Radiation imagery chemistry: process – composition – or product th – Radiation sensitive product – Identified radiation sensitive composition with color...
Reexamination Certificate
2000-11-07
2001-09-18
Letscher, Geraldine (Department: 1752)
Radiation imagery chemistry: process, composition, or product th
Radiation sensitive product
Identified radiation sensitive composition with color...
C430S386000, C430S387000
Reexamination Certificate
active
06291152
ABSTRACT:
CROSS REFERENCE TO RELATED APPLICATION
Co-filed herewith is an application under employing a bicyclic azole coupler in a silver halide photographic element for improved color rendition.
FIELD OF THE INVENTION
This invention relates to a silver halide photographic element and process for its use in which the element contains a bicyclic azole dye-forming coupler having a substituent group that provides a color photographic image having improved image dye stability.
BACKGROUND OF THE INVENTION
Conventional color photography depends on the formation of dyes and uses subtractive primaries to form the desired colors. One of the problems encountered with the dyes that form the images is their tendency to degrade when exposed to light. This is of particular importance with respect to photographic elements intended for direct viewing. Since the advent of color photography there have been ongoing efforts to improve the dye stability. Efforts have been ongoing to provide stabilized dyes which exhibit improved light stability. In particular, proposals have been made for new couplers that provide desirable dye properties but the resulting dyes often do not exhibit the satisfactory dye stability.
U.S. Pat. Nos. 5,925,503; 5,972,574; and 5,972,587 disclose 1H-pyrazolo[5,1-c]-1,2,4-triazole magenta dye-forming couplers that provide a desirable hue for silver halide photographic elements. Generic formulas for these prior art couplers are as follows:
The first and third formulae may comprise a carbonamidoethyl link to the pyrazolotriazole coupler. It has been found that the stability of the resulting dye to light exposure using these generic types of couplers is unsatisfactory.
It is a problem to be solved to provide a silver halide photographic element containing a bicyclic azole dye-forming coupler that forms an image dye that exhibits improved image dye stability.
SUMMARY OF THE INVENTION
The invention provides a photographic clement comprising a light-sensitive silver halide emulsion layer having associated therewith a bicyclic azole dye-forming coupler, having appended to a ring carbon at a non-coupling position thereof a substituent group represented by the formula:
wherein the arrow represents the point of attachment of the substituent group to a non-coupling position of the coupler;
R
1
, R
2,
R
3
and R
4
are independently selected hydrogen or substituent groups, provided that any two of R
1
, R
2,
R
3
and R
4
may join to form a ring;
R
a
and R
b
are independently hydrogen or a substituent;
each R
c
and R
d
is an independently selected hydrogen or an alkyl or aryl group, provided that any two of them may join to form a ring and n is 1 to 10;
R
e
is hydrogen or an alkyl or aryl group;
each Y is an independently selected substituent group and m is from 0 to 4; and
Z is a substituent selected from the group consisting of —C(O)R
5
, —S(O)
2
R
5
, —SOR
5
, —P(═O)(R
6
)
2
and —P(═O)(OR
6
)
2
in which R
5
is selected from the group consisting of alkyl, aryl, heterocyclic, alkoxy, aryloxy, alkylamino, and arylamino groups and each R
6
is independently selected from the group consisting of alkyl and aryl groups; provided that Z can form a ring with any one of R
c
and R
d
.
The invention also provides a process for forming an image in the element of the invention as well as a new coupler compound.
The element exhibits improved image dye stability.
DETAILED DESCRIPTION OF THE INVENTION
A variety of dye-forming coupler types have been used in photographic materials. Among the known dye-forming couplers are bicyclic azoles that contain an azole ring having a second azole ring fused thereto such as pyrazolotriazoles, pyrazolobenzimidazoles, and imidazopyrazoles. These couplers contain bridgehead nitrogen 5,5 fused ring systems and include such couplers as pyrrolo[1,2-b]pyrazoles, pyrazolo[5,1-c][1,2,4]triazoles, pyrazolo[1,5-b][1,2,4]triazoles, imidazo[1,2-b]pyrazoles, imidazo[1,5-b]pyrazoles, imidazo[1,2-a]imidazoles, imidazo[1,2-b][1,2,4]triazoles, imidazo[2,1-c][1,2,4]triazoles, imidazo[5,1-c][1,2,4]triazoles and [1,2,4]triazolo[3,4-c][1,2,4]triazole. These couplers also contain bridgehead nitrogen 5,5,6 fused ring systems and include compounds such as pyrazolo[3,2-b]benzimidazoles. These couplers may form magenta or cyan dyes, depending on the ring structure and substituents. Preferred couplers are pyrazolotriazoles represented by the Formula M:
wherein:
R
6
is hydrogen, a substituent group or a ballast group;
R
7
is a ballast group or a fused benzene ring; and
X is hydrogen or a coupling-off-group, provided that X, R
6
and R
7
contain a number of carbons sufficient to immobilize the coupler in the emulsion layer; and
Z
a
, Z
b
, and Z
c
are independently a substituted or unsubstituted methine group, ═N—,
or —NH—, provided that one of either the Z
a
-Z
b
bond or the Z
b
-Z
c
bond is a double bond and the other is a single bond, and when the Z
b
-Z
c
bond is a carbon-carbon double bond, it can be part of an aromatic ring and at least one of Z
a
, Z
b,
and Z
c
represents a methine group connected to R
7
. These couplers generally form magenta dyes when R
6
and R
7
are electron donating groups, and cyan dyes when R
6
and R
7
are electron withdrawing groups.
In one embodiment, the invention provides a photographic element comprising a light-sensitive silver halide emulsion layer having associated therewith a dye-forming coupler represented by the formula I:
wherein
X is hydrogen or a coupling-off group;
R is a fully substituted carbon atom;
R
1
, R
2
, R
3
and R
4
are independently selected hydrogen or substituent groups, provided that any two of R
1
, R
2
, R
3
and R
4
may join to for a ring;
R
a
and R
b
are independently hydrogen or a substituent;
each R
c
and R
d
is an independently selected hydrogen or an alkyl or aryl group, provided that any two of them may join to form a ring and n is 1 to 10;
R
e
is hydrogen or an alkyl or aryl group;
each Y is an independently selected substituent group and m is from 0 to 4; and
Z is a substituent selected from the group consisting of —C(O)R
5
, —S(O)
2
R
5
, —SOR
5
, —P(═O)(R
6
)
2
and —P(═O)(OR
6
)
2
in which R
5
is selected from the group consisting of alkyl, aryl, heterocyclic, alkoxy, aryloxy, alkylamino, and arylamino groups and each R
6
is independently selected from the group consisting of alkyl and aryl groups; provided that Z can form a ring with any one of R
c
and R
d
.
In formula I, X is hydrogen or a coupling-off group. Suitable coupling-off groups are more fully described hereinafter. They generally comprise a halogen or other group linked to the rest of the molecule by a heteroatom such an oxygen, sulfur, or nitrogen.
R is a fully substituted carbon atom. Typical examples are t-butyl, methylcyclopropyl, t-pentyl, methylcyclohexyl, and adamantyl.
R
1
, R
2
, R
3
and R
4
are independently selected hydrogen or substituent groups, provided that any two of R
1
, R
2
, R
3
and R
4
may join to form a ring. Suitably, R
1
, R
2
, and R
3
are substituents such as alkyl groups while R
4
is hydrogen, or a substituent such as an alkyl group.
Each Y is a substituent, and m is from 1 to 4.
In formula (I), the value of “n” may vary from 1 to 10, preferably 1 to 5 and more preferably 1 to 3. R
e
is typically a hydrogen atom although alkyl groups such as C1-C4 alkyl including methyl may be employed. Similarly, aryl groups such as phenyl may be employed.
The R
a
and R
b
substituents may be the same or different. Suitably they are hydrogen or alkyl groups. Hydrogen substituents are conveniently employed from a synthesis standpoint but better light fade resistance occurs when one of these is a substituent such as an alkyl group.
The R
c
and R
d
substituents may be the same or different hydrogen, alkyl or aryl groups and two of those substituents may join to form a ring such as a ring ba
Burns Paul A.
Fischer Susan M.
Lincoln David G.
Romanet Robert F.
Spara Paul P.
Eastman Kodak Company
Kluegel Arthur E.
Letscher Geraldine
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