Radiation imagery chemistry: process – composition – or product th – Radiation sensitive product – Identified radiation sensitive composition with color...
Reexamination Certificate
2000-07-28
2002-04-09
Letscher, Geraldine (Department: 1752)
Radiation imagery chemistry: process, composition, or product th
Radiation sensitive product
Identified radiation sensitive composition with color...
C430S385000, C430S380000, C430S566000, C430S467000, C430S484000
Reexamination Certificate
active
06368780
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to a silver halide photographic material and an image formation method using the same, and particularly to a heat developable silver halide photographic material (silver halide photothermographic material) and an image formation method using the same.
BACKGROUND OF THE INVENTION
In the field of silver halide photographic materials, the so-called color diffusion transfer process is known in which diffusible dyes are formed imagewise and fixed to image receiving materials, thereby forming color images. With respect to this process, many proposals have been made.
In this process, the diffusible dyes are generally produced as a function of development of silver halides from compounds obtained by making previously colored image formation dyes (preformed dyes) diffusion-resistant (such compounds are hereinafter referred to as “coloring materials). Accordingly, the addition of the coloring materials to layers having silver halide emulsions causes an undesirable reduction in sensitivity to exposure because of the filter effect due to dye moieties. For avoiding this problem, the coloring materials for image formation are generally added to layers apart from exposure faces of silver halide emulsion layers. This process can avoid the reduction in sensitivity caused by the filter effect, but has the disadvantage that an increase in the distance between the silver halide emulsions and the coloring materials producing the diffusible dyes causes inefficient transfer of development information from the silver halide emulsion to the coloring materials.
For improving these disadvantages, a so-called coupling system has been proposed in which dye formation is carried out by the coupling reaction of oxidation products of developing agents with couplers. This system can advantageously overcome the disadvantages of the system using the preformed dyes, because both the developing agents and the couplers are colorless. This system is therefore more preferred than the use of the coloring materials utilizing the preformed dyes. This process is described, for example, in U.S. Pat. No. 4,469,773 and JP-B-63-36487 (the term “JP-B” as used herein means an “examined Japanese patent publication”).
However, when the photographic materials contain the color developing agents for the above-mentioned coupling system, the sufficient keeping stability is insufficiently compatible with the activity of the coupling reaction.
Recently, a technique of forming diffusible dyes using color developing agents of the hydrazine family has been developed, and is described in JP-A-9-152705 (the term “JP-A” as used herein means an “unexamined published Japanese patent application”). However, compounds described herein have the problem that they are low in the color generation of cyan or magenta, or that the dyes produced are low in light fastness.
SUMMARY OF THE INVENTION
An object of the invention is to provide a silver halide photographic material excellent in color generation in development.
Another object of the invention is to provide a silver halide photographic material excellent in color reproducibility.
A further object of the invention is to provide a silver halide photographic material excellent in color image fastness, particularly, in light fastness.
A still further object of the invention is to provide a silver halide photographic material excellent in color image fastness, particularly, in light fastness at low density areas.
A still further object of the invention is to provide an image formation method using a silver halide photographic material excellent in the above-mentioned characteristics.
According to the invention, there are provided silver halide photographic materials and image formation methods having the following constitution, thereby attaining the above-mentioned objects.
(1) A silver halide photographic material comprising at least one coupler represented by the following formula (Ia):
wherein R
1
represents an alkyl group which may be optionally substituted, with the proviso that an alkyl group substituted by a halogen atom alone and an alkyl group substituted by a halogen atom and an aryl group are excluded from R
1
; R
2
and R
3
, which may be the same or different, each represents a hydrogen atom or a substituent; and X
1
represents a group which can leave by coupling with an oxidation product of a color developing agent;
(2) The silver halide photographic material described in (1), wherein R
1
of formula (Ia) is a tertiary alkyl group;
(3) The silver halide photographic material described in (1) or (2), wherein R
2
of formula (Ia) is an acylamino group, an alkoxycarbonylamino group or an ureido group;
(4) A silver halide photographic material comprising at least one coupler represented by the following formula (II):
wherein R
4
represents a tertiary alkyl group; R
5
represents a substituent; and X
2
represents a group leaving by coupling (a coupling-off group) which is linked by an oxygen atom to a mother nucleus of a phenol coupler and has a formula weight of 200 or more;
(5) The silver halide photographic material described in (4), wherein at least one of R
4
and R
5
of formula (II) is a group having a dissociative group with a pKa of 1 to 12;
(6) A silver halide photographic material comprising a support having provided thereon at least one hydrophilic colloidal layer containing at least one coupler represented by the following formula (Ib) and at least one color developing agent represented by the following formula (III):
wherein R
1
represents an alkyl group which may be optionally substituted; R
2
and R
3
, which may be the same or different, each represents a hydrogen atom or a substituent; and X
1
represents a group which can leave by coupling with an oxidation product of a color developing agent,
wherein C&agr; represents a carbon atom; Z represents a carbamoyl group, an acyl group, an alkoxycarbonyl group or an aryloxycarbonyl group; and Q represents an atomic group forming an unsaturated ring together with C&agr;;
(7) A heat developable silver halide photographic material (a silver halide photothermographic material) comprising at least one coupler represented by the following formula (IV):
wherein R
11
represents an acylamino group or an alkyl group; R
12
and R
13
each independently represents a hydrogen atom or a substituent; A represents a nitrogen atom or an oxygen atom; when A is an oxygen atom, m represents 0; when A is a nitrogen atom, M represents a —CO— group or an —SO
2
— group; R
14
represents an alkyl group, an aryl group, an alkoxyl group or an amino group, and m represents 1; —A(H)—(M—R
14
)
m
may be cyclocondensed with a benzene ring to form a 5-, 6- or 7-membered ring; R
15
represents a substituent, and n represents an integer of 0 to 4; and X
11
represents a group which can leave by coupling with an oxidation product of a color developing agent;
(8) The heat developable silver halide photographic material described in (7), wherein R
11
of formula (IV) is a tertiary alkyl group;
(9) The heat developable silver halide photographic material described in (7) or (8), wherein R
11
of formula (IV) is a tertiary alkyl group, R
12
is a hydrogen atom, and R
13
is a hydrogen atom, a halogen atom, an alkoxy group, an acylamino group, an alkoxycarbonylamino group or a carbamoylamino group;
(10) The heat developable silver halide photographic material described in (7) or (8), wherein R
11
of formula (IV) represents a tertiary alkyl group, A represents a nitrogen atom, M represents a —CO— group or an —SO
2
— group, R
14
represents an alkyl group or an aryl group, m represents 1, R
12
and R
13
each represents a hydrogen atom, R
15
represents a substituent, n represents an integer of 0 to 4, and X
11
represents a group leaving by coupling which is linked by an oxygen atom to a mother nucleus of a phenol coupler and has a formula weight of 200 or more;
(11) A heat developable silver halide photographic material comprising a support having provided thereon at least one hydrophilic colloidal layer
Katsumata Taiji
Mizukawa Yuki
Sano Satoshi
Takeuchi Kiyoshi
Birch & Stewart Kolasch & Birch, LLP
Letscher Geraldine
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