Radiation imagery chemistry: process – composition – or product th – Color imaging process – Using identified radiation sensitive composition in the...
Reexamination Certificate
2000-11-17
2002-09-17
Letscher, Geraldine (Department: 1752)
Radiation imagery chemistry: process, composition, or product th
Color imaging process
Using identified radiation sensitive composition in the...
C430S549000, C430S558000, C430S505000
Reexamination Certificate
active
06451517
ABSTRACT:
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is based upon and claims the benefit of priority from the prior Japanese Patent Application No. 11-328261, filed Nov. 18, 1999, the entire contents of which are incorporated herein by reference.
BACKGROUND OF THE INVENTION
The present invention relates to a color photographic lightsensitive material and, more particularly, to a color photographic lightsensitive material having improved processing dependence on color development and high granularity and superior image storage characteristics. The present invention also relates to a method for forming color image using this color photographic lightsensitive material.
Recently, in color photographic lightsensitive materials pyrazoloazole-based couplers having little secondary absorption near 430 nm are beginning to be used instead of 5-pyrazolone-based magenta couplers conventionally used to improve color reproduction. When this pyrazoloazole-based coupler is used, however, gradation changes or color generating property changes increase owing to pH variations in a color developer. To improve this, U.S. Pat. No. 5,342,746 has disclosed the use of oleyl alcohol, and Jpn. Pat. Appln. KOKAI Publication No. (hereinafter referred to as JP-A-)3-160442 has disclosed the combination of a compound which scavenges the oxidized form of a color developing agent and a film harder. Also, JP-A-1-315735, JP-A-2-8841, and JP-A-3-125143 have disclosed methods of decreasing the dependence on pH variations by variously changing groups for substituting pyrazoloazole. However, to make the present invention the present inventors have newly found that color generating property changes caused by pH variations cannot be well improved even by the use of the above methods, and that the problem of color generating property changes caused by pH variations cannot be radically settled when processing is performed using a color developer whose pH is 11.0 or more.
Meanwhile, in silver halide photographic lightsensitive materials the image quality properties such as the granularity and the image storage characteristics are also important properties. In most pyrazoloazole-based magenta couplers described in the patents cited above, split-off groups which couple with the oxidized form of a color developing agent are substituents except for a hydrogen atom. When this substituent is a hydrogen atom, the granularity improves but yellow stains are produced in uncolored portions by humidity and heat. The granularity is more or less improved by decreasing the coupling rate of a coupler and the oxidized form of a color developing agent. However, the influence of concentration variations in a color developing agent on color generating properties increases.
As a technique close to the present invention, JP-A-4-346342 has disclosed a technique which mixes pyrazolotriazole magenta couplers having different structures. Unfortunately, in all couplers presented as practical examples in the patents cited above, split-off groups for coupling with the oxidized form of a color developing agent are groups except for a hydrogen atom. Also, the objects of these patents are different from the objects of the present invention. So, the object of the present invention cannot be achieved by the techniques of these patents.
BRIEF SUMMARY OF THE INVENTION
It is an object of the present invention to provide a color photographic lightsensitive material having improved processing dependence on color development. In particular, it is an object of the present invention to provide a color photographic lightsensitive material having improved color generating property changes with pH variations when color development is performed using a color developer whose pH is 11.0 or more, having improved color generating property changes with concentration variations in a color developing agent, and having high granularity and superior image storage characteristics. It is another object of the present invention to provide a method for forming color image using this color photographic lightsensitive material.
The present inventors made extensive studies to achieve high granularity and good image storage characteristics and further to improve color generating property changes with pH variations on color development and color generating property changes with concentration variations in a developing agent. Consequently, the present invention is accomplished by the following means.
(1) A silver halide color photographic lightsensitive material comprising at least one emulsion layer on a support, wherein at least one of the emulsion layers contains a coupler represented by formula (1) below and a coupler represented by formula (2) below at a molar ratio of 1:9 to 9:1, and at least one of substituents X
1
and X
2
is a hydrogen atom.
In formulas (1) and (2), each of R
1
, R
2
, R
3
, and R
4
independently represents a hydrogen atom or a substituent. Each of X
1
and X
2
represents a hydrogen atom or a group capable of splitting off by coupling with the oxidized form of a developing agent. At least one of X
1
and X
2
is a hydrogen atom.
(2) A silver halide color photographic lightsensitive material comprising at least one emulsion layer on a support, wherein at least one of the emulsion layers contains a coupler represented by formula (1) below and a coupler represented by formula (3) below at a molar ratio of 1:9 to 9:1:
In formula (1), each of R
1
and R
2
independently represents a hydrogen atom or a substituent. X
1
represents a hydrogen atom or a group capable of splitting off by coupling with the oxidized form of a developing agent.
In formula (3), R
3
represents a substituted or nonsubstituted, 5- to 20-carbon secondary alkyl group or substituted or nonsubstituted, 4- to 20-carbon tertiary alkyl group. R
4
represents a hydrogen atom or a substituent.
(3) The silver halide color photographic lightsensitive material described in item (2) above, wherein a coupler represented by formula (3) has in R
3
or R
4
a dissociative substituent having a pka of 10 or less, which is measured at 25° C. in tetrahydrofuran:water=6:4.
(4) A method for forming color image, wherein the lightsensitive material described in item (1) above is subjected to imagewise exposure, negative black-and-white development, and color development in this order.
(5) The lightsensitive material described in item (1) above, characterized in that each substituent of the formula (1) is as follows:
R
1
represents a substituted or nonsubstituted alkyl group having 1 to 20 carbon atoms; R
2
represents a substituted or nonsubstituted aryl group having 6 to 20 carbon atoms; and X
1
represents a halogen atom, aryloxy group having 6 to 20 carbon atoms, or hydrogen atom.
(6) The lightsensitive material described in item (1) above, characterized in that each substituent of the formula (1) is as follows:
R
1
represents a substituted or nonsubstituted tertiary alkyl group having 4 to 20 carbon atoms; R
2
represents a substituted secondary alkyl group having 3 to 20 carbon atoms or substituted aryl group having 6 to 20 carbon atoms; and X
1
represents a hydrogen atom or chlorine atom.
(7) The lightsensitive material described in item (1) above, characterized in that each substituent of the formula (1) is as follows:
R
1
represents a nonsubstituted tertiary alkyl group having 4 to 20 carbon atoms; R
2
represents a substituted aryl group having 6 to 20 carbon atoms; and X
1
represents a chlorine atom.
(8) The lightsensitive material described in item (2) above, characterized in that each substituent of the formula (3) is as follows:
R
3
represents a substituted or nonsubstituted alkyl group having 1 to 20 carbon atoms; and R
4
represents a substituted or nonsubstituted alkyl group having 2 to 20 carbon atoms or substituted or nonsubstituted aryl group having 6 to 20 carbon atoms.
(9) The lightsensitive material described in item (2) above, characterized in that each substituent of the formula (3) is as follows:
R
3
represents a nonsubstituted tertiary alkyl group having 4 to 20 car
Fukuzawa Hiroshi
Mikoshiba Hisashi
Shimura Yoshio
Birch & Stewart Kolasch & Birch, LLP
Fuji Photo Film Co. , Ltd.
Letscher Geraldine
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