Silver halide photographic light-sensitive material

Details Silver halide photographic light-sensitive material Silver halide photographic light-sensitive material

2000-02-10

2001-03-13

Baxter, Janet (Department: 1752)

Radiation imagery chemistry: process, composition, or product th

Radiation sensitive product

Silver compound sensitizer containing

C430S604000, C430S605000

Reexamination Certificate

active

06200744

ABSTRACT:

BACKGROUND OF THE INVENTION
The present invention relates to a silver halide photographic light-sensitive material and, more particularly, to a silver halide photographic light-sensitive material which varies photographic properties little and produces fog little after storage.
Since silver halide photographic light-sensitive materials are demanded to have high sensitivity, the importance of high-aspect-ratio emulsions is increasing. As the sensitivity is increasing, variations in photographic properties caused by storage after the manufacture of photosensitive materials tend to increase. This variation in photographic properties is desired to be suppressed, particularly the technique of suppressing an increase in fog is needed. Meanwhile, variations in photographic properties in the running process are also desired to be little. That is, it is demanded to suppress both variations in photographic properties during storage and variations in photographic properties before and after the running process.
For the purpose of suppressing fog, the addition of palladium compounds such as a palladium complex of ethylenediamine is disclosed in U.S. Pat. Nos. 2,552,229 and 2,566,263 and Jpn. Pat. Appln. KOKAI Publication No. (hereinafter referred to as JP-A-)5-333480. In effect, the method has the effect of suppressing increases in fog during storage.
JP-A-8-234341 (U.S. Pat. No. 5,614,360) has disclosed that when palladium compounds of ethylenediamine are used, the viscosity does not rise even at high gelatin density. However, when photosensitive materials are stored under high-temperature, high-humidity tropical conditions, the effect of suppressing fog is unsatisfactory, so further improvements are being desired (U.S. Pat. No. 2,552,229 shows data on this storage fog under tropical conditions).
The present inventors made extensive studies and have found that variations in photographic properties caused by the running process increase when a Pd complex described in aforesaid JP-A-8-234341 (U.S. Pat. No. 5,614,360) is used.
On the other hand, no conventional technique concerning a Pd ligand has been known which uses, for the aforementioned purpose, a complex to which nitrogen of a carbamoyl group coordinates.
As described above, as the sensitivity of an emulsion rises, fog produced during storage increases. Hence, if the sensitivity is raised by increasing the aspect ratio, photographic properties, such as fog produced during storage, largely change with time. As described above, no conventional technique has been known which prevents changes in photographic properties during storage and reduces variations in photographic properties in the running process, by using a Pd(II) complex to which nitrogen of a carbamoyl group coordinates.
BRIEF SUMMARY OF THE INVENTION
It is an object of the present invention to provide a means for improving the storage stability of a silver halide photographic light-sensitive material, particularly a means for suppressing an increase in fog during storage under high-temperature, high-humidity conditions. It is another object of the present invention to provide a silver halide photographic light-sensitive material which changes photographic properties little before and after the running of development.
The above objects have been achieved by (1) to (6) below.
(1) A silver halide photographic light-sensitive material comprising at least one photosensitive silver halide emulsion layer on a support, and containing a Pd(II) complex represented by formula (I-1):
where Z
1
represents an alkylene group, an arylene group, or a divalent heterocyclic group, Q represents an ion which neutralizes electric charge of the Pd complex, m represents an integer of from 0 to 4, R
1
represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, or an arylsulfonyl group, each of X
1
and X
2
represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and each of Y
1
and Y
2
represents an organic or inorganic ligand wherein Y
1
and Y
2
may be combined to form a ring together with Pd.
(2) The silver halide photographic light-sensitive material described in item (1) above, where the Pd(II) complex is represented by formula (I-2):
where each of Z
1
and Z
2
represents an alkylene group, an arylene group, or a divalent heterocyclic group, each of R
1
and R
2
represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, or an arylsulfonyl group, and each of X
1
, X
2
, X
3
, and X
4
represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.
(3) The silver halide photographic light-sensitive material described in item (1) above, comprising at least one blue-sensitive emulsion layer, at least one green-sensitive layer, at least one red-sensitive layer, and at least one non-light-sensitive layer.
(4) The silver halide photographic light-sensitive material described in item (2) above, comprising at least one blue-sensitive emulsion layer, at least one green-sensitive layer, at least one red-sensitive layer, and at least one non-light-sensitive layer.
(5) The silver halide photographic light-sensitive material described in item (3) above, where 60% or more of a total projected area of silver halide grains contained in the photosensitive silver halide emulsion layer is occupied by tabular silver halide grains having an aspect ratio of 8 or more.
(6) The silver halide photographic light-sensitive material described in item (4) above, where 60% or more of a total projected area of silver halide grains contained in the photosensitive silver halide emulsion layer is occupied by tabular silver halide grains having an aspect ratio of 8 or more.
The present invention can improve the storage stability of a silver halide photosensitive material, particularly, can suppress an increase in fog during storage under high-temperature, high-humidity conditions, and can decrease a density change in an unexposed portion before and after the running process of development.
DETAILED DESCRIPTION OF THE INVENTION
The compound represented by formula (I-1) or (I-2) of the present invention has a structural characteristic feature that the carbamoyl group coordinates to Pd (II) at its N atom with its N-proton dissociated from the N atom. The N-proton of the carbamoyl group does not readily dissociate at low pH, but the N-protonation and the dissosiation of the N-proton (deprotonation) are in an equilibrium state in solution. Accordingly, the effect of the present invention can also be obtained even if the compound of the present invention is made into an acidic solution, in which the N atom of the carbamoyl group is protonated as noted above, and such acidic solution is used or added according to the present invention.
Compounds represented by formulas (I-1) and (I-2) of the present invention release a ligand when capturing cyan ion having adverse effect on storage stability. The present inventors, however, believe that the released ligand has no influence on the storage stability of an emulsion, since the released ligand protonates and loses its coordinating power over silver ion.
Compounds represented by formulas (I-1) and (I-2) will be described in detail below.
Z
1
, R
1
, X
1
, and X
2
in formula (I-1) have the same meanings as Z
1
, R
1
, X
1
, and X
2
in formula (I-2).
In formula (I-1), Q represents an ion which neutralizes electric charge of a Pd complex.
Examples of an anion are halogen ion, nitric acid ion, carbonic acid ion, hydrogencarbonate ion, sulfuric acid ion, sulfurous acid ion, cyano ion, cyanic acid ion, isocyanic acid ion, thiocyanic acid ion, boric acid ion, phosphonic acid ion, perchloric acid ion, organic carboxylic acid ion (e.g., formic acid ion, acetic acid ion, and oxalic acid ion), and organic sulfonic acid ion (e.g., methanesulfonic acid ion, benzenesulfonic acid ion, p-tolue

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