Radiation imagery chemistry: process – composition – or product th – Radiation sensitive product – Silver compound sensitizer containing
Reexamination Certificate
2002-02-15
2003-05-27
Schilling, Richard L. (Department: 1752)
Radiation imagery chemistry: process, composition, or product th
Radiation sensitive product
Silver compound sensitizer containing
C430S601000, C430S603000, C430S605000
Reexamination Certificate
active
06569613
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to a silver halide photographic (light-sensitive) material and a silver halide photographic emulsion for the photographic material. In particular, the present invention is concerned with a silver halide photographic material which undergoes sensitization with a hydrophilic compound containing gold with a valence of zero (which is expressed as Au(0) hereinafter) and thereby achieves high sensitivity and slight fogging.
BACKGROUND OF THE INVENTION
In order to obtain the desired sensitivity and gradation, silver halide emulsions used in silver halide photographic (light-sensitive) materials are generally subjected to chemical sensitization using various chemical substances. As representative methods for chemical sensitization, there are known a wide variety of methods including a sulfur sensitization method, a selenium sensitization method, a tellurium sensitization method, a noble metal sensitization method such as a gold sensitization method, a reduction sensitization method and various combinations of these methods. For silver halide photographic (light-sensitive) materials, high sensitivity, excellent graininess, high sharpness and rapid processing in which rate of development is increased, have recently grown in demand, and therefore various improvements to the sensitization methods have been made. Of those improved methods, most prevailingly employed methods are gold-sulfur sensitization methods using combinations of gold compounds and “labile sulfur compounds” capable of producing silver sulfide by reaction with silver ion. And they are described specifically in P. Grafkides,
Chimie et Physique Photographique
, 5th Ed., Paul Montel (1987), T. H. James (editor),
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 subjecting a silver halide emulsion to gold-sulfur sensitization, it is a general manner that a gold compound and an labile sulfur compound capable of producing silver sulfide by reaction with silver ion are added individually. Such a manner is described in the references described above,
Nippon Shashin Gakkai-shi
(Journal of the Japanese Photographic Society), Vol. 50, No. 2, from p. 108 onward (1987), and
Journal of the Optical Society of America
, Vol. 39, No. 6, from p. 494 onward.
Hitherto, the gold-sulfur sensitization has been carried out using chloroauric acid as the gold compound and a thiourea compound or a thiosulfate as the labile sulfur compound. However, the use of these compounds has various problems. For instance, it cannot increase the sensitivity to a satisfactory extent, tends to cause fogging, lowers the contrast, and becomes a cause of serious fogging upon long-term storage of photosensitive materials. Therefore, solutions to these problems have been urgently required.
On the other hand, methods of using gold compounds other than chloroauric acid in the gold-sulfur sensitization have been known. Such gold compounds include the gold complexes of thioethers as disclosed in Japanese Patent Application (Laid-Open) Nos. 6447/1963 and 85239/1987, the gold complexes of rhodanines as disclosed in Japanese Patent Application (Laid-Open) No. 147537/1989, the gold complexes of meso ions as disclosed in Japanese Patent Application (Laid-Open) No. 267249/1993, and the gold complexes of hydantoins as disclosed in Japanese Patent Application (Laid-Open) No. 268550/1993. However, all of these complexes are insufficient for resolution of those problems.
In addition, Japanese Patent Application (Laid-Open) Nos. 67032/1993, 75053/1993 and 86649/1993 disclose the gold complex compounds which are reported therein to have improving effects on an increase of fog and graininess deterioration accompanied by the fog increase during long-term storage of light-sensitive materials. Further, Japanese Patent Application (Laid-Open) No. 266826/1992 discloses the cases of using gold complexes wherein a trivalent gold ion is coordinated with tetrasubstituted thiourea molecules.
However, all of these compounds also are insufficient for resolution of the above problems.
Further, in Japanese Patent application (Laid-Open) No. 204724/1993, a method in which a gold compound and an labile selenium compound capable of producing the silver selenide by reaction with silver ion are added individually. However, in this case, the fog is extremely generated, and therefore the resolution of the above problems can not be achieved.
Also, in Langmuir, page 1075 (1999), gold fine particles in which a compound containing a mercapto group as an adsorbing group for a gold atom and a carboxyl group as a hydroxyl group is adsorbed as a stabilizer, is described. However, the effect due to a sensitizer of the gold fine particle has not been conventionally known.
SUMMARY OF THE INVENTION
The present invention is made for achieving a breakthrough in those circumstances. An objective of the present invention is therefore to provide a silver halide photographic (light-sensitive) material and a silver halide photographic emulsion for the photographic material, which undergoes gold sensitization with a compound containing gold with a valence of zero and achieves an increase in sensitivity and a reduction in fogging.
The objective is attained by the following embodiments of the present invention:
1. A silver halide emulsion, containing at least one gold-containing compound represented by composition formula (1):
[Au(0)Lm]Xn (1)
wherein Au(0) is an Au atom having a valence of zero, L is a compound having at least one group capable of being adsorbed to or coordinating with Au(0), mis a value of 0 or more including decimals, X is an ion required for neutralizing electric charge of the compound, and n is a value of 0 or more including decimals.
2. A silver halide emulsion, being chemically sensitized with a gold-containing compound represented by the foregoing composition formula (1).
3. The silver halide emulsion according to the above item 2, wherein the L in composition formula (1) is a compound having a group containing at least one atom selected from the group consisting of a sulfur atom, a selenium atom, a tellurium atom, a nitrogen atom and a phosphorus atom.
4. The silver halide emulsion according to the above item 2, wherein the compound represented by L in composition formula (1) has at least one hydrophilic group.
5. The silver halide emulsion according to the above item 4, wherein the hydrophilic group is a carboxyl group, a sulfo group or an ammonium salt.
6. The silver halide emulsion according to the above item 2, wherein the group capable of being adsorbed to or coordinating with Au(0) is a mercapto group, an alkylthio group, an arylthio group or a thiocarbonyl group.
7. The silver halide emulsion according to the above item 2, wherein the L in composition formula (1) is a compound having at least one mercapto group and at least one carboxyl group.
8. The silver halide emulsion according to the above item 2, wherein the L in composition formula (1) is thiomalic acid.
9. The silver halide emulsion according to the above item 2, wherein the L in composition formula (1) is at least one compound selected from the group consisting of a thioether compound, a selenoether compound, a telluroether compound, a thioamide compound, a selenoamide compound, a telluroamide compound, an amino group-containing compound, a phosphino group-containing compound and a nitrogen-containing heterocyclic compound.
10. The silver halide emulsion according to the above item 2, wherein the compound of composition formula (1) is in a state of a super fine grain having an average size of not greater than 10 nm.
11. The silver halide emulsion according to the above item 2, comprising silver halide grains in which at least 60% of an entire projected area of the silver halide grains are occupied by a tabular silver halide grain having an aspect ratio of at least 8.
12. The silver halide emulsion according to t
Oya Toyohisa
Suzuki Hiroyuki
Fuji Photo Film Co. , Ltd.
Schilling Richard L.
LandOfFree
Silver halide photographic emulsion does not yet have a rating. At this time, there are no reviews or comments for this patent.
If you have personal experience with Silver halide photographic emulsion, we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Silver halide photographic emulsion will most certainly appreciate the feedback.
Profile ID: LFUS-PAI-O-3028968