Radiation imagery chemistry: process – composition – or product th – Radiation sensitive product – Silver compound sensitizer containing
Reexamination Certificate
2002-07-19
2004-06-29
Chea, Thorl (Department: 1752)
Radiation imagery chemistry: process, composition, or product th
Radiation sensitive product
Silver compound sensitizer containing
C430S570000, C430S576000, C430S577000, C430S603000
Reexamination Certificate
active
06756191
ABSTRACT:
FIELD OF THE INVENTION
The invention relates to a silver halide photographic light-sensitive emulsion and also to a silver halide photographic light-sensitive material (hereafter also simply referred to a light-sensitive material) produced by the use of the emulsion having high light-sensitivity and excellent storage stability.
BACKGROUND OF THE INVENTION
A great deal of efforts has been made to increase the light-sensitivity or photographic speed of silver halide photographic light-sensitive materials. Particularly, it is strongly demanded to make higher the light-sensitivity of spectrally sensitized silver halide photographic light-sensitive materials. The spectral sensitization is an extremely important and essential technology for producing a light-sensitive material having high light sensitivity and high color reproducibility. A spectral sensitizer has a function of absorbing light of longer wavelength that is substantially not absorbed by silver halide photographic light-sensitive emulsion and transmitting the energy of the absorbed light to the silver halide. Therefore, the increasing of the supplemental amount of light by the spectral sensitizer is advantageous for raising the photographic sensitivity of the emulsion. Consequently, it has been tried to increase the supplemental amount of light by increasing the adding amount of the spectral sensitizer to the silver halide photographic light-sensitive emulsion. However, when the adding amount of the spectral sensitizer exceeds the optimum amount, it tends to cause serious desensitization. Such phenomenon, so called dye desensitization, is an occurrence of the desensitization in an inherent light sensitive region of a silver halide where the light is substantially not absorbed by the spectral sensitizer. When the dye desensitization is large, the resulting sensitivity is lowered even though the spectral sensitization is occurred. In other words, the spectral sensitization would be increased when the desensitization accompanied by a spectral sensitizer is reduced. Accordingly, the improvement of the dye sensitization is an important theme in the technology of the spectral sensitization.
It has been known that a sensitizing dye having a reducing potential of not less than −1.25 V has a low relative quantum yield, as described in
T. Tani
, “Journal of Physical Chemistry”, 94, p. 1298, 1990. For increasing the relative quantum yield of the spectral sensitization by the dye, the supersensitization by positive hole trapping is proposed in “The Theory of the Photographic Process”, p.p. 259-265, 1966.
A compound having an oxidation potential more negative than that of the spectral sensitizing dye is used together with the sensitizing dye in order to resolve the problem of the foregoing desensitization. Examples of such compound include those described in U.S. Pat. Nos. 2,313,922, 2,075,046, 2,448,858 and 2,680,686, British Patent No. 1,230,449 and Belgian Patent No. 771,168.
Sensitizing techniques using an organic electron donating compound constituted by an electron donating group and a leaving group are described in U.S. Patent Nos. 5,747,235 and 5,747,236, European Patent Nos. 786,692, 892,731 and 892,732 and International Patent Publication WO99/05570. However, a means for obtaining further high sensitivity is required since the sensitivity raising effect of such compound is insufficient and the fogging tends to be occurred.
An object of the present invention is to provide a silver halide photographic light-sensitive emulsion and a silver halide photographic light-sensitive material having high sensitivity and excellent storage stability.
SUMMARY OF THE INVENTION
The object of the invention can be achieved by the following embodiments.
1. A silver halide photographic light-sensitive emulsion comprising a silver halide and a compound represented by the following Formula (I):
wherein each X
3
and X
4
represents independently N, P, S, Se or Te; each Y
1
and Y
2
represents independently a group of carbon atoms necessary to complete a 6 to 12 membered heterocyclic ring with X
3
and X
4
.
2. The silver halide photographic light-sensitive emulsion of item 1, wherein X
3
and X
4
each represent S.
3. The silver halide photographic light-sensitive emulsion of item 1,
wherein each Y
1
and Y
2
represents independently a group of carbon atoms necessary to complete a 8 to 10 membered heterocyclic ring with X
3
and X
4
.
4. A silver halide photographic light-sensitive emulsion comprising a silver halide and a compound represented by the following Formula (II):
(Z)
k1
[(L)
k3
X]
k2
Formula (II),
wherein Z represents an organic group capable of adsorbing to the silver halide or an organic group capable of absorbing light; L is a linking group; X is a group having a moiety represented by Formula (I):
wherein each X
3
and X
4
represents independently N, P, S, Se or Te; each Y
1
and Y
2
represents independently a group of carbon atoms necessary to complete a 6 to 12 membered heterocyclic ring with X
3
and X
4
; k1 represents an integer of 0 to 4; k2 represents an integer of 1 to 4; and k3 represents an integer of 0 or 1.
5. The silver halide photographic light-sensitive emulsion of item 4, wherein X
3
and X
4
each represent S.
6. The silver halide photographic light-sensitive emulsion of item 1,
wherein the silver halide emulsion further comprises a spectral sensitizing dye.
7. The silver halide photographic light-sensitive emulsion of item 3,
wherein the silver halide emulsion further comprises a spectral sensitizing dye.
8. The silver halide photographic light-sensitive emulsion of item 4,
wherein the silver halide emulsion further comprises a spectral sensitizing dye.
9. The silver halide photographic light-sensitive emulsion of item 6,
wherein the spectral sensitizing dye is a cyanine dye or a merocyanine dye.
10. The silver halide photographic light-sensitive emulsion of item 7,
wherein the spectral sensitizing dye is a cyanine dye or a merocyanine dye.
11. The silver halide photographic light-sensitive emulsion of item 8,
wherein the spectral sensitizing dye is a cyanine dye or a merocyanine dye.
12. A silver halide photographic light-sensitive material comprising a support having thereon a photosensitive layer comprising the photosensitive silver halide emulsion of item 1.
13. A silver halide photographic light-sensitive material comprising a support having thereon a photosensitive layer comprising the photosensitive silver halide emulsion of item 3.
14. A silver halide photographic light-sensitive material comprising a support having thereon a photosensitive layer comprising the photosensitive silver halide emulsion of item 4.
DETAILED DESCRIPTION OF THE INVENTION
A cyanine dye, a merocyanine dye, a rhodacyanine dye, a tri nucleus merocyanine dye, an allopolar dye, a hemicyanine dye and a styryl dye are preferably usable as the sensitizing dye in the invention. These dyes are described in detail in, for example, F. M. Harmer, “Heterocyclic Compounds—Cyanine Dyes and Related Compounds”, John Wiley & Sons, New York, London, 1964, D. M. Sturmer, “Heterocyclic Compounds—Special topics in heterocyclic chemistry”, Sec. 18, Item 14, p.p. 482-515.
The cyanine dyes, merocyanine dyes, and rhodacyanine dyes described in U.S. Pat. No. 5,340,694, P.P. 21-22, (XI), (XII) and (XIII) are preferred.
A compound selected from the group represented by the following Formulas 4 through 8 is more preferably used as the sensitizing dye to be used in the invention.
In Formula 4, L
1
, L
2
, L
3
, L
4
, L
5
, L
6
and L
7
are each a methine group; p1 and p2 are each an integer of 0 or 1; n is an integer of 0, 1, 2 or 3; Z
1
and Z
2
are each a group of atoms necessary to complete a 5- or 6-membered nitrogen-containing heterocyclic ring; M
1
is a counter ion; ml is an integer of 0, 1, 2, 3 or 4 necessary for neutralizing the charge of the molecule; and R
1
and R
2
are each an alkyl group, an aryl group or a heterocyclic group.
In Formula 5, L
8
, L
9
, L
10
and L
11
are each a methine group; p3 is an integ
Iwai Yoshiko
Kagawa Nobuaki
Oshiyama Tomohiro
Tanaka Tatsuo
Chea Thorl
Konica Corporation
Squire Sanders & Dempsey
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