Radiation imagery chemistry: process – composition – or product th – Radiation sensitive product – Identified radiation sensitive composition with color...
Reexamination Certificate
1999-12-28
2001-02-20
Letscher, Geraldine (Department: 1752)
Radiation imagery chemistry: process, composition, or product th
Radiation sensitive product
Identified radiation sensitive composition with color...
C430S552000, C430S384000, C430S385000
Reexamination Certificate
active
06190851
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to a silver halide color photographic element containing a dispersion of a paiticular type of phenolic cyan dye-forming coupler bearing a paiticular sulfone containing 5-substituent. The invention also is directed to the compound itself, and to an imaging process employing the element.
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-foiming couplers, respectively. After exposure to light, color development is accomplished by immersing the exposed material in an aqueous alkaline solution containing an aromatic primaly amine color-developing compound. 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-foiming coupler include: efficient reaction with oxidized color developing agent, thus minimizing the necessary amounts of coupler and silver halide in the photographic element; 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, low crystallization tendency, and thus good solubility in coupler solvents and good dispersibility in gelatin during handling and manipulation for improved 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, palticularly 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, and 5,476,757; in French patents 1,478,188 and 1,479,043; and in British patent 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 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 absoptions 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-diacylaminophenols 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 hypsochromically shifted (that is, shifted to the blue or short wavelength side of the visible spectrum) and the absorption spectra are too broad with considerable amounts of undesirable blue and green absorptions and often lack sufficient stability toward light fading. Thus, these couplers are not as desired for use in color papers.
The hue of a dye is a function of both the shape and the position of its spectral absoiption 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, typically 630 to 660 nm, and more often 635 to 655 nm. Such dyes have rather large amounts 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, that is, with a steep slope on the short wavelength side. Such a dye would suitably peak at a shoiter wavelength than a dye with 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 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 that dispersions of these couplers are difficult to prepare free of crystalline material, and are not phase stable with time in cold storage. Other related patents are U.S. Pat. Nos. 5,047,314, 5,047,315, 5,057,408, and 5,162,197.
Large-scale manufacturing of photographic materials can be severely hindered when crystalline material is present in dispersions and coating melts of such dispersions. This can lead to difficulty in manufacturing by plugging filters and causing defects in coatings of photographic materials. It is therefore desirable to use dispersions which have few, if any, crystals and are stable in cold storage from the time of preparation until the time of use.
This invention relates to a selection of cyan coupler that is a narrow-bandwidth or “NB coupler” which is defined more fully hereinafter. It has been found that preparing substantially crystal free dispersions of these “NB couplers” can be difficult. It appears that the property of these couplers that enables the dye formed by them to shift hue may at the same time be responsible for difficulties in the formation of unwanted crystals. Appropriate selection of a coupler solvent can reduce the amount of crystals. However, it has been found that some “NB couplers”, particularly those with high melting points, can fail to disperse in these preferred solvents as cleanly as couplers of lower melting points.
The use of various high boiling coupler solvents is disclosed in the following U.S. patents: U.S. Pat. No. 5,726,003, U.S. Pat. No. 5,047,315, U.S. Pat. No. 5,057,408, U.S. Pat. No. 5,356,768, U.S. Pat. No. 4,882,267, U.S. Pat. No. 4,767,697, U.S. Pat. No. 4,217,410, and U.S. Pat. No. 4,840,878. Experimental work contained in this specification has shown that a number of these known solvents may be employed to reduce the amount of crystals formed, but these solvents also result in decreased coupler reactivity and increased unwanted green light absorption.
Combinations of couplers close in structure has been used to inhibit the crystal foiming tendency of these couplers since mixtures of solids often exhibit lower melting points than single substances. However for large-scale synthesis it is desirable to prepare a single coupler that has all of the desired performance features.
The problem to be solved is to provide a photographic element and process employing a dispersion containing a phenolic cyan coupler that exhibits reduced crystal formation and at the same time provides desired hue and light stability.
SUMMARY OF T
Harder John W.
Honan James S.
Mura Albert J.
Eastman Kodak Company
Kluegel Arthur E.
Letscher Geraldine
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