Radiation imagery chemistry: process – composition – or product th – Radiation sensitive product – Silver compound sensitizer containing
Reexamination Certificate
2003-01-03
2004-01-13
Le, Hoa Van (Department: 1752)
Radiation imagery chemistry: process, composition, or product th
Radiation sensitive product
Silver compound sensitizer containing
Reexamination Certificate
active
06677112
ABSTRACT:
TECHNICAL FIELD
The present invention relates to a silver halide emulsion, a production method thereof, a silver halide light-sensitive photographic material and a silver halide light-sensitive color photographic material comprising the silver halide emulsion, and an image forming method utilizing them. Particularly, the present invention relates to a silver halide emulsion, which exhibits excellent development stability and excellent latent image stability at high intensity exposure, as well as excellent fine line reproduction stability, a silver halide emulsion, which exhibits high sensitivity as well as low fog at digital exposure which is performed for a short time at high irradiance, and exhibits excellent image stability during the period from completion of the exposure to the start of photographic processing, a production method thereof, a silver halide light-sensitive photographic material and a silver halide light-sensitive color photographic material comprising the silver halide emulsion, and image forming method utilizing them.
BACKGROUND
In recent years, silver halide color paper has been employed in a variety of places due to proliferation of minilabs. Along with such proliferation, exposures during printing have been carried out under various conditions as well as various circumstances. Further, on the market, problems have occurred in which development stability is degraded due to mixing of silver bleach solution with a color developing solution. Further, in recent years, digital image processing has increasingly progressed and the need has rapidly been increased for image formation by scanning exposure, employing high intensity light sources such as light emitting diodes and semiconductor lasers. As a result, an increase in suitability for high intensity and short time exposure is highly demanded for silver halide light-sensitive color photographic materials (hereinafter occasionally referred simply to as light-sensitive materials) employed as an image forming means. Specifically, it has been found that high intensity exposure results in increased susceptibility to effects due to processing solutions and increased degradation of latent image stability.
Namely, increasingly demanded are development of light-sensitive materials which result in excellent images based on conventional photographic image formation, as well as image formation employing quick scanning under high intensity light exposure.
At the same time, the progress of silver halide light-sensitive materials, which are advantageous for image quality, cost, and mass productivity, has been greatly sought in order to compete with the rapid progress of other non-silver salt output media such as ink jet printing systems.
Conventionally, as a means to achieve a quick development process, silver chloride emulsions or silver halide emulsions, having a high silver chloride content, have been employed.
On the other hand, Japanese Patent Application Open to Public Inspection No. 64-26837 discloses an emulsion having a high silver chloride content which has a portion of a high content of silver bromide near the apex of silver halide grains. Further, Japanese Patent Application Open to Public Inspection No. 1-105940 discloses that it is possible to provide an emulsion, having a high silver chloride content, in which silver bromide is subjected to localized Ir doping so as to achieve excellent latent image stability as well as to minimize failure of the reciprocity law. Still further, U.S. Pat. No. 5,627,020 discloses a method of forming the localized portions of silver bromide employing fine Ir doped silver bromide grains. However, none of the methods result in sufficient improvement in initial latent image stability after exposure. Further, Japanese Patent Application Open to Public Inspection No. 11-109534 describes a silver halide emulsion in which a phase having a higher silver bromide proportion, which comprises iridium compounds is located near the surface of silver halide grains and a region in which the concentration of iridium compounds is higher than the outside of said phase having a higher silver bromide proportion is prepared in the inside of said phase having a higher silver bromide proportion, so that failure of the reciprocity law as well as high humidity dependence is minimized and latent image stability is enhanced. These inventions are characterized in that a localized phase containing a high proportion of silver bromide, such as 10 to 40 percent, is provided at the apex portion of silver halide grains. However, the resulting stability of silver halide emulsions as well as the resulting processing stability are insufficient.
Still further, Japanese Patent Application Open to Public Inspection No. 2001-188311 discloses a method in which a phase having a higher proportion of silver bromide as well as silver iodide is provided and the introduction of said higher proportion phase is carried out twice independently, that is, prior to the addition of antifoggants and after the same so that the resulting failure of the reciprocity law is minimized and the resulting coating composition stability is enhanced. However, the stability of the resulting silver halide emulsion is insufficient.
Widely known as examples regarding doping of cyano ligand containing complexes are European Pat. Nos. 336,425 and 336,426; Japanese Patent Application Open to Public Inspection Nos. 2-20853, 2-20854, and 5-66511; U.S. Pat. Nos. 5,132,203, 4,847,191, and 3,790,300; and Japanese Patent Publication No. 48-35373. These patents exhibit an increase in sensitivity as well as minimization of failure of the reciprocity law, however drawbacks with latent image stability as well as minimization of fogging during photographic processing are not completely overcome. Further, Japanese Patent Application Open to Public Inspection Nos. 11-24194, 11-102042, 10-293377, 8-179452, and 7-72569 and U.S. Pat. Nos. 5,360,712, 5,457,021, and 5,462,849 describe an increase in sensitivity employing organic ligand complexes, comprising imidazole as a ligand. However, improvements are demanded due to insufficient development stability as well as insufficient latent image stability under high intensity exposure.
Further, it has been proved that in digital exposure systems which have recently received much attention, conventional techniques to improve latent image stability are not capable of resulting in commercially viable quality in the adaptability for high intensity exposure over a short time. Listed as techniques applied to such a digital exposure system are, for example, a chemical sensitization and spectral sensitization method suitable for formation of the localized silver bromide phase described in U.S. Pat. No. 5,601,513 and further methods employing iodochloride emulsions described in European Pat. Nos. 750,222 and 772,079.
However, according to investigations performed by the inventors of the present invention, it has been proved that when adaptability for digital exposure is improved employing the aforesaid techniques, latent image stability is not sufficiently enhanced, and in addition, pressure resistance as well as stability for temperature variation during exposure are markedly degraded. As a result, at present, development of improving technology is urgently demanded.
SUMMARY OF THE INVENTION
An aspect of the present invention is to provide a silver halide emulsion, which exhibits excellent development stability and excellent latent image stability at high intensity exposure, as well as excellent fine line reproduction stability. An other aspect of the present invention is to provide a silver halide emulsion, which exhibits high sensitivity as well as low fog at digital exposure which is performed for a short time at high irradiance, and exhibits excellent image stability during the period from completion of the exposure to the start of photographic processing. Still other aspect of the present invention is to provide a production method of the silver halide emulsion, a silver halide light-sensitive photographic material and a sil
Kubotera Mitsuhiro
Kuroda Koichiro
Murakami Shuji
Tanaka Yuji
Konica Corporation
Le Hoa Van
Muserlian Lucas and Mercanti
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