Radiation imagery chemistry: process – composition – or product th – Radiation sensitive product – Identified radiation sensitive composition with color...
Reexamination Certificate
2002-09-24
2004-02-24
Schilling, Richard L. (Department: 1752)
Radiation imagery chemistry: process, composition, or product th
Radiation sensitive product
Identified radiation sensitive composition with color...
C430S600000, C430S614000, C430S567000, C546S213000
Reexamination Certificate
active
06696234
ABSTRACT:
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is based upon and claims the benefit of priority from the prior Japanese Patent Applications No. 2001-296577, filed Sep. 27, 2001; and No. 2002-173079, filed Jun. 13, 2002, the entire contents of both of which are incorporated herein by reference.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a silver halide photosensitive material. More particularly, the present invention relates to a silver halide color photosensitive material including a photographic emulsion that exhibits high speed and restrained fogging and that is excellent in raw stock storability and exposure humidity dependence. The present invention also relates to a method of forming images with the use of the same.
The present invention also relates to a novel isothiazolidin-3-one derivative that is useful as an intermediate for a medicament, pesticide and material for photograph and as an additive for photograph, and to a novel isothiazolidin-3-one derivative that, by adding it particularly to a silver halide photosensitive material, can restrain fogging.
2. Description of the Related Art
With respect to a silver halide photographic emulsion, an enhancement of speed/fog ratio is one of the most important tasks. Silver iodochloride emulsions having a silver iodochloride layer at the surface or subsurface portions of silver halide grains are preferred from the viewpoint that a high speed can be obtained and that the emulsion is excellent in high illumination intensity exposure adaptability. Representative examples of such silver iodochloride emulsions are disclosed in, for example, U.S. Pat. Nos. 5,550,013, 5,728,516, 5,547,827, 5,605,789, 5,726,005 and 5,736,310. However, the techniques disclosed in these patents have a drawback in that an increase of photographically unfavorable fog occurs in accordance with an increase of iodide content.
On the other hand, Jpn. Pat. Appln. KOKAI Publication No. (hereinafter also referred to as JP-A-) 4-368935 discloses that a silver halide color lightsensitive material which is excellent in raw stock storability can be obtained by the use of an adsorptive reducing compound, such as a hydroquinone compound, having an adsorption group acting on silver halide grains. However, the technique disclosed therein is silent about the effect of exhibiting low fog, high speed and excellent raw stock storability with respect to, in particular, a silver iodochloride or silver iodochlorobromide emulsion system.
Further, JP-A-9-43764 discloses that a silver halide color photosensitive material having prevented such a pressure fogging as experienced at the time of storage of a wound lengthy lightsensitive material at high temperatures, or a packaging thereof can be obtained by the use of a specific hydroxamic acid compound. However, the technique disclosed therein is silent about the raw stock storability, exposure humidity dependence and restraint on speed change over a period of from exposure to processing with respect to a silver iodochloride or silver iodochlorobromide emulsion.
As known compounds which are effective in restraining fogging with respect to emulsions containing silver chloride, silver iodochloride, silver chlorobromide, silver bromide, silver iodobromide and silver iodochlorobromide, other than the above hydroxamic acid compound, there can be mentioned, for example, hydroxyureas (JP-A's-2000-275767 and 8-246911), phenidones (JP-A-2000-330247), hydroxamic acids (JP-A's-11-282117, 9-90546, 9-90546, 9-133983, 8-114884, 8-333325 and 8-314051), heterocyclic hydroxylamines (JP-A-11-102046), hydroxysemicarbazides (JP-A-10-90819), hydroxyamines (JP-A-9-197635) and hydrazines (JP-A-7-134351 and Japanese Patent 2787630). In the techniques disclosed in these publications, there is no advantage of exhibiting low fogging and high speed, and of being excellent in the raw stock storability, exposure humidity dependence, exposure temperature dependence and restraint on speed change during the passage of time.
In the present invention, it has been found that an isothiazolidinone having a saturated ring is especially effective in restraining fogging. In JP-A-9-133977, there is a description that fogging can be reduced by adding isothiazolones (isothiazol-3-one) of similar skeleton in the step up to silver halide grain nucleation and/or stage corresponding to 60% of crystal growth. Further, in JP-A-2000-131790, it is described that fogging can be reduced by adding a certain type of isothiazolone before or during precipitation of silver halide emulsion (although there is no description regarding the raw stock storability, exposure humidity dependence and exposure temperature dependence). However, for inducing the advantages of these compounds, there has been a limitation on the timing of addition thereof to silver halide emulsion. Moreover, when the addition amount thereof is increased for inducing the advantage, desensitization occurs at an amount over a certain level to thereby occasionally invite a rupture of photographic performance prior to reaching a satisfactory level of improvement. Thus, with respect to these compounds, the appropriate range of use amount is restricted. Therefore, there has been a demand for a compound capable of solving this deficiency.
On the other hand, isothiazolidin-3-one derivatives have been utilized for uses such as medicaments and pesticides. However, only a very few compounds having no substituent or having an alkyl substituent on the carbon atoms at the 4- and 5-positions, are known. Furthermore, we could not find out through our research down to those having a hydrogen atom on the nitrogen atom at the 2-position. Such compounds that could be known are only as follows: 2-methyl-isothiazolidin-3-one, 2-butyl-isothiazolidin-3-one and 2-phenyl-isothiazolidin-3-one described in Justus Liebigs Annalen der Chemie, 679, 123-135 (1964); 2-methyl-isothiazolidin-3-one described in Journal of the Chemical Society, Perkin Transactions 1,153-158 (1985); 2-(2-propynyl)isothiazolidin-3-one and the like described in Hlevetica Chimica Acta, 70, 2232-2244 (1987); isothiazolidin-3-one described in JP-A-2000-212171; 2-octyl-isothiazolidin-3-one described in JP-A-9-157112; 2-chloromethyl-isothiazolidin-3-one described in JP-A-9-509922; and 2,4,4-trimethyl-isothiazolidin-3-one described in JP-A-61-165304. However, since required performances of the compounds vary depending on aims, solely the group of compounds that have been known so far is not sufficient, and thus development of additional isothiazolidin-3-one derivatives has been desired.
BRIEF SUMMARY OF THE INVENTION
The objects of the present invention is to solve the above problems of the prior art and to attain the following objects. The first object of the present invention is to provide a silver halide photosensitive material that exhibits high speed and restrained fogging and that is excellent in raw stock storability, with the use of an emulsion containing silver chloride, silver iodochloride, silver chlorobromide, silver bromide, silver iodobromide or silver iodochlorobromide. The second object of the present invention is to provide a silver halide photosensitive material whose exposure humidity dependence is small. The third object of the present invention is to provide a silver halide photosensitive material whose speed change over a period of from exposure to processing is small. The fourth object of the present invention is to provide novel isothiazolidin-3-one derivatives that are useful for synthetic intermediates of medicaments, pesticides and raw materials of photograph, especially those that can restrain fogging by adding them to a silver halide photosensitive material.
The inventors have made extensive and intensive studies, and has found that the objects of the present invention can be attained by the following means. Accordingly, the present invention provides
(1) a silver halide photosensitive material containing a compound of the following general formula (I):
In the formula, A
1a
represents a gr
Ichikawa Shin-ichi
Inaba Tadashi
Matsunaga Atsushi
Sakurazawa Mamoru
Takasaki Masaru
Schilling Richard L.
Sughrue & Mion, PLLC
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