Silver halide photographic material

Details Silver halide photographic material Silver halide photographic material

2000-07-12

2002-04-16

Schilling, Richard L. (Department: 1752)

Radiation imagery chemistry: process, composition, or product th

Radiation sensitive product

Silver compound sensitizer containing

C430S600000, C430S604000, C430S605000, C430S936000

Reexamination Certificate

active

06372419

ABSTRACT:

FIELD OF THE INVENTION
The present invention relates to a silver halide photographic material using a metal complex, and more particularly to a high speed silver halide emulsion using a doping technique.
BACKGROUND OF THE INVENTION
As one technique of improving the performance of a silver halide photographic material at large as desired by reforming silver halide grains, a technique of incorporating substances other than a silver ion and a halide ion into silver halide grains, i.e., a technique of doping a dopant, is known. In particular, with respect to doping techniques of transition metal ions, a number of studies have been done for years. It is generally known that a transition metal ion effectively reforms photographic performances if it gets into silver halide grains as a dopant even with an extremely trace addition amount.
For increasing the sensitivity of a silver halide emulsion, a technique of doping not only a transition metal ion but also a transition metal complex having a cyanide ion as a ligand into silver halide grains has been known. In particular, many examples are disclosed with respect to emulsions which are highly sensitized by doping with VIII group metal complexes having six cyanide ions as the ligand. As a dopant containing a cyanide ion, yellow prussiate of potash which is hexacyanoferrate (II) complex, and red prussiate of potash which is hexacyanoferrate(III) complex are disclosed in JP-B-48-35373 (the term “JP-B” as used herein means an “examined Japanese patent publication”). However, in this invention, the effect of higher sensitization is limited to the case of containing an iron ion and is not related to the kind of a ligand. There are many examples of obtaining high speed emulsions by doping with hexacyanoferrate (II) complex, e.g., those disclosed in JP-A-5-66511 (the term “JP-A” as used herein means an “unexamined published Japanese patent application”) and U.S. Pat. No. 5,132,203. High speed emulsions which can be obtained by doping with cyano complexes other than iron complexes are known, e.g., it is disclosed in JP-A-2-20853 that high speed silver halide emulsions can be obtained when silver iodochloride is doped with rhenium, ruthenium, osmium and iridium complexes. Many complexes containing other metal ions are also used as dopants and the effects brought about by doping are various, such as not only higher sensitization but also the improvement of reciprocity law failure and higher contrast. It is disclosed in U.S. Pat. No.2,448,060 that an emulsion doped with a platinum complex having a halogen ion as a ligand or a palladium (III) complex is sensitized. Emulsions which are doped with cyano complexes of iron(II) and iron(III), emulsions doped with cyano complexes of cobalt(III) as well, are disclosed in U.S. Pat. No. 3,790,390, in addition, silver halide emulsions containing spectral sensitizing dyes are disclosed. Silver halide grains formed in the presence of rhodium(III) complexes having 3, 4, 5 or 6 cyanide ions as ligands are disclosed in U.S. Pat. No. 4,847,191. It is shown in these patents that high intensity reciprocity law failure is reduced due to dopants. Silver halide emulsions doped with rhenium, ruthenium, osmium or iridium having 4 or more cyano ligands are disclosed in EP 0336425, EP 0336426, and JP-A-2-20854. It is disclosed in these patents that the sensitivity and gradation stabilities with the lapse of time are improved and low intensity reciprocity law failure is improved. Silver halide emulsions using six-coordinated vanadium, chromium, manganese, iron, ruthenium, osmium, rhenium or iridium complex containing nitrosyl or thionitrosyl ligands are disclosed in EP 0336427 and JP-A-2-20852, and low intensity reciprocity law failure is improved without lowering middle intensity sensitivity. As dopants other than transition metal ions, emulsions doped with bismuth or lead ions are disclosed in U.S. Pat. No. 3,690,888, and emulsions containing metal ions belonging to group XIII and group XIV of the Periodic Table are disclosed in JP-A-7-128778.
Among the ligands of complexes which are used as dopants the most numerous are probably cyanide ions, and halide ions are also used numerously. For example, as an example that a complex having the structure of (MCl
6
)
n−
, with M being an arbitrary metal, is doped, hexachlororuthenium, hexachloroiridium, hexachlororhodium and hexachlororhenium as disclosed in JP-A-63-184740, JP-A-1-285941, JP-A-2-20852 and JP-A-2-20855 can be exemplified. Examples of a dopant such as a six-coordinated rhenium complex containing halogen, nitrosyl, thionitrosyl, cyan, water, and thiocyan as each ligand is disclosed in EP 0336689 and JP-A-2-20855, a transition metal complex which is a six-coordinated metal complex containing carbonyl as one ligand is disclosed in JP-A-3-118535, and an emulsion containing a transition metal complex which is a six-coordinated metal complex containing oxygen atoms as two ligands is disclosed in JP-A-3-118536, these are disclosed as emulsions having useful photographic performances.
As described above, the central metals and ligands of complexes used as dopants are various, and further in recent years techniques for reforming the property of an emulsion by doping a complex having an organic compound as a ligand have come to be disclosed. Examples in which complexes having various organic compounds as ligands are used are disclosed in U.S. Pat. Nos. 5,360,712, 5,457,021, 5,462,849, EP 0709724, JP-A-7-72569 and JP-A-8-179452, and there are disclosed that the effect of increasing sensitivity is particularly large when [(NC)
5
Fe(&mgr;-4,4′-bipyridine)Fe(CN)
5
]
6−
is doped. However, the metal complexes having organic ligands disclosed in these patents have a drawback that when they are dissolved in a gelatin aqueous solution in doping to a silver halide grain, they are decomposed rapidly (it is presumed that the organic ligand parts deviate because the spectral absorption spectra vary largely). Emulsions whose high sensitivity and reciprocity law failure are improved due to doping with [Fe(CO)
4
(P (Ph)
3
)]
0
or [Fe(CO)
3
(P(Ph)
2
)]
0
are disclosed in JP-A-11-24194, however, these complexes are also unstable in water and a gelation aqueous solution and decomposed with aging when they have been completely dissolved. In JP-A-11-102042 are disclosed high speed emulsions obtained by doping with [M(CN)
5
L]
3−
(M represents Fe
2+
, Ru
2+
or Ir
3+
), [Fe(CO)
4
L]
0
, [M′(CN)
3
L]
−
(M′ represents Pd
2+
or Pt
2+
) or [IrCl
5
L]
2−
and 2-mercaptobenzimidazole, 5-methyl-s-triazolo[1.5-A]pyrimidine-7-ol, or 2-mercapto-1,3,4-oxadiazole is used as L. However, cyanide and CO in these metal complexes are liable to deviate and liberate into the system and have a harmful influence on the system. In JP-A-10-293377, it is disclosed that the emulsions doped with [RuCl
5
L′]
2−
(L′ represents imidazole, benzimidazole or derivatives thereof) are conspicuously improved in high contrast, and the sensitivity at that time becomes largely higher than that of emulsions doped with conventional desensitized high contrast dopants. However, almost all of the ligands used in the complexes in these patents are nitrogen atoms and there are almost no dopants having oxygen atoms as ligands, and examples of using complexes coordinated with oxygen atoms of ketone as dopants are not known.
When a complex having a six-coordinationated octahedral structure is incorporated into a silver halide grain as a dopant, as described in
J. Phys.: Condens. Matter
9, pp. 3227 to 3240 (1997) and other references and patents, it is thought that [AgX
6
]
5−
unit (X is a halogen ion) in the silver halide grain and the molecule of the complex are replaced, and the central metal occupies the lattice position of the Ag
+
ion, and each ligand occupies the lattice position of the halide ion. It is disclosed in U.S. Pat.

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