Silver halide photographic light-sensitive material

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

2000-07-24

2003-07-15

Letscher, Geraldine (Department: 1752)

Radiation imagery chemistry: process, composition, or product th

Radiation sensitive product

Silver compound sensitizer containing

C430S600000, C430S607000, C430S611000, C430S613000, C430S551000, C430S567000, C430S583000, C430S584000, C430S588000

Reexamination Certificate

active

06593075

ABSTRACT:

FIELD OF THE INVENTION
The present invention relates to a silver halide photographic light-sensitive material. Specifically, the invention is concerned with a silver halide photographic light-sensitive material which, though it has an increased photographic sensitivity, is improved in not only fog caused by increasing the photographic sensitivity but also storage fog arising from storage under severe conditions.
BACKGROUND OF THE INVENTION
In order to increase the intrinsic sensitivity of silver halide, a wide variety of methods have been adopted. For instance, the sensitivity increase is achieved by the use of chemical sensitizers, such as sulfur compounds, gold compounds and compounds of the group VIII metals, the combined use of those chemical sensitizers and additives enhancing their sensitizing effects, or the addition of additives capable of producing sensitizing effects depending on the species of a silver halide emulsion. Further, the sensitization techniques using organic electron donating compounds in which both electron donating group and releasing group are present are reported in U.S. Pat. Nos. 5,747,235 and 5,747,236, EP-A-786692, EP-A-893731, EP-A-893732 and WO99/05570. On the other hand, the fog accompanying a sensitivity increase and the storage fog arising from the storage under severe conditions, e.g., under circumstances of high temperature and high humidity, or in atmospheres of harmful gases produced by combustion, such as automobile exhaust gases, become problems. As compounds usable for inhibiting the fog generation, there are known mercaptotetrazoles, tetraazaindenes and the salts of thiosulfonic acid (
Research Disclosure
, Item 36544 (vol. 365, September in 1994), Section IV). The compounds recited above are however insufficient to inhibit the fog from generating with an increase of sensitivity, or conversely result in interference on the sensitivity increase. In other words, their effects are unsatisfactory. In addition, those compounds have little effects on the storage fog which generates upon storage under severe conditions, e.g., under circumstances of high temperature and high humidity, or in atmospheres of harmful gases produced by combustion, such as automobile exhaust gases. Therefore, it becomes an important subject to achieve the inhibition of the fog generation accompanying an sensitivity increase and the control of the storage fog. As other means for inhibiting the fog generation while increasing the sensitivity, the following are known.
As one means, it has been reported to combine certain sensitizers with organic compounds in themselves having very little or no sensitizing effect, thereby achieving both sensitization effect and storage stability. As examples of such a case are reported the chemical sensitization in the presence of 6-hydroxypurine in JP-B-7-11684 (the term “JP-B” as used herein means an “examined Japanese patent publication”) the combinations of tellurium sensitizers with polymeric thioethers in JP-A-6-59362 (the term “JP-A” as used herein means an “unexamined published Japanese patent application”), the combinations of selenium sensitizers with hydrazine compounds in JP-A-6-19035 and JP-A-6-202262, and the combinations of tellurium sensitizers with hydrazine compounds in JP-A-5-333469.
As another means, the compounds which in themselves has no function as a sensitizer but can increase the sensitivity and control the fog generation when added to a silver halide emulsion layer have been reported.
Examples of such compounds include the thioether compounds disclosed in JP-B-6-56473, JP-A-1-12184, JP-A-1-121846, JP-B-7-11684 and Registered Japanese Patent No. 2,604,240, ascorbic acid the derivatives thereof as disclosed in Registered Japanese Patent Nos. 2,505,262 and 2,578,188, the silver halide adsorbing hydroquinone compounds disclosed in Registered Japanese Patent No. 2,641,982, the mercapto compounds disclosed in JP-A-5-134345, the benzothiazolium salts and thiosulfonic acids disclosed in JP-A-6-161019, and the thiourea dioxide compounds disclosed in JP-A-7-92591. Even when these compounds are used, however, the sensitization effects obtained are small, and the storage fog and the fog generation accompanying a sensitivity increase are not inhibited to a satisfactory extent.
SUMMARY OF THE INVENTION
Therefore, an object of the invention is to provide a silver halide photographic emulsion having improved sensitivity and keeping quality and, more specifically, to provide a silver halide photographic light-sensitive material which has an increased photographic sensitivity but control fog generation accompanying the increase in photographic sensitivity and has reduced storage fog even when stored under severe conditions, such as under circumstances of high temperature and high humidity, or in atmospheres of harmful gases generating upon combustion, such as automobile exhaust gases.
The object mentioned above is attained with a silver halide photographic light-sensitive material having a silver halide emulsion layer that is chemically sensitized by an organic electron-donating compound and improved in storage properties by containing a weakly reducing compound.
More specifically, the following are embodiments of the invention:
1. A silver halide photographic light-sensitive material having at least one emulsion layer comprising silver halide grains, with the emulsion layer further comprising at least one compound represented by the following formula (I) and at least one compound represented by the following formula (II), (III), (IV-1), (IV-2), (V-1), (V-2), (V-3) or (VI):
(X&Parenclosest;
1
&Parenopenst;L&Parenclosest;
m
&Parenopenst;A—B)
n
  (I)
wherein X represents a silver halide adsorbing group containing at least one N, S, P, Se or Te atom, or a light absorbing group; L represents a divalent linkage group comprising at least one C, N, S or O atom; A represents an electron donating group; B represents a releasing group; 1 and m each represents 0, 1, 2 or 3; and n represents 1 or 2;
wherein R
1
, R
2
, R
3
and R
4
, which are independent of each other, each represents a hydrogen atom, an aryl group, a chain or cyclic alkyl group, a chain or cyclic alkenyl group, or an alkynyl group; and R
5
represents a chain or cyclic alkyl group, a chain or cyclic alkenyl group, an alkynyl group, an aryl group or a heterocyclic group;
(Het&Parenclosest;
k1
&Brketopenst;&Parenopenst;Q
1
&Parenclosest;
k2
&Parenopenst;Hy)]
k3
  (III)
wherein Het represents a group enabling the adsorption to silver halide grains; Q
1
represents a divalent linkage group made up of an atom or atomic group comprising at least one carbon, nitrogen, sulfur or oxygen atom; Hy represents a group having a hydrazine structure represented by R
6
R
7
N—NR
8
R
9
; R
6
, R
7
, R
8
and R
9
, which are independent of each other, each represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, or R
6
and R
7
, R
8
and R
9
, R
6
and R
8
, or R
7
and R
9
may combine with each other to complete a ring, provided that at least one among R
6
, R
7
, R
8
and R
9
is an alkylene group, an alkenylene group, an alkynylene group, an arylene group or a divalent heterocyclic ring residue to which —(Q
1
)
k2
(Het)
k1
is attached; k1 and k3 each represents 1, 2, 3 or 4; and k2 represents 0 or 1;
wherein R
10
, R
11
, R
12
and R
13
, which are independent of each other, each represents a hydrogen atom or a substituent group, provided that, when the substituent groups represented by R
10
and R
13
or those represented by R
11
and R
12
are both alkyl groups, the number of carbon atoms contained in one alkyl group is different from that in the other; R
14
, R
15
and R
16
, which are independent of each other, each represents a hydrogen atom or a substituent group; and Z represents nonmetal atoms completing a 4- to 6-membered ring;
wherein Ra
1
represents a substituted or unsubstituted alkyl group, an alkenyl group or an aryl group, Ra
2
represents a hydrogen atom or a group represented by Ra
1
, and Ra

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