 3,135,606, 3,135,734, 3,141,772,
3,142,565, 3,362,819, 3,415,644, 3,415,645, 3,415,646, and the
like.
The shifted dye developers having the formula:
D-(SID)
as defined above, are useful in photographic systems and especially
in image transfer systems. The shifted dye developers of this type
are generally diffusible in an alkaline medium. In image transfer
systems, the shifted dye developer is associated with a silver
halide emulsion wherein the silver halide emulsion is exposed and
then treated with an alkaline processing solution which permeates
the layers containing the silver halide emulsion and the shifted
dye developer to develop the exposed silver halide. In the areas
where the silver halide emulsion is developed, the shifted dye
developer is rendered relatively nondiffusing compared with the
remainder of the shifted dye developer which can diffuse imagewise
to an image-receiving layer wherein it can be mordanted. Upon
contact with an 'onium salt, which is preferably carried out near
or in the image-receiving layer, the 'onium indophenoxide image dye
is formed.
The developing group D in the above dye developers is generally
responsible for changes in diffusibility of the shifted dye
developer and, upon oxidation by reaction with exposed silver
halide or an auxiliary developer, it is preferably oxidized to a
relatively immobile form. In highly preferred embodiments, the
group defined as D is a polyhydroxy-substituted aromatic silver
halide developing function, and preferably a hydroquinone.
Black-and-white or one-color systems can be made which employ as
few as one silver halide emulsion and a shifted dye developer
selection which will provide the desired net color effect.
Subtractive multicolor systems can also be made such as, for
example, three-color systems described in detail above wherein a
blue-sensitive emulsion has associated therewith a shifted yellow
indophenol dye developer, a green-sensitive emulsion has associated
therwith a shifted magenta indophenol dye developer, and a
red-sensitive emulsion has associated therewith a shifted cyan
indophenol developer.
Generally, the shifted indophenol dye developers referred to above
can be incorporated in the photographic elements in sufficient
quantities to provide the desired image dye density after
processing as known in the art for dye image-providing materials.
The concentrations will vary, of course, depending on the type of
compound employed, the film unit structure and the like.
In accordance with this invention when indophenols are formed in
the process, they are preferably contacted with 'onium compounds to
form 'onium indophenoxides. The 'onium compounds can either be
soluble compounds which can be added by contacting the indophenol
with a solution of the 'onium compound or can be
high-molecular-weight compounds which are relatively insoluble in
water and can be placed in at least one layer of the photographic
element, such as in the mordant layer where the indophenol produces
the 'onium indophenoxide image dye.
In one embodiment, especially useful dye images have been obtained
through the combination of indophenols and quaternary ammonium
compounds. As is known, quaternary ammonium compounds are organic
compounds containing a nitrogen atom having a net positive charge.
Generally, they can be considered as derivatives of ammonium
compounds wherein the four valences usually occupied by the
hydrogen atoms are occupied by organic radicals. Generally, the
organic radicals are joined directly to the nitrogen through a
single or double carbon-to-nitrogen bond. The term "quaternary
ammonium," as used herein, is intended to cover compounds wherein
said nitrogen is one of the nuclear atoms in a heterocyclic ring,
as well as those wherein each of the four valances is attached to
separate organic radicals, e.g., tetraalkyl quaternary ammonium
compounds. As illustrations of quaternary ammonium compounds,
mention may be made of those represented by the following formulae:
##SPC10##
wherein each R is an organic radical; Y is an anion, e.g., hydroxy,
bromide, chloride, toluenesulfonate, etc.; and Z represents the
atoms necessary to complete a heterocyclic ring. As examples of
compounds within Formulae 1, 2 and 3, mention may be made of
tetraethylammonium bromide, N-ethylpyridinium bromide,
N,N-diethylpiperidinium bromide, ethylene-bis-pyridinium bromide,
1-ethylpyridinium bromide, 1-phenethyl-3-picolinium bromide,
tetraalkylammonium salts, cetyltrimethylammonium bromide,
polyalkylene oxide bis-quaternary ammonium salts such as
polyethylene oxide bis-pyridinium perchlorate, the heterocyclic
quaternary ammonium salts mentioned which form the methylene bases
including 3-methyl-2-ethylisoquinolinium bromide,
3-methylisoquinolinium methyl-p-toluenesulfonate,
1-ethyl-2-methyl-3-phenethylbenzimidazolilum bromide,
5,6-dichloro-1-ethyl-2-methyl-3-(3-sulfobutyl)benzimidazolium
betaine and the pyridinium salts below.
Other useful 'onium compounds include tertiary sulfonium and
quaternary phosphonium compounds which are represented by the
formulae:
(R).sub. 3 2.sup.+ X.sup.- TM(4)
and
(R)4P.sup.+ X.sup.- TM(5)
wherein each R is an organic radical, e.g., alkyl, aralkyl, aryl,
etc., groups; and X is an anion, e.g., hydroxy, bromide, chloride,
toleuenesulfonate, etc. As examples of tertiary sulfonium and
quaternary phosphonium compounds, mention may be made of
lauryldimethylsulfonium p-toluenesulfonate, nonyldimethylsulfonium
p-toluenesulfonate and octyldimethylsulfonium p-toluenesulfonate,
butyldimethylsulfonium bromide, triethylsulfonium bromide,
tetraethylphosphonium bromide, dimethylsulfonium
p-toluenesulfonate, dodecyldimethylsulfonium p-toluenesulfonate,
decyldimethylsulfonium p-toluenesulfonate and
ethylene-bis-oxymethyltriethylphosphonium bromide.
The 'onium compounds may be used as the hydroxide or as the salt.
When the 'onium compounds are used as the salt, the anion may be a
derivative of any acid. However, it should be noted that when the
anion is iodide, such iodide may have deleterious effects on the
emulsion and suitable precautions should be taken if it is to be in
contact with the emulsion before development is complete.
Especially good results are obtained when the 'onium compounds
employed are bromides.
Useful heterocyclic quaternary ammonium compounds which form the
methylene bases diffusible in alkaline solution have the general
formulas:
1-.gamma.-phenylpropyl-2-picolinium bromide
2,4-dimethyl-1-phenethylpyridinium bromide
2,6-dimethyl-1-phenethylpyridinium bromide
5-ethyl-2-methyl-1-phenethylpyridinium bromide
2-ethyl-1-phenethylpyridinium bromide
1-[3-(N-pyridinium bromide)propyl]-2-picolinium p-toluenesulfonate
##SPC11##
anhydro-1-(4-sulfobutyl)-2-picolinium hydroxide ##SPC12##
.alpha.-picoline-.beta.-naphthoylmethyl bromide ##SPC13##
1-.beta.-phenylcarbamoyloxyethyl-2-picolinium bromide ##SPC14##
1-methyl-2-picolinium p-toluenesulfonate
1-phenethyl-2,4,6-trimethylpyridinium bromide
1-phenethyl-4-n-propylpyridinium bromide
4 -.gamma.-hydroxypropyl-1-phenethylpyridinium bromide and
1-n-heptyl-2-picolinium bromide
In highly preferred embodiments of the invention, the image dye is
mordanted in a polymeric material such as a polymer with 'onium
groups thereon. Typical useful mordants of this type are
vinylpyridinium compounds of the type disclosed in U.S. Pat. No.
2,484,430 issued Nov. 10, 1949; polymers containing quaternary
ammonium groups such as disclosed in U.S. Ser. Nos. 734,873 by
Cohen et al filed June 6, 1968, now U.S. Pat. No. 3,625,694,
100,487 by Cohen et al filed Dec. 21, 1970, now U.S. Pat. No.
3,758,445, 100,491 by Cohen et al filed Dec. 21, 1979, now U.S.
Pat. No. 3,709,690, 709,793 by Cohen et al filed Mar. 1, 1968, now
U.S. Pat. No. 3,639,357, and U.S. Pat. Nos. 3,488,706 by Cohen et
al issued Jan. 6, 1970, and 3,557,006 by Cohen et al issued Jan.
19, 1970; and the like.
In another preferred embodiment, the mordant is an 'onium
coacervate mordant such as disclosed in Bush, U.S. Pat. No
3,271,147 issued Sept. 6, 1966.
In FIGS. 4-6, a preferred film unit of the invention is described
with the various elements magnified for purposes of illustration
only wherein like numbers appearing in the various figures refer to
like components.
In FIG. 4, rupturable container 11 is positioned transverse a
leading edge of the photosensitive laminate and is held in place by
binding means 30, which can be a pressure-sensitive tape or the
like which encloses that edge of the laminate. The other edges of
the photosensitive laminate are sealed together, either directly or
with a spacer member, to prevent leakage of processing solution
during and after photographic processing when rupturable container
11 is broken open by pressure-applying members 36 to discharge its
contents into the photosensitive laminate.
In FIG. 5, film unit 10 comprises rupturable container 11
containing, prior to passing between pressure-applying members 36,
an alkaline processing composition 12 containing an opacifying
agent and a photosensitive laminate comprising top transparent
sheet 25 coated with polymeric acid layer 24 and polymeric timing
layer 23 and a photosensitive element comprising a transparent
support layer 15 coated with an image receiving layer 16 associated
with an 'onium compound, an opaque reflecting layer 17, a
red-sensitive silver halide emulsion layer 18 associated with a
cyan dye image-providing material, barrier interlayer 19, a
green-sensitive silver halide emulsion layer 20 associated with a
magenta dye image-providing material, barrier interlayer 21, and a
blue-sensitive silver halide emulsion layer 22 associated with a
yellow dye image-providing material. Exposure of the film unit
takes place through the top transparent sheet 25 which is
preferably an actinic radiation transmissive flexible sheet
material.
In FIG. 6, film unit 10 has been passed between pressure-applying
members 36 such as would be found in a camera, thus causing
rupturable container 11 to collapse and discharge the alkaline
processing composition 12 containing an opacifying agent between
the polymeric timing layer 23 and the blue sensitive silver halide
emulsion layer 22. After development and image transfer has taken
place, a positive, right-reading image may be viewed through
transparent support 15.
The structural integrity of the photosensitive laminate can be
maintained, at least in part, by the adhesive characteristics
between the various layers of the laminate. However, the adhesion
exhibited at the interface between the polymeric timing layer 23 of
top transparent sheet 25 and underlying layer 22 is less than the
adhesion at the remaining interfaces of the laminate in order to
facilitate distribution of processing composition 12 between these
two layers.
The film unit of our invention may be constructed by assembling the
various parts in an atmosphere maintained at a pressure lower than
atmospheric pressure and by sealing the transparent sheet to the
photosensitive element along their edges in order to prevent the
admission of air between them. The exclusion of air between the
transparent sheet and the photosensitive element is desirable in
order to prevent air bubbles from being entrained in the processing
composition which would form discontinuities in the positive image.
Details of this method of assembly and other methods for assuring a
uniform distribution of processing composition between two sheets
are described in Belgian Pat. No. 711,897.
The film unit of our invention can also contain a liquid trap at
the opposite end from which processing composition is introduced in
order to trap any excess processing composition and keep it from
being expelled from the film unit. The liquid trap may also
function to let air escape, if any is present. Such liquid traps
are disclosed, for example, in Belgian Pat. No. 711,899.
The film unit of our invention may also be processed in the manner
described in Belgian Pat No. 711,898 wherein two sets of pressure
rollers are used in order to expel any air between the transparent
sheet and the photosensitive element and also to facilitate an even
distribution of processing composition between said sheet and
element. The transparent sheet in our film unit may also be fluted
along the length of the side edges, similar to the technique
described in Belgian Pat. No. 711,898, in order to assist in
distributing the processing composition evenly between the
transparent sheet and the photosensitive element.
If it is desired to have residual water in the film unit leave the
system after processing, this may be accomplished by incorporating
into the film unit a desiccating layer to absorb water or by
providing access to the atmosphere in order to let the water
evaporate, e.g., by employing a water-permeable transparent sheet
or a water-permeable film support for the photosensitive element or
by allowing water to evaporate through the liquid traps in the film
unit as described above, etc.
Rupturable container 11 can be of the type disclosed in U.S. Pat.
Nos. 2,543,181, 2,634,886, 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 composition 12 containing an opacifying
agent is contained (see FIG. 5). The longitudinal marginal seal 35
is made weaker than the end margin seals so as to become unsealed
in response to the hydraulic pressure generated within the fluid
contents 12 of the container by the application of a compressive
force to the outside walls of the container.
As illustrated in FIGS. 4 and 5, container 11 is fixedly positioned
and extends transverse a leading edge of the photosensitive
laminate so that a compressive force applied to said container will
effect a unidirectional discharge of the container's contents
between the polymeric timing layer 23 of top transparent sheet 25
and underlying layer 22. In FIG. 5, the weak longitudinal marginal
seal 35 is directed toward the interface between layers 22 and 23
to facilitate this operation.
In the performance of a multicolor diffusion transfer process
employing film unit 10, the unit is exposed to radiation incident
on the photosensitive laminate's upper surface through transparent
sheet 25, as illustrated in FIG. 5. Subsequent to exposure, the
film unit 10 is processed by passing it between pressure-applying
members 36 in order to apply compressive pressure to frangible
container 11 and to effect rupture of longitudinal seal 35 and
distribution of alkaline processing composition 12 containing an
opacifying agent between layers 23 and 24 of film unit 10. The
alkaline processing composition permeates the silver halide
emulsion layers 22, 20 and 18 to initiate imagewise development of
the silver halide. Diffusible yellow, magenta and cyan dye
image-providing materials are formed from material associated with
the silver halide emulsions in layers 22, 20 and 18 as a function
of the imagewise exposure of their associated emulsions. At least
part of the imagewise distributions of mobile yellow-, magenta- and
cyan-forming materials transfer, by diffusion, to the
image-receiving layer 16 to provide a positive dye image therein,
preferably upon contact with an 'onium compound. This positive,
right-reading image can then be viewed through transparent support
layer 15 on the opaque reflecting layer 17 background. Since the
receiving layer does not have to be stripped away from the negative
portion of the film unit, the composite structure can be maintained
intact subsequent to said processing.
In accordance with the invention, shifted dye developers permit
exposure through the required side and still retain effective
contact with the silver halide emulsion to render the dye
image-providing material nondiffusing in the developed areas, thus
avoiding severe color contamination. The shifted dye developers can
generally be incorporated in the emulsion layer or positioned
between the emulsion layer and the exposure source without
substantial competitive light absorption, so that a high-speed
photographic system with this format based on negative emulsions
and diffusible dye image-providing substances can now be made.
In a color film unit according to the 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 in addition to those
described above, 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 Pat. No. 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, 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;
the dye image-providing materials are dispersed in an aqueous
alkaline solution-permeable polymeric binder, such as gelatin, as a
separate layer about 1 to 7 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 include both naturally occurring substances such as
proteins, 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 U.S. Pat. Nos. 3,142,568 by Nottorf issued July 28, 1964,
3,193,386 by White issued July 6, 1965, 3,062,674 by Houck et al
issued Nov. 6, 1962, 3,220,844 by Houck et al issued Nov. 30, 1965,
3,287,289 by Ream et al issued Nov. 22, 1966, and 3,411,911 by
Dykstra issued Nov. 19, 1968. Particularly effective are
waterinsoluble polymers of alkyl acrylates and methacrylates,
acrylic acid, sulfoalkyl acrylates or methacrylates, those which
have cross-linking sites which facilitate hardening or curing, and
those having recurring sulfobetaine units as described in Dykstra,
Canadian Pat. No. 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 image to be
mordanted as mentioned hereinbefore. In one embodiment, the
photographic elements of this invention contain an image-receiving
layer which comprises a polyvinylpyridine mordant. However, the
dyes formed with the polyvinylpyridine mordant appear to be
distinguished from those formed with an 'onium mordant in that they
can be removed from the mordant layer by repeated washings.
Use of a pH-lowering layer in the film unit of the invention will
usually increase the stability of the transferred image. Generally,
the pH-lowering layer will effect a reduction in the pH of the
image layer from about 13 and 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 may be employed. Such
polymeric acids reduce the pH of the film unit after development to
terminate development and substantially reduce further dye transfer
and thus stabilize the dye image. Such polymeric acids comprise
polymers containing acid groups, such as carboxylic acid and
sulfonic acid groups, which are capable of forming salts with
alkali metals, such as sodium or potassium, or with organic bases,
particularly quaternary ammonium bases, such as tetramethyl
ammonium hydroxide. The polymers can also contain potentially
acid-yielding groups such as anhydrides or lactones or other groups
which are capable of reacting with bases to capture and retain
them. Generally, the most useful polymeric acids contain free
carboxyl groups, being insoluble in water in the free acid form and
which form watersoluble sodium and/or potassium salts. Examples of
such polymeric acids include dibasic acid half-ester derivatives of
cellulose, which derivatives contain free carboxyl groups, e.g.,
cellulose acetate hydrogen phthalate, cellulose acetate hydrogen
glutarate, cellulose acetate hydrogen succinate, ethyl cellulose
hydrogen succinate, ethyl cellulose acetate hydrogen succinate,
cellulose acetate succinate hydrogen phthalate; ether and ester
derivatives of cellulose modified with sulfoanhydrides, e.g., with
ortho-sulfobenzoic anhydride; polystyrene sulfonic acid;
carboxymethyl cellulose; polyvinyl hydrogen phthalate; polyvinyl
acetate hydrogen phthalate; polyacrylic acid, acetals of polyvinyl
alcohol with carboxy or sulfo-substituted aldehydes, e.g., o-, m-
or p-benzaldehyde sulfonic acid or carboxylic acid; partial esters
of ethylene/maleic anhydride copolymers; partial esters of
methylvinyl ether/maleic anhydride copolymers; etc. In addition,
solid monomeric acid materials could also be used such as palmitic
acid, oxalic acid, sebacic acid, hydrocinnamic acid, metanilic
acid, paratoluenesulfonic acid and benzenedisulfonic acid. Other
suitable materials are disclosed in U.S. Pat. Nos. 3,422,075 and
2,635,048.
The pH-lowering layer is usually about 0.3 to about 1.5 mils in
thickness and can be located in the receiver portion of the film
unit between the support and the image-receiving layer, on the
cover sheet, or it can be located anywhere within the film unit as
long as the desired function is obtained.
An inert timing or spacer layer coated over the pH-lowering layer
may also be used to "time" or control the pH reduction of the film
unit as a function of the rate at which the alkali diffuses through
the inert spacer layer. This timing layer can also be used
effectively to isolate oxidizing materials in a layer adjacent the
image-receiving layer wherein oxidant will be released after alkali
breakdown of the timing 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 polyvinly 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 12, and
preferably containing an auxiliary developing agent. 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% by weight of the processing solution is
preferred which will impart thereto a viscosity of about 100 cps.
to about 200,000 cps. If desired, an adhesive may be added to the
processing composition to increase further the adhesion of the
transparent sheet to the photosensitive element after
processing.
The alkaline processing composition employed in this invention can
also contain an auxiliary or accelerating developing agent which
does not contain the structure D-(SID) as defined above. Typical
useful auxiliary developing agents (reducing agents) are
p-methylaminophenol, 2,4-diaminophenol, p-benzylaminophenol,
hydrozuinone, toluhydroquinone, phenylhydroquinone,
4-methylphenylhydroquinone, etc. A plurality of auxiliary or
accelerating developing agents such as those disclosed in U.S. Pat.
No. 3,039,869 can also be employed. Such auxiliary or accelerating
developing agents can be employed in the liquid processing
composition or may be contained, at least in part, in any layer or
layers of the film unit such as the silver halide emulsion layers,
the dye image-providing material layers, interlayers,
image-receiving layer, etc., and are preferably coated in the
layers of the photosensitive element.
The alkaline processing composition employed in this invention can
also contain a desensitizing agent such as methylene blue,
nitro-substituted heterocyclic compounds, 4,4'-bipyridinium salts,
etc., to insure that the photosensitive element is not further
exposed after it is removed from the camera for processing.
While the alkaline processing composition used in this invention
can be employed in a rupturable container, as described previously,
to facilitate conveniently the introduction of processing
composition into the film unit between the transparent sheet and
the photosensitive element, other means of discharging processing
composition within 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, as described in Harvey, U.S. Pat. No. 3,352,674
issued November 14, 1967.
Any opacifying agent can be employed in the processing composition
in certain embodiments of our invention. Examples of opacifying
agents include carbon black, barium sulfate, zinc oxide, barium
stearate, silver flake, silicates, alumina, zirconium oxide,
zirconium acetyl acetate, sodium zirconium sulfate, kaolin, mica,
titanium dioxide, organic dyes such as the nigrosines, or mixtures
thereof in widely varying amounts depending upon the degree of
opacity desired. In general, the concentration of opacifying agent
should be sufficient to prevent further exposure of the film unit's
silver halide emulsion or emulsions by ambient actinic radiation
transversing through the top transparent sheet subsequent to
distribution of the processing solution between the top transparent
sheet and the underlying layer adjacent thereto. For example,
carbon black or titanium dioxide will generally provide sufficient
opacity when they are present in the processing solution in an
amount of from about 5 to 40% by weight. After the processing
solution and opacifying agent have been distributed into the film
unit, processing may take place out of the camera in the presence
of actinic radiation in view of the fact that the silver halide
emulsion or emulsions of the laminate are appropriately protected
by incident radiation, at one major surface by the opaque
processing composition and at the remaining major surface by the
alkaline solution-permeable opaque layer. Opaque binding tapes can
also be used to prevent edge leakage of actinic radiation incident
on the silver halide emulsion.
When titanium dioxide or other white pigments are employed as the
opacifying agent in the processing composition in our invention, it
may also be desirable to employ in cooperative relationship
therewith a pH-sensitive opacifying dye such as a phthalein dye.
Such dyes are light-absorbing or colored at the pH at which image
formation is effected and colorless or not light-absorbing at a
lower pH. Other details concerning these opacifying dyes are
described in French Pat. No. 2,026,927.
The alkaline solution-permeable, susbstantially opaque,
light-reflective layer in the photographic film unit 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-refelective 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 may be added to it, e.g., carbon black, nigrosine dyes, etc.
Another technique to increase the opacifying capaicty of the
light-reflective layer is to employ a separate opaque layer
underneath it omprising, e.g., carbon black, nigrosine dyes, etc.,
dispersed in an alkaline solution-permeable polymeric matrix such
as, for example, gelatin, polyvinyl alcohol, and the like. Such an
opaque layer would generally have a density of at least 4 and
preferably greater than 7 and would be substantially opaque to
actinic radiation. The opaque layer may also be combined with a
developer scavenger layer if one is present. The light-reflective
and opaque layers are generally 1 to 6 mils in thickness, although
they can be varied depending upon the opacifying agent employed,
the degree of opacity desired, etc.
When transparent sheets are used in film assemblies of this
invention, they can be any transparent material as long as it does
not deleteriously affect the photographic properties of the film
unit and is dimensionally stable. Typical actinic
radiation-transmissive flexible sheet materials include cellulose
nitrate film, cellulose acetate film, poly(vinyl acetal) film,
polystyrene film, poly(ethyleneterephthalate) film, poly-carbonate
film, poly-.alpha.-olefins such as polyethylene and polypropylene
film, and related films or resinous materials, as well as glass.
The transparent sheet is usually about 2 to 6 mils in thickness and
may contain an ultraviolet absorber for exposure control if
desired. In addition, an adhesive layer able to be activated by the
processing composition may be present on the transparent sheet in
order to increase its adhesion to the photosensitive element after
processing.
When transparent supports are used in film assemblies of this
invention, they can be any of the materials mentioned above for the
transparent sheet. If desired, an ultraviolet-absorbing material
can be employed in the support to prevent the dye images from
fading due to ultraviolet light.
The photosensitive substances used in this invention are preferably
silver halide compositions and can comprise silver chloride, silver
bromide, silver bromoiodide, silver chlorobromoiodide and the like,
or mixtures thereof. The emulsions may be coarse- or fine-grain and
can be prepared by any of the well-known procedures, e.g.,
single-jet emulsions, double-jet emulsions, such as Lippmann
emulsions, ammoniacal emulsions, thiocyanate or thioether ripened
emulsions such as those described in U.S. Pat. No. 2,222,264 by
Nietz et al, 3,320,069 by Illingsworth, and 3,271,157 by McBride.
Surface-image emulsions can be used or internal-image emulsions can
be used such as those described in U.S. Pat. Nos. 2,592,250 by
Davey et al, 3,204,313 by Porter et al, and 3,447,927 by Bacon et
al. 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. If desired, mixtures or surface-and
internal-image emulsions can be used as described in Luckey et al,
U.S. Pat. No. 2,996,382.
Negative-type emulsions are generally preferred, but
direct-positive emulsions can be used if desired. Typical
direct-positive emulsions include those described in U.S. Pat. Nos.
2,184,013 by Leermakers, 2,541,472 by Kendall et al, 3,367,778 by
Berriman, 3,501,307 by Illingsworth et al issued March 17, 1970,
2,563,785 by Ives, 2,456,953 by Knott et al and 2,861,885 by Land,
British Pat. No. 723,019 by Schouwenaars, and U.S. Ser. Nos.
123,005 by Evans filed Mar. 10, 1971, now U.S. Pat. No. 3,761,276,
123,006 by Milton filed Mar. 10, 1971, now U.S. Pat. No. 3,761,266,
123,007 by Gilman et al filed Mar. 10, 1971, now U.S. Pat. No.
3,761,267, 154,154 by Collier et al filed June 17, 1971, now U.S.
PAt. No. 3,726,140, 154,155 by Gilman et al filed June 17, 1971,
now abandoned and 154,224 by Gilman et al filed June 17, 1971, now
U.S. Pat. No. 3,730,723.
Generally, in the photographic elements referred to above, a
positive image record is obtain in an image-receiving layer by
mordanting the diffusible image-providing material which is not
immobilized or remains diffusible in the photosensitive portion of
the film unit. It is also appreciated that the photosensitive
element contains an image record which provides a useful image
product. In one instance, the mobile or diffusible materials can be
washed out after exposure to produce a negative image record. In
another embodiment, the silver halide emulsion can be selected to
produce a positive image record in the photosensitive portion of
the film element.
The invention can be further illustrated by the following examples
wherein the compounds identified by roman numerals are further
identified structurally in the foregoing specification.
EXAMPLE 1
A. preparation of Intermediate I-A ##SPC15##
A suspension of 12.4 g. (0.04 M.) of compound 1 in 50 ml. dry
benzene is refluxed with 10 ml. thionyl chloride for 30 minutes.
The benzene is removed, yielding an oil which is treated with 10.8
g. (0.04 M.) of compound 2 and 5 ml. of N,N-dimethylaniline in
acetone solution. This mixture is allowed to stand overnight, the
solvent is removed and the residue is recrystallized from
acetonitrile to yield 12.4 g. of solid (Intermediate I-A), m.p.
163-167.degree. C. Thin-layer chromatography shows one component.
The IR spectrum agrees with the assigned structure.
B. preparation of Intermediate I-B
A suspension of 8.4 g. (0.015 M.) of Intermediate I-A in 300 ml. of
dimethoxyethane is treated with 0.58 g. (0.015 M.) of NaH
dispersion. After stirring for 30 minutes, 5.9 g. (0.015 M.) of
compound 4 is added and the mixture is allowed to stand overnight.
The solvent is removed, yielding an oil which is dissolved in
chloroform and filtered through a silica gel pad. After removal of
the solvent, the residue is recrystallized from benzene-cyclohexane
to give 3 g. of Intermediate I-B. Thin-layer chromatography shows
one component. The IR spectrum agrees with the assigned structure.
Compound 4 is: ##SPC16##
C. preparation of Compound I (shifted yellow indophenol dye
developer)
A solution of 10 g. (0.012 M.) of Intermediate I-B in 200 ml. of
methanol is refluxed for 1 hour in a nitrogen atmosphere with 2.8
g. (0.05 M.) of potassium hydroxide dissolved in water. After
cooling, the reaction mixture is acidified with acetic acid and
extracted with ether. The ether extract is concentrated to an oil,
then recrystallized from benzene-ethyl acetate-cyclohexane to give
1 g. of Compound I. Thin-layer chromatography shows one component.
The NMR and IR spectra agree with the assigned structure.
EXAMPLE 2
This example demonstrates in a nonimage-forming format the property
of a shifted dye developoer of undergoing a spectral-absorption
change upon contact with a mordant such as an organic 'onium
compound.
A. A supported single-layer gelatinous coating, containing 250 mg.
of gelatin and 70 mg. of Compound I per square foot of coating, is
dried and spectrophotometrically evaluated. The spectrophotometric
absorption profile of Compound I contained in the so-prepared
coating is represented by Curve A in FIG. 2.
B. A sample of the above-described coating is immersed for 1 minute
in a mordant solution whose composition is given below:
hexadecyltrimethylammonium bromide 5 g. K.sub.2 HPO.sub.4 (0.5 M.)
430 ml. KH.sub.2 PO.sub.4 (1.5 M.) 70 ml. water to 1 liter pH =
7.0
Upon removal from the solution, the sample is dried and
spectrophotometrically evaluated. The absorption profile of
Compound I in the so-treated sample is represented by Curve B in
FIG. 2.
A comparison of Curves A and B in FIG. 2 shows the compound's
initial low absorption and its desirable final high absorption of
blue light.
EXAMPLE 3
This example deomonstrates in a nonimage-forming format the
trannsfer of an initially shifted dye developer to a receiver and
the production of a modanted dye in the receiver.
A. a sample of the gelatin coating described in section (A) of
Example 2 is brought into intimate contact for 30 seconds with a
mordanted receiver, a coacervate of N-n-hexadecyl-N-morpholinium
ethosulfate and methyl-tri-n-dodecylammonium p-toluenesulfonate in
the presence of the following viscous processing fluid:
potassium hydroxide 30 g. hydroxyethyl cellulose 30 g. water to 1
liter
Upon separation of the gelatin coating from the receiver, the
latter contains a uniformly distributed dense yellow dye. The
receiver is washed for 3 minutes without appreciable change in the
appearance of the yellow dye.
EXAMPLE 4
A supported multilayer photographic element is coated as
follows:
1. support;
2. layer containing 250 mg./ft..sup.2 of gelatin, 70 mg./ft..sup.2
of Compound I and 70 mg./ft..sup.2 of diethyl lauramide;
3. layer containing 250 mg./ft..sup.2 of gelatin and a silver
halide emulsion at 200 mg./ft..sup.2 of silver;
4. layer containing 80 mg./ft.2 of gelatin.
A sample of the above-described coating is exposed through a
graduated-density test object and processed in the presence of a
viscous developing solution whose composition is shown below, while
in contact for 30 seconds with a receiver containing the mordant of
Example 3. Upon separation of the coating sample from the receiver,
the latter contains a well-defined positive yellow umage of the
photographed test object.
______________________________________ Developing Solution
______________________________________ sodium hydroxide 20 g.
1-phenyl-4-methyl-4-hydroxymethyl-3- 0.75 g. pyrazolidone
hydroxyethyl cellulose 25 g. water to 1 liter pH 13.7
______________________________________
EXAMPLE 5
A. A first section of a sample of the silver halide emulsion
coating described in Example 4 is uniformly flashexposed. A second
section remains unexposed. The sample is brought into intimate
contact for 30 seconds with the coacervate mordant receiver
described in section (A) of Example 3 in the presence of a viscous
processing liquid consisting of 20 g. of sodium hydroxide, 25 g.
hydroxyethyl cellulose and 0.75 g.
1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone per liter of
aqueous solution.
Upon separation of the coating sample from the receiver, the latter
contains a dense yellow dye in the area which, during the transfer
cycle, has been opposite the unexposed section of the emulsion
coating. The rceiver is washed for 3 minutes without appreciable
change in the apperance of the yellow dye.
B. When the procedure described in section (A) above is repeated
with a processing liquid which consists of only 40 g, potassium
hydroxide and 30 g. hydroxyethyl cellulose per liter of solution,
(i.e., the auxiliary developing agent has been omitted), the
receiver contains yellow dye in both areas of contact. In this
embodiment, the auxiliary developing agent is desirable to provide
immobilizing reactions to obtain good image discrimination.
EXAMPLE 6 ##SPC17##
A solution (6-1) in dry tetrahydrofuran is treated with a mixture
of thionyl chloride and N,N-dimethylformamide in dry benzene and
heated for 30 minutes. The solvent is removed under reduced
pressure to give the acid chloride, m.p. 50-53.degree. C. The acid
chloride is dissolved in dry dioxane and added to a mixture of
(6-2) and quinoline in dry dioxane. After standing at room
temperature, the solid is collected and recrystallized from
acetonitrile to give Intermediate 6-A, m.p. 198-200.degree. C.
A solution of Intermediate 6-A in tetrahydrofuran is treated with
(6-3), followed by a solution of sodium bicarbonate in water and
methyl alcohol and stirred for 1 hour. Water is added, the solid is
collected, dissolved in chloroform and chromatographed on silica
gel to give Compound 6, m.p. 136-137.degree. C. Compound (6-3) is
as follows: ##SPC18##
Compound 6 is as follows: ##SPC19##
Compound 6 is incorporated in a gelatin layer coated on a support
and is found to transfer a cyan dye to a quaternary mordant when
contacted with an alkaline processing solution with a pH of 14. The
dye remains cyan when the pH is then adjusted to about 7.
EXAMPLE 7
Preparation of a Magenta Shifted Dye Developer ##SPC20##
A suspension of (7-b 1) in dry benzene is refluxed with thionyl
chloride and N,N-dimethylformamide for 20 minutes. The solvent is
removed under reduced pressure and the residue is dissolved in
acetic acid and added to a solution of (7-2) and sodium acetate in
acetic acid. The mixture is stirred for 2 hours, allowed to stand
overnight, then poured into water. After neutralizing with sodium
bicarbonate, the solid is collected and recrystallized from ethyl
acetate to give Intermediate 7-A, m.p. 135-136.degree. C.
A solution of Intermediate 7-A in ethyl acetate and tetrahydrofuran
is treated with sodium bicarbonate, followed by Compound 7-3), then
stirred for 1 hour. Water is added, the mixture is filtered through
celite and the filtrate is extracted with chloroform. After washing
with water, the organic layer is separated, dried and concentrated
under reduced pressure. The residue is chromatographed on silica
gel to yield Intermediate 7-B.
Compound (7-D) is as follows: ##SPC21##
A solution of Intermediate 7-B in tetrahydrofuran and pyridine is
treated with a 3% sodium carbonate solution and refluxed for 5
hours under a nitrogen atmosphere. After cooling, the solution is
poured into a dilute acetic acid solution and the solid is
collected to give Compound II identified above.
In certain embodiments according to this invention, the shifted dye
developers of this invention can be prepared as illustrated in the
following example by further reacting the oxichromic compounds of
Lestina and Bush, U.S. Ser. No. 206,949, entitled "Oxichromic
Compounds, Stabilized Oxichromic Compounds and Processes for
Preparing Same" filed Dec. 10, 1971, and incorporated herein by
reference, now abandoned and refiled as U.S. Ser. No. 426,177.
EXAMPLE 8
The oxichromic compound
4-(3,5-dichloro-4-hydroxyanilino)-2-[5-(2,5-dihydroxyphenyl)pentanoylamido
]-5-(4-pentoxy-benzamido)phenol (1.449, 2.11 .times. 10.sup..sup.-3
moles), prepared according to Lestina and Bush, U.S. Ser. No.
206,949, Example 2, is dissolved in 300 ml. of a mixture of 80% by
volume acetonitrile and 20% by volume N,N-dimethylformamide and the
solution is made 0.1 molar with sodium perchlorate. The solution is
oxidized by controlled potential electrolysis in a two-compartment
cell using a potentiostat for control and platinum electrodes at a
potential of +0.55 v. until the current has decayed to 10% of its
original value. The progress of the reaction is monitored by
occasionally recording a current-voltage curve. After 375.1
coulombs (2.05 electrons/molecule have passed, the first oxidation
wave (E.sub.1) of the lecuo dye has diminished to approximately 5%
of its original height, whereas the second wave (E.sub.2) has
retained its original height. The red solution is filtered and
water is added dropwise, causing precipitation of the product. The
red solid is collected by filtration, washed several times with
water and dried under reduced pressure. The yield is 1.4 g. or
about 100%. The current yield is also 100%. After recrystallization
from ethanol, m.p. = 200-201.degree. C.
The compound has the formula: ##SPC22##
EXAMPLE 9
The shifted dye developer of Example 8 is coated and tested as
follows:
A. a nonsilver coating is made on a cellulose acetate support with
the following layers coated in order:
1. layer containing 125 mg./ft..sup.2 of gelatin, 75 mg./ ft..sup.2
of diethyl lauramide and 50 mg./ft..sup.2 of Compound IV;
2. overcoat containing 80 mg./ft..sup.2 of gelatin.
B. a coating containing a silver halide emulsion is prepared by
coating on a cellulose acetate support the following layers:
1. layer containing 125 mg./ft..sup.2 of gelatin, 75 mg./ft..sup.2
of diethyl lauramide and 50 mg./ft..sup.2 of Compound IV;
2. layer containing a monodispersed silver bromide emulsion at 100
mg. of Ag/ft..sup.2, 10 mg./ft..sup.2 of 1-phenyl-3-pyrazolidone
and 100 mg./ft..sup.2 of gelatin;
3. overcoat containing 80 mg./ft..sup.2 of gelatin.
The nonsilver coating is evaluated on a spectrophotometer and gives
.lambda.max at 590 nm. with a Dmax of 0.55 which is shown as line A
of FIG. 3.
A portion of the nonsilver coating is soaked in a 5%
1-phenyl-3-pyrazolidone solution (H.sub.2 O and methanol) for 5
minutes wherein the color substantially disappears. A
spectrophotometric absorption curve of this coating is shown as
line B of FIG. 3.
One set each of the untreated coating and the coating treated with
1-phenyl-3-pyrazolidone is processed in contact with a receiver
sheet containing the mordant N-n-octadecyltributylammonium bromide,
using a 0.003 inch undercut roller assembly and a processing
composition made as follows:
potassium hydroxide 40 g. hydroxyethyl cellulose 30 g. water to
make 1 liter
The receiver sheet is peeled from the coated sample after
processing with substantially no dye image apparent in the treated
coating. After about 2-5 seconds' exposure to air, the reflective
density of the dye transferred from the treated sample is 2.40 with
a 30-second transfer, whereas the density from the untreated sample
is 1.80 after a 5-minute transfer as evidenced by line C of FIG.
3.
The coatings containing the silver halide emulsion are given a
stepped exposure and processed for 60 seconds with the processing
composition above while in contact with the mordanted receiver
sheet above.
There is substantially no dye in the receiver immediately after the
receiver sheet is peeled from the photosensitive element. However,
after 2-5 seconds of contact with air substantial dye density is
observed in the receiver sheet.
The incorporation of the reducing agent 1-phenyl-3-pyrazolidone in
the photographic element, along with the shifted indophenol dye
developer, appears to provide substantially no absorption of light
by the shifted dye developer and also provides faster transfer of
dye to the image-receiving layer.
When the untreated coatings are developed with a processing
solution containing 5 g. per liter of ascorbic acid (reducing
agent), fast transfer times are also obtained.
EXAMPLE 10
The oxichromic compound
4-(3,5-dichloro-4-hydroxyanilino)-3-{3-[5-(2,5-dihydroxyphenyl)pentanoylam
ido]phenylcarbamoyl}-1-phenyl-2-pyrazoline-5-one, prepared
according to Example 1-C of Stern and Machiele, U.S. Ser. No.
206,926 filed Dec. 10, 1971, and incorporated herein by reference,
is subjected to hydrogenolysis to remove the masking groups on the
developing moiety according to Example 1-F of Stern and Machiele,
U.S. Ser. No. 206,926, and then subjected to aerial oxidation to
produce the shifted dye believed to have the formula: ##SPC23##
Compound V
EXAMPLE 11:
The shifted indophenol dye developers can be incorporated into the
multicolor photosensitive element of a film transfer unit as
disclosed in U.S. Pat. No. 2,983,606, Belgian Pat. Nos. 757,959 and
757,960 granted Apr. 23, 1971, or Lestina and Bush, U.S. Ser. No.
206,836 filed Dec. 10, 1971, entitled "Oxichromic Compounds," now
abandoned and refiled as U.S. Ser. No. 308,869, all of which are
incorporated herein by reference. Compound V is incorporated in
association with a green-sensitive silver halide emulsion, Compound
IV is incorporated in association with the red-sensitive silver
halide emulsion and Compound I is incorporated in association with
the blue-sensitive silver halide emulsion layer. Compounds I, IV
and V can be coated in the respective silver halide emulsion
layers, on the exposure side of the silver halide emulsion layers,
or under the emulsion layer with respect to exposure; however, the
first two locations are preferred. An auxiliary developer and
preferably a reducing agent, such as 1-phenyl-3-pyrazolidone, are
incorporated in the photographic element in association with the
respective shifted dye developers.
The image-receiving layer contains a dye mordant which is
preferably an 'onium compound. Suitable 'onium mordants are in
coacervate of N-n-hexadecyl-N-morpholinium ethosulfate and
methyl-tri-n-dodecylammonium p-toluenesulfonate, the mordant
N-n-octadecyltributylammonium bromide, and the like.
Good three-color image transfers are obtained upon processing with
an alkaline processing solution and the image dyes remain stable
even when the pH is reduced to about 7.
Although the invention has been described in considerable detail
with particular reference to certain preferred embodiments thereof,
variations and modifications can be effected within the spirit and
scope of the invention.
* * * * *