Radiation imagery chemistry: process – composition – or product th – Radiation sensitive product – Identified radiation sensitive composition with color...
Reexamination Certificate
2000-02-28
2001-07-17
Letscher, Geraldine (Department: 1752)
Radiation imagery chemistry: process, composition, or product th
Radiation sensitive product
Identified radiation sensitive composition with color...
C430S552000, C430S553000, C430S384000, C430S385000, C430S546000, C430S551000
Reexamination Certificate
active
06261755
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to a color photographic element containing phenolic cyan couplers and in particular to a combination of two classes of phenolic cyan couplers with a specific class of UV absorber.
BACKGROUND OF THE INVENTION
In silver halide based color photography, a typical photographic element contains multiple layers of light-sensitive photographic silver halide emulsions coated on a support with one or more of these layers being spectrally sensitized to each of blue light, green light and red light. The blue, green and red light-sensitive layers typically contain yellow, magenta, and cyan dye-forming couplers, respectively. After exposure to light, color development is accomplished by immersing the exposed material in an aqueous alkali solution containing an aromatic primary amine color-developing agent. The dye-forming couplers are selected so as to react with the oxidized color-developing agent to provide yellow, magenta and cyan dyes in the so called subtractive color process to reproduce their complementary colors, blue, green and red as in the original image.
The important features for selecting the dye-forming coupler include; efficient reaction with oxidized color-developing agent, thus minimizing the necessary amounts of coupler and silver halide in the photographic element; the formation of dyes with hues appropriate for the photographic use of interest: for color photographic paper applications this requires that dyes have low unwanted side absorption leading to good color reproduction in the photographic print; minimization of image dye loss contributing to improved image permanence under both ambient illumination and conventional storage conditions; and in addition the selected dye-forming coupler must exhibit good solubility in coupler solvents, provide good dispersibility in gelatin and remain stable during handling and manipulation for maximum efficiency in manufacturing processes.
In recent years, a great deal of study has been conducted to improve dye-forming couplers for silver halide photosensitive materials in terms of improved color reproducibility and image dye stability. However, further improvements are needed, particularly in the area of cyan couplers. In general, cyan dyes are formed from naphthols and phenols as described, for example, in U.S. Pat. Nos. 2,367,351, 2,423,730, 2,474,293, 2,772,161, 2,772,162, 2,895,826, 2,920,961, 3,002,836, 3,466,622, 3,476,563, 3,552,962, 3,758,308, 3,779,763, 3,839,044, 3,880,661, 3,998,642, 4,333,999, 4,990,436, 4,960,685, 5,476,757 and 5,614,357; in French Patent Nos. 1,478,188 and 1,479,043 and in UK Patent No. 2,070,000.
These types of couplers can be used either by being incorporated in the photographic silver halide emulsion layers or externally in the processing baths. In the former case the couplers must have ballast substituents built into the molecule to prevent the couplers from migrating from one layer into another. Although these couplers have been used extensively in color photographic film and paper products, the dyes derived from them still suffer from poor stability to heat, humidity or light, low coupling efficiency or optical density, and in particular from undesirable blue and green absorptions which cause considerable reduction in color reproduction and color saturation.
Cyan couplers which have been recently proposed to overcome some of these problems are 2,5-diacylamino-phenols containing a sulfone, sulfonamido or sulfate moiety in the ballasts at the 5-position, as disclosed in U.S. Pat. Nos. 4,609,619, 4,775,616, 4,849,328, 5,008,180, 5,045,442, and 5,183,729, and Japanese patent applications JP02035450 A2, JP01253742 A2, JP04163448 A2, JP04212152 A2 and JP05204110 A2. Even though cyan image dyes formed from these couplers show improved stability to heat and humidity, enhanced optical density and resistance to reduction by ferrous ions in the bleach bath, the dye absorption maxima (&lgr;
max
) are too bathochromically shifted (i.e. shifted to the red end of the visible spectrum) and the absorption spectra are too broad, with considerable amounts of undesirable blue and green absorptions. Thus, these couplers are not practical for use in color papers.
The hue of a dye is a function of both the shape and the position of its spectral absorption band. Traditionally, the cyan dyes used in color photographic papers have had nearly symmetrical absorption bands centered in the region of 620 to 680 nm, preferably 630 to 660 nm, and more preferably 635 to 655 nm. Such dyes have rather a large amount of unwanted absorption in the green and blue regions of the spectrum.
More desirable would be a dye whose absorption band is asymmetrical in nature and biased towards the green region, i.e. with a steep slope on the short wavelength side. Such a dye would suitably peak at a shorter wavelength than a dye with a symmetrical absorption band, but the exact position of the desired peak depends on several factors including the degree of asymmetry and the shapes and positions of the absorption bands of the magenta and yellow dyes with which it is associated.
Recently, Lau et al. in U.S. Pat. No. 5,686,235 describe a particular class of cyan dye-forming coupler that has been shown to improve dye thermal stability and hue, particularly, with decreased absorption in side bands and an absorption band that is asymmetrical in nature. However it has been found in particular that dye light stability of materials containing such couplers is unsatisfactory. Some improvements to dye light and thermal stability of such cyan couplers have been obtained by the use of certain phenolic solvents and bisphenol stabilizers. However further improvement in dye light stability is still required to provide a satisfactory performance.
The 2,5-diacylaminophenol couplers in U.S. Pat. Nos. 5,047,314, 5,047,315, 5,057,408, 5,162,197 and 5,726,003 are of the type which yield dyes with symmetrical absorption bands and high side-band absorptions. The use of certain ester coupler solvents is described in both U.S. Pat. Nos. 5,047,315 and 5,057,408, where examples show these solvents with 2,5-diacylaminophenols. The couplers in these patents are typically embodied in formats with benzotriazole UV absorbers which can provide improved dye stability to light. However these patents do not provide teaching suitable for understanding how these couplers or stabilizers, and especially the couplers of U.S. Pat. No. 5,686,235, affect dye formation efficiency or how they affect unwanted side-band absorption.
Combinations of two classes of phenolic cyan dye-forming couplers are disclosed in U.S. Pat. Nos. 4,537,857, 4,552,836, 4,614,710, 4,666,826, 5,084,375, 4,820,614 and in JP 02 178,259 and JP 02 237,449.
U.S Pat. No.5,047,314 discloses a 2,5-diacylamino-phenol or 2-acylureido-5-acylaminophenol cyan coupler in combination with a 2-acylamino-5-substituted phenol cyan coupler, a benzotriazole stabilizer and a soluble polymer. However these combinations provide more unwanted green absorptions than is acceptable since the left bandwidth is too broad. Moreover there is no disclosure of a cyan coupler with a narrow left bandwidth which can provide the desired color rendition properties, as hereinafter described.
PROBLEM TO BE SOLVED BY THE INVENTION
There is still a need to provide a photographic element containing a dispersion of cyan dye-forming couplers which can provide improved light and dark stability under normal storage conditions, improved color reproduction in the generation of photographic images and high reactivity for formation of dye with oxidized color-developing agent.
SUMMARY OF THE INVENTION
The invention provides a photographic element comprising at least one light-sensitive silver halide emulsion layer having associated therewith:
(A) a phenolic cyan dye-forming “NB coupler”, as herein defined;
(B) a phenolic cyan dye-forming coupler of formula (II):
wherein:
R
3
is an unsubstituted or substituted alkyl or aryl group or a 5-10 membered heterocyclic ring which contains one or more heteroatoms selec
Gibson Danuta
Honan James S.
Rosiek Thomas A.
Eastman Kodak Company
Kluegel Arthur E.
Letscher Geraldine
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