Radiation imagery chemistry: process – composition – or product th – Thermographic process – Heat applied after imaging
Reexamination Certificate
1997-10-28
2001-05-08
Schilling, Richard L. (Department: 1752)
Radiation imagery chemistry: process, composition, or product th
Thermographic process
Heat applied after imaging
C430S380000, C430S404000, C430S543000
Reexamination Certificate
active
06228565
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a photographic silver halide photosensitive material. More particularly, the present invention relates to a silver halide color photographic photosensitive material which is useful for the improvement of an image forming technique for high-temperature processing of tabular silver chloride grains or silver halide grains composed of silver chlorobromide, silver chloroiodide or silver chloroiodobromide having a high content of silver chloride.
2. Description of the Related Art
Owing to remarkable development of color photographic photosensitive materials utilizing silver halides, high-quality color images are now easily available. For example, according to so-called ordinary color photography, color prints are obtained by taking a photograph utilizing a color negative film, processing the film, and optically printing the image information which is recorded in the processed color negative film onto color photographic printing paper. Recently, this process has made remarkable progress, and large-scale, centralized color laboratories, in which a large quantity of color prints are produced efficiently, and the so-called mini-labs which are installed in shops and are designed to use compact and simple printer-processors have spread widely. Therefore, anybody can enjoy color photography easily.
The color photography, now in common use, reproduces color by the subtractive color process. Generally, a color negative film comprises a transparent support and photosensitive layers thereon utilizing silver halide emulsions as photosensitive elements sensitive to blue, green or red wavelength regions respectively, and so-called color couplers capable of producing a yellow, magenta or cyan dye having a complementary hue of the sensitive wavelength region of each photosensitive layer. A color negative film exposed during photography, is processed in a color developing solution containing an aromatic primary amine developing agent. At this time, the developing agent develops, i.e., reduces the exposed silver halide grains, and the oxidized form of the developing agent, which is formed concurrently with the foregoing reduction, undergoes a coupling reaction with the color coupler to form dyes. The metal silvers (developed silver) generated by the development and the unreacted silver halides are removed through a bleaching and fixing process, respectively. This creates a color image on the color negative film. Subsequently, color photographic printing paper, which comprises a reflective support and photosensitive layers coated thereon having a combination of photosensitive wavelength regions and hue in each layer, similar to the color negative film, is optically exposed to light through the processed color negative film, and is then subjected to the color developing, bleaching and fixing processes as in the case of the negative film to obtain a color print having a color image composed of dye images so that an original image can be reproduced.
Although these systems are widely adopted at the present time, there is a growing demand for a simpler system. The first reason for this is that expertise and skilled operation are necessary due to the requirement of strict control of the composition and the temperature of the solutions in processing baths for the above-mentioned procedure consisting of color development, bleaching and fixation. The second reason for this is that equipment to be used exclusively for the developing process is often required, due to substances, such as developing agents and bleaching agents comprising an iron chelate compound, the discharge of which is regulated from the standpoint of environmental protection. The third reason for this is that the currently available systems do not satisfactorily fulfill the requirement for rapid reproduction of recorded images. The above-mentioned processes still take time, although this time has been shortened with recent advances in technology.
Based on this background, many improved techniques have been proposed. In particular, in order to make the developing process simple and rapid, a variety of techniques have been proposed which use silver halide grains having a higher silver chloride content (50% or more and hereinafter referred to as “silver chloride rich grains”). The use of silver chloride rich grains brings about the advantages, for example, that the processing speed increases and the reusability of the processing solutions are improved.
Consequently, in recent years, most photosensitive materials for printing, such as color photographic printing paper, use silver chloride rich grains. Under ordinary manufacturing conditions, the produced silver chloride rich grains tend to be grains in which (100) planes constitute the exterior faces of the grains (hereinafter referred to as (100) grains) The grains actually used in practice have been cubes. Recently, tabular (100) grains, having larger specific surface areas (the ratio of the surface area to the volume) with the advantages that spectral sensitization can be effectively performed and the covering power after the developing process is enhanced, have also been developed. Examples of these tabular (100) grains are disclosed in, e.g., U.S. Pat. Nos. 5,320,938, 5,264,337 and 5,292,632.
However, in the case of the photosensitive materials using the silver chloride rich grains, the development characteristics of the silver chloride rich grains cause various problems. The first problem is that it is difficult to obtain a highly sensitive photographic response at an early stage of developing process, because the high-speed development of the individual grains of the silver halide emulsion containing the silver chloride rich grains often causes the timing of the start of the development of the light-exposed grains to vary. The second problem is that any attempt to utilize the high developing capability of the silver chloride rich grains is often associated with deterioration of the graininess. Consequently, it is very difficult to fulfill the characteristics of photosensitive materials for photographing such as a wide exposure latitude and superior level of graininess by use of a silver halide emulsion composed of the silver chloride rich grains. Since these problems still remain unsolved, many fundamental problems need to be solved before the photosensitive materials for photographing using silver halide emulsions composed of silver chloride rich grains can be put to practical use. The third problem is that the silver chloride rich grains in which (100) planes constitute the exterior faces of the grains tend to cause more fogging in comparison with conventional silver bromide grains.
As an effective solution to the above-described problems, a method has been proposed recently which comprises releasing or producing diffusive dyes on an image by means of thermal development and transferring the diffusive dyes to a dye-fixing element.
According to this method, it is possible to obtain negative or positive color images by selecting the kind of dye-donating compound or silver halide to be used. The details are described in, e.g., U.S. Pat. Nos. 4,500,626, 4,483,914, 4,503,137 and 4,559,290, Japanese Patent Application Laid-Open (JP-A) Nos. 58-149,046, 59-218,443, 60-133,449 and 61-238,056, European Patent Application Laid-Open Nos. 220,746A2 and 210,660A2, and Journal of Technical Disclosure No. 87-6,199.
In another attempt to fulfill the above-mentioned requirements, a technique has been reported which will lessen the load on the environment and contribute to the simplification of the system by establishing a color image formation system without the use of the color developing agents or bleaching agents now in use in current systems. For example, IS & T's 48th Annual Conference Proceedings, p. 180, discloses a system in which the dye formed in the developing reaction is transferred to a mordant layer and thereafter a photosensitive material is stripped to remove the developed silver and unreacted silve
Asami Masahiro
Ohzeki Katsuhisa
Fuji Photo Film Co. , Ltd.
Schilling Richard L.
Sughrue Mion Zinn Macpeak & Seas, PLLC
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