This invention relates to a silver halide photographic element containing a phenolic coupler with a carbonamido group in the 2-position and a carbonamido group in the 5-position the latter bearing a strong electron withdrawing group(s), said phenolic coupler capable of forming a magenta dye when reacted with oxidized photographic color developer.
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 expanded coupler types, improved color reproducibility and image dye stability. However, further coupler types and improvements are needed. 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. More recently, cyan couplers based on 2,5-diacylaminophenols in Lau et al., in U.S. Pat. No. 5,686,235, and Begley et al., in U.S. Pat. Nos. 6,387,606, 6,251,575, 6,207,363, 6,201,125, 6,197,492, 6,197,491, 6,197,490, 6,197,489, 6,194,132, 6,190,850, 6,180,331, 6,180,328, and 6,132,947 form highly desirable cyan narrow bandwidth dyes with improved light and dark stabilities, and less unwanted green absorption. On the other hand, magenta couplers are generally formed from pyrazolones and pyrazolotriazoles as described, for example in U.S. Pat. Nos. 5,262,292, 5,925,503, 5,972,587, 5,985,533 and 4,540,654. Both the cyan and magenta 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.
The hue of a dye is a function of both the shape and the position of its spectral absorption band. Traditionally, the magenta dyes used in color photographic papers have had nearly symmetrical absorption bands centered in the region of 530 to 560 nm, more typically in the region of 540 to 555 nm. Such dyes have rather large amounts of unwanted absorption in the blue and red regions of the spectrum.
More desirable would be a dye whose absorption band could be adjusted so as to tune the slope of the curve on both the short and long wavelength sides of the absorption curve. The half-bandwidth on the short side of the curve, also called the left half-bandwidth or LBW, and the half-bandwidth on the long side of the curve, also called the right half-bandwidth or RBW are both desirably narrowed. Such a dye would suitably peak at 550 nm, 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 cyan and yellow dyes with which it is associated.
Phenolic couplers invariably react with oxidized color developer to form cyan dyes exhibiting a range of absorption maxima, bandwidths and general curve shapes. The xcexmax, or wavelength of maximum absorption, for phenolic couplers usually lies in the red region of the visible spectrum in the range of 590 nm to 680 nm, but more usually between 620 nm and 650 nm. These couplers are highly desirable in the photographic industry because the starting materials needed to prepare them are readily available, they are inexpensive, and they provide dyes with such a wide range of features to choose from.
The introduction of changes to the phenolic coupler, which would provide dyes other than cyan when reacted with oxidized color developer, would be highly desirable. In particular, shifting the absorption curve of the dye or its xcexmax from the red region of the visible spectrum 590-680 nm, into the green region of the spectrum, 530-585 nm, to provide a magenta dye would be very advantageous. Readily available and inexpensive phenols would then provide a common source of two of the dyes used in the photographic industry with a significant cost savings, thus eliminating the need for the more expensive and more difficult to manufacture magenta dye yielding pyrazolone and pyrazolotriazole based couplers.
One way to shift the xcexmax of a dye is through the careful selection and location of substituents on the dye""s chromophore. Although individual electron-withdrawing or electron-donating substituents directly attached to the chromophore of a dye is known to affect the dye hue, by shifting the xcexmax to either shorter or longer wavelength, such shifts are usually small. Shifts induced by electron-withdrawing or electron-donating substituents rarely move the dye absorption from one region of the visible spectrum to another. However, the effect of introducing a group of carefully selected electron-withdrawing or electron-donating substituents at specific locations on the dye is unknown.
Begley et al., in co-pending application Ser. No. 10/060,691 filed Jan. 30, 2002, Infrared Couplers for Incorporating and Recovering Metadata, discloses couplers with a 5-carbonamido group, specifically a substituted 5-benzoamido group containing 1 to 4 fluoro substituents. Begley et al., teaches infrared couplers with no reference to phenolic magenta couplers.
Ishii et al., U.S. Pat. No. 5,585,227 suggests certain phenolic couplers having electron withdrawing groups and teaches the use of such couplers as cyan couplers for use in a red-sensitive layer for reducing stains upon processing. There is no indication that said couplers are useful as magenta dye forming couplers in the green-sensitive layer.
Iwasaki et al., U.S. Pat. No. 6,156,489 suggests certain phenolic couplers having an electron withdrawing group with a branched xcex1-alkyl substituent on the 2-carbonamido group and teaches the use of such couplers as cyan couplers for use in a red-sensitive layer for the production of black-and-white or monochromatic images by controlling the relative rates of reaction of couplers in the red, green and blue-sensitive layers. Again, there is no indication that said couplers are useful as magenta dye forming couplers in the green-sensitive layer.
Lau et al., U.S. Pat. No. 5,962,198 suggests certain couplers having a pentafluorophenyl group and teaches their use in the formation of cyan dyes with low wavelength of maximum absorbance, narrow bandwidth and low unwanted green absorbance. Coupler IC-6 in Lau et al., column 9, teaches its use to produce a cyan dye with a xcexmax of 630 nm, column 40, line 62, and is used in a red-sensitive layer.
Masukawa, E.P. 296,780 suggests certain couplers having a pentafluorophenyl group and teaches their use in the formation of cyan dyes.
D.E. 3,045,745 and D.E. 2,529,991 refer to fluorinated alkyl groups on phenolic couplers used to generate cyan dyes.
The problem to be solved is to provide an alternative photographic element, compound, and process, employing a phenolic coupler which forms a magenta dye when reacted with an oxidized color photographic developer.
The invention provides a photographic element comprising a light-sensitive silver halide emulsion layer having associated therewith a phenolic xe2x80x9cNB magenta couplerxe2x80x9d having the formula:
wherein:
the term xe2x80x9cNB magenta couplerxe2x80x9d represents a coupler of formula (I) that forms a magenta dye with the developer 4-amino-3-methyl-N-ethyl-N-(2-methanesulfonamidoethyl) aniline sesquisulfate hydrate for which the maximum absorption of the dye upon spin coating is in the range from 520 to 590 nm and the left bandwidth (LBW) or the right bandwidth (RBW) using spin-coating, is at least 5 nm less than that of the same dye in solution form;
R1 is a heterocyclic, carbocyclic, or alkenyl group with substituents of sufficient electron withdrawing capacity to obtain a spin-coated dye as described in the preceding subparagraph that exhibits a maximum absorption in the range of 520-590 nm;
Y is H or a coupling-off group;
each Z* is an independently selected substituent group where p is independently 0 to 2;
R2 is a heterocyclic or carbocyclic ring group, or an alkyl group;
provided that when R2 is an alkyl group with an xcex1-alkyl substituent, said xcex1-alkyl substituent is unbranched; and
provided further that the combined sum of the aliphatic carbon atoms in R1, R2 and all Z* is at least 8.
The invention also provides a coupler of formula (I) and an imaging method employing the element. The magenta dye formed in the element exhibits an advantageous dye hue in having reduced levels of unwanted absorption on either or both, the short wavelength or long wavelength sides, of the spectrum and the magenta coupler of the invention exhibits advantageous solubility in photographic coupler solvents.
The invention may be generally described as summarized above. The coupler is an xe2x80x9cNB magenta couplerxe2x80x9d which is a narrow bandwidth coupler of formula (I) having substituents so that the maximum absorption of the dye upon spin coating is in the range from 520 to 590 nm and there is a reduction in the left or right bandwidths, or in both, upon spin-coating versus solution form of at least 5 nm. In accordance with the procedure, a dye is formed by combining the coupler and the developer 4-amino-3-methyl-N-ethyl-N-(2-methanesulfonamidoethyl) aniline sesquisulfate hydrate. If the left bandwidth (LBW) or the right bandwidth (RBW) of its absorption spectrum upon xe2x80x9cspin coatingxe2x80x9d a 3% w/v solution of the dye in ethyl acetate or other suitable solvent with 3% w/v of di-n-butyl sebacate coupler solvent is at least 5 nm less than the LBW or the RBW for a solution of the same dye in acetonitrile, then the coupler is an xe2x80x9cNB magenta couplerxe2x80x9d. The LBW of the spectral curve for a dye is the distance between the left side of the spectral curve and the wavelength of maximum absorption measured at a density of half the maximum. The RBW of the spectral curve is the distance between the wavelength of maximum absorption and the right side of the spectral curve measured at a density of half the maximum.
Although the specific developer identified above is used for the NB magenta coupler determination, it is understood that the effect with this developer is predictive and that the element and the couplers useful in the invention may be processed with any color developer such as the conventional p-phenylene diamine developers.
The xe2x80x9cspin coatingxe2x80x9d sample is prepared by first preparing a 3% w/v solution of the dye in ethyl acetate or other suitable solvent with 3% w/v of di-n-butyl sebacate coupler solvent. If the dye is insoluble, dissolution is achieved by the addition of methylene chloride or tetrahydrofuran. The solution is filtered and 0.1-0.2 ml is applied to a clear polyethylene terephthalate support (approximately 4 cmxc3x974 cm) and spun at 4,000 RPM using the Spin Coating equipment, Model No. EC101, available from Headway Research Inc., Garland Tex. The transmission spectra of the so prepared dye samples are then recorded.
Preferred xe2x80x9cNB magenta couplersxe2x80x9d form a dye which has a LBW or a RBW of the absorption spectra upon xe2x80x9cspin coatingxe2x80x9d a sample of the dye in di-n-butyl sebacate at least 5 nm, preferably at least 10 nm, 15 nm or 20 nm, but can fall in the range of between 5 to 40 nm less than that of the same dye in acetonitrile solution.
As used herein the term xe2x80x9csolublexe2x80x9d with reference to a coupler means that the coupler has a low tendency to crystallize out of the dispersion during 7 day aging and desirably for a further extended period of 48 hours at 45xc2x0 C.
The following limitations apply to formulae (I)-(IX) as appropriate:
Y is H or a coupling-off group. Coupling-off groups are more fully described hereinafter. Typically, Y is H, halogen such as chloro, aryloxy such as phenoxy, or alkoxy or a heterocyclic group such as those described below. Y can also be a photographically useful coupling off group or PUG, useful for the release of chemical fragments to modify the photographic image, such as development inhibitors, bleach accelerators and the like. 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, and color correction
R1 is a heterocyclic, carbocyclic, or alkenyl group with substituents of sufficient electron withdrawing capacity to obtain a spin-coated dye as described in the preceding paragraph that exhibits a maximum absorption in the range of 520-590 nm. R2 is an aryl, heterocyclic, or alkyl group. When R2 is an alkyl group with an xcex1-alkyl substituent, said xcex1-alkyl substituent is unbranched. Desirably, R1 is an aryl group with electron withdrawing groups having a sum total of Hammett Sigma values greater than 0.8. Hammett Sigma values may be found in C. Hansch and A. J. Leo, Substituent Constants for Correlation Analysis in Chemistry and Biology, Wiley, New York, N.Y. (1979). Examples of groups suitable for R1 or W1 are chloro, fluoro, cyano, carboalkoxy, acyl, sulfonyl and trifluoromethyl, and can be the same or a mix of different groups, provided that the sum total of the Hammett Sigma values is greater than 0.8. When R1 or W1 is a heterocyclic group the heteroatom or atoms comprising the heterocyclic group can also be regarded as electron withdrawing groups contributing to the Hammett Sigma values.
Each Z1, Z2, Z3 and Z* is an independently selected substituent group where p is 0 to 2. Suitable substituent groups are more fully described hereinafter. Typically p is 0. Z1, Z2, Z3, and Z* may be any substituent and, for example, may be independently selected from hydrogen, acyl, acyloxy, alkenyl, alkyl, alkoxy, amino, mono and di-substituted amino, aryl, aryloxy, carbamoyl, carbamate, carbonamido, carboxy, carboalkoxy, cyano, halogen, heterocyclic, hydroxy, nitro, oxycarbonyl, oxysulfonyl, sulfamoyl, sulfonamido, sulfonyl, sulfoxide, thio and ureido groups. Convenient substituents are hydrogen, acyl, acyloxy, alkenyl, alkyl, alkoxy, halogen, oxycarbonyl, carbonamido, carboxy, carboalkoxy, cyano, sulfonyl and sulfoxide groups. Additionally, Z1 and Z2, or Z2 and Z3 can join to form a ring. When Z1 and Z2 join to form a ring, the ring can be an aromatic or non-aromatic carbocyclic ring or heterocyclic ring. When Z2 and Z3 join to form a ring, the ring can be carbocyclic or heterocyclic. When Z1, Z2, or Z3 is alkenyl, the alkenyl group(s) can be further substituted with the aforementioned substituents, Z1xe2x80x2, Z2xe2x80x2, and Z3xe2x80x2, including additional alkenyl groups leading to couplers with conjugated double bonds. The substituents of the additional alkenyl group, Z1xe2x80x2 and Z2xe2x80x2, or Z2xe2x80x2 and Z3xe2x80x2 can also join to form a carbocyclic or heterocyclic ring. Since structures of the invention involve a double bond(s) at the 2-position, it should be realized that geometrical isomerism is possible with certain combinations of Z1, Z2 and Z3 or Z1xe2x80x2, Z2xe2x80x2, and Z3xe2x80x2. That is, cis(Z) and trans(E) isomers are possible with certain combinations of Z1, Z2 and Z3 or Z1xe2x80x2, Z2xe2x80x2, and Z3xe2x80x2. The total combined sum of the aliphatic carbon atoms in W1, R1, R2, Z1, Z2, Z3, Z1xe2x80x2, Z2xe2x80x2, Z3xe2x80x2 and all Z* groups is at least 8.
W1 independently represent the atoms necessary to form a carbocyclic or heterocyclic ring group. Examples of suitable carbocyclic rings include cyclohexyl, phenyl and naphthyl with phenyl rings being most conveniently used. Suitable heterocyclic rings include those containing 5 or 6 ring members and at least one ring heteroatom. Heterocycles useful herein may be aromatic or non-aromatic and contain at least one atom of oxygen, nitrogen, sulfur, selenium, or tellurium. They can be fused with a carbocyclic ring or with another heterocycle. They can be attached to the coupler through any of the possible points of attachment on the heterocycle. It should be realized that multiple points of attachment are possible giving rise to alternative isomers for a single heterocycle. Examples of useful heterocyclic groups are benzimidazolyl, benzoselenazolyl, benzothiazolyl, benzoxazolyl, chromonyl, furyl, imidazolyl, indazolyl, indolyl, isoquinolyl, isothiazolyl, isoxazolyl, morpholinyl, oxadiazolyl, oxazolyl, picolinyl, piperidinyl, purinyl, pyradazinyl, pyranyl, pyrazinyl, pyrazolyl, pyridyl, pyrimidinyl, pyrrolyl, pyrrolidinyl, quinaldinyl, quinazolinyl, quinolyl, quinoxalinyl, selenazoyl, tellurazolyl, tetrazolyl, tetrahydrofuryl, thiadiazolyl, thiamorpholinyl, thiatriazolyl, thiazolyl, thienyl, thiophenyl, and triazolyl groups. A particularly useful heterocyclic group is pyridyl in which the nitrogen of the heterocyclic ring may be either ortho, meta or para to the carbonyl group of the 5-carbonamide of the coupler.
In one embodiment the coupler of formula (I) is represented by formula (II):
wherein:
W1 represents the atoms necessary to complete carbocyclic ring group with electron withdrawing groups having a sum total of Hammett Sigma values greater than 0.8;
Y is hydrogen or a coupling off group;
each Z* is an independently selected substituent group where p is independently 0 to 2;
R2 is a heterocyclic or carbocyclic ring group, or an alkyl group;
provided that when R2 is an alkyl group with an xcex1-alkyl substituent, said xcex1-alkyl substituent is unbranched; and
provided further that the combined sum of the aliphatic carbon atoms in W1, R2 and all Z* is at least 8.
A preferred embodiment of the invention when W1 represents the atoms necessary to complete a carbocyclic ring is represented by formula (III):
In another embodiment, the coupler of formula (II) is represented by formula (IV):
wherein:
each Z1, Z2 and Z3 are an independently selected substituent group; and
provided that the combined sum of the aliphatic carbon atoms in W1, Z1, Z2, Z3, and all Z* is at least 8.
In still further embodiments, the coupler of formula (II) is represented by formulae (V) and (VI).
wherein:
Z 1xe2x80x2, Z2xe2x80x2, and Z3xe2x80x2 are independently selected substituent groups; and provided that the combined sum of the aliphatic carbon atoms in W1, Z1, Z2, Z3, Z1xe2x80x2, Z2xe2x80x2, and Z3xe2x80x2 and all Z* is at least 8.
Examples of suitable heterocycles for W1 are those based on a benzimidazole, benzotriazole, furan, imidazole, indazole, indole, isoquinoline, purine, pyrazole, pyridine, pyrimidine, pyrrole, quinoline, thiophene, 1,2,3-triazole, or 1,2,4-triazole ring group. Conveniently useful are the nitrogen-containing rings such as pyridine with the nitrogen in the 2-, 3-, or 4-position, as well as the various pyrimidine or pyrazole alternatives, as shown in the following coupler formulae (VII)-(IX):
The following are examples of couplers useful in the invention:
The preferred couplers useful in the invention are capable of forming dyes with color developers such as 4-amino-3-methyl-N-ethyl-N-(2-methanesulfonamidoethyl) aniline sesquisulfate hydrate that have a LBW or RBW less than 70 nm and preferably less than 60 nm. The wavelength of maximum absorption is suitably less than 580 nm and is typically less than 560 nm.
The coupler of the invention is preferably an xe2x80x9cNB magenta couplerxe2x80x9d which is a narrow bandwidth coupler of formula (I) having substituents so that there is a reduction in the left or right bandwidth in spin-coating form versus solution form of at least 5 nm. In accordance with the procedure, a dye is formed by combining the coupler and the developer 4-amino-3-methyl-N-ethyl-N-(2-methanesulfonamidoethyl) aniline sesquisulfate hydrate. If either the left bandwidth (LBW), right bandwidth (RBW) or both, of their absorption spectra upon xe2x80x9cspin coatingxe2x80x9d a 3% w/v solution of the dye in di-n-butyl sebacate solvent is at least 5 nm less than the LBW, RBW or both for a solution of the same dye in acetonitrile, then the coupler is an xe2x80x9cNB magenta couplerxe2x80x9d. The LBW of the spectral curve for a dye is the distance between the left side of the spectral curve and the wavelength of maximum absorption measured at a density of half the maximum. The RBW is the distance between the wavelength of maximum absorption and the right side of the spectral curve measured at a density of half the maximum.
The xe2x80x9cspin coatingxe2x80x9d sample is prepared by first preparing a 3% w/v solution of the dye in ethyl acetate or other suitable solvent with 3% w/v of di-n-butyl sebacate coupler solvent. If the dye is insoluble, dissolution is achieved by the addition of methylene chloride or tetrahydrofuran. The solution is filtered and 0.1-0.2 ml is applied to a clear polyethylene terephthalate support (approximately 4 cmxc3x974 cm) and spun at 4,000 RPM using the Spin Coating equipment, Model No. EC101available from Headway Research Inc., Garland Tex. The transmission spectra of the so prepared dye samples are then recorded.
Preferred xe2x80x9cNB magenta couplersxe2x80x9d form a dye which has either a LBW, RBW or both, of the absorption spectra upon xe2x80x9cspin coatingxe2x80x9d a sample of the dye in di-n-butyl sebacate at least 5 nm, preferably at least 10 nm, 15 nm or 20 nm, but can fall in the range of between 5 to 40 nm less than that of the same dye in acetonitrile solution.
Unless otherwise specifically stated, use of the term xe2x80x9csubstitutedxe2x80x9d or xe2x80x9csubstituentxe2x80x9d means any group or atom other than hydrogen. Additionally, when the term xe2x80x9cgroupxe2x80x9d is used, it means that when a substituent group contains a substitutable hydrogen, it is also intended to encompass not only the substituent""s 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, 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, 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-dodecyl amino, 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-Nxe2x80x2-ethylureido, N-phenylureido, N,N-diphenylureido, N-phenyl-N-p-tolylureido, N-(m-hexadecylphenyl)ureido, N,N-(2,5-di-t-pentylphenyl)-Nxe2x80x2-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, benzyloxycarbonyl, 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 which contain 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, and releasing or releasable groups. 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.
The materials of the invention can be used in any of the ways and in any of the combinations known in the art. Typically, the invention materials are incorporated in a melt and coated as a layer described herein on a support to form part of a photographic element. When the term xe2x80x9cassociatedxe2x80x9d 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 xe2x80x9cballastxe2x80x9d group in coupler molecules. Representative ballast groups include substituted or unsubstituted alkyl or aryl groups containing 8 to 48 carbon atoms. Representative substituents on such groups include alkyl, aryl, alkoxy, aryloxy, alkylthio, hydroxy, halogen, alkoxycarbonyl, aryloxcarbonyl, carboxy, acyl, acyloxy, amino, anilino, carbonamido, carbanoyl, alkylsulfonyl, arylsulfonyl, sulfonamido, and sulfamoyl groups wherein the substituents typically contain 1 to 42 carbon atoms. Such substituents can also be furter substituted.
The photographic elements 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, and subbing layers.
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 P010 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.
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 is referred to herein by the term xe2x80x9cResearch Disclosurexe2x80x9d. 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 employed in 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. 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. The information contained in the September 1994 Research Disclosure, Item No. 36544 referenced above, is updated in the September 1996 Research Disclosure, Item No. 38957. Certain desirable photographic elements and processing steps, including those useful in conjunction with color reflective prints, are described in Research Disclosure, Item 37038, February 1995.
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, and color correction. When the coupling-off group has an advantageous affect on the layer in which it is released or in an adjacent layer, it is also known as a photographically useful group or PUG. The PUG can be attached to the coupler directly, or it can be attached through a linking or timing group. More detailed descriptions of PUGs, linking groups and timing groups useful for Y in formula (I) are described below under materials which release PUGs in association with materials of the invention.
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, 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 UK. Patents and published application 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 in addition to those of the invention may be included in the element such as couplers that form cyan dyes upon reaction with oxidized color developing agents which are described in such representative patents and publications as: xe2x80x9cFarbkuppler-eine Literature Ubersicht,xe2x80x9d published in Agfa Mitteilungen, Band III, pp. 156-175 (1961) as well as in 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; 4,746,602; 4,753,871; 4,770,988; 4,775,616; 4,818,667; 4,818,672; 4,822,729; 4,839,267; 4,840,883; 4,849,328; 4,865,961; 4,873,183; 4,883,746; 4,900,656; 4,904,575; 4,916,051; 4,921,783; 4,923,791; 4,950,585; 4,971,898; 4,990,436; 4,996,139; 5,008,180; 5,015,565; 5,011,765; 5,011,766; 5,017,467; 5,045,442; 5,051,347; 5,061,613; 5,071,737; 5,075,207; 5,091,297; 5,094,938; 5,104,783; 5,178,993; 5,813,729; 5,187,057; 5,192,651; 5,200,305 5,202,224; 5,206,130; 5,208,141; 5,210,011; 5,215,871; 5,223,386; 5,227,287; 5,256,526; 5,258,270; 5,272,051; 5,306,610; 5,326,682; 5,366,856; 5,378,596; 5,380,638; 5,382,502; 5,384,236; 5,397,691; 5,415,990; 5,434,034; 5,441,863; EPO 0 246 616; EPO 0 250 201; EPO 0 271 323; EPO 0 295 632; EPO 0 307 927; EPO 0 333 185; EPO 0 378 898; EPO 0 389 817; EPO 0 487 111; EPO 0 488 248; EPO 0 539 034; EPO 0 545 300; EPO 0 556 700; EPO 0 556 777; EPO 0 556 858; EPO 0 569 979; EPO 0 608 133; EPO 0 636 936; EPO 0 651 286; EPO 0 690 344; German OLS 4,026,903; German OLS 3,624,777. and German OLS 3,823,049. Typically such couplers are phenols, naphthols, or pyrazoloazoles.
Couplers that form magenta dyes upon reaction with oxidized color developing agent are described in such representative patents and publications as: xe2x80x9cFarbkuppler-eine Literature Ubersicht,xe2x80x9d published in Agfa Mitteilungen, Band III, pp. 126-156 (1961) as well as U.S. Pat. Nos. 2,311,082 and 2,369,489; 2,343,701; 2,600,788; 2,908,573; 3,062,653; 3,152,896; 3,519,429; 3,758,309; 3,935,015; 4,540,654; 4,745,052; 4,762,775; 4,791,052; 4,812,576; 4,835,094; 4,840,877; 4,845,022; 4,853,319; 4,868,099; 4,865,960; 4,871,652; 4,876,182; 4,892,805; 4,900,657; 4,910,124; 4,914,013; 4,921,968; 4,929,540; 4,933,465; 4,942,116; 4,942,117; 4,942,118; U.S. Pat. Nos. 4,959,480; 4,968,594; 4,988,614; 4,992,361; 5,002,864; 5,021,325; 5,066,575; 5,068,171; 5,071,739; 5,100,772; 5,110,942; 5,116,990; 5,118,812; 5,134,059; 5,155,016; 5,183,728; 5,234,805; 5,235,058; 5,250,400; 5,254,446; 5,262,292; 5,300,407; 5,302,496; 5,336,593; 5,350,667; 5,395,968; 5,354,826; 5,358,829; 5,368,998; 5,378,587; 5,409,808; 5,411,841; 5,418,123; 5,424,179; EPO 0 257 854; EPO 0 284 240; EPO 0 341 204; EPO 347,235; EPO 365,252; EPO 0 422 595; EPO 0 428 899; EPO 0 428 902; EPO 0 459 331; EPO 0 467 327; EPO 0 476 949; EPO 0 487 081; EPO 0 489 333; EPO 0 512 304; EPO 0 515 128; EPO 0 534 703; EPO 0 554 778; EPO 0 558 145; EPO 0 571 959; EPO 0 583 832; EPO 0 583 834; EPO 0 584 793; EPO 0 602 748; EPO 0 602 749; EPO 0 605 918; EPO 0 622 672; EPO 0 622 673; EPO 0 629 912; EPO 0 646 841, EPO 0 656 561; EPO 0 660 177; EPO 0 686 872; WO 90/10253; WO 92/09010; WO 92/10788; WO 92/12464; WO 93/01523; WO 93/02392; WO 93/02393; WO 93/07534; UK Application 2,244,053; Japanese Application 03192-350; German OLS 3,624,103; German OLS 3,912,265; and German OLS 40 08 067. Typically such couplers are pyrazolones, pyrazoloazoles, or pyrazolobenzimidazoles that form magenta dyes upon reaction with oxidized color developing agents.
Couplers that form yellow dyes upon reaction with oxidized color developing agent are described in such representative patents and publications as: xe2x80x9cFarbkuppler-eine Literature Ubersicht,xe2x80x9d published in Agfa Mitteilungen; Band III; pp. 112-126 (1961); as well 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; 4,758,501; 4,791,050; 4,824,771; 4,824,773; 4,855,222; 4,978,605; 4,992,360; 4,994,361; 5,021,333; 5,053,325; 5,066,574; 5,066,576; 5,100,773; 5,118,599; 5,143,823; 5,187,055; 5,190,848; 5,213,958; 5,215,877; 5,215,878; 5,217,857; 5,219,716; 5,238,803; 5,283,166; 5,294,531; 5,306,609; 5,328,818; 5,336,591; 5,338,654; 5,358,835; 5,358,838; 5,360,713; 5,362,617; 5,382,506; 5,389,504; 5,399,474;. 5,405,737; 5,411,848; 5,427,898; EPO 0 327 976; EPO 0 296 793; EPO 0 365 282; EPO 0 379 309; EPO 0 415 375; EPO 0 437 818; EPO 0 447 969; EPO 0 542 463; EPO 0 568 037; EPO 0 568 196; EPO 0 568 777; EPO 0 570 006; EPO 0 573 761; EPO 0 608 956; EPO 0 608 957; and EPO 0 628 865. 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: UK. 861,138; 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 No. 2,644,194 and German OLS No. 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 xe2x80x9cuniversalxe2x80x9d or xe2x80x9cwashoutxe2x80x9d 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. No. 4,301,235; U.S. Pat. No. 4,853,319 and U.S. Pat. No. 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 xe2x80x9cwrongxe2x80x9d 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; UK. Pat. No. 1,530,272; and Japanese 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 0.05 to 1.0 and generally 0.1 to 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 materials may be used in association with materials that release Photographically Useful Groups (PUGS) 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; EP 301,477; U.S. Pat. No. 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 (UK Patent 2,097,140; UK. Patent 2,131,188); electron transfer agents (U.S. Pat. No. 4,859,578; U.S. Pat. No. 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 invention materials may also be used in combination with 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 xe2x80x9csmearingxe2x80x9d couplers (e.g. 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 materials may further be used in combination with image-modifying compounds that release PUGS such as xe2x80x9cDeveloper Inhibitor-Releasingxe2x80x9d 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 xe2x80x9cDeveloper-Inhibitor-Releasing (DIR) Couplers for Color Photography,xe2x80x9d 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 which 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 a preferred embodiment, 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 xe2x80x94SRI; 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, xe2x80x94COORV and xe2x80x94NHCOORV 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 xe2x80x9cuniversalxe2x80x9d 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; 4,861,701, Japanese 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. No. 4,438,193; U.S. Pat. No. 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:
It is also contemplated that the concepts of the present invention may be employed to obtain reflection color prints as described in Research Disclosure, November 1979, Item 18716, available from Kenneth Mason Publications, Ltd, Dudley Annex, 12a North Street, Emsworth, Hampshire P0101 7DQ, England, incorporated herein by reference. Materials of the invention may be coated on pH adjusted support as described in U.S. Pat. No. 4,917,994; on a support with reduced oxygen permeability (EP 553,339); with epoxy solvents (EP 164,961); with nickel complex stabilizers (U.S. Pat. No. 4,346,165; U.S. Pat. No. 4,540,653 and U.S. Pat. No. 4,906,559 for example); with ballasted chelating agents such as those in U.S. Pat. No. 4,994,359 to reduce sensitivity to polyvalent cations such as calcium; and with stain reducing compounds such as described in U.S. Pat. No. 5,068,171. Other compounds useful in combination with the invention are disclosed in Japanese Published Applications described in Derwent Abstracts having accession numbers as follows: 90-072,629, 90-072,630; 90-072,631; 90-072,632; 90-072,633; 90-072,634; 90-077,822; 90-078,229; 90-078,230; 90-079,336; 90-079,337; 90-079,338; 90-079,690; 90-079,691; 90-080,487; 90-080,488; 90-080,489; 90-080,490; 90-080,491; 90-080,492; 90-080,494; 90-085,928; 90-086,669; 90-086,670; 90-087,360; 90-087,361; 90-087,362; 90-087,363; 90-087,364; 90-088,097; 90-093,662; 90-093,663; 90-093,664; 90-093,665; 90-093,666; 90-093,668; 90-094,055; 90-094,056; 90-103,409; 83-62,586; 83-09,959.
Conventional radiation-sensitive silver halide emulsions can be employed in the practice of this invention. Such emulsions are illustrated by Research Disclosure, Item 38755, September 1996, I. Emulsion grains and their preparation.
Especially useful in this invention are tabular grain silver halide emulsions. Tabular grains are those having two parallel major crystal faces and having an aspect ratio of at least 2. The term xe2x80x9caspect ratioxe2x80x9d is the ratio of the equivalent circular diameter (ECD) of a grain major face divided by its thickness (t). Tabular grain emulsions are those in which the tabular grains account for at least 50 percent (preferably at least 70 percent and optimally at least 90 percent) of the total grain projected area. Preferred tabular grain emulsions are those in which the average thickness of the tabular grains is less than 0.3 micrometer (preferably thinxe2x80x94that is, less than 0.2 micrometer and most preferably ultrathinxe2x80x94that is, less than 0.07 micrometer). The major faces of the tabular grains can lie in either {111} or {100} crystal planes. The mean ECD of tabular grain emulsions rarely exceeds 10 micrometers and more typically is less than 5 micrometers.
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. Pat. No. 4,439,520, Wilgus et al U.S. Pat. No. Pat. No. 4,434,226, Solberg et al U.S. Pat. No. 4,433,048, Maskasky U.S. Pat. No. Pat. Nos. 4,435,501, 4,463,087 and 4,173,320, 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 and 5,614,359, and Irving et al U.S. Pat. No. 5,667,954.
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 chloride {111} tabular grain emulsions are illustrated by Wey U.S. Pat. No. 4,399,215, Wey et al U.S. Pat. No. 4,414,306, Maskasky U.S. Pat. Nos. 4,400,463, 4,713,323, 5,061,617, 5,178,997, 5,183,732, 5,185,239, 5,399,478 and 5,411,852, and Maskasky et al U.S. Pat. Nos. 5,176,992 and 5,178,998. Ultrathin high chloride {111} tabular grain emulsions are illustrated by Maskasky U.S. Pat. Nos. 5,271,858 and 5,389,509.
High chloride {100} tabular grain emulsions are illustrated by Maskasky U.S. Pat. Nos. 5,264,337, 5,292,632, 5,275,930 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 and 5,663,041, 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.
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 Evans et al. 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. If desired xe2x80x9cRedox Amplificationxe2x80x9d as described in Research Disclosure XVIIIB(5) may be used.
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. 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 3xe2x80x2 15xe2x80x3 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 xe2x80x9csingle use camerasxe2x80x9d, xe2x80x9clens with filmxe2x80x9d, or xe2x80x9cphotosensitive material package unitsxe2x80x9d.
Another type of color negative element is a color print. Such an element is designed to receive an image optically printed from an image capture color negative element. A color print element may be provided on a reflective support for reflective viewing (e.g. a snap shot) or on a transparent support for projection viewing as in a motion picture. Elements destined for color reflection prints are provided on a reflective support, typically paper, employ silver chloride emulsions, and may be optically printed using the so-called negative-positive process where the element is exposed to light through a color negative film which has been processed as described above. The element is sold packaged with instructions to process using a color negative optical printing process, for example the Kodak RA-4 process, as generally described in PCT WO 87/04534 or U.S. Pat. No. 4,975,357, to form a positive image. Color projection prints may be processed, for example, in accordance with the Kodak ECP-2 process as described in the H-24 Manual. Color print development times are typically 90 seconds or less and desirably 45 or even 30 seconds or less.
A reversal element is capable of forming a positive image without optical printing. To provide a positive (or reversal) image, the color development step is preceded by development with a non-chromogenic developing agent to develop exposed silver halide, but not form dye, and followed by uniformly fogging the element to render unexposed silver halide developable. Such reversal elements are typically sold packaged with instructions to process using a color reversal process such as the Kodak E-6 process as described in The British Journal of Photography Annual of 1988, page 194. Alternatively, a direct positive emulsion can be employed to obtain a positive image.
The above elements are typically sold with instructions to process using the appropriate method such as the mentioned color negative (Kodak C-41), color print (Kodak RA-4), or reversal (Kodak E-6) process.
Preferred 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 bleaching, fixing, or bleach-fixing, to remove silver or silver halide, washing, and drying
The compound of the invention is a coupler compound as described in the foregoing description of the photographic element. The process of the invention includes a method of forming an image in the described silver halide element after the same has been exposed to light comprising contacting the exposed element with a color developing compound such as a para phenylene diamine.
A direct-view photographic element is defined as one which yields a color image that is designed to be viewed directly (1) by reflected light, such as a photographic paper print, (2) by transmitted light, such as a display transparency, or (3) by projection, such as a color slide or a motion picture print. These direct-view elements may be exposed and processed in a variety of ways. For example, paper prints, display transparencies, and motion picture prints are typically produced by optically printing an image from a color negative onto the direct-viewing element and processing though an appropriate negative-working photographic process to give a positive color image. Color slides may be produced in a similar manner but are more typically produced by exposing the film directly in a camera and processing through a reversal color process or a direct positive process to give a positive color image. The image may also be produced by alternative processes such as digital printing.
Each of these types of photographic elements has its own particular requirements for dye hue, but in general they all require cyan dyes that whose absorption bands are less deeply absorbing (that is, shifted away from the red end of the spectrum) than color negative films. This is because dyes in direct viewing elements are selected to have the best appearance when viewed by human eyes, whereas the dyes in color negative materials designed for optical printing are designed to best match the spectral sensitivities of the print materials.
The compound of the invention is the coupler compound as described in the foregoing description of the photographic element. The process of the invention includes a method of forming an image in the described silver halide element after the same has been exposed to light comprising contacting the exposed element with a color developing compound such as a para phenylene diamine.


Winter Flash-Demented

Jojo and Jimie visited every Sunday for Tea. Miss Vivienne prepared for their visit with anticipation and precision. Hair, make-up, dress all just so. The Tea and finger sandwiches made just the way they liked them.

Vivienne was a stickler for the tradition of Sunday Tea with her sons.

“Miss Vivienne, it’s time for your bath now,” Carol said as she began pulling the chair away from the table.

“Oh, hello dear you just missed my boys they would have loved to see you.”

Carol removed Miss Vivienne’s hearing aids and gently placed her in the tub with the help of Betsy.

“What is wrong with her, I didn’t see any visitors.”

Carol glanced up at the new girl and smiled ruefully. “Miss Vivienne has been with us a long time. She is demented as can be, has been ever since she killed her husband and sons fifty years ago.”

It is a new season, time for a Winter of Disturbing Flashes. Flash in the Pan is brought to you by the remarkable Red of M3 fame, to join in the fun read the rules at the link provided and get to flashing!

The word this week isDemented with a word limit of 150. Demented comes in at 150.

Comments

Have you seen the new words Val, boys and their toys being the theme, of course you have and now all we need to do is write them into our next FTP 🙂 I am looking forward to the challenge are you my dear friend? 🙂 If you notice anything different about my Space don’t worry, it was just me making a complete bollocks of an early Spring Clean 😦 Next time I will leave the cleaning up to someone that knows how NOT to balls a Space up 😦 lmao

Have a lovely start to your Monday Val
and be wicked and naughty, like me 😉 😉

I have, should be amusing. I am fighting the seasonal cold from hades right now so not having much fun. Have 180 blogs to read from the last few days. Terrible but hopefully today I can stay awake long enough to read them.

I know what you mean about the cold virus, I too am just getting rid of one, I can’t complain though as it is the first one I have had in two years, but what a stinker 😦 lol

Hey you don’t need to worry about any back-blogs on mine, I had a glitch and lost just about everything on my Space including all my pictures, but no problemo I will be adding some back soon, and some new postings, starting today 🙂

Have a lovely Tuesday and don’t be going crazy on the cleaning every room scenario, a nice gentle pace will suffice or I will have to send my Zombies round and you know what those are like 🙂 lmao

Can you tell I replied from my Space? 😦 lol
That reader and reply is a good idea but it
makes one lazy and I hadn’t realised that I
had already mentioned my glitch in the earlier
comment 😦 What a wally I am 🙂 lol

I know Val and my heart feels for you, Everything that happens has a reason, and although the pain is still raw, I know you will rise to its challenge and overcome, And somewhere off into the future you will look back and smile and know that it all had purpose for what is to come…
New Beginnings cannot come unless we let go of the old… And even if that choice wasn’t yours, I know that 2014 will bring you closer to YOU..
Much Love xxx
Sue x

Eric, you made me guffaw. We would have to wonder that wouldn’t we! But then I suspect it is a bit of was she already in the throes of her dementia when she did them in? Or alternatively was the entire episode the cause and spite the reason. We will never know.

I am slow still in reading but trying to establish better patterns. Trying to stop my little pity party and start being more me again. The holidays are nearly over, maybe that means the hardest part is as well. I look forward to your posts.

visit, read the article and thanks for posting your article is quite good and we hope that all our friends all success and thank you all, greetings Merry Christmas and a blessed New Year to you and yours. 🙂


The Netherlands were a goal down and Spain in a manner of control before RVP blew that all apart in the most amazing fashion. He met a diagonal cross with a glorious diving header that took the ball up and over Iker Casillas. It also sparked a “craze” called Persie-ing, where social media filled with images of people, err, laying on their loungeroom floors face down.

Robin van Persie’s beautiful goal.Source:Getty Images

3 Gary Lewin’s injury, v Italy.

It was a such a tense match, decided by Mario Balotelli’s header at the back post. We’re used to an element of farce in England World Cup games, but not to this extent. The England physio Gary Lewin landed on a bottle during the celebrations and broke his ankle, ruling him out of the tournament.

France’s second in an convincing win over a terrible Honduras was the first awarded by goal line technology. FIFA has, for so many years, resisted the rise of technology and four years ago England were robbed of a legitimate goal when the shot from Frank Lampard landed well inside the goal line.

This time a Karim Benzema shot rebounded off the post to the goalkeeper Eduardo Valladres who fumbled it over. The ref went with goal and then the tech backed him up. We don’t say this much but: “Thanks, FIFA”.

5 The foam, it vanishes.

While we’re at it, FIFA, it’s not just high tech that we love. That low tech foam that keeps players back 10m at a freekick then vanishes into the turf? Love it!

6 Colombian goal celebrations.

Colombia’s first goal in an exciting 3-0 drubbing of Greece was their first in 16 years, and they celebrated with glee. Now every strike is a chance for the Colombians to get their boogie on and they were at it again on Friday morning when they beat the Ivory Coast.

The team is fast becoming a fan favourite for their togetherness and shared joy.

United States' John Brooks seems shocked by his winning goal.Source:AP

7 John Brooks’s winning goal for USA.

Teammate Clint Dempsey got the game underway with a goal inside a minute, and then suffered an ugly broken nose, but the iconic moment of this game came from a complete unknown.

The 21-year-old US centreback Brooks reacted with shock, and it looked as if one of us had wandered out there and scored at a World Cup.

8 Guillermo Ochoa’s save v Brazil.

We’ve seen strikers signed to big money deals on the back of a brilliant goal, but Mexico’s Ochoa could be about to parlay his brilliant parry into a massive and unexpected payday.

Ochoa is a big name in his home country, but had just been released by his French club team.

Now, according to transfer rumour mills, Barcelona, Arsenal and Liverpool are chasing his signature.

Guillermo Ochoa saves from Neymar.Source:Getty Images

9 Mark Bresciano’s thoughtfulness.

It’s the photo, by Herald Sun snapper George Salpigtidis, that’s swept the world. Mark Bresciano reaching down before the Socceroos’ match with Chile to tie the laces of a young boy on crutches who had escorted the players onto the field.

Bresciano was able to look outside the pressure bubble of the moments before a match.

To him, it was no big deal

“The boy was a little slow walking out and I noticed his shoelace undone so I did what any parent would do, any player for that matter, I just helped him out and tied it back up.”

Australia's Mark Bresciano comes out with a boy on crutches and help him tie up his shoe laces. Pic: George Salpigtidis.Source:News Corp Australia

10 Lionel Messi’s goal.

The world’s number one player hadn’t enjoyed the best of starts against Bosnia-Herzegovina. And a few minutes before his magic moment he floated a freekick over the crossbar and was booed by some in the crowd.

Then it came. He received the ball on the left and weaved with one of those typical Messi surges, embarrassing defenders with sleight of foot and then curling a beauty into the bottom corner. Cue delirium.

Lionel Messi of Argentina reacts after scoring his team's second goal.Source:Getty Images

11 Muller’s hat-trick and Pepe’s red card.

Portgual’s wild man Pepe just couldn’t help himself. Muller, the three goal star of this game, felt a slap on the chin and went down gripping his face. It might have ended with a freekick or yellow but as Muller whined on the ground. Pepe came over and brought his head to meet the Germans. Hardly a painful butt, but enough to have Pepe sent off.

They came into the tournament having won their past three major championships, including the 2010 World Cup. Their reputation was built around rock solid defence but the demise of Iker Casillas as a world class keeper, and the obvious ageing of the midfield stars, combined with the brilliance of the Dutch, tore them to pieces. Xavi Hernandez was dropped for the Chile game and it was like La Rojas had lost their beating heart.

Spain's goalkeeper and captain Iker Casillas. “What have I done”?Source:AFP

13 Neymar’s tears.

Talk about the weight of a nation. You get the impression that Brazil’s latest young superstar tears up at the slightest provocation but it all became too much ahead of the Mexico game.

Neymar broke down in the anthem. On the field he tried hard but was denied by the brilliance of Guillermo Ochoa, and a lack of spark in the forward line ahead of him.

Neymar of Brazil cries during the anthem ahead of the Mexico gameSource:Getty Images

14 Tim Cahill’s volley rocket.

Cahill’s fifth World Cup might not have been his most significant but it was certainly his best. Taking a diagonal cross from Ryan McGowan first time off his weaker left foot he thumped the ball in off the cross bar against Holland to bring comparisons with an iconic goal from Dutch star Marco van Basten, fittingly Cahill’s boyhood idol when he played for his favourite team AC Milan.

15 Luis Suarez double sinks England.

Just because it was predictable didn’t make it any less thrilling. His first goal was a neat header off a chip from Edinson Cavani. Wayne Rooney cancelled it out with a tap in, but then the Liverpool man rose to the occasion superbly.

Bursting into the box on the right he seemed to stumble only to regain his poise and smash the ball past Joe Hart. All this after knee surgery that ruled him out of the opening game. Suarez also dissolved into tears after the game, and you knew that for him, this was personal, although he still had feelings for his club captain, Steven Gerrard.

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A project I have been working on these past few days, Czechosudetia is based off information from an alternate history book I got for Christmas (the information is actually OTL). There were several suggestions for the regional division of Czechoslovakia, one of them gave autonomous regions to the Germans. In the end, this was discarded for dividing the country by historical lands. Czechia, Moravia-Silesia, Slovakia and Ruthenia. Meanwhile you had two major raging problems. The Germans suddenly became a minority which, after centuries of being the major nationality did not sit well with their mindset and they regretted not being a, as we call it "státotvorný národ", nationality which formed the core of the new country like the Czechs and Slovaks. Meanwhile, the Slovaks were dissatisfied by the slow progress of decentralizing powers from Prague and while the Hlinka's Party (which later collaborated with the Nazis) was for more autonomy, there were two more sides. There was a part of the populace which believed that Slovakia should rejoin Hungary in a federal union while a part opted for integration into Poland. In OTL, Hlinka's party recieved almost 50% of the votes at one point . . . but what if?What if the regional division of Czechoslovakia, that was chosen in the end, was the nationality-based division? The Czech lands would be divided in such a way that the Germans would have a greater say in the running of the state. Naturally the Slovaks would feel more threatened, loosing their position as the major nationality of the state and falling to third place, and would see this as the Czechs going back on their word of a Czechoslovak state. The Hilnka's Party wins the Slovak elections in a landslide victory and after a few years, Slovakia officially secedes from Czechoslovakia. But what then? The Hungarian-oriented citizens clash in elections with the Polish-oriented side with the Hilnka-backers laying about to both sides resulting in a bloody Slovak civil war or the War in the Tatras. The state splits into three with the northeastern lands joining Poland, Subcarpathian Ruthenian and the Hungarian southalnds joining Hungary and a hardcore-nationalistic rump Slovak state centered around the southwestern lowlands and running up along the border with Czechia to Zilina.Meanwhile in Czechia, as the Germans rise to second place, they clamor for a position similar to the Slovaks and though the rights of Czechs and Germans were equal (In OTL too. The contrary was Nazi propaganda) they demanded the status of a core nationality. This they got through a semi-federalization. Czechosudetia cannot truly be called a unitary state but neither is it a federation. While each "state" meets in a parliament with devolved cultural, educational and minor economic powers, most of the decision-making is held in Prague where the upper chamber of the parliament consists of a 50/50 devided chamber between Germans and Czechs. Bohemia and Moravia send delegates into the Czech half while Sudetenland, Deutshbohmen and Niederbohmen send delegates to the German side. The seats in the lower chamber are divided proportionately to the population and gets candidates from the minor regions or "Župas" regardless of nationality.As to the coat of arms, it is quartered with two Bohemian lions, a Sudetan eagle and a Moravian eagle. It's topped off by the Premyslid eagle to symbolize the harmony between the Czechs and Germans in this new state and it's descendance from the Bohemia of old.For those of you who are about to ask, no the flag is NOT that of the German empire, yes the arms are based off the protectorate of Bohemia-Moravia and yes the numbers in the chart are accurate (dated to 1930 I think) and lastly yes, the territory in the smaller map DOES correspond to the living areas populated by the Germans where I only left out the exclaves and instead was quite generous in allocating land to the actual states themselves. If anybody asks these question, they can expect the middle finger from meAs to the languages I chose, knowing Anglophones, they will use the German names for the German states while retaining "Bohemia" and "Moravia" for the Czech ones -_- So I at least took the liberty of marking the cities in the correct languages.CREDITS:Lion, eagle and shield shape are edited from Wikimedia commons - LINK Please excuse the exporting errors on the Moravian eagle, I've been tinkering with it for over an hour now, trying to eradicate them (not the Germans) but with only limited success.


The purpose of this contract is to obtain services in the following areas: 1) quality control and improvement of cancer data, 2) development of geospatial systems for visualization and dissemination of cancer data, 3) statistical activities including development of software, methods and statistical applications for analysis of cancer data


Q:

Apply function within dplyr group

I'm trying to calculate the number of seats parties should have in municipal councils using a function from the electoral package, and have a long-format dataframe that is sorted according to municipalities.
However, I seem unable to get the function to work within the groups, and instead get the following error:

Error in seats_ha(parties = mandates$party, votes = mandates$votes, n_seats = 25,  :    every party name must be unique

I have tried using both do() and group_map(), as this is what was suggested in this thread: Run a custom function on a data frame in R, by group, and summarise would not work since the function is expected to return several rows of values, not one summary value.
I have also tried using the dHondt()-function from the coalitions package, but to no avail, just a different error:
When using do:

Error: Results 1, 2 must be data frames, not integer

When using group_map:

Error: Can't convert an integer vector to function

Does anyone have an idea on how to solve this? :)
Some sample code:
library(tidyverse)
library(electoral)
mandates <- data.frame(municipality = c("A","A","A","B","B","B"),
                           party = c("1","2","3","1","2","3"),
                           votes = c(125,522,231,115,321,12),
                           seats = c(25,25,25,25,25,25))
    mandates <- mandates %>% group_by(municipality) %>%
            group_map(seats_ha(parties = mandates$party, votes = mandates$votes, n_seats = 25, method = "dhondt"))

Preferably I'd like it to use the seats variable for n_seats, since there are a different number of seats in each municipality, but getting it to work with 25 seats set is a good start.

A:

you can simply use mutate in this case:
mandates %>% group_by(municipality) %>%
 mutate(x = seats_ha(parties = party, votes = votes, n_seats = 25, method = "dhondt"))
    # A tibble: 6 x 5
# Groups:   municipality [2]
  municipality party votes seats     x
  <fct>        <fct> <dbl> <dbl> <int>
1 A            1       125    25     3
2 A            2       522    25    15
3 A            3       231    25     7
4 B            1       115    25     6
5 B            2       321    25    19
6 B            3        12    25     0

Mutate can always be used when applying a function which takes (one or more) vector arguments and returns a vector of the same size.
If you want to use n_seats as well you could group with respect to municipality and seats (I would assume that the number of seats within each municipality is the same). Therefore:
mandates %>% group_by(municipality, seats) %>%
 mutate(x = seats_ha(parties = party, votes = votes, n_seats = seats[1], method = "dhondt"))


300 F.Supp. 665 (1969)
Deborah ROBINSON, by her next friend Wilbert Robinson, et al., Plaintiffs,
and
Judy Lewis, by her next friend Violet Lewis, and Debra Braxton, by her next friend Mary Braxton, Intervenors,
v.
John BRADLEY, individually and as principal of the Martin Luther King Middle School, Thomas McAuliffe, individually and as Assistant Superintendent of the Boston Schools, Patricia Dupres, as public school teacher at the Martin Luther King Middle School, John P. Holland, as Clerk of the Dorchester District Court, Defendants.
Civ. A. No. 69-546.
United States District Court D. Massachusetts.
June 20, 1969.
Michael L. Altman, Boston Legal Assistance Project, Boston, Mass., for plaintiffs.
Gerard Powers, Edith W. Fine, Asst. Corp. Counsel, City of Boston, Boston, Mass., for City of Boston, McAuliffe, Dupres & Bradley.
Bruce G. McNeill, Howard M. Miller, Asst. Attys. Gen., Boston, Mass., for defendant Holland.
Before COFFIN, Circuit Judge, and FORD and CAFFREY, District Judges.

OPINION OF THE COURT
COFFIN, Circuit Judge.
This is an action for both injunctive and declaratory relief. Jurisdiction is invoked under 28 U.S.C. § 1343. Plaintiffs, students at the Martin Luther King Middle School, a Boston public school, are minors and bring this action by next friends.[1] Plaintiffs seek to restrain the enforcement, operation, *666 and execution of the Massachusetts "threats" statute [Mass.Gen.Laws ch. 275, § 2 et seq.] and a declaratory judgment that said statute is unconstitutional. 28 U.S.C. §§ 2201, 2281 et seq.[2] Defendant Bradley is principal of the Martin Luther King Middle School; defendant Dupres is a teacher at said King School; defendant McAuliffe is an Assistant Superintendent, administratively responsible for the operation of a number of public schools within the city of Boston, including the Martin Luther King Middle School; the defendant John P. Holland is the clerk of the Dorchester District Court in the city of Boston which has jurisdiction over minor criminal offenses committed within a section of the city of Boston in which the Martin Luther King Middle School is located.
On May 21, 1969, defendant Dupres appeared in Dorchester District Court to seek a juvenile delinquency complaint against plaintiff Deborah Robinson. The alleged basis of this complaint was a "threat" made to this defendant by plaintiff Robinson on May 12, 1969, while defendant was teaching a class at the King School. Defendant alleged that plaintiff came up to the door of her classroom, knocked on it several times, and asked to be admitted into the room. After defendant refused, plaintiff allegedly stated to her through the closed door: "If you come outside, I will beat you up."
Defendant Holland subsequently issued a complaint from the Dorchester District Court charging the plaintiff Robinson with juvenile delinquency for allegedly violating the Massachusetts "threats" statute. Mass.Gen.Laws ch. 275, § 2 et seq.[3] Prior to the issuance of the complaint, however, plaintiffs filed a motion, pursuant to 28 U.S.C. § 2281 et seq., in the United States District Court for the convening of a three-judge district court. On June 4, 1969 a three-judge court was convened and on the same date the court heard oral argument. Legal memoranda were subsequently filed.
Plaintiffs make several constitutional attacks on the statute  that it is vague and overbroad, in that it fails to provide adequate notice of criminal conduct and lends itself to arbitrary enforcement; that its "peace bond" provisions are violative of both the Eight and Fourteenth Amendments; and that it has a chilling effect on constitutionally protected speech. No allegation of bad faith is made.[4]
The first question we face is whether we have equitable jurisdiction to grant injunctive relief under the teachings of Dombrowski v. Pfister, 380 U.S. 479, 85 S.Ct. 1116, 14 L.Ed.2d 22 (1965), and Cameron v. Johnson, 390 U.S. 611, 88 S.Ct. 1335, 20 L.Ed.2d 182 (1968).[5] We start with the proposition *667 that our jurisdiction must rest on allegations which bring this case within the "special circumstances" justifying departure from the general principle that "[f]ederal interference with a State's good-faith administration of its criminal law `is peculiarly inconsistent with our federal framework' * * *. [Dombrowski v. Pfister] 380 U.S. at 484, 85 S.Ct. at 1119, 1120." Cameron v. Johnson, supra, 390 U.S. at 618, 88 S.Ct. at 1339.
In Dombrowski the Court dealt with a mix of two factors: a state subversives registration law which was facially unconstitutional because of vagueness and overbreadth; and a series of harassing arrests, searches, and threats of prosecution. It was not made explicit in that case whether either the facial unconstitutionality of vagueness and overbreadth or the bad faith conduct of state officials would have been a sufficient ground for the relief given. It is possible to read Dombrowski as requiring both grounds, either ground, or solely bad faith.
In Cameron, however, the Court characterized the holding in Dombrowski as resting on the bad faith conduct. "In short, we viewed Dombrowski to be a case presenting a situation of the `impropriety of [state officials] invoking the statute in bad faith to impose continuing harassment in order to discourage appellants' activities * * *.'" Id. 390 U.S. at 619, 88 S.Ct. at 1339. And Mr. Justice Fortas in dissent spoke as clearly to this interpretation.
"Dombrowski's remedy is justified only when First Amendment rights, which are basic to our freedom, are imperiled by calculated, deliberate state assault. And those who seek federal intervention bear a heavy burden to show that the State, in prosecuting them, is not engaged in use of its police power for legitimate ends, but is deliberately invoking it to harass or suppress First Amendment rights. Dombrowski should never be invoked when the State is, in substance and truth, engaged in the enforcement of valid criminal laws. Ordinarily, the presumption that the State's motive was law enforcement and not interference with speech or assembly will carry the day." Id. at 623, 88 S.Ct. at 1342.
Plaintiffs  who have made no assertion that defendants have acted in bad faith[6]  contend that since the Court in Cameron was not dealing with any issue other than that of bad faith, its comments cannot be taken as a definitive delineation of the reach of Dombrowski. The Commonwealth disagrees, contending that a sine qua non of federal equitable jurisdiction is a state's deliberate use of police power to harass or suppress First Amendment rights.
We do not find it necessary to resolve this issue, for we do not view Mass.Gen. Laws ch. 275 as facially unconstitutional because of vagueness or overbreadth. We observe, first, that "overbreadth" in this case is an allegation which, to have substance, assumes that the statute is *668 reasonably capable of being interpreted as to embrace every menacing remark against another's person or property, without regard to the seriousness of the intention, the capability of implementing the threat, or the presence of any "just cause" for fear. The statute is not like those in Dombrowski v. Pfister, supra; Zwickler v. Koota, 389 U.S. 241, 88 S.Ct. 391, 19 L.Ed.2d 444 (1967); or Keyishian v. Board of Regents, 385 U.S. 589, 87 S.Ct. 675, 17 L.Ed.2d 629 (1967) where the facial invalidity stemmed from an overbreadth, inherent in the incurably precise and clear statutory language. Here, however, if we assume arguendo that the statute is capable of reasonably foreseeable court interpretation confining it within constitutional bounds, the argument as to overbreadth drops out.
We view the statute before us as inviting such an interpretation. While ancient, it has never been interpreted, possibly because the critical words have carried traditional meanings within the common understanding. The object of the legislation, indeed, is specific enough without more. The "person or property of another" needs no exegesis.[7]
Plaintiffs focus their attack on sections 2 and 6 of the statute.[8] Specifically, plaintiffs challenge as impermissably vague both section 2's proscription of "threats" of the commission of a crime and the mandate of section 6 that punishment is to be imposed only if there is "just cause to fear that such crime will be committed".
The word "threat" has a well established meaning in both common usage and in the law. It is "the expression of an intention to inflict evil, injury, or damage on another". Webster's New International Dictionary, n. 1 (1966 ed. unabridged). In law "threat" has universally been interpreted to require more than the mere expression of intention. It has, in fact, been interpreted to require both intention and ability in circumstances which would justify apprehension on the part of the recipient of the threat. See, e. g., Landry v. Daley, supra at 962; State of Maine v. Cashman, 217 A.2d 28 (Me.1966); State of Connecticut v. Boyer, 2 Conn.Cir. 288, 198 A.2d 222 (Conn.1963).[9]
We read the "just cause" proviso of section 6 as incorporating the elements of the "threats" language of section 2. That is, only if there is that intention and ability, which would justify apprehension by the recipient in the circumstances, is there "just cause to fear that *669 such crime will be committed by the person complained of * * *." Mass.Gen. Laws ch. 275, § 6. Insofar as First Amendment protection is concerned, this reading of the phrase would seem to equate "just cause" with "clear and present danger" or its variants. The term "just cause" is, of course, a common term used in a wide variety of instances, both in Massachusetts and elsewhere.[10]
Moreover, the speech involved here, if not "hard core" in the sense of being proscribed (i. e., the plaintiff's remark may not be punishable) does not present the danger of "chilling effect" on protected activities.[11]
Finally, even if, despite the fact that the words are of long standing tradition and usage in the law, the statute is in need of construction, on which we imply no judgment, there are state procedural avenues available, apart from criminal prosecutions. Plaintiffs may have two options: equitable relief, Kenyon v. City of Chicopee, 320 Mass. 528, 70 N.E.2d 241 (1946), or a proceeding under the Massachusetts Declaratory Judgment Act, Mass.Gen.Laws ch. 231A; Massachusetts Ass'n of Tobacco Distributors v. State Tax Commission, 1968 Mass.Adv.Sh. 489, 491, 235 N.E.2d 557; Commonwealth v. Baird, 1969 Mass.Adv. Sh. 727, 735, 247 N.E.2d 574.
We therefore conclude that there is no basis for the exercise of equitable jurisdiction. Our view of the issues of vagueness and overbreadth also disposes of the request for declaratory relief.
Order accordingly.
NOTES
[1]  Plaintiffs Judy Lewis and Debra Braxton were allowed to intervene in this action after the original and amended complaints were filed.
[2]  The amended complaint contained a count under 42 U.S.C. § 1983 as well. Plaintiffs then moved that this count be severed from their complaint. Defendants do not object. The motion is hereby granted.
[3]  The intervening minor plaintiffs alleged that defendant Dupres has accused them of violating the "threats" statute and also alleged that a juvenile delinquency complaint would be sought against them on June 10, 1969. We are informed that no such complaint has yet been issued.
[4]  Plaintiffs also allege that procedures in the Dorchester District Court are so deficient that they have "no adequate remedy at law" in Massachusetts courts. In their memorandum plaintiffs assert "that the procedures in the Dorchester District Court are such that it is impossible for them to have a fair trial" and that the "absence of fair procedures in the Dorchester Court are sufficient `special circumstances' to warrant the exercise of this court's equitable power. See Hulett v. Julian, 250 F.Supp. 208 (M.D.Ala. 1966)."
[5]  Plaintiffs argued that, at the outset of this federal proceeding, there was no state prosecution which had gone so far as to constitute a pending proceeding and that therefore § 2283 is not applicable. The complaint in this case was filed on May 21, 1969 at 1:38 p. m. Plaintiffs' uncontested affidavit avers that defendant Dupres first presented her request for complaints to a probation officer in the Dorchester District Court at approximately 2:30 p. m. on May 21. Defendants have not argued that the Commonwealth proceedings commenced prior to this suit. While the issue is not important in the light of our decision, and the state of the record not entirely clear, we hold that § 2283 is not a bar to these proceedings. Dombrowski v. Pfister, supra at 587, n. 4, 85 S.Ct. 1116.
[6]  Except, perhaps, obliquely by allegations that the procedures applicable to juveniles in the Dorchester District Court afford inadequate protection. These allegations are not, in our view, to be equated with the kind of selective activities directed to the suppression of speech connoted by the bad faith label in Dombrowski and Cameron. Unlike the situation described in Hulett v. Julian, 250 F.Supp. 208 (M. D.Ala.1966), cited by plaintiffs, any alleged defects in District Court procedure may be raised through available state law channels. See text infra.
[7]  Plaintiffs argue that "another" could refer to the Commonwealth, based on the interpretation of that word in a trespass statute.

Apart from the obvious comment that the meaning of the same word may vary from statute to statute depending upon the context, we see no inherent constitutional defect in proscribing a serious threat against the property of a corporation or a governmental entity. Cf. Landry v. Daley, 280 F.Supp. 938, 964 (N.D. Ill.1968).
[8]  Section 2 reads as follows:

"If complaint is made to any such court or justice that a person has threatened to commit a crime against the person or property of another, such court or justice shall examine the complainant and any witnesses who may be produced, on oath, reduce the complaint to writing and cause it to be subscribed by the complainant."
Section 6 states:
"If, upon such examination, it is found that there is not just cause to fear that such crime will be committed by the person complained of, he shall be forthwith discharged; and if it is found that the complaint is unfounded, frivolous or malicious, the complainant may be ordered to pay the expenses of prosecution."
[9]  The word "threat" appears in several federal statutes and the courts have uniformly adopted the construction of "threats" discussed above. See, e. g., United States v. Prochaska, 222 F.2d 1 (7th Cir.), cert. denied, 350 U.S. 836, 76 S.Ct. 73, 100 L.Ed. 746 (1955); Berry Brothers Buick, Inc. v. General Motors Corp., 257 F.Supp. 542 (E.D.Pa.1966), aff'd per curiam, 377 F.2d 552 (3d Cir. 1967).
[10]  The Supreme Court's remark in Thornhill v. Alabama, 310 U.S. 88, 60 S.Ct. 736, 84 L.Ed. 1093 (1940), that the phrase "without just cause or legal excuse" has no meaning either inherent or historical, is clearly inapposite here. The statute there proscribed "loitering without just cause" and the statement was made against the background of a state court construction prohibiting peaceful picketing in a labor dispute by a single individual.
[11]  This is clearly true in the case of the plaintiff Robinson; for as the Commonwealth points out, she, hopefully, does not wish to continue threatening to "beat up" her teacher.

With respect to the two intervening plaintiffs, there is no evidence regarding their conduct. In this regard, we note that the absence of evidence raises a serious question of standing. In view of our disposition of the case, we do not consider this issue.