Radiation imagery chemistry: process – composition – or product th – Radiation sensitive product – Silver compound sensitizer containing
Reexamination Certificate
2000-07-06
2002-02-12
Schilling, Richard L. (Department: 1752)
Radiation imagery chemistry: process, composition, or product th
Radiation sensitive product
Silver compound sensitizer containing
C430S601000, C430S603000, C430S605000, C430S600000
Reexamination Certificate
active
06346372
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to a silver halide photographic light-sensitive material, more specifically, the present invention relates to a silver halide photographic light-sensitive material favored with high sensitivity, small generation of fogging, high contrast, small increase in the fog during a long-term storage of the light-sensitive material and small fluctuation in the sensitivity due to aging after the exposure.
BACKGROUND OF THE INVENTION
The silver halide emulsion for use in silver halide photographic light-sensitive materials is usually subjected to chemical sensitization using various chemical substances so as to obtain desired sensitivity, gradation and the like. Representative known examples of the chemical sensitization include sulfur sensitization, selenium sensitization, tellurium sensitization, noble metal sensitization using gold or the like, reduction sensitization and combinations thereof. In recent years, the silver halide photographic light-sensitive material is strongly demanded to have high sensitivity, excellent graininess, high sharpness and rapid processability for allowing expedited progress of the development or the like and to this purpose, various improvements have been made on the above-described sensitization methods. Among these, most commonly used is the gold-sulfur sensitization method using a so-called labile sulfur compound capable of reacting with silver ion to produce silver sulfide, and a gold compound. This sensitization method is specifically described, for example, in P. Grafkides,
Chimie et Physique Photographique
, 5th ed., Paul Montel (1987), T. H. James (compiler),
The Theory of the Photographic Process
, 4th ed., Macmillan (1977), and H. Frieser,
Die Grundlagen der Photographischen Prozesse mit Silber
-
halogeniden
, Akademische Verlagasgeselshaft (1968).
In general, for applying the gold-sulfur sensitization to a silver halide emulsion, a method of separately adding a labile sulfur compound capable of reacting with the silver ion to generate silver sulfide, and a gold compound is used. This method is described in the above-described publications and additionally in
Nippon Shashin Gakkai Shi
(
Journal of Japan Photographic Society
), Vol. 50, No. 2, page 108 et seq. (1987),
Journal of the Optical Society of America
, Vol. 39, No. 6, page 494 et seq. (1949) and the like.
In the methods described in these publications, a chloroauric acid is used as the gold compound and a thiourea compound or a thiosulfate is used as the labile sulfur compound. However, with use of these compounds, various problems are present, for example, the degree of increase in the sensitivity is not satisfied, fogging readily occurs, the gradation is in low contrast and when the light-sensitive material is stored for a long period of time, fog is seriously generated. Means for solving these problems are strongly demanded.
On the other hand, with respect to the method of applying gold-sulfur sensitization using a gold compound other than the chloroauric acid, methods of using a gold complex of thioethers described in JP-B-38-6447 (the term “JP-B” as used herein means an “examined Japanese patent publication”) and JP-A-62-85239 (the term “JP-A” as used herein means an “unexamined published Japanese patent application”), a gold complex of rhodanines described in JP-A-1-147537, a gold complex of mesoions described in JP-A-4-267249, a gold complex of hydantoins described in JP-A-4-268550, or a gold complex of water-soluble group-containing mercapto compounds described in JP-B-45-8831 and EP-A-915371 are known. These compounds all are, however, incapable of satisfactorily solving the above-described problems.
JP-A-4-67032, JP-A-4-75053 and JP-A-4-86649 describe gold complex compounds having an improvement effect on the increase of fog due to aging of the light-sensitive material over a long period of time, and on the resulting deterioration in graininess; and also, JP-A-3-266828 discloses an example of using a gold complex obtained by coordinating a thiourea as the sulfur sensitizer to a trivalent gold ion. However, these compounds all are incapable of exhibiting satisfactory action to solve the above-described problems, either.
Furthermore, JP-A-4-204724 describes a method for applying gold-selenium sensitization to a silver halide emulsion, where a labile selenium compound capable of reacting with silver ion to produce silver selenide, and a gold compound are separately added. However, in this case, fog seriously increases and the above-described problems cannot be solved.
Particularly, in an internal latent image-type direct positive silver halide emulsion, the gold sensitization speck is known to act as an effective sensitization center at the chemical sensitization of the core but, as conventionally acknowledged, also form fogged nuclei giving rise to the reduction in the density of the reversal positive performance due to the excess use of the gold sensitizer (e.g., chloroauric acid) or the prolonged post-ripening time. Therefore, it is keenly demanded to form a high-sensitivity gold sensitization center while reducing the formation of fogged nuclei as much as possible.
In the photographic art, the mercapto compound is well known to have an effect of preventing fogging and is used by coordinating it to a gold complex. For example, there are known a method of using a complex in which a mercapto compound is one-coordinated to gold described in JP-A-8-69075, a method of using a gold complex of a mercapto compound substituted by a sulfonic acid group described in JP-B-45-8831, a method of using a gold complex of a two-coordinate and symmetric water-soluble group-containing mercapto compound described in European Patent 915371, a method of using a gold complex in which a tetra-substituted thiourea and a heterocyclic mercapto compound are coordinated at the same time to gold described in U.S. Pat. No. 5,912,111, a method of using a gold complex having asymmetrically coordinated therein a heterocyclic mercapto compound and a mesoionic compound described in U.S. Pat. No. 5,912,112, and a method of using an asymmetric gold complex having coordinated therein a mercapto compound and at the same time a thiosulfonic acid compound described in JP-A-9-118685. However, these methods are still deficient particularly in the fog/sensitivity ratio and cannot solve the above-descried problems.
SUMMARY OF THE INVENTION
The present invention has been made under these circumstances and the object of the present invention is to provide a silver halide photographic light-sensitive material favored with low fog, high sensitivity, small generation of fog during a long-term storage, small fluctuation in the sensitivity due to aging after the exposure, and high contrast by using a specific gold complex.
The above-described object can be attained by the silver halide photographic light-sensitive material described below.
[1] A silver halide photographic light-sensitive material comprising a support having thereon at least one silver halide emulsion layer, which contains at least one compound represented by the following formula (1) or (A-1):
{L
1
—A
1
—Y
1
—Au(I)—Y
2
—A
2
—L
2
}X
n
(1)
wherein L
1
and L
2
, which may be the same or different, each represents a group containing a labile sulfur group, labile selenium group or labile tellurium group capable of reacting with silver halide to produce silver sulfide, silver selenide or silver telluride, Y
1
and Y
2
, which may be the same or different, each represents a coordination group capable of forming a complex with gold, A
1
and A
2
, which may be the same or different, each represents a divalent linking group or a mere bond, X represents a counter salt necessary for neutralizing the electric charge of the compound, and n represents a number of from 0 to 1:
{B
1
—Au(I)—B
2
}X
n
(A-1)
wherein B
1
and B
2
, which may be the same or different, each represents an azole compound, B
2
represents a compound containing at least one of a labile sul
Matsunaga Atsushi
Sasaki Hirotomo
Yoshikawa Masaru
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