Radiation imagery chemistry: process – composition – or product th – Radiation sensitive product – Silver compound sensitizer containing
Reexamination Certificate
2003-03-20
2004-06-15
Letscher, Geraldine (Department: 1752)
Radiation imagery chemistry: process, composition, or product th
Radiation sensitive product
Silver compound sensitizer containing
C430S583000, C430S588000, C430S591000, C430S572000, C430S599000, C430S603000
Reexamination Certificate
active
06750003
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to a novel methine dye compound, particularly a linking type methine dye compound having two chromophores linked thereto, and to a silver halide photographic material containing it.
BACKGROUND OF THE INVENTION
Methine compounds have hitherto been used as a spectral sensitizing dye of silver halide photographic materials. With respect to technologies for enhancing a light absorbance of silver halide grains, those that have been known up to the date will be given below. In order to enhance the light absorbance per grain, it is necessary to increase an adsorption density of the sensitizing dye to the silver halide grains. The usual spectral sensitizing dyes are adsorbed in a monomolecular layer substantially in closest packaging, but cannot be adsorbed any more.
In order to solve this problem, there have been found some proposals. In
Photographic Science and Engineering
, Vol. 20, No. 3, page 97 (1976), P. B. Gilman, Jr., et al. adsorbed a cationic dye in a first layer and further adsorbed an anionic dye in a second layer by an electrostatic force. In U.S. Pat. No. 3,622,316, G. B. Bird, et al. underwent multi-layer adsorption of plural dyes on silver halide grains to achieve the sensitization by the contribution of a Forster model excitation energy transfer.
In JP-A-63-138341 and JP-A-64-84244, Sugimoto, et al. underwent spectral sensitization by energy transfer from a luminescent dye.
All of these technologies are concerned with trials to adsorb the dye in an amount of the saturated adsorption amount or more onto the silver halide grains. However, there were involved problems such that an effect for achieving high sensitivity is not so revealed and that the inherent desensitization increases.
On the other hand, binary dyes in which two or more non-conjugated dye chromophores are covalently linked are disclosed in U.S. Pat. Nos. 2,393,351, 2,425,772, 2,518,732, 2,521,944 and 2,592,196 and European Patent No. 565,083. However, these patents did not intend to enhance the light absorbance. As one positively intending to enhance the light absorbance, in U.S. Pat. Nos. 3,622,317 and 3,976,493, G. B. Bird, et al. proposed to adsorb a linking type sensitizing dye molecule having plural cyanine chromophores to increase the light absorbance, thereby attempting to achieve the sensitization by energy transfer. However, a remarkable effect for achieving high sensitivity is not obtained.
In JP-A-64-91134, Ukai, et al. propose to adsorb at least one substantially non-adsorbing dye containing at least two sulfo groups or carboxy groups on a spectral sensitizing dye capable of being adsorbed on a silver halide.
Further, in JP-A-6-27578, Vishwakarma, et al. undergo spectral sensitization using a binary dye in which an adsorbing cyanine dye and a non-adsorbing oxonol dye to silver halides are linked to each other. Moreover, in European Patent No. 887700A1, Parton, et al. undergo spectral sensitization using a binary dye in which an adsorbing cyanine dye and a non-adsorbing merocyanine dye are linked to each other using a specified linking group. However, in any of these cases, it may not be said that high sensitivity is thoroughly achieved by the contribution of energy transfer.
In addition, in JP-A-6-57235, Vishwakarma, et al. disclose a process of producing a binary dye in which a cyanine dye and a merocyanine dye are linked to each other. However, there are no working examples in which high sensitivity was achieved using this binary dye as a sensitizing dye for silver halide photographic material.
As described above, in any of the methods as described in the above-cited patents and literature references, sufficiently high sensitivity was not achieved. Accordingly, it has been considered necessary to perform further technical developments.
SUMMARY OF THE INVENTION
Accordingly, an object of the invention is to provide a novel methine-linked dye and a high-sensitivity silver halide photographic material containing it.
The foregoing object of the invention has been attained by the following means.
(1) A silver halide photographic material comprising a support and at least one photosensitive silver halide emulsion layer thereon, wherein the emulsion layer contains a compound represented by the following formula (1).
Dye1-&Parenopenst;L
1
&Parenopenst;Dye2)
m1
)
m2
.CIy Formula (1)
In the formula, Dye1 represents a first chromophore; Dye2 represents a xanthene dye; L
1
represents a linking group; m1 represents an integer of from 1 to 5; m2 represents an integer of from 1 to 5; CI represents an ion for neutralizing a charge; and y represents a number necessary for neutralizing the charge.
(2) The silver halide photographic material as set forth in (1) as above, wherein the xanthene dye is represented by the following formula (2).
In the formula, X
3
represents an oxygen atom or a sulfur atom; R
11
represents any one of —OM, —SM, and —NR
2
OR
21
; R
12
represents any one of ═O, ═S, and ═
+
NR
22
R
23
; M represents a proton or a cation; R
20
to R
23
each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group; R
20
and R
21
, or R
22
and R
23
may be linked to each other to form a ring; R
13
to R
19
each independently represents a hydrogen atom or a substituent; and in R
11
to R
19
, the adjacent substituents may be linked to each other to form a ring.
(3) The silver halide photographic material as set forth in (2) as above, wherein in the formula (2), X
3
represents an oxygen atom.
(4) The silver halide photographic material as set forth in (2) or (3) as above, wherein in the formula (2), R
13
represents an unsubstituted or substituted aryl group.
(5) The silver halide photographic material as set forth in (4) as above, wherein in the formula (2), R
13
represents a phenyl group substituted with any one of a carboxyl group, an alkoxycarbonyl group, a carbamoyl group, a sulfo group, a halogen atom, an amino group, a hydroxyl group, an alkyl group, and an alkoxy group.
(6) The silver halide photographic material as set forth in any one of (2) to (5) as above, wherein in the formula (2), R
1
, represents any one of —OM and —NR
2
OR
21
; and R
12
represents any one of ═O and ═
+
NR
22
R
23
.
(7) The silver halide photographic material as set forth in any one of (2) to (6) as above, wherein in the formula (2), R
11
represents —OM; R
12
represents ═O; and all of R
14
, R
15
, R
17
, and R
18
represent a halogen atom.
(8) The silver halide photographic material as set forth in any one of (2) to (6) as above, wherein in the formula (2), R
1
, represents —NR
2
OR
21
; R
12
represents ═
+
NR
22
R
23
; and R
14
, R
15
, R
17
, and R
18
each independently represents a hydrogen atom or an alkyl group.
(9) The silver halide photographic material as set forth in any one of (1) to (8) as above, wherein in the compound represented by the formula (1), Dye1 represents any one of a cyanine chromophore, a merocyanine chromophore, and an oxonol chromophore.
(10) The silver halide photographic material as set forth in any one of (1) to (9) as above, wherein in the compound represented by the formula (1), Dye1 represents a cyanine chromophore.
(11) The silver halide photographic material as set forth in any one of (1) to (10) as above, wherein in the compound represented by the formula (1), L
1
represents -G
1
-(A
1
-G
2
)
t1
-, wherein G
1
and G
2
each independently represents an alkylene group, an alkenylene group, or an arylene group; A
1
represents anyone of —O—, —S—, —SO
2
—, —NR
3
—, —COO—, —CONR
4
—, and —SO
2
NR
5
—, regardless of the left or right direction; R
3
to R
5
each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group; and t1 represents an integer of from 1 to 10.
(12) The silver halide photographic material as set forth in any one of (1) to (11) as above, wherein the compound represented by the formula (1) is represented by the following formula (
Fuji Photo Film Co. , Ltd.
Letscher Geraldine
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