REVELATEURS ANTAEONISTES BLOQUES, A BASE D'ESTERS D'HYDROQUINONE, POUR LES ASSEMBLAGES DE TRANSFERT DE COULEUR

HYDROQUINONE ESTER BLOCKED COMPETING DEVELOPERS FOR COLOR TRANSFER ASSEMBLAGES

Abrégé anglais

ABSTRACT OF THE DISCLOSURE
Hydroquinone esters are incorporated in photo-
graphic elements for color diffusion transfer assemblages
and release a competing developer upon contact with a
processing composition, The hydroquinone esters are
employed in a concentration sufficient, upon hydrolysis, to
reduce substantially all the silver in the silver halide
emulsion.

Revendications

- 37 -
WHAT IS CLAIMED IS:
1. In a photographic element comprising a
support having thereon at least one photosensitive silver
halide emulsion layer having associated therewith a
ballasted, redox-dye-releasing compound, the improvement
wherein said element contains a hydroquinone ester having
the following formula:
<IMG>
wherein:
X is hydrogen, COR or SO2R;
X1 is COR or SO2R;
R is an alkyl group having from 1 to about 20
carbon atoms or an aryl group having from 6 to about 12
carbon atoms; and
Z is hydrogen, an alkyl group having from 1 to
about 6 carbon atoms, an alkoxy group having from 1 to about
6 carbon atoms, or an aryl group having from about 6 to
about 8 carbon atoms;
said ester being present in a concentration sufficient, upon
hydrolysis, to reduce substantially all the silver in said
silver halide emulsion.
2. The photographic element of Claim 1 wherein
said hydroquinone ester is 2-methylhydroquinone monoacetate,
2-methoxyhydroquinone monoacetate, 2-methylhydroquinone
monobenzoate, 2-methoxyhydroquinone monobenzoate, hydro-
quinone diacetate, hydroquinone monoacetate, hydroquinone
monohexanoate, 3-t-butyl-4-hydroxyphenyl acetate, hydro-

- 38 -
quinone monobenzoate, 2-ethoxyhydroquinone monoacetate,
2-ethoxyhydroquinone monobenzoate, p-methylsulfonyloxyphenol
or p-tolylsulfonyloxyphenol.
3. The photographic element of Claim 1 wherein
said hydroquinone ester is present in a concentration of
from about 4 to about 10 mg/dm2.
4. The photographic element of Claim 1 wherein
said dye releasing compound is a ballasted sulfonamido
compound which is alkali-cleavable upon oxidation to
release a diffusible color-providing moiety from a benzene
nucleus, said compound having the formula:
<IMG>
wherein:
Col is a dye or dye precursor moiety;
Ballast is an organic ballasting radical of such
molecular size and configuration as to render said compound
nondiffusible in said photographic element during develop-
ment in an alkaline processing composition;
G is OR2 or NHR3 wherein R2 is hydrogen or a
hydrolyzable moiety and R3 is hydrogen or an alkyl group
of 1 to 22 carbon atoms;
Y represents the atoms necessary to complete a
benzene nucleus, a naphthalene nucleus or a 5- to 7-membered
heterocyclic ring; and
n is a positive integer of 1 to 2 and is 2 when G
is OR2 or when R3 is hydrogen or an alkyl group of less
than 8 carbon atoms.
5. The photographic element of Claim 4 wherein
said dye-releasing compound is a p-sulfonamidonaphthol.

- 39 -
6. The photographic element of Claim 1 wherein
said hydroquinone ester is 2-methylhydroquinone monobenzoate.
7. The photographic element of Claim 1 wherein
said hydroquinone ester is hydroquinone monoacetate.
8. In a photographic element comprising a
support having thereon a red-sensitive silver halide emul-
sion layer having a ballasted, redox, cyan dye-releasing
compound associated therewith, a green-sensitive silver
halide emulsion layer having a ballasted, redox, magenta
dye-releasing compound associated therewith, and a blue-
sensitive silver halide emulsion layer having a ballasted,
redox, yellow dye-releasing compound associated therewith,
the improvement wherein each said emulsion layer contains
a hydroquinone ester having the following formula:
<IMG>
wherein:
X is hydrogen, COR or SO2R,
X1 is COR or SO2R;
R is an alkyl group having from l to about 20
carbon atoms or an aryl group having from 6 to about 12
carbon atoms; and
Z is hydrogen, an alkyl group having from 1 to
about 6 carbon atoms, an alkoxy group having from 1 to about
6 carbon atoms, or an aryl group having from about 6 to
about 8 carbon atoms;
said ester being present in a concentration sufficient, upon
hydrolysis, to reduce substantially all the silver in each
said silver halide emulsion.

- 40 -
9. The photographic element of Claim 8 wherein
said hydroquinone ester is 2-methylhydroquinone monoacetate,
2-methoxyhydroquinone monoacetate, 2-methylhydroquinone
monobenzoate, 2-methoxyhydroquinone monobenzoate, hydro-
quinone diacetate, hydroquinone monoacetate, hydroquinone
monohexanoate, 3-t-butyl-4-hydroxyphenyl acetate, hydro-
quinone monobenzoate, 2-ethoxyhydroquinone monoacetate,
2-ethoxyhydroquinone monobenzoate, p-methylsulfonyloxyphenol
or p-tolylsulfonyloxyphenol.
10. The photographic element of Claim 8 wherein
said hydroquinone ester is present in a concentration of
from about 4 to about 10 mg/dm2.
11. In a photographic assemblage to be processed
by an alkaline processing composition, said assemblage com-
prising:
(a) a photographic element comprising a support
having thereon at least one photosensitive
silver halide emulsion layer having asso-
ciated therewith a ballasted, redox-dye-
releasing compound; and
(b) a dye image-receiving layer;
the improvement wherein said photographic element contains
a hydroquinone ester having the following formula:
<IMG>
wherein:
X is hydrogen, COR or SO2R;
X1 is COR or SO2R;
R is an alkyl group having from 1 to about 20
carbon atoms or an aryl group having from 6 to about 12
carbon atoms; and

- 41 -
Z is hydrogen, an alkyl group having from 1 to
about 6 carbon atoms, an alkoxy group having from 1 to about
6 carbon atoms, or an aryl group having from about 6 to
about 8 carbon atoms;
said ester being present in a concentration sufficient, upon
hydrolysis, to reduce substantially all the silver in said
silver halide emulsion.
12. In a photographic assemblage comprising:
(a) a photographic element comprising a support
having thereon at least one photosensitive
silver halide emulsion layer having asso-
ciated therewith a ballasted, redox-dye-
releasing compound;
(b) a dye image-receiving layer; and
(c) an alkaline processing composltion and means
for discharging same within said assemblage;
said assemblage containing a silver halide developing agent,
the improvement wherein said photographic element contains
a hydroquinone ester having the following formula:
<IMG>
wherein:
X is hydrogen, COR or SO2R;
X1 is COR or SO2R;
R is an alkyl group having from 1 to about 20
carbon atoms or an aryl group having from 6 to about 12
carbon atoms; and
Z is hydrogen, an alkyl group having from 1 to
about 6 carbon atoms, an alkoxy group having from 1 to about
6 carbon atoms, or an aryl group having from about 6 to
about 8 carbon atoms;
said ester being present in a concentration sufficient, upon
hydrolysis, to reduce substantially all the silver in said
silver halide emulsion.

- 42 -
13. The assemblage of Claim 12 wherein:
(a) said dye image-receiving layer is located
between said support and said silver halide
emulsion layer; and
(b) said assemblage also includes a transparent
cover sheet over the layer outermost from
said support.
14. The assemblage of Claim 13 wherein said cover
sheet has thereon, in sequence, a neutralizing layer and a
timing layer.
15. The assemblage of Claim 14 wherein said
discharging means is a rupturable container containing said
alkaline processing composition and an opacifying agent,
said container being so positioned during processing of said
assemblage that a compressive force applied to said container
will effect a discharge of the container's contents between
said transparent sheet and the layer outermost from said
support.
16. In a photographic assemblage comprising:
(a) a photographic element comprising a support
having thereon a red-sensitive silver halide
emulsion layer having associated therewith a
ballasted, redox, cyan dye-releasing compound,
a green-sensitive silver halide emulsion layer
having associated therewith a ballasted,
redox, magenta dye-releasing compound, and a
blue-sensitive silver halide emulsion layer
having associated therewith a ballasted,
redox, yellow dye-releasing compound;
(b) a dye image-receiving layer; and
(c) an alkaline processing composition and means
containing same for discharge within said
assemblage;

- 43 -
said assemblage containing a silver halide developing agent,
the improvement wherein each said emulsion layer contains
a hydroquinone ester having the following formula:
<IMG>
wherein:
X is hydrogen, COR or SO2R;
X1 is COR or SO2R;
R is an alkyl group having from 1 to about 20
carbon atoms or an aryl group having from 6 to about 12
carbon atoms; and
Z is hydrogen, an alkyl group having from 1 to
about 6 carbon atoms, an alkoxy group having from 1 to about
6 carbon atoms, or an aryl group having from about 6 to
about 8 carbon atoms;
said ester being present in a concentration sufficient, upon
hydrolysis, to reduce substantially all the silver in each
said silver halide emulsion.
17. The photographic assemblage of Claim 16 wherein
said hydroquinone ester is 2-methylhydroquinone monoacetate,
2-methoxyhydroquinone monoacetate, 2-methylhydroquinone
monobenzoate, 2-methoxyhydroquinone monobenzoate, hydro-
quinone diacetate, hydroquinone monoacetate, hydroquinone
monohexanoate, 3-t-butyl-4-hydroxyphenyl acetate, hydro-
quinone monobenzoate, 2-ethoxyhydroquinone monoacetate,
2-ethoxyhydroquinone monobenzoate, p-methylsulfonyloxyphenol
or p-tolylsulfonyloxyphenol.
18. The photographic assemblage of Claim 16
wherein said hydroquinone ester is present in a concentra-
tion of from about 4 to about 10 mg/dm2.

- 44 -
19. The photographic assemblage of Claim 16
wherein said dye-releasing compound is a ballasted sulfon-
amido compound which is alkali-cleavable upon oxidation to
release a diffusible color-providing moiety from a benzene
nucleus, said compound having the formula:
<IMG>
wherein:
Col is a dye or dye precursor moiety;
Ballast is an organic ballasting radical of such
molecular size and configuration as to render said compound
nondiffusible in said photographic element during develop-
ment in an alkaline processing composition;
G is OR2 or NHR3 wherein R2 is hydrogen or a
hydrolyzable moiety and R3 is hydrogen or an alkyl group
of 1 to 22 carbon atoms;
Y represents the atoms necessary to complete a
benzene nucleus, a naphthalene nucleus or a 5- to 7-membered
heterocyclic ring; and
n is a positive integer of 1 to 2 and is 2 when G
is OR2 or when R3 is hydrogen or an alkyl group of less
than 8 carbon atoms.
20. The photographic assemblage of Claim 19
wherein said dye-releasing compound is a p-sulfonamido-
naphthol.
21. In an integral photographic assemblage com-
prising:
(a) a photosensitive element comprising a trans-
parent support having thereon the following
layers in sequence: a dye image-receiving
layer, an alkaline solution-permeable, light-

- 45 -
reflective layer, an alkaline solution-
permeable, opaque layer, a red-sensitive
silver halide emulsion layer having asso-
ciated therewith a ballasted, redox, cyan
dye-releasing compound, a green-sensitive
silver halide emulsion layer having associa-
ted therewith a ballasted, redox, magenta
dye-releasing compound, and a blue-sensitive
silver halide emulsion layer having associa-
ted therewith a ballasted, redox, yellow dye-
releasing compound;
(b) a transparent sheet superposed over said
blue-sensitive silver halide emulsion layer
and comprising a transparent support having
thereon, in sequence, a neutralizing layer
and a timing layer; and
(c) a rupturable container containing an alkaline
processing composition and an opacifying
agent which is so positioned during proces-
sing of said assemblage that a compressive
force applied to said container will effect
a discharge of the container's contents
between said transparent sheet and said
blue-sensitive silver halide emulsion layer;
said assemblage containing a silver halide developing agent,
the improvement wherein each said emulsion layer contains
a hydroquinone ester having the following formula:
<IMG>
wherein:
X is hydrogen, COR or SO2R;
X1 is COR or SO2R;
R is an alkyl group having from 1 to about 20
carbon atoms or an aryl group having from 6 to about 12
carbon atoms; and

- 46 -
Z is hydrogen, an alkyl group having from 1 to
about 6 carbon atoms, an alkoxy group having from 1 to about
6 carbon atoms, or an aryl group having from about 6 to
about 8 carbon atoms;
said ester being present in a concentration sufficient, upon
hydrolysis, to reduce substantially all the silver in each
said silver halide emulsion.
22. In a process for producing a photographic
image in color in an imagewise-exposed photographic ele-
ment comprising a support having thereon at least one
photosensitive silver halide emulsion layer having asso-
ciated therewith a ballasted, redox-dye-releasing com-
pound, said process comprising:
treating said element with an alkaline processing
composition in the presence of a silver halide developing
agent to effect development of each exposed silver halide
emulsion layer, whereby:
(a) an imagewise distribution of said dye is
formed as a function of said development of
said silver halide emulsion layer; and
(b) at least a portion of said imagewise dis-
tribution of said dye diffuses out of said
element,
the improvement wherein said photographic element contains a
hydroquinone ester having the following formula:
<IMG>
wherein:
X is hydrogen, COR or SO2R;
X1 is COR or SO2R;
R is an alkyl group having from 1 to about 20
carbon atoms or an aryl group having from 6 to about 12
carbon atoms; and

- 47 -
Z is hydrogen, an alkyl group having from 1 to
about 6 carbon atoms, an alkoxy group having from 1 to about
6 carbon atoms, or an aryl group having from about 6 to
about 8 carbon atoms;
said ester being present in a concentration sufficient, upon
hydrolysis, to reduce substantially all the silver in said
silver halide emulsion.
23. The process of Claim 22 wherein said image-
wise distribution of said dye diffuses to a dye image-
receiving layer.
24. The process of Claim 22 wherein said
hydroquinone ester is 2-methylhydroquinone monoacetate,
2-methoxyhydroquinone monoacetate, 2-methylhydroquinone
monobenzoate, 2-methoxyhydroquinone monobenzoate, hydro-
quinone diacetate, hydroquinone monoacetate, hydroquinone
monohexanoate, 3-t-butyl-4-hydroxyphenyl acetate, hydro-
quinone monobenzoate, 2-ethoxyhydroquinone monoacetate,
2-ethoxyhydroquinone monobenzoate, p-methylsulfonyloxyphenol
or p-tolylsulfonyloxyphenol.
25. The process of Claim 22 wherein said
hydroquinone ester is present in a concentration of from
about 4 to about 10 mg/dm2.
26. The process of Claim 22 wherein said dye-
releasing compound is a ballasted sulfonamido compound which
is alkali-cleavable upon oxidation to release a diffusible
olor-providing moiety from a benzene nucleus, said compound
aving the formula:
<IMG>

- 48 -
wherein:
Col is a dye or dye precursor moiety;
Ballast is an organic ballasting radical of such
molecular size and configuration as to render said compound
nondiffusible in said photographic element during develop-
ment in an alkaline processing composition;
G is OR2 or NHR3 wherein R2 is hydrogen or a
hydrolyzable moiety and R3 is hydrogen or an alkyl group
of 1 to 22 carbon atoms;
Y represents the atoms necessary to complete a
benzene nucleus, a naphthalene nucleus or a 5- to 7-membered
heterocyclic ring; and
n is a positive integer of 1 to 2 and is 2 when G
is OR2 or when R3 is hydrogen or an alkyl group of less
than 8 carbon atoms.
27. The process of Claim 26 wherein said dye-
releasing compound is a p-sulfonamidonaphthol.

Description

7~:~
BLOCKED COMPETING DEVELOPERS
FOR COLOR TRANSFER ASSEMBLAGES
This invention relates to photography, and more
particularly to photographic assemblages ~or color di~fu-
sion trans~er photography wherein a hydroquinone ester isemployed in a photographic element in a high concentration
to release a competing developer upon contact with a
processing composition.
Various formats for color integral transfer ele-
ments are described in the prior art, such as U.S. Patents
3,415,644; 3,415,645; 3,415,646; 3,647,437; 3,635,707;
3,756,815 and Canadian Patents 928,559 and 674,082. In
these formats, the image-receiving layer containing the
photographic image for viewing can remain permanently attached
and integral with the image generating and ancillary layers
present in the structure when a transparent support is
employed on the viewing side o~ the assemblage. The ~mage
is formed by dyes, produced in the image generating units,
diffusing through the layers of the structure to the dye -
20 image-receiving layer. After exposure of the assemblage, an ~
alkaline processing composition permeates the various layers ~ -
to initiate development of the exposed photosensitive silver
halide emulsion layers. The emulsion layers are developed
in proportion to the extent of the respective exposures, and
25 the image dyes which are formed or released in the respective
image generating layers begin to diffuse throughout the
structure. At least a portion of the imagewise distribution
of diffusible dyes diffuse to the dye image-receiving layer -
to form an image of the original sub;ect. ``
Other so-called "peel-apart" formats for color
diffusion transfer assemblages are described, for example,
in U.S. Patents 2,~83,60~; 3,362,819; and 3,362,821. In
these formats, the image-receiving element is separated from
the photosensitive element after development and transfer of
35 the dyes to the image-receiving layer.
,`~` ''

w~
Competing developing agents have been used in
various photographic assemblages heretofore. ~or example,
~esearch Disclosure 15162, November 1976, on page 79, dis-
closes that combinations of certain developing agents with
alkali-soluble competing developers such as hydroquinone,
methylhydroquinone and t-butylhydroquinone are especially
useful in achieving the desired sensitometric curve shape of
the dye image in diffusion transfer assemblages, such as
those employing dye releasers described therein. In diffu-
sion transfer systems, optimum development temperatures arenot always obtainable. At high temperatures, such as 32 to
35C, there is faster development with more dye being
released, causing a significant loss in speed, an increase in
DmaX and an increase in Dmin. The presence of a competing
developing agent in the processing composition in the right
concentration will help to alleviate the problem somewhat,
since it will develop silver but will not cause any dye to
be released. The Dmin can be lowered in this manner, but
the speed loss remains. The increase in DmaX is also still
there, but is not as noticeable to the eye.
Another problem with employing a competing devel-
oper in the processing composition-concerns the variability
of the developer layer thickness, or DLT, in a given film
unit. In camieras where the operator hand cranks the film
units out of the camera, the speed at which he operates the
crank will affect the DLT -- e.g., a fast cranking motion
will provide a relatively low DLT. In cameras having a
motor drive, the DLT varies with the viscosity of the
processing composition, the temperature of processing, etc.
This variable DLT, in turn, magnifies the variability of a
competing developer employed in the processing composition, /
since it is employed at a relatively low concentration. -
U.S. Patent 3,462,266 relates to oxazines and
bisoxazines which are cleaved to hydroquinones under alka-
line conditions. The compounds are described as beingauxiliary developer precursors in dye developer image transfer
systems. Other halogenated acyl hydroquinone derivative
developers are described in U.S. Patent 3,246,988. These
-~

compounds release an active developer upon processing with
an alkaline processing composition.
U.S. Patent 3,816,12~ describes the use o cer-
tain alkyl and haloalkyl esters as an auxiliary developer
S in a diffusion transfer system, preferably employi~g a dye
developer. This patent does not describe, however~ the
use of the particular compounds of the instant invention
in the large amounts described herein for use in a color
image transfer process employing ballasted, redox, dye-
releasing compounds.
Canadian Patent Application Serial No. 312,741 ofAbbott, October 5, 1978, and assigned to the same assignee
as the instant application, relates to the use of hydroqui-
none esters in or behind a particular timing layer. The use
of such compounds in the particular location and in the
amounts described herein are not disclosed in the Abbott
application, however.
In accordance with our invention, we have found that
competing developing agents may be utilized in such a way as
to significantly reduce the speed loss attendant with high
temperature development described above. An improvement in
latitude of development time and processing temperature
variation is also achieved, as well as eliminating the
variability of the competing developer concentration with
variability in DLT.
In accordance with our invention, a photographic
element is provided which comprises a support having thereon
at least one photosensitive silver halide emulsion layer
having associated therewith a ballasted, redox-dye-releasing
compound, the element containing a hydroquinone ester having
the following formùla:
OX
~ ~ z
OX~
'.

V'7~:~
wherein:
x is hydrogen, COR or SO2R;
xl is COR or SO2R;
... .
~, . , :~ . : .

R is an alkyl (including substituted alkyl) group
having from 1 to about 20 carbon atoms or an aryl (including
substituted aryl~ group having from 6 to about 12 carbon
atoms; and
Z is hydrogen, an alkyl (including substituted
alkyl~ group having from 1 to about 6 carbon atoms, an alkoxy
group having from 1 to about 6 carbon atoms, or an aryl
(including substituted aryl~ group having from about 6 to
about 8 carbon atoms;
the ester being present in a concentration sufficient, upon
hydrolysis, to reduce substantially all the silver in the
silver halide emulsion.
Upon processing the photographic element with an
alkaline processing composition, which preferably contains
a developing agent, the acyl or sulfonyl groups are hydro-
lyzed to the corresponding hydroquinone. This hydroquinone
then acts as a competing developer with the other developing
agent in the system. In addition, the unexposed silver
halide grains are reduced somewhat by the released hydro-
quinone which is a very strong reducing agent. This willhave the effect of preventing further silver development by
the other developing agent. Since dye is not released by the
oxidized hydroquinone, "shut-down" is achieved quite rapidly
and post-processing dye-release is minimized. Very good
image discrimination is therefore achieved.
In the above formula, Z can be hydrogen; an alkyl
group of 1 to about 6 carbon atoms, such as methyl, ethyl,
isopropyl, t-butyl, etc; an alkoxy group of 1 to about 6
carbon atoms, such as methoxy or ethoxy; or an aryl group
having 6 to about 8 carbon atoms, such as phenyl, m-tolyl,
p-methoxyphenyl, etc, as long as the compound will diffuse at
a sufficient rate when the acyl or sulfonyl group or groups
are hydrolyzed. In a similar manner, when each of X and Xl in
the formula is an acyl or sulfonyl group, any such group such
as acetyl, propionyl, benzoyl, ethoxycarbonyl, ethoxalyl,
methylsulfonyl, tolylsulfonyl, etc, can be employed, so long
as it can be hydrolyzed to the corresponding hydroquinone.
As described above, the hydroquinone esters are
employed in a concentration sufficient, upon hydrolysis, to

-- 5 --
reduce substantially all the silver in the silver halide emul-
sion. If the concentration is lower, the DmaX and development
time latitude are substantially reduced, as will become appar-
ent from the examples hereafter. Good results have been ob-
tained when the hydroquinone ester is employed in a concentra-
tion of from about 4 to about 10 mg/dm2 of photographic element.
The hydroquinone esters can be incorporated in any
layer of the photographic element, such as the silver halide
emulsion layer, the dye-releaser layer, interlayer, etc.
Preferably, the hydroquinone ester is employed in the silver
halide emulsion layer. When a three-color element is
employed, each emulsion layer will have associated there-
with the hydroquinone ester in the amount stated above.
Examples of hydroquinone esters useful in our
invention include the following:
(1) Hydroquinone diacetate
O
O-C-CH
O-C-C~13
O
(2) Hydroquinone monohexanoate
O
-C-CsH 1 -n
~"- :
OH ~:
(3) 3-t-butyl-4-hydroxyphenyl acetate
O ~.
O--~-CH3
~/ \C CH
,~ OH CH
. ~ . - : ,.. ,: .:
. ` ' .

- 6 -
(4) Hydroquinone monoacetate
O
O-C-CH
~1,
OH
(5) Hydroquinone monobenzoate
- 0~ :
O-C-C H
6 5
I ~
~"
OH
(6) 2-Methylhydroqulnone monoacetate ~
~ . . .
O-C-CH
~t \CH3 ~ .
OH
(7) 2-Methoxyhydroquinone monoacetate
O ~,
O-C-CH `::
~ `n ~:
~t OCH3
OH ~
''' :.
- '
.. ..

-- 7 --
(8) 2-Methylhydroquinone monobenzoate
O
O--C--C H
\CH
OH
(9) 2-Methoxyhydroquinone monobenzoate
O
O--C--C H
~1,
~`~ OC H
OH
(10) 2-Ethoxyhydroquinone monoacetate
O
1~
O--C--C H
t C2H6
OH
tll) 2-Ethoxvhydroquinone monobenzoate
O
O-C-C H '
6 5
".
~ ~ C 2 H '
OH
-. .

2v7~
-- 8 --
(12) p-Methylsulfonyloxyphenol
OH
8~ ,~
S2 CH3
(13) p-Tolylsulfonyloxyphenol
OH
~1''
O--SOæ--C~H4CH3
As stated above, the dye image-providing material
employed in our invention is a ballasted, redox-dye-
releasing (RDR) compound. Such compounds are well known to
those skilled in the art and are, generally speaking, com-
pounds which will redox with oxidized developing agent or
electron transfer agent to release a dye, such as by alka-
line hydrolysis, or prevent the release of dye, such as by
intramolecular nucleophilic displacement. Such nondiffus- ;
ible RDR's can be positive-working compounds, as described
in U.S. Patent 3,980,479, British Patent 1,464,104 and U.S.
25 Patent No. 4,139,379 issued February 13, 1979 of Chasman
et al. Such nondiffusible RDR's can also be negative-work-
ing compounds, as described in U.S. Patents 3,728,113 of
Becker et al; 3,725,062 of Anderson and Lum; 3,698,897 of
Gompf and Lum; 3,628,952 of Puschel et ali 3,443,939 and
30 3,443,940 of Bloom et al; 4,053,312 of Fleckenstein;
4,076,529 of Fleckenstein et al; 4,055,428 of Koyama et al;
German Patents 2,505,248 and 2,729,820; Research Disclosure
15157, November, 1976; and Research Disclosure 15654, - -
April, 1977.
In a preferred embodiment of our invention, the
dye-releasers such as those in the Fleckenstein et al U.S.
Patent 4,076,529 are employed. In this embodiment, the
., ~ ~ ' ` . ~ ` :

- ~iU~
-8a-
dye-releasing compound is a ballasted sulfonamido compound
which is alkali-cleavable upon oxidation to release a
diffusible color-providing moiety from a benzene nucleus,
~,~
. ~. , .

Ji7 $~
g
the compound having the formula:
G
~ ;y ~ (Ba i l ast) n_l
NHSO2--Co I
wherein:
Col is a dye or dye precursor moiety,
Ballast is an organic ballasting radical of such
molecular size and configuration as to render the compound
nondiffusible in the photosensitive element during develop-
ment in an alkaline processing composition;
G is OR2 or NHR3 wherein R2 is hydrogen or a
hydrolyzable moiety and R3 is hydrogen or an alkyl group
of 1 to 22 carbon atoms;
Y represents the atoms necessary to complete a
benzene nucleus, a naphthalene nucleus or a 5- to 7-membered
heterocyclic ring; and
n is a positive integer of 1 to 2 and is 2 when G
is OR2 or when R3 is hydrogen or an alkyl group of less
than 8 carbon atoms.
- In a more preferred embodiment of our invention,
the nondiffusible RDR's are ballasted p-sulfonamidonaphthol
compounds, each of which has a color-providing moiety
attached thereto through a sulfonamido group which is
alkali-cleavable upon oxidation. For further details con-
cerning the above-described sulfonamido compounds, including
sulfonamidonaphthol compounds, and specific examples of
same, reference is made to the above-mentioned Fleckenstein
et al U.S. Patent 4,076,529.
A process for producing a photographic image in
color according to our invention comprises:
treating an imagewise-exposed photographic element,
as described above, with an alkaline processing composition
in the presence of a silver halide developing agent to
effect development of each exposed silver halide emulsion
layer, whereby:
- " . ; : -
~: ~

-- 10 --
(a) an imagewise distribution of dye is formed as
a function of the development o~ the silver
halide emulsion layer; and
(b) at least a portion of the imagewise distribu-
tion of the dye diffuses out of the element~
such as to a dye image-receiving layer.
A process for producing a photographic image in
color according to our invention using a preferred element
as described above wherein the nondiffusible RDR is a bal-
lasted compound having a color-providing moiety attached
thereto through a sulfonamido group which is alkali-cleavable
upon oxidation comprises:
treating said element which has been imagewise-
exposed with an alkaline processing composition in the pres-
ence of a silver halide developing agent to effect development
of each exposed silver halide emulsion layer, whereby:
(a) the developing agent becomes oxidized;
(b) the oxidized developing agent cross-oxidizes
the sulfonamido compound;
(c) the oxidized sulfonamido compound then cleaves,
thus forming an imagewise distribution of the
color-providing moiety as a function of the
development of the silver halide emulsion layer;
and
(d) at least a portion of the imagewise distribu-
tion of the color-providing moiety diffuses
out of the element, such as to a dye image-
receiving layer.
It will be appreciated that, after processing the
photographic elements described above, there remains in the
elements, after transfer has taken place, an imagewise dis-
tribution of dye in addition to developed silver. A color
image comprising residual nondiffusible compound may be
obtained in these elements if the residual silver and silver
halide are removed in any conventional manner well known to
those skilled in the photographic art, such as a bleach bath
followed by a fix bath, a bleach-fix bath, etc. The image-
wise distribution of dye may also diffuse out of these ele-
ments into these baths, if desired, rather than to an image-
~ 40 receiving element.
" . ... .. . .. ..

t7~
The photographic element in the above-described
processes can be treated with an alkaline processing composi-
tion 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 this invention contains the developing agent for develop-
ment, although the composition could also be solely an
alkaline solution where the developer ~s incorporated in
the photographic element, the image-receiving element or the
process sheet, in which case the alkaline solution serves to
activate the incorporated developer.
A photographic film unit or assemblage in accord-
ance with this invention is adapted to be processed by
an alkaline processing composition, and comprises:
1) a photographic element as described above; and
2) a dye image-receiving layer.
In this embodiment, the processing composition may be inserted
into the film unit, such as by inter~ecting processing
solution with communicating members similar to hypodermic
syringes which are attached either to a camera or camera
cartridge. The processing composition may also be applied
by means of a swab or by dipping in a bath, if so desired.
In a preferred embodiment of the invention, the assemblage
itself contains the alkaline processing composition and
means containing same for discharge within the film unit,
such as a rupturable container which is adapted to be posi-
tioned during processing of the film unit so that a com-
pressive force applied to the container by pressure-applying
members, such as would be found in a camera designed for in-
camera processing, will effect a discharge of the container's
contents within the film unit.
The dye image-receiving layer in the above-described
film unit can be located on a separate support adapted to be
superposed on the photographic element after exposure thereof.
Such image-receiving elements are generally disclosed, for
example, in U.S. Patent 3,362,819. When the means for dis-
. ' ~ . . ,-
.
. :, .- - .:
~ .
- . ~ . ;
~ , .

3'7~
- 12 -
charging the processing composition is a rupturable container,
it is usually positioned in relation to the photographic ele-
ment 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 con-
tents between the image-receiving element and the outermost
layer o~ the photographic element. A~ter processing, the dye
image-receiving element is separated ~rom the photographic
element.
The dye image-receiving layer in the above-described
film unit can also be located integral with the photographic
element between the support and the lowermost photosensitive
silver halide emulsion layer. One useful format for integral
receiver-negative photographic elements is disclosed in
Belgian Patent 757,960. In such an.embodiment, the support
for the photographic element is transparent and is coated
with an image-receiving layer, a substantially opaque light-
reflective layer, e.g., TiO2, and then the photosensitive
layer or layers described above. After exposure of the
photographic 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 photographic element as the
film unit is withdrawn from the camera. The processing
composition develops each exposed silver halide emulsion
layer, and dye images, formed as a function of development,
diffuse to the image-receiving layer to provide a positive,
right-reading image which is viewed through the transparent
support on the opaque re~lecting layer background. For
other details concerning the format of this particular
integral film unit, reference is made to the above-mentioned
Belgian Patent 757,960.
Another format for integral negative-receiver
photographic elements in which the present invention can be
employed is disclosed in Belgian Patent 757,959. In this
embodiment, the support for the photographic element is
transparent and is coated with the image-receiving layer, a

- 13 -
substantially opaque, light-reflective layer and the photo-
sensitive layer or layers described above. A rupturable
container, containing an alkaline processing composition and
an opaci~ier, is positioned between the top layer and a
5 transparent cover sheet which has thereon a neutralizing
layer and a timing layer. The film unit is placed in a
camera, exposed through the transparent cover sheet and then
passed through a pair of pressure-applying members in the
camera as it is being removed therefrom. The pressure-
applying members rupture the container and spread processingcomposition and opacifier over the negative portion of the film
unit to render it light-insensitive. The processing composi-
tion develops each silver halide layer and dye images, formed
as a result of development, diffuse to the image-receiving
15 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 Belgian Patent 757,959.
Still other useful integral formats in which this
invention can be employed are described in U.S. Patents
3,415,644; 3,415,645; 3,415,646; 3,647,437; and 3,635,707.
In most of these formats, a photosensitive silver halide
emulsion is coated on an opaque support, and a dye image-
25 receiving layer is located on a separate transparent support
superposed over the layer outermost from the opaque support.
In addition, this transparent support also preferably con-
tains a neutralizing layer and a timing layer underneath the
dye image-receiving layer.
Another embodiment of the invention uses the image~
reversing technique disclosed in British Patent 904,364,
page 19, lines 1 through 41. In this process, the dye-
releasing compounds are used in combination with physical
development nuclei in a nuclei layer contiguous to the photo-
35 sensitive silver halide negative emulsion layer. The film
unit contains a silver halide solvent~ preferably in a rup-
turable container with the alkaline processing composition.
The film unit or assembly of the present invention
may be used to produce positive images in single- or multi-
.
: - ~ . . , ~.
: - . ~ ~ ' ;: ,
: - . . .

- 14 ~
colors. In a three-color system, each silver halide emulsion
layer of the film assembly will have associated therewith a
dye image-pro~iding material which possesses a predominant
spectral absorption within the region o~ the visible spectrum
to which said silver halide emulsion is sensitive, i.e., the
blue-sensitive silver halide emu:Lsion 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 dyeimage-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, i.e., the dye image-providing material may be
coated in a separate layer underneath the silver halide emul-
sion layer with respect to the exposure direction.
The concentration of the dye image-providing mater-
ial that is employed in the present invention may be varied
over a wide range, depending upon the particular compound
employed and the results desired. For example, the dye image-
providing material may be coated in a layer at a concentration
of 0.1 to 3 g~m2. The dye image-providing material may be
dispersed in a hydrophilic film-forming natural material or
25 synthetic polymer, such as gelatin, polyvinyl alcohol, etc, ~;
which is adapted to be permeated by aqueous alkaline proces-
sing composition.
A variety of silver halide developing agents can
be employed in this invention. Specific examples o~ devel-
opers or ~TA compounds which can be employed in this inven-
tion include hydroquinone compounds, such as hydroquinone,
2,5-dichlorohydroquinone, 2-chlorohydroquinone and the like;
aminophenol compounds, such as 4-aminophenol, _-methylamino-
phenol, N,N-dimethylaminophenol, 3-methyl-4-aminophenol,
3,5-dibromoaminophenol and the like; catechol compounds, such
as catechol, 4-cyclohexylcatechol, 3-methoxycatechol, 4-(N-
octadecylamino)catechol and the like; phenylenediamine com-
pounds, such as N,N-diethyl-_-phenylenediamine, 3-methyl- ;
N,N-diethyl-~-phenylenediamine, 3-methoxy-N-ethyl-N-ethoxy-
~.
., . , -. .-,- ...................... , " ,.,., ,~ ,., . :
. . :. - . , . . , ~: ................ : ,, .
, ~

~.~2~
- 15 -
p-phenylenediamine, N,N,N',N'-tetramethyl-~-phenylenediamine
and the like. In highly preferred embodiments, the ETA is a
3-pyrazolidinone compound~ such as 1-phenyl-3-pyrazolidinone
(Phenidone), l-phenyl-4,4-dimethyl-3-pyrazolidinone (Dimezone),
4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidinone, l-m-tolyl-
3-pyrazolidinone, 1-p-tolyl-3-pyrazolidinone, 1-phenyl-4-methyl-
3-pyrazolidinone, 1-phenyl-5-methyl-3-pyrazolidinone, l-phenyl-
4,4-bis-(hydroxymethyl~-3-pyrazolidinone, 1,4-dimethyl-3-
pyrazolidinone, 4-methyl-3-pyrazolidinone, 4,4-dimethyl-3-
pyrazolidinone, 1-(3-chlorophenyl)-4-methyl-3-pyrazolidinone,
1-(4-chlorophenyl~-4-methyl-3-pyrazolidinone, 1-(3-chloro-
phenyl2-3-pyrazolidinone, 1-(4-chlorophenyl)-3-pyrazolidinone,
1-(4-tolyl)-4-methyl-3-pyrazolidinone, 1-(2-tolyl)-LI~methyl-
3-pyrazolidinone, 1-(4-tolyl~-3-pyrazolidinone, 1-(3-tolyl)-3-
pyrazolidinone, 1-(3-tolyl)-4,4-dimethyl-3-pyrazolidinone,
1-(2-trifluoroethyl~-4,4-dimethyl-3-pyrazolidinone, 5-methyl-
3-pyrazolidinone, and the like. A combination of different
ETA's, such as those disclosed in U.S. Patent 3,o39,869, can
also be employed. Such 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 photographic
element or film unit to be activated by the alkaline proces-
sing composition, such as in the silver halide emulsion
layers, the dye image-providing material layers, interlayers,
image-receiving layer, etc.
In using dye image-providing materials in the
invention which produce diffusible dye images as a function
of development, either conventional negative-working or
direct-positive silver halide emulsions may be employed. If
the silver halide emulsion employed is a direct-positive
silver halide emulsion, such as an internal-image emulsion
designed for use in the internal image reversal process, or
a fogged, direct-positive emulsion such as a solarizing
emulsion, which is developable in unexposed areas, a positive
image can be obtained on the dye image-receiving layer by
using ballasted, re~ox, dye-releasers. 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

-16-
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 cross-oxidizes the dye-releasing compounds and
the oxidized form of the compounds then undergoes a base-
catalyzed reaction to release the 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 diffuse 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 lowers the pH of the film unit or image
receiver to stabilize the image.
Internal-image silver halide emulsions useful in
this invention are described more fully in the November 1976
edition of Research Disclosure, pages 7~ through 79.
The various silver halide emulsion layers of a
color film assembly employed in this invention can be dis-
posed in the usual order, i.e~, the blue-sensitive silver
halide emulsion layer first with respect to the exposure
side, followed by the green-sensitive and red-sensitive
silver halide emulsion layers. If desired, a yellow dye
layer or a yellow colloidal silver layer can be present
between the blue-sensitive and green-sensitive silver halide
emulsion layers 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 rupturable container employed in certain
embodiments of this invention can be of the type disclosed
:~ ... . - "
... ~., .: . . .

-17-
in U.S. Patents 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 con-
tainers comprise a rectangular sheet of fluid- and air-
impervious material folded long:itudinally 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.
Generally speaking, except where noted otherwise,
the silver halide emulsion layers employed in the invention
10 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 0.2 to 7 microns in thickness; and the
15 alkaline solution-permeable polymeric interlayers, e.g.,
geltain, are about 0.2 to 5 microns in thickness. Of course
these thicknesses are approximate only and can be modified
according to the product desired.
Any material can be employed as the image-receiving
20 layer in this invention as long as the desired function of
mordanting or otherwise fixing the dye images is obtained.
The particular material chosen will, of course, depend upon
the dye to be mordanted. Suitable matexials are disclosed
on pages 80 through 82 of the November 1976 edition of
25 Research Disclosure.
Use of a pH-lowering material in the film units
of this 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
30 about 13 or 14 to at least 11 and preferably 5 to 8 within
a short time after imbibition. Suitable materials and
their functions are disclosed on pages 22 and 23 of the
July 1974 edition of Research Disclosure, and pages 35
through 37 of the ~uly 1975 edition of Research Disclosure.
A timing or inert spacer layer can be empl~yed in
) the practice of this invention over the pH-lowering layer
:, : .
.: ., . : .
~, ; . :

-18-
which "times" or controls the pH reduction as a function of
the rate at which the alkaline composition diffuses through
the inert spacer layer. Examples of such timing layers and
their functions are disclosed in the Research Disclosure
articles mentioned in the paragraph above concerning pH-
lowering layers.
The alkaline processing composition employed in
this invention is the conventional aqueous solution of an
alkaline material, e.g., alkali metal hydroxides or carbon-
ates such as sodium hydroxide, sodium carbonate or an aminesuch as diethylamine, preferably processing a p~l in excess
of 11, and preferably containing a developing agent as
described previously. Suitable materials and addenda
frequently added to such compositions are disclosed on pages
79 and 80 of the November 1976 edition of Research
Disclosure.
The alkaline solution-permeable, substantially
opaque, light-reflective layer employed in certain embodi-
ments of photographic film units used in this invention
are described more fully in the November 1976 edition of
Research Disclosure, page 82.
The supports for the photographic elements used
in this invention can be any material, as long as it does
not deleteriously affect the photographic properties of the
film unit and is dimensionally stable. Typical flexible
sheet materials are descrbied on page 85 of the November
1976 edition of Research Disclosure.
While the invention has been described with refer-
ence to layers of silver halide emulsions and dye image-
providing materials, dotwise coating, such as would beobtained 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-
~5 providing substances. After deveIopment, the transferreddyes would tend to fuse together into a continuous tone.
'

--19--
The silver halide emulsions useful in this inven-
tion, both negative-working and direct-positive ones, are
well known to those skilled in the art and are described
in Product Licensing Index, Volllme 92, December 1971,
publication 9232, page 107, paragraph I, "Emulsion types";
they may be chemically and spectrally sensitized as describ-
ed on page 107, paragraph III, "Chemical sensitization",
and pages 108 and 109, paragraph XV, "Spectral sensitiza-
tion", of the above article; they can be protected against
the production of fog and can be stabilized against loss of
sensitivity during keeping by employing the materials
described on page 107, paragraph V, "Antifoggants and stabi-
lizers", of the above article; they can contain development
modifiers, hardeners, and coating aids as described on
pages 107 and 108, paragraph IV, "Development modi~iers";
paragraph VII, "Hardeners"; and paragraph XII, "Coating
aids", of the above article; they and other layers in the
photographic elements used in this invention can contain
plasticizers, vehicles and filter dyes descrbied on page
108, paragraph XI, "Plasticizers and lubricants", and
paragraph VIII, "Vehicles", and page 109, paragraph XVI,
"Absorbing and filter dyes", of the above article; they and
other layers in the photographic elements used in this in-
vention may contain addenda which are incorporated by using
the procedures described on page 109, paragraph XVII,
"Methods of addition", of the above article; and they can
be coated by using the various techniques described on
page 109, paragraph XVIII, "Coating procedures", of the
above article.
The term "nondiffusing" used herein has the meaning
commonly applied to the term in photography and denotes
materials that for all practical purposes do not migrate
or wander through organic colloid layers, such as gelatin,
in the photographic elements of the invention in an alkaline
. 35 medium and preferably when processed in a medium having a
pH of 11 or greater. The same meaning is to be attached
' ~ ~ . . ...
- . ....i, ..
.

-19a-
to the term "immobile". The term "di~fusible" as applied to
the materials of this i.nvention has the converse meaning
and denotes mater-

- 20 -
ials having the property o~ di~fusing effectively through the
colloid layers of the photographic elements in an alkaline
medium. "Mobile" has the same meaning as "diffusiblel'.
The term "associated therewith" as used herein is
intended to mean that the materials can be in either the same
or different layers, so long as the materials are accessible
to one another.
The following examples are provided to further
illustrate the invention.
Example 1 -- Preparation and Testing of Retained
Image Element ___
(A). A photographic element (A) was prepared by
coating the following layers in the order recited on a
poly(ethylene terephthalate) film support. Quantities are
parenthetically given in mg/dm2.
(1) Magenta RDR~ (10.8) and green-sensitive, nega-
tive, silver bromoiodide emulsion /silver (10)
and gelatin (15)7, and 4-methyl-4-hydroxy-
methyl-l-phenyl-3-pyrazolidinone developing
agent (0.5); and
(2) Gelatin overcoat (8).
OH
~o~ ~CONH(CH2) 4--0~ C5H71 t
~C H s C 5 H "--t
S O S O
NH--~
-N=N-~ O--CO--c 2 H 5
; ~
.. . . . . .
- : :.' : .:
~, . . .

- 21 -
(B). Photographic element (B) was prepared which
was the same as element (A), except that layer (2) contained
Compound 8 described above (6.9~.
(C). Photographic element (C) was prepared whlch
was the same as element (A), except that layer (2) contained
Compound 6 described above (5).
Samples of each of the above-prepared photosensi-
tive elements were given a green exposure in a sensitometer.
The exposed samples were then processed at 20C for 1, 2 and
5 minutes by rupturing a pod containing a viscous processing
composition between the photosensitive element and a dye
image-receiving element as described below. The thickness
of the processing composition layer was 0.14 mm.
The processing composition was as follows:
Potassium hydroxide 40 g
Potassium bromide 10 g
ll-Aminoundecanoic acid10 g
Oxalic acid 5 g
Hydroxyethylcellulose30 g
Water to make 1 liter
The dye image-receiving element consisted of a
paper support having thereon the following mordant in gelatin:
~CH2 -- CH -- CH -- CH_ _ :
O= C~ ~C- O
( C H 2 ) 3 C I
CH5--N'D--CH
In the exposed areas of the photographic element',
the magenta RDR is oxidized by the oxidized developing agent,

- 22 -
and then in the alkaline medium releases a magenta dye which
diffuses to the dye image-receiving layer. A retained
magenta image is obtained which is positive with respect
to the original. The following sensitometric results on
the retained image of the photog:raphic element were obtained:
;.
.: , .. ,, . . - .
~......... . .
,
- : ::: ~': ' ~ : ~ :

-- 23 --
o ~ ~
~ ~ ,
~: ~ o o o
cdl ~ o
o (~I ,
L~
E~
~ ~ e ~ ~ ~
rn ~ O O O
H
~ O I ~ ¦ ~ 3
E /
1 ~13 ~
'~
~,
~) C~J CO '~`'
O O :'-
~1
3 L''
O
~:h :,
m v ~:
o ~

- 24 -
The results indicate that the color discrimina-
max and Dmin or ~D) decreased
rapidly for the control element as the development time was
increased, and became nil at 5 minutes. The color dis-
crimination of the elements of the invention, however,diminished much more slowly as the development time was
increased. The photographic eleménts of the invention thus
exhibit a greater latitude as regards the development time.
As indicated above, the hydroquinone released
from the hydroquinone ester develops silver in the unexposed
areas, as well as in the exposed areas, without the concurrent
release of dye. The amount of developed silver was measured
in the photographic elements as follows:

~IJ~l
- 25 -
a~
o ~ oo o
~ a~ o~ o o~
b7 X S~
L~ ~ U~ Lr\ ~
tq td ~ o~
o a~
X¢ 3 ~_
a~ a~ :
O ~ L~
E~ ~q ~ S~ ~ o co ::
H ~: ~ C o r~ O ~:
~ ~ ~ ' , .
~ c) tu a) K~ 0~
h O ~) r~
~¢
:;'~ '
I .~ ~
H ~ :,
O
$~ O
¢ ~1 3 O ~.:
~ ~tn o
U~ ~ 1~ L~
O ~ ., . . .
X~ r~
";`
~ .':
S~ S~
a~ ~ :, ~
~ g a: v
~1 V
¢ ~ :

- 26 -
Example 2 -- Processing Temperature Variation of
Retained Ima~e Element
Example 1 was repeated, except that samples of
elements (A~, (B) and (C) were processed ~or 2 minutes at
20C, 25C and 30C. The following sensitometric results
on the retained image of the photographic elements were
obtained:

J~
~1 o ~ ~
,,
~, ~ U~
¦ . . U`\
o o o
X ~
~ o ~ ~ :.
td ~1 ~D ~D ''"'
~~ o ~ ~ ,
G~ ~) ~ ~ :,
E~ o ~ ~
~o ~ ~ o o o ''
H rl
H
H ~q X L~
~ ~ ~ O ~i ~
El ~ ~'.'
Lr~ ',''
o ~
oo ~ ~ ~ ~ '~,
0,1 ~ O O O :,' '
:'
X ~ 3 C-
N
:~
m c~a~ o
C~ .
~ ¢

- 28 -
The results indicate that the control element was
very sensitive to an increase in processing temperature,
and the color discrimination became nil at 25C. The color
discrimination of the elements of the invention, however,
were much less sensitive to an increase in the processing
temperature. The photographic elements of the invention
thus exhibit a greater processing temperature latitude.
Example 3 -- Concentration Variation of Hydroquinone
Ester-Retained Ima~e Element
(D). A photographic element (D) was prepared by
coating the following layers in the order recited on a
poly(ethylene terephthalate) film support. Quantities are
parenthetically given in mg/dm2.
(1) Magenta RDR of Example 1 (8.7); and
(2) Green-sensitive, negative silver bromoiodide
emulsion /silver (10) and gelatin (15)7, and
4-methyl-4-hydroxymethyl-1-phenyl-3-pyrazoli-
dinone developing agent (0.5).
(E). Photographic element (E) was prepared which
was the same as element (D), except that layer (2) contained
compound 6 described above (0.8). (This amount is insuffi-
cient to reduce all the silver in the silver halide emulsion.) ~ -
(F). Photographic element (F) was prepared which
was the same as element (D), except that layer (2) contained
compound 6 described above (5~;
Samples of each of the above-prepared photosensi-
tive elements were exposed and processed as in Example 1 at
20C, but with development times of 45 seconds, 1, 2 and 5
minutes. The following sensitometric results on the
30 retained image of the photographic element were obtained: ;

11~7~1
-- 29 --
u~ ~1 o o
~ ~1 o o o
X
~ o o ~U
0 ~ ~ O ~1
~ ~ o o o
~ ~ ~1 '
~ ~ ~ o ~U
U~
O
H ~J ~ ¦
E - ~ ~xl
~
<I r~
O¦ ~ ~1 ~D
U~ ~ ~i O
U~ ~C
J ~ O Lr~ ~_
~O
O
E E E o o u~
~ o o
~ J~ ~ ,
r
o o

~ i_ 2'~
- 30 -
The results indicate that the color discrimination
decreased rapidly for the control element (D) as the develop-
ment time was increased, and became nil at 5 minutes. For
the control element (E) which contained an amount of compound
6 which is insurficient to reduce all of the silver in the
silver halide emulsion, the DmaX was relatively low and the
color discrimination also decreased rapidly as the develop-
ment time was increased. The color discrimination of
element (F) of the invention, however, decreased much more
slowly as the development time was increased. The photo-
graphic element of the invention thus exhibits a greater
latitude in development tlme.
Example 4 -- Processing Temperature and Concentration
Variation of Hydroquinone Ester-Retained
Image Element _ _
Example 3 was repeated, except that samples of
elements (D), (E) and (F) were processed for 2 mlnutes at
20C, 25C and 30C. The following sensitometric results
on the retained image of the photographic element were
obtained:
. : . : ,.; :: ~; . .
. .: . i . : : ..

-- 31 --
~1 o o ~ (
ov ~
o o o
xl Lr~
~ o o ~
~ ~1 ~
a) c ~ o
E~ V ~ 1 N
~ ~`J ~ O O
Ul X
O ~ ~ O
m Cl I
E~
~ ~
O ~ O O O :
lo~=t
q~ '~
O
~ O \
~ 0 ~3 O O 11~ ~:
¢ V
O O
V V '
~ ~ .
i"~ ~: , . . : ' ' , , '' '
:

- 32 -
The results lndicate that control element (D)
was very sensitive to an increase in processing temperature,
and the color discrimination became nil at 30C. For con-
trol element (E), the DmaX was relatively low and the color
discrimination also decreased rapidly as the development
temperature was increased. The color discrimination of
element (F) of the invention, however, did not decrease
with increasing development temperatures, and thus had a
greater latitude in this respect.
0 Example 5 -- Concentration Variation of Hydroquinone
Ester-Transferred Image _
Samples of elements (D~, (E) and (F) of Example 3
were exposed and processed as in Example 1, except that the
following processing composition was used:
Potassium hydroxide 40 g
Potassium bromide 10 g
Hydroxyethylcellulose 30 g
Water to make 1 liter
Processing took place at 20C for 45 seconds,
1~ 2 and 5 minutes. The following sensitometric results
on the image transferred to the dye image-receiving element
were obtained:
: ' ' , ~ ,:
.
-;~ : :
-
. ~

LO L~
~1 '`' ''-`

~ ~ o o
Lr
~ ~ ~ ~ :~
C-~OO
a)
~1
~ ~ Q O O
~ ~I X
E-l E~ t~
d
H U:l 11
~:; h 0 o 0
1~ P~ ~ ~ L~
~ a~E~ ~o ~ ~ .
l ~
H Q
¢~ ~ ~1 ~ ~ ~
O ~ O O O
Ll~ ~C :~
~e ,, ~
~:
O ~
~ ~ ~ . ~.
~ O ~ 0~ .
~o
e o Q O O ~ :`:
C~
O
~d _ S~
s~
~o ~ O O ~ ~
C~ ~) :`'
~ ~ ~,
,

- 34 -
The results indicate that the color discrimination
decreased rapidly for the control element (D) as the develop-
ment time was increased and became substantially nil at
5 minutes. For the control element (E), the Dmin increased
with increased processing time, while the color discrimina-
tion decreased. For the element (F) of the lnvention,
however, the color discrimination did not decrease with
increased processing time, and thus has a greater latitude
in this aspect.
Example`6 -- Processing Temperature and Concentration
Variation of Hydroquinone Ester-Transferred
Ima~e
5 _ . . _ .
Example 5 was repeated, except that samples of
elements (D), tE) and (F) were processed ~or 2 minutes at
20C, 30C and 40C. The following sensitometric results
on the image transferred to the dye image-receiving element
were obtained:
r -: : .
',,, ~ ~

- 35 -
~1 o o
V
oO ~ U~
3 ~ t~J 01 ,~
xl
L~
:'
~ ~
~ E; oV ~1 ~ 3 U~
H ~ O ~ ~ ~`J H O
~:1 al Xl ~ ,.
~ O ~!, N ~J
~; ~
1~; ~,
I--I <~1 r-i r-i ~
::. V ~ :~
E~ oO ~ ~o o o~ ,
X U~ '~
~ L~
'
0~ '
~a oo
~ O ~ O O IS~
¢ V
O O
S^~
V V
',
. ', . . -
.. ~
': '
. ~ , . . . . .
,: ' ., ' I

- 36 -
The results indicate that control element (D) was
very sensitive to an increase ln processing temperature,
and the color discrimination became nil at 40C. For con-
trol element (E), the color discrimination also decreased
rapidly as the development temperature was increased. The
color discrimination of the element (F) of the invention,
however, was substantially higher than the control elements
at all processing temperatures, and thus has a greater
latitude in development temperatures.
The invention has been described in detail with
particular reference to preferred embodiments thereof, but
it will be understood that variations and mod~fications
can be effected within the spirit and scope of the inven-
tion.
,
- . ~ ..
- :........ - :.
- - :. ., ~ :