Silver halide photographic material

Details Silver halide photographic material Silver halide photographic material

2001-03-26

2003-05-20

Baxter, Janet (Department: 1752)

Radiation imagery chemistry: process, composition, or product th

Radiation sensitive product

Silver compound sensitizer containing

C430S570000, C430S574000, C430S573000, C430S576000, C430S577000, C430S580000, C430S581000, C430S583000, C430S585000, C430S586000, C430S589000, C430S567000, C430S569000, C430S600000, C430S945000, C430S963000

Reexamination Certificate

active

06566044

ABSTRACT:

FIELD OF THE INVENTION
The present invention relates to silver halide photographic emulsions and silver halide photographic materials using said emulsions. More specifically, the present invention provides silver halide photographic emulsions exhibiting an excellent solution storage stability and silver halide photographic materials exhibiting low fog, excellent graininess and less residual color after rapid processing.
BACKGROUND OF THE INVENTION
It is well known that sensitizing dyes used for spectral sensitization have noticeable effects on the performance of silver halide photographic materials. Trivial structural changes of sensitizing dyes often give an extreme influence on various photographic properties such as speed, fog, storage stability, residual color (i.e. , coloration after processing) or graininess. Similar phenomena are observed when two or more kinds of sensitizing dyes are used together. In both cases, it is substantially impossible to predict such influences in advance. Hence, emulsion researchers have synthesized a vast number of sensitizing dyes and studied the photographic effects of various combinations of those sensitizers for many years In spite of such efforts, the prediction of the photographic properties obtained by the use of sensitizing dyes is still almost impossible.
While photographic materials are expected to have higher speeds as well as better image quality, rapider photographic processing and reduction of processing waste for environmental protection are also urgently demanded. Therefore, technologies to achieve a high photographic speed by spectrally sensitizing silver halide grains without causing adverse effects such as fog or residual color are becoming more and more important.
Tabular grains are advantageous for spectral sensitization as the surface area per grain volume (specific surface area) is large, thus permitting the adsorption of a large amount of sensitizing dyes and improving speed/graininess ratio. On the other hand, the sensitizing dyes tend to remain in the material after processing, and the problem of residual color is serious as compared to the emulsions consisting of regular grains.
Separately, rapid processing that is eagerly expected tends to increase the amount of residual sensitizing dyes in the emulsion, thus making the problem of residual color more serious. Accordingly, techniques of reducing residual color have been earnestly expected.
It is already known that enhancement of the hydrophilic property of sensitizing dyes is effective to reduce residual color. However, the adsorption of hydrophilic dyes on silver halide grains is generally weak, causing adverse effects on the photographic properties of the resulting emulsion including speed reduction. Such a conflict has set a severe limitation on the improvement of residual color.
Moreover, a large amount of sensitizing dye adsorbed on the surface of tabular grains hinders the function of gelatin as protective colloid, leading to the sticking of grains in particular with high aspect ratios initiated by mutual contact of the main crystal plane. Such grain sticking readily proceeds to aggregation, which causes various adverse effects such as increase of fog and decrease of sensitivity as well as deterioration of graininess at solution storage of emulsion. The means for dissolving the problems is described in JP-A-6-332091 (The term “JP-A” as used herein means an “unexamined published Japanese patent application”), which discloses a method of adding a fine grain silver iodo-bromide emulsion that is substantially insoluble in water, during or after the chemical sensitization of the main emulsion. However, this method is applicable only to limited types of emulsion; in particular, it is not applicable to silver halide emulsions with high chloride contents. Thus, alternative methods applicable to the emulsions with high chloride content have been expected.
SUMMARY OF THE INVENTION
The object of the present invention is to provide silver halide photographic emulsions having an excellent solution storage stability, and silver halide photographic materials which have high sensitivity and excellent graininess showing reduced residual color ven after rapid processing.
As the result of our extensive study, the problems described above have been solved by the materials and method described in the following embodiments (1) to (14).
(1) A silver halide photographic material comprising at least one silver halide photographic emulsion layer provided on a support, wherein the emulsion layer contains at least one compound represented by formula (I) and at least one compound represented by formula (II):
wherein Y represents an atomic group necessary to form a heterocyclic ring or an atomic group necessary to form a benzene ring condensed with a heterocyclic ring, which may further be condensed with another carbocyclic ring or another heterocyclic ring or may be substituted; Z
1
and Z
2
each represents an atomic group or a single bond necessary to form a nitrogen-containing heterocyclic ring which may be further condensed with another carbocyclic ring or heterocyclic ring or may be substituted; R represents an alkyl group, an aryl group or a heterocyclic ring; D represents a group necessary to form a methine dye; L
1
and L
2
each represents a methine group; p is an integer of 0 or 1; M represents a counter ion and m is an integer of 0 or 1 or more necessary to neutralize the charge of the molecule:
wherein Z
31
and Z
32
each represents an atomic group necessary to form anitrogen-containing heterocyclic ring which may be condensed with an aromatic or a non-aromatic carbocyclic ring and may be substituted, provided that the atomic group is not condensed with an aromatic or non-aromatic heterocyclic ring; R
31
and R
32
each represents an alkyl group, an aryl group or a heterocyclic ring; L
31
, L
32
, L
33
, L
34
, L
35
, L
36
and L
37
each represents a methine group; p
31
and p
32
each represents an integer of 0 or 1 ; n
3
represents an integer of from 0, 1, 2, 3 or 4 ; M
3
represents a counter ion and m
3
is an integer of 0 or 1 or more necessary to neutralize the charge of the molecule.
(2) The silver halide photographic material as described in (1), wherein Y in formula (I) represents an atomic group necessary to form a pyrrole ring, a furan ring or a thiophene ring that may be condensed with a carbocyclic ring or a heterocyclic ring and may be substituted, or an atomic group to form a benzene ring condensed with a pyrrole ring, a furan ring or a thiophene ring.
(3) The silver halide photographic material as described in (1), wherein Y in formula (I) represents an atomic group necessary to form a pyrrole ring, a furan ring or a thiophene ring that may be condensed with a carbocyclic ring or a heterocyclic ring and may be substituted.
(4) The silver halide photographic material as described in (1), wherein the formula (I) is chosen from formula (Ia):
wherein Y
11
represents an atomic group necessary to form a pyrrole ring, a furan ring, a thiophene ring, an indole ring, a benzofuran ring or a benzothiophene ring, which may be further condensed with a carbocyclic ring or a heterocyclic ring and may be substituted; X
11
represents an oxygen atom, a sulfur atom, a selenium atom or NR
13; R
11
, R
12
and R
13
each represents an alkyl group, an aryl group or a heterocyclic ring; Z
11
represents an atomic group necessary to form a nitrogen-containing heterocyclic ring, which may be further condensed with a heterocyclic ring and may be substituted; L
11
, L
12
, L
13
, L
14
and L
15
each represents a methine group; p
1
represents an integer of 0 or 1; n
1
represents an integer of from 0, 1, 2, 3 or 4; M
1
represents a counter ion and m
1
is an integer of 0 or 1 or more necessary to neutralize the charge of the molecule.
(5) The silver halide photographic material as described in (1), wherein the formula (I) is chosen from formula (Ib):
wherein Y
21
represents an atomic group necessary to form a pyrrole ring, a furan ring or a thiophene ring, which may be furt

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