Radiation imagery chemistry: process – composition – or product th – Radiation sensitive product – Silver compound sensitizer containing
Reexamination Certificate
2001-05-01
2004-07-13
Chea, Thorl (Department: 1752)
Radiation imagery chemistry: process, composition, or product th
Radiation sensitive product
Silver compound sensitizer containing
C430S567000, C430S570000, C430S572000, C430S576000, C430S583000, C430S584000, C430S600000, C430S603000
Reexamination Certificate
active
06762015
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to a silver halide photographic emulsion and a silver halide photographic material. More specifically, the present invention relates to a silver halide photographic emulsion which is high speed and hardly causes residual color after processing even in rapid processing, and to a silver halide photographic material.
BACKGROUND OF THE INVENTION
A great deal of endeavors have been done to improve sensitivity of a silver halide photographic material and to reduce residual color after processing. The improvements of the sensitivity and the quality of photographic materials have been required more and more on one hand, the demands for shortening of photographic processing speed and the reduction of waste solutions in view of environmental protection have increased on the other hand in particular in recent years, hence the importance of techniques of spectrally sensitizing silver halide grains in high sensitivity without causing harmful influences such as fog and residual color has been increasingly raised.
It is known that the sensitizing dye for use in spectral sensitization gives large influences on the performances of silver halide photographic materials. In the sensitizing dye, a little structural difference largely affects photographic performances such as sensitivity, fog, storage stability and residual color after processing and photographic performances are also largely influenced by using two or more sensitizing dyes in combination, but it is difficult to forecast the effect in advance. Therefore, many researchers have synthesized a large number of sensitizing dyes and endeavored to examine the combined use of a variety of sensitizing dyes and investigate the photographic performances. However, it is the present situation that the photographic performances cannot be forecast yet.
The tabular grain is preferred for use in spectral sensitization in that it is large in the ratio of the surface area to the volume (specific surface area), hence it can absorb a large amount of sensitizing dye, but residual color after processing increases the more. Residual color is observed as fog and the problem of fog is more serious than in regular grains. On the other hand, the main current of the color developing time in color print materials is 180 seconds at present. Further shortening of the processing time is required but if the processing time is shortened, the residual amount of the sensitizing dye used in an emulsion increases and the problem of fog becomes more serious. Therefore, a technique which can reduce the fog attributable to residual color has been desired.
SUMMARY OF THE INVENTION
The objects of the present invention is to provide a silver halide photographic emulsion which is high speed and hardly causes residual color after processing even in rapid processing, and to provide a silver halide photographic material.
As a result of eager investigation of the problems, the present invention has been accomplished by the following means (1) to (12).
(1) A silver halide photographic emulsion which contains at least two sensitizing dyes represented by the following formula (I).
Dye-((A)
r
Q)
q
(M)
m
(I)
wherein Dye represents a dye moiety; A represents a linking group; Q represents a dissociable group; r represents 0 or 1; q represents an integer of 2 or more, provided that at least one Q represents —SO
3
H and at least one Q represents a dissociable group other than —SO
3
H; M represents a counter ion; and m represents a number of 0 or more necessary to neutralize the electric charge in the molecule, and when m represents 2 or more, M's need not be the same.
(2) The silver halide photographic emulsion as described in the above item (1), wherein the dissociable group other than —SO
3
H is selected from the group consisting
of —COOH, —CONHSO
2
R, —SO
2
NHCOR, —SO
2
NHSO
2
R, —CONHCOR, —OSO
3
H, —PO(OH)
2
, —OPO(OH)
2
, —B(OH)
2
, —OB(OH)
2
, —ArOH, and —ArSH, wherein R represents an alkyl group, an aryl group, a heterocyclic group, an alkoxyl group, an aryloxy group, a heterocyclic oxy group, or an amino group, and Ar represents an arylene group.
(3) The silver halide photographic emulsion as described in the above item (1) or (2), wherein the sensitizing dyes are cyanine dyes.
(4) The silver halide photographic emulsion as described in the above item (1), (2) or (3), wherein the sensitizing dyes are represented by the following formula (II):
wherein R
1
and R
2
each represents a substituted alkyl, aryl or heterocyclic group, and R
1
is substituted with —SO
3
H and R
2
is substituted with a dissociable group other than —SO
3
H; Y
1
and Y
2
each represents an atomic group necessary to form a 5- or 6-membered nitrogen-containing heterocyclic ring, and Y
1
and Y
2
may be condensed with other carbocyclic ring or heterocyclic ring; V
1
and V
2
each represents a substituent; n
1
and n
2
each represents an integer of 0 or more (preferably 6 or less, more preferably 2 or less), and when n
1
and n
2
each represents 2 or more, V
1
and V
2
may be the same with or different from each other; L
1
, L
2
, L
3
, L
4
, L
5
, L
6
and L
7
each represents a methine group; p
1
represents 0, 1, 2 or 3, p
2
and p
3
each represents 0 or 1, and when p
1
represents 2 or 3, repeating L
2
and L
3
may be the same with or different from each other; M
1
represents a counter ion; and m
1
represents a number of 0 or more necessary to neutralize the electric charge in the molecule.
(5) The silver halide photographic emulsion as described in the above item (1), (2), (3) or (4), wherein at least one sensitizing dye is represented by the following formula (III) and at least one sensitizing dye is represented by formula (IV):
wherein R
11
and R
12
each represents a substituted alkyl, aryl or heterocyclic group, and R
11
is substituted with —SO
3
H and R
12
is substituted with a dissociable group other than —SO
3
H; X
11
and X
12
each represents an oxygen atom, a sulfur atom, a selenium atom, NR
15
, CR
16
R
17
, or L
13
═L
14
; R
15
, R
16
and R
17
each represents a substituted or unsubstituted alkyl, aryl or heterocyclic group; L
13
and L
14
each represents a methine group; V
11
and V
12
each represents a substituent; n
11
and n
12
each represents an integer of 0 or more (preferably 4 or less, more preferably 2 or less), and when n
11
and n
12
each represents 2 or more, V
11
and V
12
may be the same with or different from each other; L
11
represents a methine group;M
11
represents a counter ion; and m
11
represents a number of 0 or more necessary to neutralize the electric charge in the molecule;
wherein R
13
and R
14
each represents a substituted alkyl, aryl or heterocyclic group, and at least one of R
13
and R
14
is substituted with —SO
3
H and the other is substituted with a dissociable group other than —SO
3
H; X
13
and X
14
each represents an oxygen atom, a sulfur atom, a selenium atom, NR
18
, CR
19
R
20
, or L
15
═L
16
; R
18
, R
19
and R
20
each represents a substituted or unsubstituted alkyl, aryl or heterocyclic group; L
15
and L
16
each represents a methine group; Z
11
represents a benzene ring or a naphthalene ring; Z
12
represents a naphthalene ring; V
13
and V
14
each represents a substituent; n
13
and n
14
each represents an integer of 0 or more (n
13
represents preferably 4 or less, more preferably 2 or less, and n
14
epresents preferably 6 or less, more preferably 2 or less), and when n
13
and n
14
each represents 2 or more, V
13
and V
14
may be the same with or different from each other; L
12
represents a methine group; M
12
represents a counter ion; and m
12
represents a number of 0 or more necessary to neutralize the electric charge in the molecule.
(6) The silver halide photographic emulsion as described in the above item (5), wherein the dissociable group other than —SO
3
H is selected from the group consisting
of —COOH, —CONHSO
2
R, —SO
2
NHCOR, —SO
2
NHSO
2
R, and —CONHCOR, wherein R represents an alkyl group, an aryl group, a heterocyclic g
Hioki Takanori
Nakamura Tetsuo
Chea Thorl
Fuji Photo Film Co. , Ltd.
Sughrue & Mion, PLLC
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