Radiation imagery chemistry: process – composition – or product th – Radiation sensitive product – Identified radiation sensitive composition with color...
Reexamination Certificate
1997-03-25
2001-01-09
Letscher, Geraldine (Department: 1752)
Radiation imagery chemistry: process, composition, or product th
Radiation sensitive product
Identified radiation sensitive composition with color...
C430S505000, C430S955000, C430S957000, C430S543000, C430S553000, C430S555000, C430S557000, C430S558000
Reexamination Certificate
active
06171771
ABSTRACT:
FIELD OF THE INVENTION
This invention relates to a photographic element containing a DIR coupler.
BACKGROUND OF THE INVENTION
Many silver halide photographic elements, in particular color negative films, contain so-called DIR (development inhibitor releasing) couplers. In addition to forming imaging dye, DIR couplers release inhibitors that can restrain silver development in the layer in which release occurs as well as in other layers of a multilayer photographic material. DIR couplers can help control gamma (contrast), enhance sharpness (acutance), reduce granularity and provide color correction via interlayer interimage effects. U.S. Pat. No. 3,933,500 broadly discloses DIR couplers with azole-type coupling off groups.
PROBLEM TO BE SOLVED BY THE INVENTION
There has been a need for more effective DIR couplers. DIR couplers that release inhibitors that efficiently reduce silver development are desired. DIR couplers that are effective with silver chloride emulsions are also needed. In addition it is desirable that such couplers have high reactivity to maximize rates and efficiencies of inhibitor release and minimize the amount of DIR coupler in the photographic element. It is also necessary that the DIR couplers be stable toward long term storage or toward storage at elevated temperatures. DIR couplers that show acceptably low continued coupling when films containing them are placed in a bleach solution immediately after development (i.e. with no intervening stop bath) are also needed. The DIR couplers of this invention possess all of these desirable properties. They are also easily synthesized.
SUMMARY OF THE INVENTION
This invention relates to photographic elements, such as color negative films, which contain one or more aromatic bicyclic heterocycles containing an imidazole or pyrazole nucleus which can be used as coupling-off groups to give DIR couplers. The preferred coupling-off groups are purines or 1H-pyrazolo[3,4-d]pyrimidines.
One aspect of this invention comprises a photographic element comprising a support bearing one or more silver halide emulsions and one or more DIR couplers of structure I or II below:
wherein:
Z is a moiety which can react with oxidized developer to release a coupling-off group;
R
1
is a hydrogen atom or a substituent selected from the group consisting of halogen atom, alkyl, aryl, alkoxy, alkylthio, arylthio, amino, alkylamino, arylamino, carbonamido, carbamoyl, alkoxycarbonyl, aryloxycarbonyl, aryloxy, arylcarbonyl, alkylcarbonyl, sulphonyl and sulphonamido groups;
each of the R
2
substituents is a halogen atom or a substituent selected from the group consisting of alkyl, aryl, alkoxy, alkylthio, arylthio, amino, alkylamino, arylamino, carbonamido, carbamoyl, alkoxycarbonyl, aryloxycarbonyl, aryloxy, arylcarbonyl, alkylcarbonyl, sulphonyl and sulphonamido groups;
X represents the atoms required to make a second ring which is aromatic and contains at least one nitrogen atom; and
n is between 0 and the number of carbon atoms in the second ring, with the proviso that if R
1
is hydrogen, n is at least 1.
ADVANTAGEOUS EFFECT OF THE INVENTION
The DIR couplers of the invention efficiently reduce silver development, including development of silver chloride emulsions, and are readily synthesized.
DETAILED DESCRIPTION OF THE INVENTION
As noted above, the photographic element containing a DIR coupler of Structure I or II. In structures I and II, Z is a moiety which can react with oxidized developer to release the coupling-off group. In preferred embodiments of the invention, Z is selected from beta-dicarbonyl compounds, such as acylacetanilides, beta-ketoketones and beta-ketoesters, and indanones, pyrazoloazoles, phenols, and naphthols. The number of carbon atoms in R
1
and all R
2
substitutents is preferably between 2 and 12.
In a preferred embodiment of the invention, the DIR coupler of structure I or II is of structure III or IV, respectively:
wherein:
Z is as described above;
R
1
is as described above; and
each of R
3
and R
4
is a hydrogen atom, a halogen atom, or a substituent selected from the group consisting of alkyl, aryl, alkoxy, alkylthio, arylthio, amino, alkylamino, arylamino, carbonamido, carbamoyl, alkoxycarbonyl, aryloxycarbonyl, aryloxy, arylcarbonyl, alkylcarbonyl, sulphonyl and sulphonamido groups, with the proviso that the total number of carbon atoms in groups R
1
, R
3
and R
4
taken together is at least 2. The number of carbon atoms in groups R
1
, R
2
and R
3
is preferably between 2 and 15 carbon atoms. Preferably the combined sum of Hammett sigma para values for R
1
, R
3
, and R
4
is less than 1.0. The use of Hammett sigma values to describe chemical properties is well established in the literature and is discussed, for example, in “Exploring QSAR, fundamentals and Applications in Chemistry and Biology”, C. Hansch and A. Leo, American Chemical Society, Washington, D.C. 1995; “The Chemists Companion”, A. J. Gorden and R. A. Ford, John Wiley & Sons, New York, 1979; and A. Leo in “Comprehensive Medicinal Chemistry”, edited by C. Hansch, P. G. Sammes, and J. B. Taylor, Permagon Press, New York, 1972. Generally, sigma values increase with increasing electron-withdrawing power of the substituent. The sigma value for hydrogen is equal to zero.
In another preferred embodiment of the invention, the DIR coupler of formula III or IV is of structure V or VI, respectively:
wherein:
each of the R
5
substituents is a halogen atom, or a substituent selected from the group consisting of alkyl, aryl, alkoxy, alkylthio, arylthio, carbonamido, carbamoyl, alkoxycarbonyl, aryloxycarbonyl, aryloxy, acyloxy, arylcarbonyl, alkylcarbonyl, sulphonyl, sulphonamido, sulfoxyl, sulfonate and cyano groups;
R
6
is a group selected from the group consisting of tertiary alkyl, cyclic tertiary alkyl, aryl, heterocycle, arylamino and alkylamino groups;
R
7
is a substituent selected from the group consisting of alkyl, aryl, alkoxy, alkylthio, arylthio, amino, alkylamino, arylamino, carbonamido, carbamoyl, alkoxycarbonyl, aryloxycarbonyl, aryloxy, arylcarbonyl, alkylcarbonyl, sulphonyl and sulphonamido groups, with the proviso that R
7
has at least two carbon atoms; and
p is between 0 and 5.
In yet another preferred embodiment of the invention, the DIR coupler of structure V or VI is of structure VII and VIII, respectively:
wherein:
R
8
is a tertiary alkyl group or a phenyl group;
Y is a halogen atom or an alkoxy group;
each R
9
substituent is in the 4- or 5-position relative to the anilino nitrogen atom and is a halogen atom or a substituent selected from the group consisting of alkyl, phenyl, carbonamido, carbamoyl, alkoxycarbonyl, aryloxycarbonyl, sulphonamido, sulphamoyl, acyloxy, acyl, alkylsulphonyl, arylsulphonyl, sulphoxyl, sulphonate, trifluoromethyl and cyano groups;
m is 0 or 1; and
R
10
is an alkylthio group, an arylthio group or a carbonamido group represented by —NHCOR
11
where R
11
is an alkyl, a phenyl, an alkoxy or a phenoxy group, with the proviso that R
10
contains at least two carbon atoms.
The alkyl substituents comprising R
1
, R
2
, R
3
, R
4
, R
5
, R
7
, R
9
and R
11
may be branched, unbranched or cyclic and may be substituted or unsubstituted. The alkoxy, alkylthio, alkylamino, alkyloxycarbonyl and alkylcarbonyl groups comprising R
1
, R
2
, R
3
, R
4
, R
5
and R
7
may be branched or unbranched and may be substituted or unsubstituted. The aryl, arylthio, arylamino, carbonamido, carbamoyl, aryloxycarbonyl, aryloxy, arylcarbonyl, sulphonyl and sulphonamido substituents comprising R
1
, R
2
, R
3
, R
4
, R
5
and R
7
may be substituted or unsubstituted. The heterocycles comprising R
6
may be pyrrole, indole, pyridine, thiophene, furan, quinoline, benzofuran, benzothiophene, pyrimidine, pyridazine, imidazole, benzimidazole, indazole and pyrazole. The tertiary alkyl, tertiary cyclic alkyl, aryl, heterocycle, arylamino and alkylamino groups comprising R
6
can be substituted or unsubstituted. The tertiary alkyl group and phenyl groups comprising R
8
can be substituted or unsubstituted. The phenyl, carbo
Allway Philip A.
Merkel Paul B.
Poslusny Jerrold N.
Steele David A.
Eastman Kodak Company
Letscher Geraldine
Rice Edith A.
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