Radiation imagery chemistry: process – composition – or product th – Radiation sensitive product – Silver compound sensitizer containing
Reexamination Certificate
2000-08-11
2002-12-10
Baxter, Janet (Department: 1752)
Radiation imagery chemistry: process, composition, or product th
Radiation sensitive product
Silver compound sensitizer containing
C430S559000, C430S570000, C430S573000, C430S578000, C430S581000, C430S586000, C430S583000, C430S599000, C430S600000, C430S603000, C430S607000, C430S611000, C430S613000, C430S614000
Reexamination Certificate
active
06492102
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to silver halide emulsions, and silver halide light sensitive photographic materials and thermally developable silver halide photographic materials, each of which contains the silver halide emulsion.
BACKGROUND OF THE INVENTION
Silver halide light sensitive photographic materials are prepared employing silver halide grains exhibiting superior characteristics such as high sensitivity, memory and a high S/N ratio. However, the longest inherent sensitivity edge of the silver halide grains is in the vicinity of 500 nm, so that spectral sensitization by the use of sensitizing dyes is indispensable to provide sensitivity at the longer wavelength side. Particularly with recent progress in light sources, importance of photosensitive materials sensitive to the laser wavelength region increases in the field of recording materials for industrial use. On the other hand, reduction of processing effluent is strongly demanded in terms of environmental protection and saving space in the field of the recording materials for industrial use. In this regard, there appeared an image recording system for medical use using semiconductor lasers as a light source and without using liquid system processing chemicals.
Spectral sensitization techniques for silver halide infrared sensitive photographic materials are described in U.S. Pat. Nos. 3,582,344 and 5,013,642; European Patent420,012; Russian Patents 1,549,027, 1,596,961 and 1,780,427; JP-B 3-10391 and 6-52387 (hereinafter, the term, JP-B refers to published Japanese Patent); JP-A (hereinafter, the term, JP-A refers to unexamined and published Japanese Patent Application) 3-138638, 3-138642, 3-235940, 3-242944, 3-244667, 4-311948, 4-312577, 5-72660, 5-45773, 5-45774, 5-45775, 5-72660, 5-72661, 5-265120, 5-341432, 6-194781, 6-222491, 6-222492, 6-250323, 6-301141, 6-317868, 6-332103, 6-324425, 7-175158, 7-306512, 8-194282, 8-201959, 9-281638, 9-281639, 9-288326, 9-288327, 9-292672, and 9-292673; PCT/JP-A 9-5100122. Further, techniques for anti-halation are described in JP-A 7-13295 and U.S. Pat. No. 5,380,635.
Photographic materials to be exposed to infrared rays have advantages that visible absorption caused by sensitizing dyes or anti-halation dyes can be greatly reduced, enabling to form a photographic material substantially having no color. However, a sensitizing dye having an absorption maximum in the infrared region has a long conjugated chain so that the conjugated chain is easily affected by the surrounding to be liable to variation, i.e., the difference between the lowest unoccupied level and the highest occupied level is small and the lowest unoccupied level of a sensitizing dye is close to the conduction band level of silver halide grains, producing problems that fogging is liable to occur, sensitivity is lowered after storage over a period of a long time or variation in sensitivity is easily caused by the temperature or humidity at the time of exposure.
The problems of sensitivity, storage stability and performance variation are marked not only in wet-type photographic materials but also in thermally developable photographic materials (which are also referred to as photothermographic materials). To overcome such problems of infrared sensitization, supersensitization techniques were disclosed, including, for example, supersensitizers for infrared described in European Patent 176,483, 203,698, 465,730 and 509,253; U.S. Pat. Nos. 4,946,962 and 5,024,928; JP-A 61-69063, 62-299838, 63-159840, 2-67546, 2-134630, 2-157744, 4-184332, 4-255841, 5-45833, 5-45834, 5-313289, 6-289555, 8-262612 and 9-211773. Further, examples of the infrared supersensitizers for use in photothermographic materials include aminopolycarboxylic acid derivatives described in JP-A 2-4241, aromatic heterocyclic mercapto compounds and aromatic heterocyclic disulfide compounds. However, it was proved that the aminopolycarboxylic acid derivatives were weak in a supersensitization effect, leading to lower sensitivity and the use of the aromatic heterocyclic mercapto compounds and aromatic heterocyclic disulfide compounds resulted in reduced sensitivity after being stored under high humid conditions. Techniques for enhancing storage stability include, for example, cyclic carbonyl compounds described in JP-A 7-146527 and disulfide compounds having specific structure described in JP-A 10-90823, 10-90824, 10-90825, 10-319534 and 11-4489. However, these techniques were not sufficient in supersensitization and storage stability so that further improvements are desired.
SUMMARY OF THE INVENTION
Accordingly, it is an object of the present invention to provide a red or infrared sensitive silver halide emulsion exhibiting high sensitivity and low fog and little sensitivity variation caused by changing the exposure condition, a silver halide photographic material and silver halide photothermographic material which contain the silver halide emulsion.
The above object of the invention can be accomplished by the following constitution:
1. A silver halide emulsion comprising at least a compound represented by the following formula (1), (2) or (3):
wherein Y
1
represents a hydrogen atom, a direct bond or an amidino group; W
11
represents a hydrogen atom, an aliphatic hydrocarbon group, an aryl group, a heterocyclic group or an amidino group; V
21
represents a hydrogen atom, an aliphatic hydrocarbon group, an aryl group, a heterocyclic group, RS group or an amidino group, in which R is an alkyl group, aryl group or a heterocyclic group; T and T
21
each represent a bivalent aliphatic hydrocarbon linkage group or a direct bond; T
11
represents a bivalent liking group comprised of aliphatic hydrocarbon group; J
1
, J
2
, J
21
, J
22
and J
23
each represent a bivalent linking group containing at least one of an oxygen atom, sulfur atom and nitrogen atom or a direct bond; J
11
represents a bivalent linking group containing at least one of an oxygen atom, sulfur atom and nitrogen atom; Ar
1
and Ar
21
each represent an aromatic hydrocarbon group; ArH
1
, ArH
11
and ArH
21
each represent an aromatic hydrocarbon group or an aromatic heterocyclic group; k1 is an integer of 1 or 2; k21 is an integer of 2 to 4; q
11
, q
12
and q
21
are each an integer of 0 and 1 and q11+q12≠0; Q represent a k21-valent linking group attached via the J
22
group to any one of V
21
, T
21
and ArH
21
.
2. A silver halide emulsion comprising a compound represented by the following formula (4):
wherein ArH
31
represents an aromatic hydrocarbon group or an aromatic heterocyclic group; T
31
represents a bivalent aliphatic hydrocarbon linkage group or a direct bond; J
31
represents a bivalent linking group containing at least one of an oxygen atom, sulfur atom and nitrogen atom or a direct bond; Ra, Rb, Rc and Rd each represent a hydrogen atom, an acyl group, an aliphatic hydrocarbon group, an aryl group or a heterocyclic group, or Ra and Rb, Rc and Rd, Ra and Rc, or Rb and Rd combine with each other to form a nitrogen containing ring; M
31
represents an ion necessary to neutralize an intramolecular charge; and k
31
represent the number of the ion necessary to neutralize an intramolecular charge;
3. The silver halide emulsion described in 1 or 2, wherein the emulsion further comprises at least a compound represented by the following formula (S-1) or (S-2):
wherein Z
1
, Z
2
and Z
11
each represent a nonmetallic atom necessary to form a 5- or 6-membered nitrogen containing heterocyclic ring, which may be monocyclic or condensed ring; L
1
through L
9
and L
11
through L
15
each represent a methine group; R
1
, R
2
, R
11
and R
12
each represent an aliphatic group; R
13
and R
14
each represent a hydrogen atom, a substituent group or an atomic group necessary to form a condensed ring between R
13
and R
14
; X
1
and X
11
each represent an ion necessary to balance with an intramolecular charge; p1 and p11 represent the number necessary to balance with an intramolecular charge; and m1, m2 and n11 are each an integer of 0 or 1;
4. A silver hali
Kagawa Nobuaki
Kita Noriyasu
Baxter Janet
Bierman, Muserlian and Lucas
Konica Corporation
Walke Amanda C.
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