Radiation imagery chemistry: process – composition – or product th – Radiation sensitive product – Identified radiation sensitive composition with color...
Reexamination Certificate
1999-07-21
2001-02-20
Letscher, Geraldine (Department: 1752)
Radiation imagery chemistry: process, composition, or product th
Radiation sensitive product
Identified radiation sensitive composition with color...
C430S505000, C430S955000, C430S957000, C430S607000, C430S613000, C430S614000, C430S615000, C430S599000, C430S600000
Reexamination Certificate
active
06190849
ABSTRACT:
FIELD OF THE INVENTION
This invention relates to a color photographic element containing a tetrazole derivative dispersed in one light sensitive layer and containing in a second light sensitive layer having a different spectral sensitivity than the first layer, a mild inhibitor releasing coupler.
BACKGROUND OF THE INVENTION
It is an object of silver halide-based color photographic materials to reproduce colors in both an accurate (in terms of hue) and vivid (in terms of saturation) manner. In practice, the reproduction of color by such materials is limited in two ways. First, the sensitivity of the silver halide emulsions to a desired single light color is not perfect and they will absorb some amount of light of undesired color. This leads to formation of dye in the wrong color record resulting in less pure hues. For example, the red sensitivity of the emulsions generally occurs at longer wavelengths than the human eye. If the red sensitivity of the film is moved closer to the eye maximum sensitivity, its sensitivity to green light also increases. Thus in such situations, the red sensitive layer is partially exposed during green light exposures leading to the formation of some cyan dye along with magenta dye. This alters the hue of the image and decreases its saturation. Second, the image dyes formed are not perfect in hue and have unwanted side absorbencies. Thus, some density in the unwanted color regions is formed in addition to the desired density, again degrading color saturation. Finally in some circumstances, it is desirable to increase color saturation to a greater degree than the actual image in order to make the image visually more pleasing.
It is well known to that color reproduction of such materials can be partially controlled by the use of imagewise development inhibitor releasing (DIR) couplers. During development, DIR couplers react with oxidized developer to release an inhibitor fragment or a precursor of an inhibitor fragment which can diffuse out of that layer and into a different color record where inhibition occurs. This has the overall effect of reducing the amount of dye formed in one color record as a function of exposure of another and can effectively be used to manipulate hue and increase color saturation. This process is called interimage. For example, a film with a DIR coupler in the green layer and given a mostly green exposure will cause a decrease in development in the red record due to the action of the inhibitor released in the green. This causes less cyan dye to be formed than when the inhibitor was not present. The final green image will have less red density and its overall saturation will be increased. It should be noted that all possible colors are not weighted equally in terms of creating a pleasing overall image and that the reproduction of some key colors (for example, flesh tones, green grass, blue sky, etc.) is more important than others.
The creation of interimage effects with DIR couplers is deficient in a number of ways. First, the inhibitor fragment (or precursor) released from the DIR coupler is free to diffuse in all directions. Thus, the inhibitor can affect both of the other color records, even if it was desired to only affect one. For example, putting the DIR coupler in the green will decrease the amount of blue development as well as the red. The amount of interimage effects on the blue and red records from the green are linked and cannot be manipulated separately. This non-specificity of interimage effects limits the ability to control and manipulate color reproduction of the key colors.
Second, the fragment released from the DIR will cause inhibition in the layer in which it is released. This can lead to over-inhibition of the layer in which the DIR coupler is located resulting in low contrast and a loss in sensitivity to light, particularly with strong inhibitor fragments. It is possible to avoid this in part by using milder inhibitors or by using timing groups to delay the introduction of the free inhibitor fragment. In such situations, the diffusion pathlength of the inhibitor fragment is increased and seasoning of the fragments into the developer becomes a problem. In order to avoid these seasoning effects, mild inhibitor fragments often have a hydrolyzable substituent which, upon hydrolysis in the developer solution, renders them inactive after a period of time. Examples are shown in U.S. Pat. Nos. 4,782,012, 4,477,563, 4,937,179, 5,004,677, DE-A 3909486, DE-A-3209486, EP-A-167,168, EP-A-488,310, EP-A-440,466 and EP-A-219,173.
Substituted mercaptotetrazoles are commonly known in the art as inhibitor fragments and as antifoggants. As inhibitor fragments, they are attached to a coupling moiety through a sulfur or nitrogen atom and do not interact with silver until coupling occurs and the sulfur atom is freed; for example, see U.S. Pat. No. 3,227,554 and C. R. Barr et al, Photogr. Sci. Eng., 74, 214 (1969). As part of a DIR, the mercaptotetrazole will not have a free —S—H or —N—H group. Generally, it is desirable that the mercaptotetrazoles released from DIRs are partially water soluble so that they are free to diffuse to other layers to cause interimage. As antifoggants, these materials are generally at least partially water soluble or soluble in water-miscible solvents such as methanol and are added directly to silver emulsions before coating of the film or added directly to the developer solutions. The use of various solublized mercaptotetrazoles as antifoggants is shown, for example, in Research Disclosure, June 1984, pp 274-278; U.S. Pat. Nos. 4,952,485; 5,362,620; 5,244,779; 4,963,475; 3,266,897; Belgian Patent 747,628, UK Patent 1,275,701; JP-05-313282; EP 454149A1; JP-02-207248; EP 509519A2 and EP 337370A2. U.S. Pat. No. 4,770,991 also describes a wide variety of mercaptotetrazoles (maximum ClogP=7.02) in a high contrast black and white film. JP 63-24255 describes a wide variety of mercaptotetrazoles, all with ClogP of less than 5.0, with a silver chloride emulsion in a format with inhibitor releasers.
U.S. Pat. Nos. 5,032,499, 4,837,141 and JP 62-138850 describe the use of a wide variety of photographic restrainers (including tetrazoles) in thermally developable light sensitive materials. JP 10-50047 describes a wide variety of anti-silver sludging agents (including tetrazoles) in a non-light sensitive cleaning film.
JP-08-328214A2 discloses the use of various solubilized heterocyclic thiols containing strongly acidic groups or their salts (for example, sulfonic and carboxylic acids) in combination with development inhibitor releasing couplers for improved sharpness and storage stability.
EP 0 369 486 B1 describes the use of mercaptobenzimidiazoles, mercaptobenzothiazoles or mercaptobenzooxazoles for use with fine silver chloride emulsions in a non-light sensitive protective layer to remove inhibiting species. The fine silver chloride is described at being at least 1.0 exposure units less light sensitive than the least light-sensitive imaging silver halide emulsion.
A problem to be solved is to provide a color photographic element having improved color reproduction.
SUMMARY OF THE INVENTION
The invention provides a color photographic element comprising:
a) a first light sensitive silver halide emulsion layer containing a tetrazole compound of Formula I:
wherein when R
1
is hydrogen, then R
2
is an alkyl, aryl, alkoxy , aryloxy, alkylthio or arylthio, sulfoxyl, sulfonyl, sulfamoyl, —O—CO—, —O—SO
2
—, a heterocyclic group, a carbonyl group or an amino group or when R
2
is a thiol (—SH) group, then R
1
is an alkyl, aryl or heterocyclic group provided further that the ClogP for the compound of Formula I is at least 2.0 and less than 7.8; and
b) a second light sensitive silver halide emulsion layer, having a spectral sensitivity different from that of the first light sensitive silver halide emulsion layer, containing a compound of Formula II:
COUP—(TIME)
j
—INH II
wherein:
1) COUP is a coupler parent group capable of forming a dye upon reaction with an oxidized developer;
2) TIME is a ti
Burns Paul A.
Friedrich Louis E.
Singer Stephen P.
Eastman Kodak Company
Kluegel Arthur E.
Letscher Geraldine
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