Radiation imagery chemistry: process – composition – or product th – Radiation sensitive product – Identified radiation sensitive composition with color...
Reexamination Certificate
1993-10-22
2002-04-02
Schilling, Richard L. (Department: 1752)
Radiation imagery chemistry: process, composition, or product th
Radiation sensitive product
Identified radiation sensitive composition with color...
C430S555000
Reexamination Certificate
active
06365334
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to photographic elements having a layer containing both a 1-aryl-4-aryloxy-2-pyrazolin-5-one magenta coupler, and a sulfide, sulfoxide or sulfone compound.
BACKGROUND OF THE INVENTION
In a silver halide photographic element, a color image is formed when the material is exposed to light and then subjected to color development with a primary amine developer. The color development results in imagewise reduction of silver halide and production of oxidized developer. The oxidized primary amine developer subsequently reacts with one or more incorporated dye-forming couplers to form dye in an imagewise fashion. Some couplers, referred to as DIR couplers, release a development inhibitor compound or fragment upon coupling with the oxidized primary amine developer. Further, some of these DIR couplers release the inhibitor compound or fragment with a time delay. These are sometimes referred to as DIAR couplers.
A variety of magenta dye-forming coupler types have been used in color photographic materials. These include pyrazoloazole couplers, 1-phenyl-3-acylamino-2-pyrazolin-5-one couplers and 1-phenyl-3-anilino-2pyrazolin-5-one couplers. U.S. Pat. Nos. 3,419,391, 3,519,429 and 4,248,962, 4,585,728, 4,692,529, 4,724,198, and 4,977,073 disclose couplers which include 1-aryl-4-aryloxy-2-pyrazolin-5-one type couplers.
Many compounds, including sulfur-containing addenda, have been previously tried or suggested for use in conjunction with couplers in an effort to improve coupler activity. For example, Rody et al disclose cyclic sulfide, sulfoxide and sulfone stabilizers in U.S. Pat. Nos. 4,933,271, 5,006,665 and 5,070,007. Cyclic sulfoxide and sulfone stabilizers are also disclosed in U.S. Pat. No. 5,017,465. Sulfone-containing addenda are used in combination with magenta dye-forming couplers in U.S. Pat. No. 4,770,987. Yamada et al disclose combinations of magenta dye-forming couplers, phenolic compounds and sulfide or sulfoxide compounds in U.S. Pat. No. 4,113,488. Combinations of sulfoxide or sulfone compounds and pyrazolotriazole magenta dye-forming couplers are disclosed in U.S. Pat. No. 5,232,821 of Merkel et al.
Magenta dye-forming coupler compositions of high activity that efficiently react with oxidized developer are, however, still needed. There is also a need for magenta dye-forming DIR (including DIAR) coupler compositions that efficiently release development inhibitors.
SUMMARY OF THE INVENTION
It has been found that while 1-aryl-4-aryloxy-2pyrazolin-5-one type couplers can have high activity and high dye forming ability, such couplers tend to be unstable toward aerial oxidation and are therefore impractical. While various compounds might be considered for use with such couplers in an attempt to alleviate the foregoing problem, we have found that surprisingly certain sulfide, sulfoxide or sulfone addenda when used in combination with 1-aryl-4-aryloxy-2-pyrazolin-5-one magenta dye-forming couplers can dramatically improve their oxidative stability.
The present invention therefore provides a photographic element comprising a silver halide emulsion having a layer comprising a silver halide emulsion, a 1-aryl-4-aryloxy-2pyrazolin-5-one magenta dye forming coupler, and a sulfide, sulfoxide or sulfone compound.
Embodiments of the Invention
In the present invention, it is preferred that the magenta dye forming coupler has structure Ia or Ib, below, and the sulfide, sulfoxide or sulfone compounds have structures VI, VII and VIII, respectively:
wherein:
R1 is an aryl group;
R2 is an alkyl group, an acylamino group, an anilino group, a carbamoyl group or an alkoxy group;
R3 is a substituent any of which may be the same or different; and
n is an integer from 0 to 4;
wherein:
R8 and R9 are independently an alkyl group, an alkylene group, an alkenyl group or an aryl group, or R8 and R9 may together form a ring including the sulfur atom, the total number of carbon atoms in R8 and R9 together being at least 12.
It should be noted that throughout this application a reference to any type of “group” includes both the unsubstituted and substituted group described. Various substituents can include known substituents, such as halogen (for example, chloro, fluoro, bromo, iodo), alkoxy (for example, methoxy, ethoxy), substituted or unsubstituted alkyl (for example, methyl, trifluoromethyl), alkenyl, thioalkyl (for example, methylthio or ethylthio), substituted and unsubstituted aryl (for example, phenyl, thienyl, furyl, pyrrolyl) and others known in the art. Alkyl substituents may specifically include “lower alkyl”, that is having from 1 to 6 carbon atoms, for example, methyl, ethyl, and the like. Additionally, substituents may form bridged linkages. Further, with regard to any alkyl group, alkylene group or alkenyl group, it will be understood that these can be branched or unbranched and include ring structures.
Preferably R2 is an alkyl group. Especially preferred are couplers of structure Ia or Ib, in which R2 is of structure IIa or IIb, below:
wherein:
R4 is hydrogen, an alkyl group or an aryl group;
R5 is an aryl group or an alkyl group; and
X is an amino group, an anilino group, a carbonamido group, a sulfonamido group, an acyloxy group, an alkoxy carbonyl group, a carbamoyl group, a sulfamoyl group, an alkylthio group, an arylthio group, an alkyl sulfoxide group, an aryl sulfoxide group, an alkyl sulfonyl group or an aryl sulfonyl group.
It is preferable that the total number of carbon atoms in R1, R2 and R3 taken together be at least 14, and more preferably at least 16 to minimize coupler water solubility and wandering.
An anilino group for R2 is less preferred because it tends to reduce coupler stability toward aerial oxidation. When R2 is an acylamino or an anilino group, it is preferred that at least one R3 is an electron-withdrawing group to improve coupler stability. Electron withdrawing groups are discussed in March,
Advanced Organic Chemistry,
pages 20-21, 228-229, 386-387, 494-497. In particular, preferred electron withdrawing substituents would have a Hammett &sgr;
p
constant of greater than 0.1 and preferably between 0.1 and 1.0 (for example, between any of 0.3, 0.4, 0.5 or 0.6 and 1.0). Hammett &sgr;
p
values are discussed in
Advanced Organic Chemistry
3rd Ed., J. March, (John Wiley Sons, NY; 1985). Note that the “p” subscript refers to the fact that the &sgr; values are measured with the substituents in the para position of a benzene ring. Additional tables relating to Hammett &sgr;
p
constants can be found in
Chemical Reviews
Volume 91, pages 165-195 (authored by C Hansch et al.). Examples of electron-withdrawing groups include nitro, cyano, sulfamoyl, sulfonamido, alkylsulfonyl, arylsulfonyl, carbamoyl, carbonamido, alkoxycarbonyl, aryloxycarbonyl and trifluoromethyl groups and halogen atoms, such as chlorine and fluorine.
Also particularly useful for the practice of this invention are development inhibitor-releasing couplers in which one of R3 contains a development inhibitor group that is released after the aryloxy group couples off when the 1-aryl-4-aryloxy-2-pyrazolin-5-one coupler reacts with oxidized developer. Particularly useful inhibitor-releasing couplers of structure Ia or Ib are those in which the 4-aryloxy coupling-off group shown in formula Ia or Ib is of structure III, IV or V, below:
wherein
Q and W are electron-withdrawing groups, any of which may be the same or different;
p is 0, 1 or 2;
m is 0 or 1;
R6 is hydrogen, phenyl or an alkyl group; and
R7 is an alkyl group containing 1 to 10 carbon atoms or a phenyl group; and
IN is a development inhibitor moiety.
In formulae IV and V above, Q is preferably in the para position with respect to the oxygen.
Development inhibitor moieties, IN, useful for the couplers of this invention include oxazoles, thiazoles, diazoles, triazoles, oxadiazoles, thiadiazoles, oxathiazoles, thiatriazoles, benzotriazoles, tetrazoles, benzimidazoles, indazoles, isoindazoles, mercaptotetrazoles, selenotetrazoles, mercaptobenzothiazoles, selenobenzothiazoles, mercaptobenzoxazole
Anderson Lawrence Glenn
Bown David Hales
Merkel Paul Barrett
Mooberry Jared Ben
Poslusny Jerrold Neal
Eastman Kodak Company
Kluegel Arthur E.
Schilling Richard L.
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