Radiation imagery chemistry: process – composition – or product th – Radiation sensitive product – Silver compound sensitizer containing
Reexamination Certificate
2000-02-25
2001-07-24
Chea, Thorl (Department: 1752)
Radiation imagery chemistry: process, composition, or product th
Radiation sensitive product
Silver compound sensitizer containing
C430S591000, C430S613000, C430S614000, C430S619000, C430S944000
Reexamination Certificate
active
06265146
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to thermally developable photosensitive materials and in particular to thermally developable infrared-sensitive photographic materials of enhanced sensitivity, reduced variation in sensitivity following pre-exposure storage and improved silver image tone.
BACKGROUND OF THE INVENTION
As is different from conventional silver halide light sensitive photographic materials, there is no fixing process after development in thermally developable photosensitive materials. In the thermally developable photosensitive materials, there are, however, problems such that silver image tone easily varies. Recently, as a light source used for the thermally developable photosensitive materials are employed a laser light source at wavelengths in the infrared region due to its high energy and low price. In response thereto are employed thermally developable photosensitive materials which are spectrally sensitized with an infrared sensitizing dye. It has been commonly known that infrared-sensitizing dyes are inferior in adsorption to silver halide, as compared to visible region-sensitizing dyes, producing problems such as low sensitivity or marked reduction in sensitivity following pre-exposure storage. A technique of using an infrared sensitizing dye is disclosed in JP-A 5-66515 (hereinafter, the term, JP-A means an unexamined and published Japanese Patent Application). This technique, however, does not address any thermally developable photosensitive material and is not directed to solving problems such as reduction in sensitivity during pre-exposure storage or variation of silver image tone after development of thermally developable photosensitive materials. Binders used in thermally developable photosensitive materials are different from those used in conventional silver halide photographic materials, and therefore adsorption of spectrally sensitizing dyes used in the thermally developable photosensitive materials are also different from binder matrix of gelatin in the conventional silver halide photographic materials. Further, the thermally developable photosensitive material is added with an organic silver salt, a reducing agent and a silver cluster-bleaching agent which also exhibits antifogging function or an acid capable of adjusting thermal development. However, there has not been developed a means for improving silver image tone or pre-exposure storage stability, without deteriorating the function of such addenda.
SUMMARY OF THE INVENTION
Accordingly, it is a first object of the present invention to provide a thermally developable photosensitive material with higher sensitivity and reduced desensitization during pre-exposure storage.
A second object of the invention is to provide a thermally developable photosensitive material with improved silver image tone.
A third object of the invention is to provide an image recording method and an image forming method by use of the thermally developable photosensitive materials described above.
As a result of the studies by the inventors of the present invention, the above objects of the invention can be accomplished by the following constitution:
1. A thermally developable photosensitive material comprising a support having thereon an organic silver salt, a binder, a photosensitive silver halide, a spectrally infrared sensitizing dye and a heteroatom containing a macrocyclic compound;
2. A thermally developable photosensitive material comprising a support having thereon an organic silver salt, a binder, a photosensitive silver halide, a heteroatom-containing macrocyclic compound and an infrared sensitizing dye represented by the following formula (1), (2), (3) or (4):
Formula (1)
Formula (2)
wherein Y
1
, Y
2
and Y
11
each are independently an oxygen atom, sulfur atom, selenium atom or —CH═CH—; L
1
to L
9
and L
11
to L
15
each are independently a methine group; R
1
, R
2
, R
11
and R
12
each are independently an aliphatic group; R
3
, R
4
, R
13
and R
14
each are independently an alkenyl group, a cycloalkyl group or a heterocyclic group; W
1
, W
2
, W
3
, W
4
, W
11
, W
12
, W
13
and W
14
each are independently a hydrogen atom, a substituent or a non-metallic atom group necessary to form a condensed ring by bonding between W
1
and W
2
, W
3
and W
4
, W
11
and W
12
, or W
13
and W
14
; X
1
and X
11
each are an ion necessary to compensate for an intramolecular charge; k1 and k11 each are a number of the ion necessary to compensate for the intramolecular charge; ml is 0 or 1; and n1, n11 and n12 each are 0, 1 or 2, provided that n11 and n12 are not 0 at the same time;
Formula (3)
Formula (4)
wherein Y
21
, Y
22
and Y
31
each are independently an oxygen atom, a sulfur atom, a selenium atom, —C(Ra)(Rb)— group or —CH═CH— group, in which Ra and Rb each are a lower alkyl group, a cycloalkyl group, an aralkyl group, a lower alkoxyl group, an aryl group and a halogen atom; R
21
, R
22
, R
31
and R
32
each are independently an aliphatic group; Rc and Rd each are independently a lower alkyl group, a cycloalkyl group, an aralkyl group, an aryl group or a heterocyclic group; W
21
, W
22
, W
23
, W
24
, W
31
, W
32
, W
33
and W
34
each are independently a hydrogen atom, a substituent or a non-metallic atom group necessary to form a condensed ring by bonding between W
21
and W
22
, W
23
and W
24
, W
31
and W
32
, or W
33
and W
34
; V
21
to V
29
, and V
31
to V
33
each are independently a hydrogen atom, a halogen atom, an amino group, an alkylthio group, an arylthio group, a lower alkyl group, a lower alkoxyl group, an aryl group, an aryloxyl group, a heterocyclic group or a non-metallic atom group necessary to form a 5- to 7-membered ring by bonding between V
21
and V
23
, V
22
and V
24
, V
23
and V
25
, V
24
and V
26
, V
25
and V
27
, V
26
and V
28
, V
27
and V
29
, or V
31
and V
33
; X
21
and X
31
each are an ion necessary to compensate for an intramolecular charge; 121 and 131 each an ion necessary to compensate for an intramolecular charge; k21 and k22 each are 0 or 1; n21, n22, n31 and n32 each are 0, 1 or 2, provided that n21 and n22, or n31 and n32 are not 0 at the same time;
3. The thermally developable photosensitive material described in 1 or 2 above, wherein the photosensitive silver halide grain has an average iodide content of 0.1 to 10 mol % in the vicinity of the grain surface;
4. An image recording method, wherein a thermally developable photosensitive material described in any one of 1 to 3 above is exposed by using a laser exposure apparatus, in which scanning laser light is not exposed at an angle substantially vertical to the exposed surface of the photosensitive material;
5. An image recording method, wherein a thermally developable photosensitive material described in any one of 1 to 3 above is exposed by using a laser exposure apparatus, in which scanning laser light is longitudinally multiple;
6. An image recording method, wherein a thermally developable photosensitive material described in any one of 1 to 3 above is thermally developed in a state of containing an organic solvent of 40 to 4500 ppm.
REFERENCES:
patent: 5246828 (1993-09-01), Okuyama et al.
patent: 5393655 (1995-02-01), Sasaki et al.
patent: 5571664 (1996-11-01), Siegel et al.
patent: 5763153 (1998-06-01), Tsuzuki et al.
patent: 798129 (1997-01-01), None
patent: 838722 (1998-04-01), None
patent: 6230507 (1994-08-01), None
patent: 9281631 (1997-10-01), None
European Search Report EP 00 30 1621 XP 000073364 Research Disclosure, pp. 208 to 214 JP06/230507, Abstract, 1 p.
Bierman Jordan B.
Bierman, Muserlian and Lucas
Chea Thorl
Konica Corporation
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