Patent Grant
7629112
The present invention relates to color silver halide photographic materials containing preformed, permanent yellow colorants that are not removed or discolored during processing. In a particular, it relates to color negative photographic elements (“color films”) and motion picture origination films.
A typical color silver halide photographic material contains at least one layer sensitized to each of the three primary regions of the visible spectrum. They usually contain at least one blue-sensitive layer with a yellow image dye forming coupler, at least one green-sensitive layer with a magenta image dye forming coupler, and at least one red-sensitive layer with a cyan image dye forming coupler.
In addition to the spectral sensitizing dyes used to sensitize the light-sensitive silver halide emulsion grains to the different regions of the spectrum and the yellow, magenta, and cyan dyes that are formed from dye-forming couplers to form the final color image, it is common to incorporate additional dyes or colorants for different purposes in the various light-sensitive and non-light sensitive layers. For example, absorber dyes (such as acutance dyes) are frequently employed in the light-sensitive layers to absorb light between the silver halide emulsion grains to reduce light scatter and improve image acutance or to control the light sensitivity (photographic speed). These dyes are described in numerous publications such as U.S. Pat. Nos. 4,312,941, 4,391,884, 4,956,269, and 5,308,747. It is also common to use filter dyes to regulate the spectral composition of the incident light falling on a particular light-sensitive photographic layer. These dyes may be used in a non-light-sensitive layer, which is arranged above a light-sensitive silver halide emulsion layer or between two light-sensitive emulsion layers in order to protect the underlying emulsion layers from the action of light of the wavelength absorbed by the dye. For example, many color photographic materials contain a yellow dye filter layer that is usually arranged between the blue-sensitive layers and the underlying green-sensitive layers and red-sensitive layers in order to keep blue light away from the green-sensitive layers and red-sensitive layers. Filter dyes are also described in many publications such as U.S. Pat. Nos. 5,213,956 and 5,776,667, GB published applications 695,873 and 760,739, and EP Publication 430,186A1. It is also known to use dyes as anti-halation dyes in a layer below the light-sensitive layers to prevent light from reflecting back into the emulsion layers from the backside of the film support resulting in unwanted light scatter and halation effects as described in U.S. Pat. Nos. 4,288,534, 4,294,916, 5,262,289, and 5,380,635. In general, all of these dyes, except for the color image dyes, are irreversibly discolored or almost completely washed out of the layers during photographic processing so that no unwanted coloration remains on the exposed and developed photographic film.
The use of pre-formed, permanent dyes in color photographic elements that are not discolored or removed during processing have also been disclosed. These dyes are used in color negative photographic materials to adjust the blue, green, or red densities to a standard level for a nominally exposed and processed color negative film in order to achieve optimum performance during printing onto photographic paper. Technological advances in color negative films have reduced the contribution of other film components to the overall blue, green, and red minimum densities (Dmin) and midtones. For example, features such as DIR technology have diminished the once dominant role that colored masking couplers played in defining color saturation. Similarly, advances in silver halide spectral sensitization have led to a lower level of retained sensitizing dyes. In order to operate effectively in these legacy systems, minimum and midtone densities have been adjusted in modern color negative films by the use of colored, but otherwise inert, materials. These dyes are also used in color transparency materials to provide a neutral appearance in the minimum density areas. It is well known to use permanent dyes for these purposes that are synthesized by the reaction of photographic couplers with oxidized color developing agents. The pre-formed dyes are typically dispersed in an organic solvent using conventional dispersion making techniques and are subsequently incorporated into one or more layers of the photographic element. These dyes often have the advantage of having the same chemical structure and dye hue as the color image dyes that are formed in the film in-situ during photographic processing. However, they are relatively insoluble materials that require high levels of organic solvents to provide stable dispersions. This necessitates use of increased levels of binder in order to retain good film physical properties. They also suffer from the disadvantages of being relatively inefficient light absorbers and rather expensive to synthesize compared to a number of commercially available dyes and pigments that are commonly used as colorants in other industries.
The use of yellow pigments as colorants for toner particles in color electrophotography is well known in the prior art as disclosed for example in U.S. Pat. Nos. 2,644,814 (Ernst), 3,345,293 (Bartoszewicz et al.), 3,998,747 (Yamakami et al.), and 4,035,310 (Mammino et al.). Colorants are also widely used in inkjet ink formulations as described in U.S. Pat. Nos. 5,977,207 (Yui et al.), 5,989,701 (Goetzen et al.), and 6,231,655 (Marritt). Yellow pigments have also been employed as colorants in a light sensitive materials containing silver halide, a polymerizable layer, and a reducing agent used for forming color proofs in the field of digital color printing as disclosed for example in U.S. Pat. Nos. 5,304,454, 5,326,667, 5,328,800, 5,612,167, and 5,714,303 (all by Yokoya et al.).
Color photographic materials have been designed with compounds that provide minimum density upon reaction with a color photographic developer. For example, in the Comparative Examples described below, one such color producing-compound is labeled as “CD-1”.
Minimum density colorants have thus been employed simply to provide light absorption within a specific region of the visible spectrum. There is a need for such compounds to provide high “potency” (high density per/mg/m2) as “dummy” dyes that do not change during exposure and development, while meeting the specific spectral requirements of the particular color photographic element. It would be desirable to use colorants that do not require a color photographic developer for color formation. It would also be desirable to find lower cost colorants that can be incorporated into color photographic materials without the use of organic solvents so lower gelatin levels can be used to provide thinner film layers.
The present invention provides a silver halide color photographic element comprising a support having thereon at least one blue light sensitive layer, at least one green light sensitive layer, and at least one red light sensitive layer,
the color photographic element further comprising within at least one layer, a permanent, pre-formed yellow colorant that is present in an amount to provide a status M blue density greater than 0.003 per mg/m2.
In some embodiments of this invention, a silver halide color photographic element comprises a support having thereon, in order:
optionally, an antihalation layer,
one or more red light sensitive silver halide layers,
one or more green light sensitive silver halide layers, and
one or more blue light sensitive silver halide layers,
the color photographic element further comprising within at least one layer, a permanent, pre-formed yellow colorant that is present only in either the antihalation layer if present, or in a red light or green light sensitive silver halide layer, in an amount of from about 5 to about 200 mg/m2, and the colorant has an average particle size of from about 0.05 to about 1 μm, and
the yellow colorant is a pigment that is represented by one of the following Structures (I), (II), and (III):
wherein R1, R2, R3, and R4 each independently represent substituents,
wherein R5, R6, R7, and R8 each independently represent substituents, and
wherein R9, R10, R11, and R12 each independently represent substituents, or
the yellow colorant is a yellow dye that is represented by either Structure (IV) or (V):
wherein R13 represents an alkyl, cycloalkyl, or aryl group,
R14 represents an alkoxy, aryloxy, or NHR18NR18R19 group, or R14 represents the atom necessary to complete a 6-membered ring fused to the benzene ring,
R15 and R16 independently are alkyl, cycloalkyl, or aryl groups, or R15 and R16 can be joined together to form, along with the nitrogen to which they are attached, a 5- or 6-membered heterocyclic ring,
R17 represents hydrogen or a halogen, carbamoyl, alkoxycarbonyl, acyl, alkyl, cycloalkyl, aryl, or dialkylamino group,
R18 and R19 are independently alkyl, cycloalkyl, or aryl groups, or R18 and R19 may be joined together to form, along with the nitrogen to which they are attached, a 5- or 6-membered heterocyclic ring, and
wherein R represents an alkyl or aryl group,
R20 and R21, are independently hydrogen, or alkyl or aryl groups with the proviso that only one of R20 and R21 may be hydrogen at the same time, or R20 and R21 may be combined together with the nitrogen to which they are attached to form a heterocyclic ring system,
R22 is and alkyl or aryl groups,
n represents 0 or 1, and Z1 represents the atoms necessary to complete a 5- or 6-membered heterocyclic ring.
This invention also provides a method for providing a color negative image comprising:
A) imagewise exposing a silver halide color photographic element comprising a support having thereon at least one blue light sensitive silver halide layer, at least one green light sensitive silver halide layer, and at least one red light sensitive silver halide layer,
the color photographic element further comprising within at least one layer, a permanent, pre-formed yellow colorant that is present in an amount to provide a status M blue density greater than 0.003 per mg/m2, to provide a latent color image in the imaged element, and
B) contacting the imaged element with a color developing agent to provide a color negative image.
In many embodiments, the yellow colorants are incorporated into the photographic elements as solid particle dispersions that contain no permanent organic solvents and have a maximum absorption between 420 and 480 mm.
Color silver halide photographic elements incorporating the yellow colorants described herein have excellent sensitometry and acceptable color reproduction even though the yellow colorants are present at lower levels than normal to allow cost savings. In many embodiments, the colorants can be incorporated with minimal or no organic solvents and thus enable a reduced organic load that may lead to improved film physical properties.
The silver halide color photographic elements of this invention can be capture or origination elements such as color negative films or motion picture origination films, but they are not limited to such films.
Typically, the silver halide photographic element of the present invention is a color element which comprises a support, optionally bearing an antihalation layer comprising colloidal metallic silver or one or more antihalation dyes, or a layer on the backside of the support containing carbon black (remjet backing), a cyan dye image-forming unit comprised of at least one red-sensitive silver halide emulsion layer having associated therewith at least one cyan dye-forming coupler, a magenta dye image-forming unit comprising at least one green-sensitive silver halide emulsion layer having associated therewith at least one magenta dye-forming coupler, and a yellow dye image-forming unit comprising at least one blue-sensitive silver halide emulsion layer having associated therewith at least one yellow dye-forming coupler.
In another embodiment, it is also possible that the separate color forming layers are collapsed into one or more layers so that the element produces only neutral images. Any such imaging elements may be processed via thermal means only or can be processed using phenylenediamine-based developers. In most embodiments, the color silver halide elements are negative working silver halide elements. But in other embodiments, the silver halide photographic elements are capture or origination elements such as a color negative film or a motion picture origination film.
In one embodiment, the yellow colorants used in the practice of this invention are yellow dyes that are described in U.S. Pat. Nos. 4,743,582 (Evans et al.) and 4,866,029 (Evans et al.), the contents of which are incorporated by reference. These yellow dyes can be represented by the following Structures (IV) and (V):
wherein R13 represents a substituted or unsubstituted alkyl group having from 1 to about 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having from 5 to about 7 carbon atoms, or a substituted or unsubstituted aryl group having from 6 to about 10 carbon atoms.
R14 represents a substituted or unsubstituted alkoxy group having from 1 to about 10 carbon atoms, a substituted or unsubstituted aryloxy group having from 1 to about 10 carbon atoms, a NHR18NR18R19 group, or has the atoms necessary to complete a 6-membered ring fused to the benzene ring.
R15 and R16 are independently defined as for R13, or R15 and R16 can be joined together to form, along with the nitrogen to which they are attached, a 5- or 6-membered substituted or unsubstituted heterocyclic ring.
R17 represents hydrogen, or a halogen, carbamoyl, substituted or unsubstituted alkoxycarbonyl, acyl, substituted or unsubstituted alkyl group having from 1 to about 10 carbon atoms, substituted or unsubstituted cycloalkyl group having from 5 to about 7 carbon atoms, substituted or unsubstituted aryl group having from 6 to about 10 carbon atoms, or a substituted or unsubstituted dialkylamino group.
R18 and R19 are independently substituted or unsubstituted alkyl groups having from 1 to about 10 carbon atoms, substituted or unsubstituted cycloalkyl groups having from 5 to about 7 carbon atoms, or substituted or unsubstituted aryl groups having from 6 to about 10 carbon atoms, or R6 and R7 may be joined together to form, along with the nitrogen to which they are attached, a 5- or 6-membered substituted or unsubstituted heterocyclic ring.
Z represents hydrogen or the carbon or hetero atoms necessary to complete a 5- or 6-membered substituted or unsubstituted ring.
wherein R represents a substituted or unsubstituted alkyl group having from 1 to about 6 carbon atoms or a substituted or unsubstituted aryl group having from 6 to about 10 carbon atoms.
R20 and R21 independently represent hydrogen, with the proviso that only one of R20 and R21 may be hydrogen at the same time, a substituted or unsubstituted alkyl group having from 1 to about 6 carbon atoms, or a substituted or unsubstituted aryl group having from 6 to about 10 carbon atoms, or R20 and R21 may be combined together with the nitrogen to which they are attached to form a substituted or unsubstituted heterocyclic ring system.
R22 can be defined the same as, n represents 0 or 1, and Z1 represents the atoms necessary to complete a 5- or 6-membered substituted or unsubstituted heterocyclic ring.
In most embodiments of the invention, the yellow dyes or pigments are incorporated as solid particle dispersions that contain no permanent organic solvents and have a maximum absorption between 420 and 480 nm.
Some representative useful yellow pigments include but are not limited to, C. I. Pigment Orange 31, C. I. Pigment Orange 43, C. I. Pigment Yellow 3, C. I. Pigment Yellow 12, C. I. Pigment Yellow 13, C. I. Pigment Yellow 14, C. I. Pigment Yellow 15, C. I. Pigment Yellow 17, C. I. Pigment Yellow 65, C. I. Pigment Yellow 73, C. I. Pigment Yellow 74, C. I. Pigment Yellow 83, C. I. Pigment Yellow 93, C. I. Pigment Yellow 94, C. I. Pigment Yellow 97, C. I. Pigment Yellow 98, C. I. Pigment Yellow 120, C. I. Pigment Yellow 138, C. I. Pigment Yellow 151, C. I. Pigment Yellow 154, C. I. Pigment Yellow 155, C. I. Pigment Yellow 156, C. I. Pigment Yellow 175, C. I. Pigment Yellow 180, C. I. Pigment Yellow 181, C. I. Pigment Yellow 185, and C. I. Pigment Yellow 194.
In other embodiments, useful yellow pigments may be represented by the following Structures (I), (II), and (III):
wherein R1, R2, R3, and R4 independently represent various organic substituents that would be readily apparent to one skilled in the art.
wherein R5, R6, R7, and R8 independently represent various organic substituents that would be readily apparent to one skilled in the art.
wherein R9, R10, R11, and R12 independently represent various organic substituents that would be readily apparent to one skilled in the art.
In Structures (I)-(III), suitable groups for R1 through R12 include hydrogen, halide, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, an oxycarbonyl group (—OCOR), an ester of a carboxylic acid (—CO2R), a carbonamide group (—NR—COR), a carbamoyl group (—CONR2), a thioether group, a sulfoxide group, a sulfone group, a cyano group, a heterocyclic group, or a nitro group. Two adjacent R groups can be joined together to form a substituted or unsubstituted annulated aromatic ring. For example, R can be hydrogen, a substituted or unsubstituted alkyl group including methyl, ethyl, n-butyl, or t-butyl, or a substituted or unsubstituted aryl group such as phenyl, naphthyl or p-chlorophenyl.
The yellow dyes or pigments of the present invention are located in either a light sensitive or non-light sensitive layer in the imaging element. In some examples, they are located in a non-light sensitive layer such as a protective overcoat on top of imaging layers (and furthest from the support), an interlayer between an imaging layer and the protective overcoat, in an interlayer between any two imaging layers, an interlayer between an imaging layer and the antihalation layer, an antihalation layer, an interlayer between the antihalation layer and the support, or in a layer on the support opposite to the imaging layers. The same or different yellow colorants can be present in multiple non-light sensitive layers. These non-light sensitive layers can contain other components useful in those layers such as other dyes, scavengers and the like as one skilled in the art would readily understand. In many embodiments, the yellow colorants can be incorporated into non-light sensitive layers that are “below” (closer to the support) all of the blue light-sensitive silver halide layers.
In some embodiments, the colorant is located in a non-photosensitive layer that is located between the support and all red light sensitive silver halide layers.
In other embodiments, the same or different yellow colorants are incorporated into one or more light-sensitive silver halide layers as long as they are “below” the blue light sensitive layers. For example, the colorant can be located only in a red light sensitive silver halide layer.
The yellow colorants useful in the invention are not usually significantly water-soluble and should not diffuse into other layers upon long-term storage before processing nor diffuse out of the element intact during processing. They are typically incorporated as dispersion; that is, a finely divided state suspended in a medium. Suitable dispersions are either as a conventional oil-in-water dispersion (see U.S. Pat. Nos. 2,322,027, 2,698,794, 2,787,544, 2,801,170, and 2,801,171), a precipitated dispersion (see GB Publication 1,077,426 and U.S. Pat. Nos. 2,870,012 and 4,970,139), a polymeric or loaded latex dispersion (see U.S. Pat. Nos. 3,619,195 and 4,199,363), or as a solid particle dispersion (see U.S. Pat. Nos. 5,718,388, 5,500,331, and 5,478,705). Solid particle dispersions are particularly useful since they contain no permanent organic solvent or latex polymers, which require higher gelatin levels to maintain acceptable film physical properties.
The average particle size of the yellow dye or pigment, in dispersed form, is generally from about 0.01 to about 10 μm or typically from about 0.05 to about 1 μm.
The amount of yellow colorant (dye or pigment) used in a color negative film depends on the aim blue density values for the specific film and on the amount of other materials being used in the film that contribute blue density such as: image dyes, masking couplers, sensitizing dye stain, etc. It also depends, of course, on the blue light absorbing efficiency of the permanent yellow dye or pigment employed. The exact amount of additional blue density required cannot be predicted except on a case-by-case basis. Generally, for typical color negative silver halide photographic films, the permanent yellow colorant levels range from about 5 to about 500 mg/m2, or typically from about 5 to about 200 mg/m2, or from about 5 to about 100 mg/m2. Two or more colorants may be in combination to obtain the required spectral absorption.
Representative yellow colorants useful in this invention include but are not limited to:
Unless otherwise specifically stated, use of the term “substituted” or “substituent” in defining the yellow colorants means any group or atom other than hydrogen. Additionally, when the term “group” is used, it means that when a substituent group contains a substitutable hydrogen, it is also intended to encompass not only the substituents unsubstituted form, but also its form further substituted with any substituent group or groups as herein mentioned, so long as the substituent does not destroy properties necessary for photographic utility. Suitably, a substituent group may be halogen or may be bonded to the remainder of the molecule by an atom of carbon, silicon, oxygen, nitrogen, phosphorous, or sulfur. The substituent may be, for example, halogen (such as chlorine, bromine, or fluorine), nitro, hydroxyl, cyano, carboxyl, or groups which may be further substituted, such as alkyl, including straight or branched chain or cyclic alkyl, such as methyl, trifluoromethyl, ethyl, t-butyl, 3-(2,4-di-t-pentylphenoxy) propyl, and tetradecyl, alkenyl (such as ethylene and 2-butene), alkoxy (such as methoxy, ethoxy, propoxy, butoxy, 2-methoxyethoxy, sec-butoxy, hexyloxy, 2-ethylhexyloxy, tetradecyloxy, 2-(2,4-di-t-pentylphenoxy)ethoxy, and 2-dodecyloxyethoxy), aryl (such as phenyl, 4-t-butylphenyl, 2,4,6-trimethylphenyl, and naphthyl), aryloxy (such as phenoxy, 2-methylphenoxy, alpha- or beta-naphthyloxy, and 4-tolyloxy), carbonamido (such as acetamido, benzamido, butyramido, tetradecanamido, alpha-(2,4-di-t-pentyl-phenoxy)acetamido, alpha-(2,4-di-t-pentylphenoxy)butyramido, alpha-(3-pentadecylphenoxy)-hexanamido, alpha-(4-hydroxy-3-t-butylphenoxy)-tetradecanamido, 2-oxo-pyrrolidin-1-yl, 2-oxo-5-tetradecylpyrrolin-1-yl, N-methyltetradecanamido, N-succinimido, N-phthalimido, 2,5-dioxo-1-oxazolidinyl, 3-dodecyl-2,5-dioxo-1-imidazolyl, and N-acetyl-N-dodecylamino, ethoxycarbonylamino, phenoxycarbonylamino, benzyloxycarbonylamino, hexadecyloxycarbonylamino, 2,4-di-t-butylphenoxycarbonylamino, phenylcarbonylamino, 2,5-(di-t-pentylphenyl)carbonylamino, p-dodecyl-phenylcarbonylamino, p-tolylcarbonylamino, N-methylureido, N,N-dimethylureido, N-methyl-N-dodecylureido, N-hexadecylureido, N,N-dioctadecylureido, N,N-dioctyl-N′-ethylureido, N-phenylureido, N,N-diphenylureido, N-phenyl-N-p-tolylureido, N-(m-hexadecylphenyl)ureido, N,N-(2,5-di-t-pentylphenyl)-N′-ethylureido, and t-butylcarbonamido; sulfonamido, such as methylsulfonamido, benzenesulfonamido, p-tolylsulfonamido, p-dodecylbenzenesulfonamido, N-methyltetradecylsulfonamido, N,N-dipropyl-sulfamoylamino, and hexadecylsulfonamido; sulfamoyl, such as N-methylsulfamoyl, N-ethylsulfamoyl, N,N-dipropylsulfamoyl, N-hexadecylsulfamoyl, N,N-dimethylsulfamoyl; N-[3-(dodecyloxy)propyl]sulfamoyl, N-[4-(2,4-di-t-pentylphenoxy)butyl]sulfamoyl, N-methyl-N-tetradecylsulfamoyl, and N-dodecylsulfamoyl; carbamoyl, such as N-methylcarbamoyl, N,N-dibutylcarbamoyl, N-octadecylcarbamoyl, N-[4-(2,4-di-t-pentylphenoxy)butyl]carbamoyl, N-methyl-N-tetradecylcarbamoyl, and N,N-dioctylcarbamoyl; acyl, such as acetyl, (2,4-di-t-amylphenoxy)acetyl, phenoxycarbonyl, p-dodecyloxyphenoxycarbonyl methoxycarbonyl, butoxycarbonyl, tetradecyloxycarbonyl, ethoxycarbonyl, benrzyloxycarbonyl, 3-pentadecyloxycarbonyl, and dodecyloxycarbonyl; sulfonyl, such as methoxysulfonyl, octyloxysulfonyl, tetradecyloxysulfonyl, 2-ethylhexyloxysulfonyl, phenoxysulfonyl, 2,4-di-t-pentylphenoxysulfonyl, methylsulfonyl, octylsulfonyl, 2-ethylhexylsulfonyl, dodecylsulfonyl, hexadecylsulfonyl, phenylsulfonyl, 4-nonylphenylsulfonyl, and p-tolylsulfonyl; sulfonyloxy, such as dodecylsulfonyloxy, and hexadecylsulfonyloxy; sulfinyl, such as methylsulfinyl, octylsulfinyl, 2-ethylhexylsulfinyl, dodecylsulfinyl, hexadecylsulfinyl, phenylsulfinyl, 4-nonylphenylsulfinyl, and p-tolylsulfinyl; thio, such as ethylthio, octylthio, benzylthio, tetradecylthio, 2-(2,4-di-t-pentylphenoxy)ethylthio, phenylthio, 2-butoxy-5-t-octylphenylthio, and p-tolylthio; acyloxy, such as acetyloxy, benzoyloxy, octadecanoyloxy, p-dodecylamidobenzoyloxy, N-phenylcarbamoyloxy, N-ethylcarbamoyloxy, and cyclohexylcarbonyloxy; amine, such as phenylanilino, 2-chloroanilino, diethylamine, dodecylamine; imino, such as 1 (N-phenylimido)ethyl, N-succinimido or 3-benzylhydantoinyl; phosphate, such as dimethylphosphate and ethylbutylphosphate; phosphite, such as diethyl and dihexylphosphite; a heterocyclic group, a heterocyclic oxy group or a heterocyclic thio group, each of which may be substituted and that contains a 3- to 7-membered heterocyclic ring composed of carbon atoms and at least one hetero atom selected from the group consisting of oxygen, nitrogen and sulfur, such as 2-furyl, 2-thienyl, 2-benzimidazolyloxy or 2-benzothiazolyl, quaternary ammonium (such as triethylammonium), and silyloxy (such as trimethylsilyloxy).
If desired, the substituents may themselves be further substituted one or more times with the described substituent groups. The particular substituents used may be selected by those skilled in the art to attain the desired photographic properties for a specific application and can include, for example, hydrophobic groups, solubilizing groups, blocking groups, releasing or releasable groups, etc. When a molecule may have two or more substituents, the substituents may be joined together to form a ring such as a fused ring unless otherwise provided. Generally, the above groups and substituents thereof may include those having up to 48 carbon atoms, typically 1 to 36 carbon atoms and usually less than 24 carbon atoms, but greater numbers are possible depending on the particular substituents selected.
When the term “associated” is employed, it signifies that a reactive compound is in or adjacent to a specified layer where, during processing, it is capable of reacting with other components.
To control the migration of various components, it may be desirable to include a high molecular weight hydrophobe or “ballast” group in coupler molecules. Representative ballast groups include substituted or unsubstituted alkyl or aryl groups containing 8 to 42 carbon atoms. Representative substituents on such groups include but are not limited to, alkyl, aryl, alkoxy, aryloxy, alkylthio, hydroxy, halogen, alkoxycarbonyl, aryloxycarbonyl, carboxy, acyl, acyloxy, amino, anilino, carbonamido, carbamoyl, alkylsulfonyl, arylsulfonyl, sulfonamido, and sulfamoyl groups wherein the substituents typically contain 1 to 42 carbon atoms. Such substituents can also be further substituted.
The photographic elements of this invention can be single color elements or multicolor elements. Multicolor elements contain image dye-forming units sensitive to each of the three primary regions of the spectrum. Each unit can comprise a single emulsion layer or multiple emulsion layers sensitive to a given region of the spectrum. The layers of the element, including the layers of the image-forming units, can be arranged in various orders as known in the art. In an alternative format, the emulsions sensitive to each of the three primary regions of the spectrum can be disposed as a single segmented layer.
A typical multicolor photographic element comprises a support bearing a cyan dye image-forming unit comprised of at least one red-sensitive silver halide emulsion layer having associated therewith at least one cyan dye-forming coupler, a magenta dye image-forming unit comprising at least one green-sensitive silver halide emulsion layer having associated therewith at least one magenta dye-forming coupler, and a yellow dye image-forming unit comprising at least one blue-sensitive silver halide emulsion layer having associated therewith at least one yellow dye-forming coupler. The element can contain additional layers, such as filter layers, interlayers, overcoat layers, subbing layers, and the like. In one embodiment of the invention the emulsions containing the dye layered grains containing the antenna dye described herein are in the cyan and/or magenta dye forming units. Particularly useful is a silver halide photographic element wherein the silver halide photographic element further comprises a yellow filter dye in a layer between the support and the green sensitized layer closest to the support. A useful filer dye is shown below.
If desired, the photographic element can be used in conjunction with an applied magnetic layer as described in Research Disclosure, November 1992, Item 34390 published by Kenneth Mason Publications, Ltd., Dudley Annex, 12a North Street, Emsworth, Hampshire PO10 7DQ, ENGLAND, and as described in Hatsumi Kyoukai Koukai Gihou No. 94-6023, published Mar. 15, 1994, available from the Japanese Patent Office, the contents of which are incorporated herein by reference. When it is desired to employ the inventive materials in a small format film, Research Disclosure, June 1994, Item 36230, provides suitable embodiments. A useful support for small format film is annealed poly(ethylene naphthalate) or poly(ethylene terephthalate).
In the following discussion of suitable materials for use in the emulsions and elements of this invention, reference will be made to Research Disclosure, September 1996, Item 38957, available as described above, which will be identified hereafter by the term “Research Disclosure”. The contents of the Research Disclosure, including the patents and publications referenced therein, are incorporated herein by reference, and the Sections hereafter referred to are Sections of the Research Disclosure.
Except as provided, the silver halide emulsion-containing elements of this invention can be either negative-working or positive-working as indicated by the type of processing instructions (i.e. color negative, reversal, or direct positive processing) provided with the element. Usually the elements are negative working. Suitable emulsions and their preparation as well as methods of chemical and spectral sensitization are described in Sections I through V. Various additives such as UV dyes, brighteners, antifoggants, stabilizers, light absorbing and scattering materials, and physical property modifying addenda such as hardeners, coating aids, plasticizers, lubricants and matting agents are described, for example, in Sections II and VI through VIII. Color materials are described in Sections X through XIII. Suitable methods for incorporating couplers and dyes, including dispersions in organic solvents, are described in Section X(E). Scan facilitating is described in Section XIV. Supports, exposure, development systems, and processing methods and agents are described in Sections XV to XX. Certain desirable photographic elements and processing steps are described in Research Disclosure, Item 37038, February 1995.
The following discussion relates to coupling species present in the elements. Coupling-off groups are well known in the art. Such groups can determine the chemical equivalency of a coupler, i.e., whether it is a 2-equivalent or a 4-equivalent coupler, or modify the reactivity of the coupler. Such groups can advantageously affect the layer in which the coupler is coated, or other layers in the photographic recording material, by performing, after release from the coupler, functions such as dye formation, dye hue adjustment, development acceleration or inhibition, bleach acceleration or inhibition, electron transfer facilitation, color correction and the like.
The presence of hydrogen at the coupling site provides a 4-equivalent coupler, and the presence of another coupling-off group usually provides a 2-equivalent coupler. Representative classes of such coupling-off groups include, for example, chloro, alkoxy, aryloxy, hetero-oxy, sulfonyloxy, acyloxy, acyl, heterocyclyl such as oxazolidinyl or hydantoinyl, sulfonamido, mercaptotetrazole, benzothiazole, mercaptopropionic acid, phosphonyloxy, arylthio, and arylazo. These coupling-off groups are described in the art, for example, in U.S. Pat. Nos. 2,455,169, 3,227,551, 3,432,521, 3,476,563, 3,617,291, 3,880,661, 4,052,212 and 4,134,766, and in GB Patents and published application U.S. Pat. Nos. 1,466,728, 1,531,927, 1,533,039, 2,006,755A and 2,017,704A, the disclosures of which are incorporated herein by reference.
Image dye-forming couplers may be included in the elements such as couplers that form cyan dyes upon reaction with oxidized color developing agents which are described in such representative patents and publications as U.S. Pat. Nos. 2,367,531, 2,423,730, 2,474,293, 2,772,162, 2,895,826, 3,002,836, 3,034,892, 3,041,236, 4,333,999, and 4,883,746 and “Farbkuppler-eine LiteratureUbersicht,” published in Agfa Mitteilungen, Band III, pp. 156-175 (1961). Usually such couplers are phenols and naphthols that form cyan dyes on reaction with oxidized color developing agent.
Couplers that form magenta dyes upon reaction with oxidized color developing agent are described in such representative patents and publications as U.S. Pat. Nos. 2,311,082, 2,343,703, 2,369,489, 2,600,788, 2,908,573, 3,062,653, 3,152,896, 3,519,429, 3,758,309, and 4,540,654, and “Farbkuppler-eine LiteratureUbersicht,” published in Agfa Mitteilungen, Band III, pp. 126-156 (1961). Usually such couplers are pyrazolones, pyrazolotriazoles, or pyrazolobenzimidazoles that form magenta dyes upon reaction with oxidized color developing agents.
Couplers that form yellow dyes upon reaction with oxidized and color developing agent are described in such representative patents and publications as U.S. Pat. Nos. 2,298,443, 2,407,210, 2,875,057, 3,048,194, 3,265,506, 3,447,928, 4,022,620, 4,443,536, 4,840,884, 5,447,819, 5,457,004, 5,998,121, 6,132,944, and 6,569,612, and “Farbkuppler-eine LiteratureUbersicht,” published in Agfa Mitteilungen, Band III, pp. 112-126 (1961). Such couplers are typically open chain ketomethylene compounds.
Couplers that form colorless products upon reaction with oxidized color developing agent are described in such representative patents as GB Patent 861,138 and U.S. Pat. Nos. 3,632,345, 3,928,041, 3,958,993, and 3,961,959. Typically such couplers are cyclic carbonyl containing compounds that form colorless products on reaction with an oxidized color developing agent.
Couplers that form black dyes upon reaction with oxidized color developing agent are described in such representative patents as U.S. Pat. Nos. 1,939,231, 2,181,944, 2,333,106, and 4,126,461, German OLS Nos. 2,644,194 and 2,650,764. Typically, such couplers are resorcinols or m-aminophenols that form black or neutral products on reaction with oxidized color developing agent.
In addition to the foregoing, so-called “universal” or “washout” couplers may be employed. These couplers do not contribute to image dye-formation. Thus, for example, a naphthol having an unsubstituted carbamoyl or one substituted with a low molecular weight substituent at the 2- or 3-position may be employed. Couplers of this type are described, for example, in U.S. Pat. Nos. 5,026,628, 5,151,343, and 5,234,800.
It may be useful to use a combination of couplers any of which may contain known ballasts or coupling-off groups such as those described in U.S. Pat. Nos. 4,301,235, 4,853,319, and 4,351,897. The coupler may contain solubilizing groups such as described in U.S. Pat. No. 4,482,629. The coupler may also be used in association with “wrong” colored couplers (e.g. to adjust levels of interlayer correction) and, in color negative applications, with masking couplers such as those described in EP 213,490, Japanese Published Application 58-172,647, U.S. Pat. Nos. 2,983,608; 4,070,191, and 4,273,861, German Applications DE 2,706,117 and DE 2,643,965, GB Patent 1,530,272, and Japanese Published Application 58-113935. The masking couplers may be shifted or blocked, if desired.
Typically, couplers are incorporated in a silver halide emulsion layer in a mole ratio to silver of from about 0.05 to about 1.0 or from about 0.1 to about 0.5. Usually the couplers are dispersed in a high-boiling organic solvent in a weight ratio of solvent to coupler of 0.1 to 10.0 and typically 0.1 to 2.0 although dispersions using no permanent coupler solvent are sometimes employed.
The invention elements may be used in association with materials that accelerate or otherwise modify the processing steps e.g. of bleaching or fixing to improve the quality of the image. Bleach accelerator releasing couplers such as those described in EP 193,389 and 301,477, and U.S. Pat. Nos. 4,163,669, U.S. Pat. No. 4,865,956, and U.S. Pat. No. 4,923,784, may be useful. Also contemplated is use of the compositions in association with nucleating agents, development accelerators or their precursors (GB Patents 2,097,140 and 2,131,188); electron transfer agents (U.S. Pat. Nos. 4,859,578 and 4,912,025); antifogging and anti color-mixing agents such as derivatives of hydroquinones, aminophenols, amines, gallic acid; catechol; ascorbic acid; hydrazides; sulfonamidophenols; and non color-forming couplers.
The elements may also include filter dye layers comprising colloidal silver sol or yellow, cyan, and/or magenta filter dyes, either as oil-in-water dispersions, latex dispersions or as solid particle dispersions. Additionally, they may be used with “smearing” couplers (as described in U.S. Pat. No. 4,366,237; EP 96,570; U.S. Pat. No. 4,420,556; and U.S. Pat. No. 4,543,323.) Also, the compositions may be blocked or coated in protected form as described, for example, in Japanese Application 61/258,249 or U.S. Pat. No. 5,019,492.
The invention elements may further include one or more image-modifying compounds such as “Developer Inhibitor-Releasing” compounds (DIR's). DIR's useful in conjunction with the compositions of the invention are known in the art and examples are described in U.S. Pat. Nos. 3,137,578; 3,148,022; 3,148,062; 3,227,554; 3,384,657; 3,379,529; 3,615,506; 3,617,291; 3,620,746; 3,701,783; 3,733,201; 4,049,455; 4,095,984; 4,126,459; 4,149,886; 4,150,228; 4,211,562; 4,248,962; 4,259,437; 4,362,878; 4,409,323; 4,477,563; 4,782,012; 4,962,018; 4,500,634; 4,579,816; 4,607,004; 4,618,571; 4,678,739; 4,746,600; 4,746,601; 4,791,049; 4,857,447; 4,865,959; 4,880,342; 4,886,736; 4,937,179; 4,946,767; 4,948,716; 4,952,485; 4,956,269; 4,959,299; 4,966,835; 4,985,336 as well as in patent publications GB 1,560,240; GB 2,007,662; GB 2,032,914; GB 2,099,167; DE 2,842,063, DE 2,937,127; DE 3,636,824; DE 3,644,416 as well as the following European Patent Publications 272,573; 335,319; 336,411; 346, 899; 362, 870; 365,252; 365,346; 373,382; 376,212; 377,463; 378,236; 384,670; 396,486; 401,612; 401,613.
Such compounds are also disclosed in “Developer-Inhibitor-Releasing (DIR) Couplers for Color Photography,” C. R. Barr, J. R. Thirtle and P. W. Vittum in Photographic Science and Engineering, Vol. 13, p. 174 (1969), incorporated herein by reference. Generally, the developer inhibitor-releasing (DIR) couplers include a coupler moiety and an inhibitor coupling-off moiety (IN). The inhibitor-releasing couplers may be of the time-delayed type (DIAR couplers) which also include a timing moiety or chemical switch that produces a delayed release of inhibitor. Examples of typical inhibitor moieties are oxazoles, thiazoles, diazoles, triazoles, oxadiazoles, thiadiazoles, oxathiazoles, thiatriazoles, benzotriazoles, tetrazoles, benzimidazoles, indazoles, isoindazoles, mercaptotetrazoles, selenotetrazoles, mercaptobenzothiazoles, selenobenzothiazoles, mercaptobenzoxazoles, selenobenzoxazoles, mercaptobenzimidazoles, selenobenzimidazoles, benzodiazoles, mercaptooxazoles, mercaptothiadiazoles, mercaptothiazoles, mercaptotriazoles, mercaptooxadiazoles, mercaptodiazoles, mercaptooxathiazoles, telleurotetrazoles or benzisodiazoles. In some embodiments, the inhibitor moiety or group is selected from the following formulas:
wherein RI is selected from the group consisting of straight and branched alkyls of from 1 to about 8 carbon atoms, benzyl, phenyl, and alkoxy groups and such groups containing none, one or more than one such substituent; RII is selected from RI and —SRI; RIII is a straight or branched alkyl group of from 1 to about 5 carbon atoms and m is from 1 to 3; and RIV is selected from the group consisting of hydrogen, halogens and alkoxy, phenyl and carbonamido groups, —COORV and —NHCOORV wherein RV is selected from substituted and unsubstituted alkyl and aryl groups.
Although it is typical that the coupler moiety included in the developer inhibitor-releasing coupler forms an image dye corresponding to the layer in which it is located, it may also form a different color as one associated with a different film layer. It may also be useful that the coupler moiety included in the developer inhibitor-releasing coupler forms colorless products and/or products that wash out of the photographic material during processing (so-called “universal” couplers).
A compound such as a coupler may release a PUG directly upon reaction of the compound during processing, or indirectly through a timing or linking group. A timing group produces the time-delayed release of the PUG such groups using an intramolecular nucleophilic substitution reaction (U.S. Pat. No. 4,248,962); groups utilizing an electron transfer reaction along a conjugated system (U.S. Pat. Nos. 4,409,323, 4,421,845, and 4,861,701, Japanese Published Applications 57-188035; 58-98728; 58-209736; 58-209738); groups that function as a coupler or reducing agent after the coupler reaction (U.S. Pat. Nos. 4,438,193 and 4,618,571) and groups that combine the features describe above. It is typical that the timing group is of one of the formulas:
wherein IN is the inhibitor moiety, RVII is selected from the group consisting of nitro, cyano, alkylsulfonyl; sulfamoyl; and sulfonamido groups; a is 0 or 1; and RVI is selected from the group consisting of substituted and unsubstituted alkyl and phenyl groups. The oxygen atom of each timing group is bonded to the coupling-off position of the respective coupler moiety of the DIAR.
The timing or linking groups may also function by electron transfer down an unconjugated chain. Linking groups are known in the art under various names. Often they have been referred to as groups capable of utilizing a hemiacetal or iminoketal cleavage reaction or as groups capable of utilizing a cleavage reaction due to ester hydrolysis such as U.S. Pat. No. 4,546,073. This electron transfer down an unconjugated chain typically results in a relatively fast decomposition and the production of carbon dioxide, formaldehyde, or other low molecular weight by-products. The groups are exemplified in EP 464,612, EP 523,451, U.S. Pat. No. 4,146,396, Japanese Kokai 60-249148 and 60-249149.
Suitable developer inhibitor-releasing couplers for use in the present invention include, but are not limited to, the following:
Moreover, speed enhancing materials such as those described in U.S. Pat. Nos. 6,455,242, 6,426,180 6,350,564, and 6,319,660 may be used.
Unless indicated otherwise, compounds used directly in a photographic element can be added to a mixture containing silver halide before coating or, more suitably, be mixed with the silver halide just prior to or during coating. In either case, additional components like couplers, doctors, surfactants, hardeners and other materials that are typically present in such solutions may also be present at the same time. Coupling materials are generally not water-soluble and cannot be added directly to the solution. They may be added directly if dissolved in an organic water miscible solution such as methanol, acetone or the like or more preferably as a dispersion. A dispersion incorporates the material in a stable, finely divided state in a hydrophobic organic solvent (often referred to as a coupler solvent or permanent solvent) that is stabilized by suitable surfactants and surface active agents usually in combination with a binder or matrix such as gelatin. The dispersion may contain one or more permanent solvents that dissolve the material and maintain it in a liquid state. Some examples of suitable permanent solvents are tricresylphosphate, N,N-diethyllauramide, N,N-dibutyllauramide, p-dodecylphenol, dibutylphthalate, di-n-butyl sebacate, N-n-butylacetanilide, 9-octadecen-1-ol, ortho-methylphenyl benzoate, trioctylamine and 2-ethylhexylphosphate. Useful classes of solvents are carbonamides, phosphates, alcohols and esters. When a solvent is present, it is preferred that the weight ratio of compound to solvent be at least 1 to 0.5, or at least 1 to 1. The dispersion may require an auxiliary coupler solvent initially to dissolve the component but this is removed afterwards, usually either by evaporation or by washing with additional water. Some examples of suitable auxiliary coupler solvents are ethyl acetate, cyclohexanone and 2-(2-butoxyethoxy)ethyl acetate. The dispersion may also be stabilized by addition of polymeric materials to form stable latexes. Examples of suitable polymers for this use generally contain water-solubilizing groups or have regions of high hydrophilicity. Some examples of suitable dispersing agents or surfactants are Alkanol XC sodium dodecyl benzene sulfonate or saponin. The materials used in the invention may also be dispersed as an admixture with another component of the system such as a coupler or an oxidized developer scavenger so that both are present in the same oil droplet. It is also possible to incorporate the materials of the invention as a solid particle dispersion; that is, a slurry or suspension of finely ground (through mechanical means) compound. These solid particle dispersions may be additionally stabilized with surfactants and/or polymeric materials as known in the art. Also, additional permanent solvent may be added to the solid particle dispersion to help increase activity.
The silver halide used in the photographic elements may be silver iodobromide, silver bromide, silver chloride, silver chlorobromide, silver chloroiodobromide, and the like. The grain size of the silver halide may have any distribution known to be useful in photographic compositions, and may be either polydispersed or monodispersed.
The silver halide grains to be used in the invention may be prepared according to methods known in the art, such as those described in Research Disclosure I and The Theory of the Photographic Process, 4th edition, T. H. James, editor, Macmillan Publishing Co., New York, 1977. These include methods such as ammoniacal emulsion making, neutral or acidic emulsion making, and others known in the art. These methods generally involve mixing a water soluble silver salt with a water soluble halide salt in the presence of a protective colloid, and controlling the temperature, pAg, pH values, etc., at suitable values during formation of the silver halide by precipitation.
Especially useful in this invention are radiation-sensitive tabular grain silver halide emulsions. Tabular grains are silver halide grains having parallel major faces and an aspect ratio of at least 2, where aspect ratio is the ratio of grain equivalent circular diameter (ECD) divided by grain thickness (t). The equivalent circular diameter of a grain is the diameter of a circle having an average equal to the projected area of the grain. A tabular grain emulsion is one in which tabular grains account for greater than 50 percent of total grain projected area. In preferred tabular grain emulsions tabular grains account for at least 70 percent of total grain projected area and optimally at least 90 percent of total grain projected area. It is possible to prepare tabular grain emulsions in which substantially all (>97%) of the grain projected area is accounted for by tabular grains. The non-tabular grains in a tabular grain emulsion can take any convenient conventional form. When coprecipitated with the tabular grains, the non-tabular grains typically exhibit a silver halide composition as the tabular grains.
The tabular grain emulsions can be either high bromide or high chloride emulsions. High bromide emulsions are those in which silver bromide accounts for greater than 50 mole percent of total halide, based on silver. High chloride emulsions are those in which silver chloride accounts for greater than 50 mole percent of total halide, based on silver. Silver bromide and silver chloride both form a face centered cubic crystal lattice structure. This silver halide crystal lattice structure can accommodate all proportions of bromide and chloride ranging from silver bromide with no chloride present to silver chloride with no bromide present. Thus, silver bromide, silver chloride, silver bromochloride and silver chlorobromide tabular grain emulsions are all specifically contemplated. In naming grains and emulsions containing two or more halides, the halides are named in order of ascending concentrations. Usually high chloride and high bromide grains that contain bromide or chloride, respectively, contain the lower level halide in a more or less uniform distribution. However, non-uniform distributions of chloride and bromide are known, as illustrated by U.S. Pat. Nos. 5,508,160, 5,512,427, 5,372,927, and 5,460,934, the disclosures of which are here incorporated by reference.
It is recognized that the tabular grains can accommodate iodide up to its solubility limit in the face centered cubic crystal lattice structure of the grains. The solubility limit of iodide in a silver bromide crystal lattice structure is approximately 40 mole percent, based on silver. The solubility limit of iodide in a silver chloride crystal lattice structure is approximately 11 mole percent, based on silver. The exact limits of iodide incorporation can be somewhat higher or lower, depending upon the specific technique employed for silver halide grain preparation. In practice, useful photographic performance advantages can be realized with iodide concentrations as low as 0.1 mole percent, based on silver. It is usually typical to incorporate at least 0.5 (optimally at least 1.0) mole percent iodide, based on silver. Only low levels of iodide are required to realize significant emulsion speed increases. Higher levels of iodide are commonly incorporated to achieve other photographic effects, such as interimage effects. Overall iodide concentrations of up to 20 mole percent, based on silver, are well known, but it is generally preferred to limit iodide to 15 mole percent, more preferably 10 mole percent, or less, based on silver. Higher than needed iodide levels are generally avoided, since it is well recognized that iodide slows the rate of silver halide development.
Iodide can be uniformly or non-uniformly distributed within the tabular grains. Both uniform and nonuniform iodide concentrations are known to contribute to photographic speed. For maximum speed it is common practice to distribute iodide over a large portion of a tabular grain while increasing the local iodide concentration within a limited portion of the grain. It is also common practice to limit the concentration of iodide at the surface of the grains. Preferably the surface iodide concentration of the grains is less than 5 mole percent, based on silver. Surface iodide is the iodide that lies within 0.02 nm of the grain surface.
With iodide incorporation in the grains, the high chloride and high bromide tabular grain emulsions within the contemplated of the invention extend to silver iodobromide, silver iodochloride, silver iodochlorobromide and silver iodobromochloride tabular grain emulsions.
When tabular grain emulsions are spectrally sensitized, as herein contemplated, it is preferred to limit the average thickness of the tabular grains to less than 0.3 μm. For example, the average thickness of the tabular grains is less than 0.2 μm. In a specific preferred form the tabular grains are ultrathin—that is, their average thickness is less than 0.07 μm.
The useful average grain ECD of a tabular grain emulsion can range up to about 15 μm. Except for a very few high speed applications, the average grain ECD of a tabular grain emulsion is conventionally less than 10 μm, with the average grain ECD for most tabular grain emulsions being less than 5 μm.
The average aspect ratio of the tabular grain emulsions can vary widely, since it is quotient of ECD divided by grain thickness. Most tabular grain emulsions have average aspect ratios of greater than 5, with high (>8) average aspect ratio emulsions being generally preferred. Average aspect ratios ranging up to 50 are common, with average aspect ratios ranging up to 100 and even higher, being known.
The tabular grains can have parallel major faces that lie in either {100} or {111} crystal lattice planes. In other words, both {111} tabular grain emulsions and {100} tabular grain emulsions are within the specific contemplation of this invention. The {111} major faces of {111} tabular grains appear triangular or hexagonal in photomicrographs while the {100} major faces of {100} tabular grains appear square or rectangular.
High chloride {111} tabular grain emulsions are illustrated by U.S. Pat. Nos. 4,399,215, 4,414,306, 4,400,463, 4,713,323, 5,061,617, 5,178,997, 5,183,732, 5,185,239, 5,399,478, 5,411,852, 5,176,992, 5,178,998, 4,783,398, 4,952,508, 4,983,508, 4,804,621, 5,178,998, and 5,252,452. Ultrathin high chloride {111} tabular grain emulsions are illustrated by U.S. Pat. Nos. 5,271,858 and 5,389,509.
Since silver chloride grains are most stable in terms of crystal shape with {100} crystal faces, it is common practice to employ one or more grain growth modifiers during the formation of high chloride {111} tabular grain emulsions. Typically the grain growth modifier is displaced prior to or during subsequent spectral sensitization, as illustrated by U.S. Pat. Nos. 5,176,991, 5,176,992, 5,221,602, 5,298,387 and 5,298,388, the disclosures of which are here incorporated by reference.
Useful high chloride tabular grain emulsions are {100} tabular grain emulsions, as illustrated by the following patents, here incorporated by reference: Maskasky U.S. Pat. Nos. 5,264,337, 5,292,632, 5,275,930, 5,607,828 and 5,399,477, House et al U.S. Pat. No. 5,320,938, Brust et al U.S. Pat. No. 5,314,798, Szajewski et al U.S. Pat. No. 5,356,764, Chang et al U.S. Pat. Nos. 5,413,904, 5,663,041, and 5,744,297, Budz et al U.S. Pat. No. 5,451,490, Reed et al U.S. Pat. No. 5,695,922, Oyamada U.S. Pat. No. 5,593,821, Yamashita et al U.S. Pat. Nos. 5,641,620 and 5,652,088, Saitou et al U.S. Pat. No. 5,652,089, and Oyamada et al U.S. Pat. No. 5,665,530. Ultrathin high chloride {100} tabular grain emulsions can be prepared by nucleation in the presence of iodide, following the teaching of House et al and Chang et al, cited above. Since high chloride {100} tabular grains have {100} major faces and are, in most instances, entirely bounded by {100} grain faces, these grains exhibit a high degree of grain shape stability and do not require the presence of any grain growth modifier for the grains to remain in a tabular form following their precipitation.
In their most widely used form tabular grain emulsions are high bromide {111} tabular grain emulsions. Such emulsions are illustrated by Kofron et al U.S. Pat. No. 4,439,520, Wilgus et al U.S. Pat. No. 4,434,226, Solberg et al U.S. Pat. No. 4,433,048, Maskasky U.S. Pat. Nos. 4,435,501, 4,463,087 4,173,320 and 5,411,851 5,418,125, 5,492,801, 5,604,085, 5,620,840, 5,693,459, 5,733,718, Daubendiek et al U.S. Pat. Nos. 4,414,310 and 4,914,014, Sowinski et al U.S. Pat. No. 4,656,122, Piggin et al U.S. Pat. Nos. 5,061,616 and 5,061,609, Tsaur et al U.S. Pat. Nos. 5,147,771, '772, '773, 5,171,659 and 5,252,453, Black et al 5,219,720 and 5,334,495, Delton U.S. Pat. Nos. 5,310,644, 5,372,927 and 5,460,934, Wen U.S. Pat. No. 5,470,698, Fenton et al U.S. Pat. No. 5,476,760, Eshelman et al U.S. Pat. Nos. 5,612,175, 5,612,176 and 5,614,359, and Irving et al U.S. Pat. Nos. 5,695,923, 5,728,515 and 5,667,954, Bell et al U.S. Pat. No. 5,132,203, Brust U.S. Pat. Nos. 5,248,587 and 5,763,151, Chaffee et al U.S. Pat. No. 5,358,840, Deaton et al U.S. Pat. No. 5,726,007, King et al U.S. Pat. No. 5,518,872, Levy et al U.S. Pat. No. 5,612,177, Mignot et al U.S. Pat. No. 5,484,697, Olm et al U.S. Pat. No. 5,576,172, Reed et al U.S. Pat. Nos. 5,604,086 and 5,698,387.
Ultrathin high bromide {111} tabular grain emulsions are illustrated by Daubendiek et al U.S. Pat. Nos. 4,672,027, 4,693,964, 5,494,789, 5,503,971 and 5,576,168, Antoniades et al U.S. Pat. No. 5,250,403, Olm et al U.S. Pat. No. 5,503,970, Deaton et al U.S. Pat. No. 5,582,965, and Maskasky U.S. Pat. No. 5,667,955. High bromide {100} tabular grain emulsions are illustrated by Mignot U.S. Pat. Nos. 4,386,156 and 5,386,156.
High bromide {100} tabular grain emulsions are known, as illustrated by Mignot U.S. Pat. No. 4,386,156 and Gourlaouen et al U.S. Pat. No. 5,726,006.
In many of the patents listed above (starting with Kofron et al, Wilgus et al and Solberg et al, cited above) speed increases without accompanying increases in granularity are realized by the rapid (a.k.a. dump) addition of iodide for a portion of grain growth. Chang et al U.S. Pat. No. 5,314,793 correlates rapid iodide addition with crystal lattice disruptions observable by stimulated X-ray emission profiles.
Localized peripheral incorporations of higher iodide concentrations can also be created by halide conversion. By controlling the conditions of halide conversion by iodide, differences in peripheral iodide concentrations at the grain corners and elsewhere along the edges can be realized. For example, Fenton et al U.S. Pat. No. 5,476,76 discloses lower iodide concentrations at the corners of the tabular grains than elsewhere along their edges. Jagannathan et al U.S. Pat. Nos. 5,723,278 and 5,736,312 disclose halide conversion by iodide in the corner regions of tabular grains.
Crystal lattice dislocations, although seldom specifically discussed, are a common occurrence in tabular grains. For example, examinations of the earliest reported high aspect ratio tabular grain emulsions (e.g., those of Kofron et al, Wilgus et al and Solberg et al, cited above) reveal high levels of crystal lattice dislocations. Black et al U.S. Pat. No. 5,709,988 correlates the presence of peripheral crystal lattice dislocations in tabular grains with improved speed-granularity relationships. Ikeda et al U.S. Pat. No. 4,806,461 advocates employing tabular grain emulsions in which at least 50 percent of the tabular grains contain 10 or more dislocations. For improving speed-granularity characteristics, it is preferred that at least 70 percent and optimally at least 90 percent of the tabular grains contain 10 or more peripheral crystal lattice dislocations.
The silver halide emulsion may comprise tabular silver halide grains having surface chemical sensitization sites including at least one silver salt forming epitaxial junction with the tabular grains and being restricted to those portions of the tabular grains located nearest peripheral edges.
The silver halide tabular grains of the photographic material may be prepared with a maximum surface iodide concentration along the edges and a lower surface iodide concentration within the corners than elsewhere along the edges.
In the course of grain precipitation one or more dopants (grain occlusions other than silver and halide) can be introduced to modify grain properties. For example, any of the various conventional dopants disclosed in Research Disclosure, Item 38957, Section I. Emulsion grains and their preparation, sub-section G. Grain modifying conditions and adjustments, paragraphs (3), (4) and (5), can be present in the emulsions of the invention. Especially useful dopants are disclosed by Marchetti et al., U.S. Pat. No. 4,937,180, and Johnson et al., U.S. Pat. No. 5,164,292. In addition it is specifically contemplated to dope the grains with transition metal hexacoordination complexes containing one or more organic ligands, as taught by Olm et al U.S. Pat. No. 5,360,712, the disclosure of which is here incorporated by reference.
It is specifically contemplated to incorporate in the face centered cubic crystal lattice of the grains a dopant capable of increasing imaging speed by forming a shallow electron trap (hereinafter also referred to as a SET) as discussed in Research Disclosure Item 36736 published November 1994, here incorporated by reference. SET dopants are known to be effective to reduce reciprocity failure. In particular the use of Ir+3 or Ir+4 hexacoordination complexes as SET dopants is advantageous.
Iridium dopants that are ineffective to provide shallow electron traps (non-SET dopants) can also be incorporated into the grains of the silver halide grain emulsions to reduce reciprocity failure.
The contrast of the photographic element can be further increased by doping the grains with a hexacoordination complex containing a nitrosyl or thionitrosyl ligand (NZ dopants) as disclosed in U.S. Pat. No. 4,933,272 (McDugle et al.), the disclosure of which is here incorporated by reference.
The emulsions can be surface-sensitive emulsions, i.e., emulsions that form latent images primarily on the surfaces of the silver halide grains, or the emulsions can form internal latent images predominantly in the interior of the silver halide grains. The emulsions can be negative-working emulsions, such as surface-sensitive emulsions or unfogged internal latent image-forming emulsions, or direct-positive emulsions of the unfogged, internal latent image-forming type, which are positive-working when development is conducted with uniform light exposure or in the presence of a nucleating agent. Tabular grain emulsions of the latter type are illustrated by U.S. Pat. No. 4,504,570.
Photographic elements can be exposed to actinic radiation, typically in the visible region of the spectrum, to form a latent image and can then be processed to form a visible dye image. Processing to form a visible dye image includes the step of contacting the element with a color developing agent to reduce developable silver halide and oxidize the color developing agent. Oxidized color developing agent in turn reacts with the coupler to yield a dye.
With negative-working silver halide, the processing step described above provides a negative image. One type of such element, referred to as a color negative film, is designed for image capture. Preferably the materials of the invention are silver halide color negative films. Speed (the sensitivity of the element to low light conditions) is usually critical to obtaining sufficient image in such elements. Such elements are typically silver bromoiodide emulsions coated on a transparent support and are sold packaged with instructions to process in known color negative processes such as the Kodak C-41 process as described in The British Journal of Photography Annual of 1988, pages 191-198. If a color negative film element is to be subsequently employed to generate a viewable projection print as for a motion picture, a process such as the Kodak ECN-2 process described in the H-24 Manual available from Eastman Kodak Co. may be employed to provide the color negative image on a transparent support. Color negative development times are typically 3′ 15″ or less and desirably 90 or even 60 seconds or less.
The photographic element of the invention can be incorporated into exposure structures intended for repeated use or exposure structures intended for limited use, variously referred to by names such as “one time use camera”, “single use cameras”, “lens with film”, or “photosensitive material package units”.
Useful color developing agents are p-phenylenediamines such as 4-amino-N,N-diethylaniline hydrochloride, 4-amino-3-methyl-N,N-diethylaniline hydrochloride, 4-amino-3-methyl-N-ethyl-N-(2-methanesulfonamidoethyl)aniline sesquisulfate hydrate, 4-amino-3-methyl-N-ethyl-N-(2-hydroxyethyl)aniline sulfate, 4-amino-3-(2-methanesulfonamidoethyl)-N,N-diethylaniline hydrochloride and 4-amino-N-ethyl-N-(2-methoxyethyl)-m-toluidine di-p-toluene sulfonic acid.
Development is usually followed by the conventional steps of at least bleaching, fixing, or bleach-fixing, to remove silver or silver halide, washing, and drying. Useful color development processes and chemistries are also described for example, in U.S. Pat. Nos. 6,022,676 (Schmittou et al.), 6,410,215 (Cole), 6,482,579 (Kapecki et al.), and 6,998,227 (Youngblood et al.).
The following examples are intended to illustrate, but not to limit the invention:
An oil-in-water dispersion of comparison yellow dye CD-1 in coupler solvent S-1 (tricresylphosphate) at a dye/solvent ratio of 1:0.75 was mixed with additional dispersions of other photographically useful compounds, gelatin, surfactants, and distilled water and was coated on a cellulose acetate butyrate support as Coating 1. Component laydowns are given in mg/m2 in Table I.
BVSM hardener at 1.75% of total gelatin
BVSM=1,1′-(methylene(sulfonyl))bis-ethane (CAS 3278-22-6)
Chemical structures of materials used in this coating format are given below:
After hardening, samples of each of the films were processed using KODAK Flexicolor C-41 and their status M blue densities were measured.
Additional experimental coating variations, in which alternative yellow dyes were substituted for YD-1 and coated at 50 mg/m2, are described in Table II below.
The results in Table II illustrate that the yellow dyes and pigments of the present invention provide higher status M blue densities and greater blue densities per coated level of dye than the comparison yellow dye of the prior art.
The structure of comparison yellow dye CD-1 is given below:
Multilayer films of this invention were produced by coating the following layers on a cellulose triacetate film support (coverage are in grams per meter squared, emulsion sizes as determined by the disc centrifuge method and are reported in diameter×thickness in micrometers). Surfactants, coating aids, emulsion addenda (including 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene), sequestrants, thickeners, lubricants and tinting dyes were added to the appropriate layers as is common in the art. Couplers and other non-water soluble materials were added as conventional oil-in-water dispersions as known in the art.
Multilayer Photographic Film Format:
Layer 1 (Antihalation layer): gelatin at 2.01, colloidal metallic silver at 0.300; ILS-1 at 0.160; DYE-2 at 0.067; YD-1 at 0.028; Potassium iodide at 0.007 and a mixture of UV-2 and UV-3 at 0.083 each
Layer 2 (Slow cyan layer): a blend of two red-sensitized tabular silver iodobromide emulsions: (i) a 0.72×0.11, 4.5% I (sensitized with a mixture of RSD-2 and RSD-3) at 0.055, (ii) a 0.55×0.08, 1.5% 1 (sensitized with a mixture of RSD-1 and RSD-2) at 0.150; cyan dye-forming couplers C-1 at 0.170, C-2 at 0.056 and C-3 at 0.090; bleach accelerator releasing coupler B-1 at 0.068; image modifier D-1 at 0.008; D-2 at 0.024; masking coupler MC-1 at 0.020 and gelatin at 1.50.
Layer 3 (Mid cyan layer): a blend of two red-sensitized (both with a mixture of RSD-2 and RSD-3) iodobromide tabular emulsions: (i) a 1.25×0.12, 3.7% I at 0.060 and (ii) a 0.72×0.11 μm, 4.5 mole % I at 0.132; C-1 at 0.125; C-2 at 0.041; Y-1 at 0.090; B-1 at 0.017; D-1 at 0.040; D-2 at 0.019; MC-1 at 0.018; B-1 at 0.017 and gelatin at 0.82.
Layer 4 (Fast cyan layer): a blend of two red-sensitized (both with a mixture of RSD-2 and RSD-3) iodobromide tabular emulsions: (i) 2.0×0.13 μm, 3.7 mole % I at 0.070 and (ii) 1.25×0.12 μm, 3.7 mole % I at 0.230; C-1 at 0.045; C-2 at 0.015, C-3 at 0.024; D-2 at 0.013; MC-1 at 0.019 and gelatin at 0.45.
Layer 5 (Interlayer): ILS-1 at 0.066; S-1 at 0.003 and gelatin at 0.446.
Layer 6 (Slow magenta layer): a blend of two green sensitized (both with a mixture of GSD-1 and GSD-2) emulsions: (i) 0.36×0.13 μm, 4.8 mole % iodide at 0.065 and (ii) 0.55×0.08, 1.5 mole % iodide at 0.081; magenta dye-forming coupler M-1 at 0.135; MC-2 at 0.125; yellow image modifier D-3 at 0.024 and gelatin at 1.063.
Layer 7 (Mid magenta layer): a blend of two green-sensitized (both with a mixture of GSD-1 and GSD-2) silver iodobromide tabular emulsions: (i) 0.36×0.13 μm, 4.8 mole % iodide at 0.180 and (ii) 0.78×0.11 microns, 4.5 mole % iodide at 0.130; M-1 at 0.062; MC-2 at 0.050; D-3 at 0.020; D-1 at 0.010; ILS-2 at 0.011 and gelatin at 0.981.
Layer 8 (Fast magenta layer): a blend of two green-sensitized silver iodobromide tabular emulsions: (i) 1.27×0.13 μm, 6 mole % iodide (sensitized with a mixture of GSD-1, GSD-2 and GSD-3) at 0.100 and (ii) 0.78×0.11 microns, 4.5 mole % iodide (sensitized with a mixture of GSD-1 and GSD-2 at 0.050; addenda H-1 at 0.010; M-1 at 0.030; MC-2 at 0.033, B-1 at 0.003 and gelatin at 1.063.
Layer 9 (Interlayer): ILS-1 at 0.072, S-1 at 0.040 and gelatin at 0.490.
Layer 10 (Slow yellow layer): A blend of three blue sensitized emulsions: (i) 1.606×0.13 μm, 3 mole % iodide (sensitized with BSD-1) at 0.030, (ii) 0.75×0.13 microns, 3 mole % iodide (sensitized with a mixture of BSD-1 and BSD-2) at 0.125 and (iii) 0.38×0.12 microns, 3 mole % iodide (sensitized with a mixture of BSD-1 and BSD-2) at 0.205; Y-1 at 0.970; D-6 at 0.033; D-1 at 0.016; B-1 at 0.010 and gelatin at 1.611 with bis(vinylsulfonyl)methane hardener at 1.8% of total gelatin weight is streamed into this layer during application to the support.
Layer 11 (Fast yellow layer): A blend of two blue sensitized emulsions: (i) 2.8×0.12 μm, 4.2 mole % iodide (sensitized with a mixture of BSD-1 and BSD-2) at 0.110 and (ii) 1.60×0.13 microns, 3 mole % iodide (sensitized with BSD-1) at 0.115; Y-1 at 0.260; D-6 at 0.088; B-1 at 0.005 and gelatin at 0.650.
Layer 12 (UV Filter Layer): silver bromide Lippman emulsion at 0.210; UV-2 and UV-3 both at 0.115 and gelatin at 0.560.
Layer 13 (Protective overcoat): a blend of permanent and soluble Matte beads and gelatin at 0.867.
Formulas for materials used in the above formats are as follows:
Samples ML-2 and ML-3 were prepared as ML-1 except for the changes indicated ML-2=ML 1 except omit YD-1 add 0.106 CD-1 to layer 1 mL-3=ML 1 except omit YD-1 from layer 1
The above multilayer coatings were given a neutral stepped exposure, followed by processing in the KODAK FLEXICOLOR™ (C-41) process as described in British Journal of Photography Annual, 1988, pp 196-198. Red, Green and Blue density were read at minimum density using status M filters. The Green and Red densities were virtually equivalent for all of the multilayer examples in the following Table III.
It is well known that physical properties of color photographic films, such as adhesion and scratch resistance, improve as the ratio of gelatin to organic materials is increased. This ratio is sometimes referred to as the “gel/junk” ratio. This ratio can be increased by increasing the gelatin, but this increases cost. It is more desirable to reduce the amount of organic materials if possible but quite often this is limited by the solubility of the materials of interest. The present invention overcomes this limitation by enabling the introduction of the yellow colorant without the use of any additional organic solvent.
The “gel/junk” ratio is a simple calculation, and equals the gelatin level of each layer divided by the sum of the coverage of all organic materials (for example, color-forming couplers, coupler solvents, and other materials) except gelatin in that layer.
The above multilayer coatings were given a neutral stepped exposure, followed by processing in the KODAK FLEXICOLOR™ (C-41) process as described in British Journal of Photography Annual, 1988, pp 196-198. Red, Green and Blue density were read using status M filters. The Green and Red densities were virtually equivalent for all of the multilayer examples in his table.
The results in Table III illustrate that use of the yellow colorant according to this invention provided higher blue density per coated level of colorant than the comparison yellow dye.
The invention has been described in detail with particular reference to certain preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention
| Number | Name | Date | Kind |
|---|---|---|---|
| 5304454 | Yokoya et al. | Apr 1994 | A |
| 5326667 | Yokoya et al. | Jul 1994 | A |
| 5328800 | Yokoya et al. | Jul 1994 | A |
| 5612167 | Yokoya et al. | Mar 1997 | A |
| 5714303 | Yokoya et al. | Feb 1998 | A |
| 6033838 | Fitterman et al. | Mar 2000 | A |
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| 7368230 | Hosokawa et al. | May 2008 | B2 |
