Radiation imagery chemistry: process – composition – or product th – Radiation sensitive product – Identified radiation sensitive composition with color...
Reexamination Certificate
2000-11-14
2002-07-09
Letscher, Geraldine (Department: 1752)
Radiation imagery chemistry: process, composition, or product th
Radiation sensitive product
Identified radiation sensitive composition with color...
C430S502000, C430S503000, C430S512000, C430S543000, C430S555000, C430S557000, C430S558000, C430S955000, C430S449000
Reexamination Certificate
active
06416943
ABSTRACT:
FIELD OF THE INVENTION
This invention relates to color photographic materials capable of forming a neutral silver-based image. In particular, it relates to color photographic elements capable of forming a color image and additionally comprising a light sensitive silver halide emulsion layer containing a coupler that forms a neutral silver-based image upon processing.
BACKGROUND OF THE INVENTION
Color photographic elements are those that depend on the presence of colored dye or dyes to produce an image. The image may be multicolor, single color, or neutral due to balancing of the image dyes. Color photographic elements are processed using so-called developers that react with the color couplers present in the element to form the colored dye image. Black and white developers that form a silver image are not suitable as color developers.
Motion picture print film, the film that is shown in movie theaters, commonly employs an optical analog soundtrack along an edge of the film. During projection of the motion picture images, a light source illuminates the analog soundtrack and a photosensor senses the light passing through and modulated by the soundtrack to produce an audio signal that is sent to amplifiers of the theater sound system. While the most common soundtracks are of the “variable area” type wherein the signal is recorded in the form of a varying ratio of opaque to relatively clear area along the soundtrack, “variable density” soundtracks are also known wherein the absolute density is uniformly varied along the soundtrack. Common sound systems incorporate a photodiode in the projector whose radiant sensitivity peaks at approximately 800-1000 nm (depending on the type of photodiode), which detects the predominant infra-red (IR) radiation emitted by common tungsten lamps.
Color photographic films having an auxiliary metallic silver image are well known, for example see French Patent No. 912,605. The auxiliary silver image is useful for optically recording a sound track since silver is opaque to electromagnetic radiation in the range of 800-1000 nm whereas photographic dyes are generally transparent in this region. This allows a detector to read the silver image in the presence of a dye image. However, developed silver and residual silver halide must still be removed from the colored image portion of the film while at the same time, the silver image representing the sound track must be retained. A number of methods have been devised to retain the silver sound track image while still allowing for the removal of the unwanted silver; for example, see U.S. Pat. Nos. 1,973,463, 2,113,329, 2,263,019, 2,243,295, 2,286,747, 2,143,787, 2,258,976 and 2,235,033. A dye soundtrack may also be formed in color motion picture film in accordance with conventional exposing and color development processing. Such dye soundtracks may be formed in multiple photosensitive emulsion layers of the motion picture film, or may be restricted to a single emulsion layer as set forth in U.S. Pat. No. 2,176,303. These all suffer from the disadvantage that some portions of the film require a special and separate treatment relative to other portions of the film. The silver image may be reformed selectively in the soundtrack area of the film through selective application of a second developer solution after initial uniform color development (which develops exposed silver halide in both the picture area and soundtrack area up to silver metal and generates image dye), stop bath and fixer (arrests development and removes undeveloped silver halide), and bleach (converts exposed, developed silver back to silver halide in both the picture area and soundtrack area) steps. The second development step typically comprises application of a thick, viscous solution of a conventional black and white developer with a cellulose compound such as nitrosyl in a stripe solely onto the soundtrack area of the film, causing the silver halide in the soundtrack area to be selectively developed back into silver metal, while not affecting the silver halide in the image area. A subsequent fixing step then removes the silver halide from the image area, while leaving a silver image corresponding to the soundtrack exposure. Such processing is described for the Kodak ECP-2B Process, e.g., in Kodak Publication No. H-24, Manual For Processing Eastman Color Films. Various other techniques are also known for retaining silver in the soundtrack area, but all such approaches invariably entail certain processing disadvantages, such as critical reactant concentration control and area-selective reactant application requirements. Examples of such techniques, e.g., are set forth in U.S. Pat. Nos. 2,220,178, 2,341,508, 2,763,550, 3,243,295, 3,705,799, and 4,139,382.
It is known that materials that inhibit the bleaching of metallic silver, (so-called bleach inhibitors) are useful for the creation of an auxiliary silver image, for example see U.S. Pat. Nos. 3,715,208 and 3,869,287. These bleach inhibitors are generally materials that strongly coordinate to silver surfaces. It is also known that such bleach inhibitors may be released in an imagewise fashion from a coupler parent (so-called Bleach Inhibitor Releasers or BIRs); for example see U.S. Pat. No. 3,705,801. Bleach inhibitors and BIRs suffer from the disadvantage of interacting with the silver used to generate the colored dye image resulting in inhibition of silver development and color image as well as partially preventing bleaching and silver removal in those areas.
It is known that the silver-based images described above can be generated in a layer separate from the visibly colored image dye layers and that this layer can be sensitized to various wavelengths of light different from the image dye layers, for example, see British Patent 1 504 908 and U.S. Pat. No. 3,737,312.
EP 410726A1 describes the use of S-substituted beta-thioacrylamides as microbiocides.
A problem to be solved is to provide a photographic element that is capable of forming colored dyes and silver images in which the generation of the silver image does not affect the colored dye image and without requiring separate treatments for different regions of the film.
SUMMARY OF THE INVENTION
The invention provides a color photographic element suitable for forming both a colored dye image and a neutral silver-based image, comprising a support bearing at least one light-sensitive silver halide emulsion layer containing a coupler capable of forming a colored dye upon development, and bearing a further light-sensitive silver halide emulsion layer containing a coupler which is capable of releasing a thiovinyl group upon development that is capable of reacting to form a neutral silver-based image.
The invention also provides a novel coupler and imaging method. Embodiments of the invention offer a photographic element that is capable of forming colored dyes and neutral silver-based images in which the generation of the silver image is accomplished without affecting the colored dye image and without requiring separate treatments for different regions of the element.
DETAILED DESCRIPTION OF THE INVENTION
The invention is summarized above. Suitably, the silver image forming coupler is substituted at the coupling site with the sulfur atom of a thiovinyl group or a temporary linking or timing group that, in turn, connects the coupling site with the sulfur of a thiovinyl group. As used herein the term thiovinyl group does not include any compound where the vinyl double bond is part of an aromatic carbocyclic or aromatic heterocyclic ring. Conveniently, the invention provides a photographic element in which the silver image-forming coupler is represented by Formula I:
wherein COUPLER represents a species that reacts with oxidized developer, TIME is a linking or timing group, x is 0, 1 or 2 and R
1
, R
2
and R
3
are independently selected hydrogen or substituents with the proviso that R
1
and R
2
may join together provided they are not, together with the intervening double bond, part of a carbocyclic or heterocyclic aromatic ring system.
The in
Bodden Anabisdally I.
Hill Susan D.
Romanet Robert F.
Singer Stephen P.
Kluegel Arthur E.
Letscher Geraldine
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