Radiation imagery chemistry: process – composition – or product th – Radiation sensitive product – Silver compound sensitizer containing
Reexamination Certificate
2001-09-25
2003-11-18
Letscher, Geraldine (Department: 1752)
Radiation imagery chemistry: process, composition, or product th
Radiation sensitive product
Silver compound sensitizer containing
C430S567000, C430S599000, C430S604000, C430S605000, C430S963000, C430S945000, C430S570000, C430S581000, C430S583000, C430S585000, C430S586000, C430S587000, C430S572000, C430S574000, C430S576000, C430S577000
Reexamination Certificate
active
06649336
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to a silver halide photographic light-sensitive material for photographing, more specifically, the present invention relates to improvements in the stability of a light-sensitive material comprising silver chloroiodide or silver chloroiodobromide grains having a high silver chloride content.
BACKGROUND OF THE INVENTION
For the purpose of attaining simple and rapid development processing, various techniques using so-called high silver chloride grains having a high silver chloride content (a grain having a silver chloride content of 90% or more and hereinafter referred to as a “high silver chloride grain”) have been proposed. The use of high silver chloride grain is advantageous in that the development speed increases and at the same time, reusability of the processing solution increases. From these reasons, the light-sensitive material for printing, such as color printing paper, is predominated by the type using high silver chloride grains.
On the other hand, the emulsion for use in the printing material is demanded to have high sensitivity and low fogging. JP-A-8-234345 (the term “JP-A” as used herein means an “unexamined published Japanese patent application”) discloses a technique of incorporating a slight amount of silver iodide into a high silver chloride grain, which is effective for obtaining high sensitivity. Furthermore, U.S. Pat. No. 5,268,264 discloses a technique for obtaining high sensitivity by doping a hexacyano complex which is considered to provide a shallow electron trap. The elevation in sensitivity considered ascribable to the shallow electron trap is observed also when a hexacyano complex is doped into a silver chloride emulsion. However, accompanying the introduction of silver iodide and the doping of a hexacyano complex, fogging increases and a technique for reducing the fogging is demanded. Furthermore, severe pressure fogging is liable to occur by the introduction of silver iodide and the doping of a hexacyano complex. The term “pressure fogging” as used herein means a phenomenon such that a development center is formed due to pressure or rubbing applied to the surface of a light-sensitive material by a transportation roller or the like during the processing such as exposure or development, and a color irrelevant to the image is formed.
In the present application, a time period (dry to dry) from the initiation of processing (contact with a developer) to the completion of drying is defined as the processing time. In the processing of a color print material, a color processing time of 180 seconds is predominating at present, however, more reduction in the processing time is demanded. Accompanying the reduction in the processing time, the transportation speed of equipment increases and thereby the pressure to a light-sensitive material also increases. Furthermore, in order to cope with the rapid processing, the developer must have a high temperature and a high concentration, namely, a highly active developer is necessary, and this causes ready occurrence of pressure fogging. Accordingly, a technique of reducing the pressure fogging is demanded.
For reducing the pressure fogging, a method of introducing a defect into the inside is known, however, this technique requires to use iodide in a high concentration and raises a problem of development inhibition. Furthermore, the internal defect is difficult to control and moreover, reduces the surface sensitivity or sometimes causes pressure desensitization (a phenomenon such that the sensitivity decreases due to a pressure). On the other hand, a low concentration iodide is often used on the grain surface so as to strengthen the adsorption of sensitizing dyes, however, the low concentration iodide is known to increase the pressure fogging and improvements on this point is also demanded.
JP-A-7-140581 discloses a method of reducing the pressure fogging using a specific dye. The sensitizing dye for use in the present invention is disclosed in Japanese Patent (registered) No. 2791499 and JP-A-2000-63690, where, however, the introduction of iodide is not referred to as an essential matter and particularly, in the latter, silver chloride is disclosed as a preferred embodiment. As such, these publications by no means suggest the present invention.
SUMMARY OF THE INVENTION
The object of the present invention is to provide a high silver chloride photographic light-sensitive material having high sensitivity and reduced in fogging.
The object of the present invention has been attained by the following means.
1. A silver halide photographic light-sensitive material comprising at least one silver halide emulsion layer, wherein the silver halide grain contained in the emulsion layer is silver chloroiodide or silver chloroiodobromide having a silver chloride content of 90 mol % or more and a silver iodide content of 0.01 to 1.0 mol %, at least one hexacyano complex is doped in an amount of at least 1×10
−7
mol % based on the total silver amount, and the emulsion layer contains a methine dye represented by the following formula (I):
wherein Y represents an atomic group necessary for forming a heterocyclic ring or an atomic group necessary for forming a benzene ring condensed with a heterocyclic ring, which may further be condensed with another carbon ring or heterocyclic ring or may have a substituent, Z
1
and Z
2
each represents a single bond or an atomic group necessary for forming a nitrogen-containing heterocyclic ring which may further be condensed with another carbon ring or heterocyclic ring or may have a substituent, R represents an alkyl group, an aryl group or a heterocyclic group, D represents a group necessary for forming a methine dye, L
1
and L
2
each represents a methine group, p represents 0 or 1, M represents a counter ion, and m represents a number of 0 or more necessary for neutralizing the electric charge within the molecule.
2. The silver halide photographic light-sensitive material as described in 1, wherein in formula (I), Y represents an atomic group necessary for forming a pyrrole ring, a furan ring, a thiophene ring or a benzene ring condensed with a pyrrole ring, a furan ring or a thiophene ring, and the ring formed by Y may be condensed with another carbon ring or heterocyclic ring or may have a substituent.
3. The silver halide photographic light-sensitive material as described in 1, wherein the formula (I) is selected from the following formula (II):
wherein Y
11
represents an atomic group necessary for forming a pyrrole ring, a furan ring or a thiophene ring, or an atomic group necessary for forming an indole ring, a benzofuran ring or a benzothiophene ring, which may further be condensed with another carbon ring or heterocyclic ring or may have a substituent, 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 group, Z
11
represents an atomic group necessary for forming a nitrogen-containing heterocyclic ring which may further be condensed with another carbon ring or heterocyclic ring or may have a substituent, L
11
, L
12
, L
13
, L
14
and L
15
each represents a methine group, p1 represents 0 or 1, n1 represents 0, 1, 2, 3 or 4, M
1
represents a counter ion and m1 represents a number of 0 or more necessary for neutralizing the electric charge within the molecule.
4. The silver halide photographic light-sensitive material as described in 1, wherein the formula (I) is selected from the following formula (III):
wherein Y
21
represents an atomic group necessary for forming a pyrrole ring, a furan ring or a thiophene ring, which may further be condensed with another carbon ring or heterocyclic ring or may have a substituent, X
21
and X
22
each represents an oxygen atom, a sulfur atom, a selenium atom or NR
23
, R
21
, R
22
and R
23
each represents an alkyl group, an aryl group or a heterocyclic group, V
21
, V
22
, V
23
and V
24
each represents a hydrogen atom or a substituent, provided that two adjacent subst
Nakamura Tetsuo
Ohzeki Katsuhisa
Fuji Photo Film Co., LTD
Letscher Geraldine
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