A silver halide photographic material is disclosed, comprising at least one silver halide emulsion layer provided on a support, the emulsion layer comprising a silver halide emulsion containing at least two sensitizing dyes represented by the following general formula (I):

The present invention relates to a silver halide photographic material. More particularly, the present invention relates to a silver halide photographic material which exhibits a high sensitivity and leaves little undesired color unextinguished (i.e., little residual color) even after rapid process.
A great effort has heretofore been made to enhance the sensitivity of silver halide photographic light-sensitive materials and allow the silver halide photographic materials to leave less undesired color unextinguished (i.e., less residual color) after processing. In addition to photographic requirements for higher sensitivity and image quality, there has been a growing demand for the enhancement of photographic processing speed, reduction of the amount of waste liquid under the necessity of meeting environmental protection, etc. It has thus been desired to develop a technique for spectrally sensitizing silver halide grains to a high degree without having adverse effects such as fog and color remaining (i.e., residual color).
It has been known that sensitizing dyes for use in spectral sensitization have a great effect on the properties of silver halide photographic materials. Even a small structural difference between sensitizing dyes has a great effect on photographic properties such as sensitivity, fog, storage stability and color remaining after processing. Further, the combined use of two or more sensitizing dyes, too, have a great effect on photographic properties. It is difficult to predict these effects. Many researchers have heretofore synthesized a large number of sensitizing dyes. Many researchers have also made studies of combined use of a large number of sensitizing dyes and efforts to examine the photographic properties. However, it is the status quo that the photographic properties cannot still be predicted.
A tabular silver halide grain has a great surface area per volume (specific surface area) and thus is advantageous for spectral sensitization because it can adsorb a large amount of a sensitizing dye. Such a tabular silver halide grain is also useful in the improvement of sensitivity/graininess. However, it accordingly causes more dye color remaining (i.e., dye-residual color). This color remaining problem is more severe than caused by regular grains.
On the other hand, it has been desired to reduce the photographic processing time. However, when the processing time is reduced, the emulsion leaves more sensitizing dyes unprocessed, causing more severe color remaining problem. In some photofinishing laboratories, photographic light-sensitive materials are processed with processing solutions having varied formulations or rinsed at low temperatures, occasionally causing severe color remaining. It has thus been keenly desired to develop a technique for lessening color remaining of sensitizing dyes.
The occurrence of color remaining of sensitizing dyes depends greatly on the hydrophobicity of the dyes. In other words, the more hydrophilic is a dye, the less occurs color remaining. On the other hand, however, the dye exhibits a reduced adsorptivity to the surface of silver halide grains, having adverse effects on photographic properties such as sensitivity drop and deterioration of preservability. Thus, it is not desired to render a dye excessively hydrophilic. In short, in order to lessen color remaining while keeping desired photographic properties, it is necessary to select the hydrophilicity or hydrophobicity of a dye appropriately. The inventors disclose in Japanese Patent Application (Laid-Pen) No. 2001-75224 that the optimum selection of various substituents on sensitizing dyes makes it possible to attain both desired photographic properties and minimization of color remaining.
However, the recent trend is that factors such as rise of aspect ratio of tabular silver halide grains and further rise of the added amount of sensitizing dyes cause another problem. In other words, it has been made obvious that when a large amount of a sensitizing dye is added to a tabular grain, the sensitizing dye adsorbed at a high percent coverage causes gelatin to lose its function as a protective colloid. In particular, tabular grains having a high aspect ratio are subject to contact of main planes and coalescence of grains and hence agglomeration, causing side effects such as increased occurrence of fog or sensitivity drop during aging of emulsion in the form of solution and deterioration of graininess. As a countermeasure against these difficulties there has been known a method as disclosed in Japanese Patent Application (Laid-Open) No. 1994-332091 involving the addition of a fine emulsion of substantially insoluble silver bromoiodide grains during or after the chemical sensitization of a silver halide emulsion. However, this approach cannot be applied to all emulsions. It has been desired to provide a substitute for this approach.
An object of the present invention is to provide a silver halide photographic material which exhibits a high sensitivity and leaves little undesired color unextinguished (i.e., little residual color) even after rapid processing or processing under severe conditions.
As a result of extensive studies, the object of the present invention was accomplished by the following aspects (1) to (11) of the present invention:
(1) A silver halide photographic material comprising at least one silver halide emulsion layer provided on a support, the emulsion layer comprising a silver halide emulsion containing at least two sensitizing dyes represented by the following general formula (I):
wherein X represents an oxygen atom, sulfur atom, selenium atom or NRxe2x80x2; R and Rxe2x80x2 each represent a substituted or unsubstituted alkyl, aryl or heterocyclic group; D represents a group required to form a methine dye; M represents a counter ion; and m represents a number of not smaller than 0 required to neutralize the electric charge in the molecule.
(2) The silver halide photographic material according to the above item (1), wherein the two sensitizing dyes each are a cyanine dye.
(3) The silver halide photographic material according to the above item (1) or (2), wherein the two sensitizing dyes each are represented by the following general formula (II):
wherein X1 and X2 each represent an oxygen atom, sulfur atom, selenium atom or NR3; R1, R2 and R3 each represent a substituted or unsubstituted alkyl, aryl or heterocyclic group; Y1 represents a condensed ring which may have substituents; L1, L2 and L3 each represent a methine group; n1 represents 0, 1, 2 or 3, with the proviso that when n1 is 2 or 3, the plurality of L2""s and L3""s each may be the same or different; M1 represents a counter ion; and m1 represents a number of not smaller than 0 required to neutralize the electric charge in the molecule.
(4) The silver halide photographic material according to the above item (3), wherein n1 in the two sensitizing dyes are the same.
(5) The silver halide photographic material according to the above item (3), wherein X1 and X2 each are selected from the group consisting of oxygen atom and sulfur atom.
(6) The silver halide photographic material according to any one of the above items (1) to (5), wherein the two sensitizing dyes each have at least two dissociative groups.
(7) The silver halide photographic material according to the above item (6), wherein the sensitizing dyes each have at least one xe2x80x94SO3H group and at least one dissociative group other than xe2x80x94SO3H.
(8) The silver halide photographic material according to the above item (7), wherein the dissociative group other than xe2x80x94SO3H is selected from the group consisting of xe2x80x94COOH, xe2x80x94CONHSO2Z, xe2x80x94SO2NHCOZ, xe2x80x94SO2NHSO2Z and xe2x80x94CONHCOZ in which Z represents an alkyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, heterocyclyloxy group or amino group.
(9) A silver halide photographic material comprising at least one silver halide emulsion layer provided on a support, the emulsion layer comprising a silver halide emulsion containing at least one cyanine dye represented by the following general formula (III):
wherein R11 and R12 each represent a substituted or unsubstituted alkyl group, with the proviso that at least one of R11 and R12 is substituted by a xe2x80x94COOH group; X11 and X12 each represent an oxygen atom or sulfur atom; Y11 represents a condensed naphthalene ring which may have substituents; A1 represents a hydrogen atom or unsubstituted alkyl group; n11 represents 0 or 1; M11 represents a counter ion; and m11 represents a number of not smaller than 0 required to neutralize the electric charge in the molecule.
(10) The silver halide photographic material according to any one of the above items (1) to (9), wherein the silver halide emulsion in at least one emulsion layer comprises at least one sensitizing dye represented by the following general formula (III) and at least one sensitizing dye represented by the following general formula (IV):
wherein R21 and R22 each represent a substituted or unsubstituted alkyl group, with the proviso that at least one of R21 and R22 is substituted by a dissociative group other than xe2x80x94SO3H group; X21 and X22 each represent an oxygen atom or sulfur atom; Y21 represents a condensed benzene ring which may have substituents; A2 represents a hydrogen atom or unsubstituted alkyl group; n21 represents 0 or 1; M21 represents a counter ion; and m21 represents a number of not smaller than 0 required to neutralize the electric charge in the molecule.
(11) The silver halide photographic material according to any one of the above items (1) to (10), wherein the emulsion comprising sensitizing dyes represented by the general formula (I) comprises tabular grains having an aspect ratio of not smaller than 2 incorporated therein in a proportion of not smaller than 50% based on the total projected area of the silver halide grains incorporated therein.
(12) The silver halide photographic material according to any one of the above items (1) to (11), wherein the emulsion comprising sensitizing dyes represented by the general formula (I) is subjected to chemical sensitization with a selenium sensitizer.
The sensitizing dyes to be used in the present invention will be further described hereinafter.
In the present invention, when a specific moiety is referred to as xe2x80x9cgroupxe2x80x9d, it means that the moiety may not be substituted itself or may be substituted by one or more (maximum allowable number of) substituents. For example, the term xe2x80x9calkyl groupxe2x80x9d as used herein is meant to indicate a substituted or unsubstituted alkyl group. The substituents employable in the compounds of the present invention include any substituents regardless of whether or not they are substituted.
The substituent, if represented by V, is not specifically limited. Examples of the substituent represented by V include halogen atom, alkyl group such as alkyl group (e.g., cycloalkyl group, bicycloalkyl group), alkenyl group (e.g., cycloalkenyl group, bicycloalkenyl group, tricycloalkenyl group) and alkinyl group, aryl group, heterocyclic group, cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (including anilino group), ammonio group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamonylamino group, alkylsulfonylamino group, arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, arylazo group, heterocyclic azo group, imido group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, phospho group, silyl group, hydrazino group, ureido group, and other known substituents.
More specifically, V represents a halogen atom (e.g., fluorine, chlorine, bromine, iodine), alkyl group [straight-chain, branched or cyclic substituted or unsubstituted alkyl group, including alkyl group (e.g., C1-C30 alkyl group (i.e., alkyl group having 1 to 30 carbon atoms) such as methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl), cycloalkyl group (preferably C3-C30 substituted or unsubstituted cycloalkyl group such as cyclohexyl, cyclopentyl and 4-n-dodecylcyclohexyl), bicycloalkyl group (preferably C5-C30 substituted or unsubstituted bicycloalkyl group such as bicyclo[1.2.2]heptane-2-il and bicyclo[2.2.]octane-3-il), tricyclo structure having many cyclic structures, etc. The alkyl groups in the substituents described later (e.g., alkyl group in alkylthio group) include the following alkenyl group, cycloalkenyl group, bicycloalkenyl group, alkinyl group, etc. in addition to the foregoing concept of alkyl group], alkenyl group [straight-chain, branched or cyclic substituted or unsubstituted alkenyl group, including alkenyl group (preferably C2-C30 substituted or unsubstituted alkenyl group such as vinyl, allyl, prenyl, gelanyl, oleyl), cycloalkenyl group (preferably C3-C30 substituted or unsubstituted cycloalkenyl group such as 2-cyclopentene-1-il and 2-cyclohexene-1-il), bicycloalkenyl group (substituted or unsubstituted bicycloalkenyl group, preferably C5-C30 substituted or unsubstituted bicycloalkenyl group such as bicyclo[2.2.1]hepto-2-ene-1-il and bicyclo[2.2.2]octo-2-ene-4-il)], alkinyl group (preferably C2-C30 substituted or unsubstituted alkinyl group such as ethinyl, propargyl and trimethylsilyl ethinyl), aryl group (preferably C6-C30 substituted or unsubstituted aryl group such as phenyl, p-tollyl, naphthyl, m-chlorophenyl and o-hexadecanoylaminophenyl), heterocyclic group (preferably monovalent group obtained by removing one hydrogen atom from a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic compound, more preferably C3-C30 5- or 6-membered aromatic heterocyclic group such as 2-furyl, 2-chenyl, 2-pyrimidinyl and 2-benzothiazolyl or cationic heterocyclic group such as 1-methyl-2-pyridinio and 1-methyl-2-quinolinio), cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group (preferably C1-C30 substituted or unsubstituted alkoxy group such as methoxy, ethoxy, isopropoxy, t-butoxy, n-octyloxy and2-methoxyethoxy), aryloxy group (preferably C6-C30 substituted or unsubstituted aryloxy group such as phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy and 2-tetradecanoylaminophenoxy), silyloxy group (preferably C3-C20 silyloxy group such as trimethylsilyloxy and t-butyldimethylsilyloxy), heterocyclicoxy group (preferably C2-C30 substituted or unsubstituted heterocycyclicoxy group such as 1-phenyltetrazol-5-oxy or 2-tetrahydropyranyl), acyloxy group (preferably formyloxy group, C2-C30 substituted or unsubstituted alkylcarbonyloxy group or C6-C30 substituted or unsubstituted arylcarbonyloxy group such as formyloxy, acetyloxy, pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy), carbamoyloxy group (preferably C1-C30 substituted or unsubstituted carbamoyloxy group such as N,N-dimethylcarbamoyloxy, N,N-diethylcarbamoyloxy, morpholinocarbonyloxy, N,N-di-n-octylaminocarbonyloxy, N-n-octylcarbamoyloxy), alkoxycarbonyloxy group (preferably C2-C30 substituted or unsubstituted alkoxycarbonyloxy group such as methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy and n-octylcarbonyloxy), aryloxycarbonyloxy group (preferably C7-C30 substituted or unsubstituted aryloxycarbonyloxy group such as phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy and p-n-hexadecyloxyphenoxycarbonyloxy), amino group (preferably amino group, C1-C30 substituted or unsubstituted alkylamino group or C6-C30 substituted or unsubstituted anilino group such as amino, methylamino, dimethylamino, anilino, N-methylanilino and diphenylamino), ammonio group (preferably ammonio group, and ammonio group substituted by C1-C30 substituted or unsubstituted alkyl group, aryl group or heterocyclic group such as trimethylammonio, triethylammonio and diphenylmethylammonio), acylamino group (preferably formylamino group, C1-C30 substituted or unsubstituted alkylcarbonylamino group or C6-C30 substituted or unsubstituted arylcarbonylamino group such as formylamino, acetylamino, pivaloylamino, lauroylamino, benzoylamino and 3,4,5-tri-n-octyloxyphenylcarbonylamino), aminocarbonyl amino group (preferably C1-C30 substituted or unsubstituted aminocarbonylamino group such as carbamoylamino, N,N-dimethylaminocarbonylamino, N,N-diethylaminocarbonylamino and morpholinocarbonylamino), alkoxycarbonylamino group (preferably C2-C30 substituted or unsubstituted alkoxycarbonylamino group such as methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino and N-methylmethoxycarbonylamino), aryloxycarbonylamino group (preferably C7-C30 substituted or unsubstituted aryloxycarbonylamino group such as phenoxycarbonylamino, p-chlorophenoxycarbonylamino and m-(n-octyloxy)phenoxycarbonylamino), sulfamoylamino group (preferably C0-C30 substituted or unsubstituted sulfamoylamino group such as sulfamoylamino, N,N-dimethylaminosulfonylamino and N-n-octylaminosulfonylamino), alkylsulfonylamino group or arylsulfonylamino group (preferably C1-C30 substituted or unsubstituted alkylsulfonylamino group or C6-C30 substituted or unsubstituted arylsulfonylamino group such as methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino and p-methylphenylsulfonylamino), mercapto group, alkylthio group (preferably C1-C30 substituted or unsubstituted alkylthio group such as methylthio, ethylthio and n-hexadecylthio), arylthio group (preferably C6-C30 substituted or unsubstituted arylthio group such as phenylthio, p-chlorophenylthio and m-methoxyphenylthio), heterocyclic thio group (preferably C2-C30 substituted or unsubstituted heterocyclic thio group such as 2-benzothiazolylthio and 1-phenyltetrazole-5-ilthio), sulfamoyl group (preferably C0-C30 substituted or unsubstituted sulfamoyl group such as N-ethylsulfamoyl, N-(3-dodecyloxypropyl)sulfamoyl, N,N-dimethylsulfamoyl, N-acetylsulfamoyl, N-benzoylsulfamoyl and N- (Nxe2x80x2-phenylcarbamoyl) sulfamoyl), sulfo group, alkylsulfinyl group or arylsulfinyl group (preferably C1-C30 substituted or unsubstituted alkylsulfinyl group or C6-C30 substituted or unsubstituted arylsulfinyl group such as methylsulfinyl, ethylsulfinyl, phenylsulfinyl and p-methylphenylsulfinyl), alkylsulfonyl group or arylsulfinyl group (preferably C1-C30 substituted or unsubstituted alkylsulfonyl group or C6-C30 substituted or unsubstituted arylsulfonyl group such as methylsulfonyl, ethylsulfonyl, phenylsulfonyl, p-methylphenylsulfonyl), acyl group (preferably formyl group, C2-C30 substituted or unsubstituted alkylcarbonyl group, C7-C30 substituted or unsubstituted arylcarbonyl group or C4-C30 substituted or unsubstituted heterocyclic carbonyl group having carbonyl groups bonded to each other via carbon atom such as acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, p-n-octyloxyphenylcarbonyl, 2-pyridylcarbonyl and 2-furylcarbonyl), aryloxycarbonyl group (preferably C7-C30 substituted or unsubstituted aryloxycarbonyl group such as phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl and p-t-butylphenoxycarbonyl), alkoxycarbonyl group (preferably C2-C30 substituted or unsubstituted alkoxycarbonyl group such as methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl and n-octadecyloxycarbonyl), carbamoyl group (preferably C1-C30 substituted or unsubstituted carbamoyl group such as carbamoyl, N-methylcarbamoyl, N,N-dimethylcarbamoyl, N,N-di-n-octylcarbamoyl and N-(methylsulfonyl) carbamoyl), arylazo group or heterocyclic azo group (preferably C6-C30 substituted or unsubstituted arylazo group or C3-C30 substituted or unsubstituted heterocyclic azo group such as phenylazo, p-chlorophenylazo and 5-ethylthio-1,3,4-thiadiazole-2-ilazo), imido group (preferably N-succinimido, N-phthalimido), phosphino group (preferably C2-C30 substituted or unsubstituted phosphino group such as dimethylphosphino, diphenylphosphino and methylphenoxyphosphino), phosphinyl group (preferably C2-C30 substituted or unsubstituted phosphinyl group such as phosphinyl, dioctyloxyphosphinyl and diethoxyphosphinyl), phosphinyloxy group (preferably C2-C30 substituted or unsubstituted phosphinyloxy group such as diphenoxyphosphinyloxy and dioctyloxyphosphinyloxy), phosphinylamino group (preferably C2-C30 substituted or unsubstituted phosphinylamino group such as dimethoxyphosphinylamino and dimethylaminophosphinylamino), phospho group, silyl group (preferably C3-C30 substituted or unsubstituted silyl group such as trimethylsilyl, t-butyldimethylsilyl and phenyldimethylsilyl), hydrazino group (preferably C0-C30 substituted or unsubstituted hydrazino group such as trimethylhydrazino) or ureido group (preferably C0-C30 substituted or unsubstituted ureido group such as N,N-dimethylureido).
Two V""s may be connected to each other to have a structure having rings condensed to each other (aromatic or non-aromatic hydrocarbon ring or heterocycle. These rings may be further combined to form a polycyclic condensed ring. Examples of the ring include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, fluorene ring, triphenylene ring, naphthacene ring, biphenyl ring, pyrrole ring, furan ring, thiphene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indolizine ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolizine ring, quinoline ring, isoquinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, carbazole ring, phenanthridine ring, acridine ring, phenanthroline ring, thianthrene ring, chromene ring, xanthene ring, phenoxathiin ring, phenothiazine ring, and phenazine ring).
Among the foregoing substituents V, those having a hydrogen atom may be freed of hydrogen atom, and then substituted by the foregoing substituents. Examples of such a composite substituent include acylsulfamoyl group, alkylsulfonylacarbamoyl group, and arylsulfonylcarbamoyl group. Examples of these composite substituents include methylsulfonylcarbamoyl, p-methylphenylsulfonylcarbamoyl, acetylsulfamoyl, and benzoylsulfamoyl.
The sensitizing dye to be incorporated in the silver halide photographic material of the present invention is represented by the general formula (I). One emulsion in at least one emulsion layer contains two different dyes. The sensitizing dye of the general formula (I) will be further described hereinafter.
In the general formula (I), X represents an oxygen atom, sulfur atom, selenium atom or NRxe2x80x2. Rxe2x80x2 represents a substituted or unsubstituted alkyl, aryl or heterocyclic group. X preferably represents an oxygen atom or sulfur atom.
R and Rxe2x80x2 each represent a substituted or unsubstituted alkyl, aryl or heterocyclic group.
The alkyl group represented by R or Rxe2x80x2 is a C1-C18, preferably C1-C7, particularly C1-C4 unsubstituted alkyl group (e.g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, dodecyl, octadecyl) or C1-C18, preferably C1-C7, particularly C1-C4 substituted alkyl group {Examples of the substituents on these substituted alkyl groups include the various substituents represented by V (e.g., aryl group, unsaturated hydrocarbon group, carboxyl group, sulfo group, sulfato group, cyano group, halogen atom (e.g., fluorine, chlorine, bromine, iodine), hydroxyl group, mercapto group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, carbamoyl group, sulfamoyl group, heterocyclic group, alkylsulfonylcarbamoyl group, acylcarbamoyl group, acylsulfamoyl group, alkylsulfonylsulfamoyl group (These substituents may be further substituted))}.
The aryl group represented by R or Rxe2x80x2 is a C6-C20, preferably C6-C15, more preferably C6-C10 unsubstituted aryl group (e.g., phenyl, 1-naphthyl) or C6-C26, preferably C6-C21, more preferably C6-C16 substituted aryl group {Examples of the substituents on these substituted alkyl groups include the various substituents represented by V (e.g., alkyl group, aryl group, unsaturated hydrocarbon group, carboxyl group, sulfo group, sulfato group, cyano group, halogen atom (e.g., fluorine, chlorine, bromine, iodine), hydroxyl group, mercapto group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, carbamoyl group, sulfamoyl group, heterocyclic group, alkylsulfonylcarbamoyl group, acylcarbamoyl group, acylsulfamoyl group, alkylsulfonylsulfamoyl group (These substituents may be further substituted))}, preferably phenyl group.
The heterocyclic group represented by R or Rxe2x80x2 is a C1-C20, preferably C1-C15, more preferably C1-C10 unsubstituted heterocyclic group (e.g., pyrrole, furan, thiophene) or C1-C26, preferably C1-C21, more preferably C1-C16 substituted heterocyclic group {Examples of the substituents on these substituted heterocyclic groups include the various substituted represented by V}.
R and Rxe2x80x2 each are preferably a substituted group having an acid group or dissociative proton {group which can undergo dissociation (e.g., dissociation of proton or the like) to become an anionic group}, i.e., group which can have a negative charge such as proton-dissociative acid group which dissociates in a proportion of not smaller than 90% at a pH of from 5 to 10, e.g., carboxyl group, sulfo group, phosphonate group, boronate group, xe2x80x94CONHSO2xe2x80x94, xe2x80x94SO2NHSO2xe2x80x94, xe2x80x94CONHCOxe2x80x94, xe2x80x94SO2NHCOxe2x80x94}, more preferably an alkyl group substituted by the foregoing group having an acid group or dissociative proton, more preferably a substituted alkyl group containing any of carboxyl group, sulfo group, alkylsulfonylcarbamoyl group (e.g., methanesulfonylcarbonyl), acylcarbamoyl group (e.g., acetylcarbamoyl), acylsulfamoyl group (e.g., acetylsulfamoyl), and alkylsulfonylsulfamoyl group (e.g., methanesulfonyl sulfamoyl). Particularly preferred among these groups are carboxymethyl group, 2-sulfoethyl group, 3-sulfopropyl group, 3-sulfobutyl group, 4-sulfobutyl group, and methanesulfonylcarbamoylmethyl group.
M is incorporated in the general formula to indicate the presence of cation or anion when it is required to neutralize the ionic charge of dye. Which a dye is a cation or anion or whether or not the dye has a net ionic charge depends on its substituents. Representative examples of the cation include hydrogen ion (H+), inorganic cation such as alkaline metal ion (e.g., sodium ion, potassium ion, lithium ion) and alkaline earth metal ion (e.g., calcium ion), and organic ion such as ammonium ion (e.g., ammonium ion, tetraalkylammonium ion, triethylammonium ion, pyridinium ion, ethylpyridinium ion, 1,8-diazabicyclo[5.4.0]-7-undecenium ion). The anion may be either an inorganic anion or organic anion. Examples of the inorganic or organic anion include halide anion (e.g., fluoride ion, chloride ion, bromide ion, iodide ion), substituted arylsulfonate ion (e.g., p-toluenesulfonate ion, p-chlorobenzenesulfonate ion), aryldisulfonate ion (e.g., 1,3-benzenesulfonate ion, 1,5-naphthalenedisulfonate ion, 2,6-naphthalenedisulfonate ion), alkylsulfate ion (e.g., methylsulfate ion), sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate ion, picrate ion, acetate ion, and trifluoromethanesulfonate ion. Further, ionic polymers or other dyes having a charge of polarity opposite that of the dye may be used.
Preferred among these cations are sodium ion, potassium ion, triethylammonium ion, tetraethylammonium ion, pyridinium ion, ethylpyridinium ion, and methylpyridinium ion. Preferred among these anions are perchlorate ion, iodide ion, bromide ion, and substituted arylsulfonante ion (e.g., p-toluenesulfonate ion).
The suffix m represents a number of not smaller than 0 required to equilibrate electric charge. The suffix m is 0 when an intramolecular salt is formed. The suffix m is preferably from not smaller than 0 to not greater than 4.
D is a group required to form a methine dye. Any methine dye can be formed by D. Preferred examples of methine dye to be used herein include cyanine dye, melocyanine dye, rhodacyanine dye, trinuclear melocyanine dye, tetranuclear melocyanine dye, allopolar dye, hemicyanine dye, and styryl dye. For the details of these dyes, reference can be made to F. M. Hamer, xe2x80x9cHeterocyclic Compounds-Cyanine Dyes and Related Compoundsxe2x80x9d, John Wiley and Sons, New York, London, 1964, D. M. Sturmer, xe2x80x9cHeterocyclic Compounds-Special Topics in Heterocyclic Chemistryxe2x80x9d, Chapter 18, Article 14, pp. 482-515, etc.
Preferred examples of the general formula of these dyes are shown in U.S. Pat. No. 5,994,051, pp. 32-36, and U.S. Pat. No. 5,747,236, pp. 30-34. Preferred examples of the general formula of cyanine dye, melocyanine dye and rhodacyanine dye include general formulae (XI), (XII) and (XIII) disclosed in U.S. Pat. No. 5,340,694, columns 21-22 (with the proviso that n12, n15, n17 and n18 are not restricted but each are an integer of not smaller than 0 (preferably not greater than 4)). Preferred among these dyes are cyanine dye, melocyanine dye, and rhodacyanine dye. Particularly preferred among these dyes is cyanine dye.
The general formula (I), if the cyanine dye is formed by D or in like cases, may be represented by the following resonance formula (Ixe2x80x2):
The sensitizing dye to be used in the present invention will be further described hereinafter.
In the present invention, one emulsion comprises at least two sensitizing dyes represented by the general formula (I). More preferably, the two sensitizing dyes represented by the general formula (I) each are a methine dye selected from the group consisting of those represented by the following general formulae (V), (VI), (VII) and (VIII).
wherein X and R are the same as defined in the general formula (I); L51, L52, L53, L54 and L55 each represent a methine dye; p5 represents 0 or 1; n5 represents 0, 1, 2, 3 or 4; Y51 represents an atomic group required to form a 5- or 6-membered nitrogen-containing heterocyclic group and may be condensed with other carbon rings or heterocyclic rings or may have substituents; M5 represents a counter ion; m5represents a number of from not smaller than 0 to not greater than 4 required to neutralize the electric charge in the molecule; and R51 represents a substituted or unsubstituted alkyl, aryl or heterocyclic group.
wherein X and R are the same as defined in the general formula (I); L61 and L62 each represent a methine dye; n6 represents 0, 1, 2, 3 or 4; Y61 represents an atomic group required to form an acidic nucleus and may be condensed with other carbon rings or heterocyclic rings or may have substituents; M6 represents a counter ion; and m6 represents a number of from not smaller than 0 to not greater than 4 required to neutralize the electric charge in the molecule.
wherein X and R are the same as defined in the general formula (I); L71, L72, L73, L74, L75, L76 and L77 each represent a methine dye; p7 represents 0 or 1; n71 and n72 each represent 0, 1, 2, 3 or 4; Y71 and Y72 each represent an atomic group required to form a 5- or 6-membered nitrogen-containing heterocyclic group and may have substituents, with the proviso that Y72 maybe further condensed with other carbon rings or heterocyclic rings; M7 represents a counter ion; m7 represents a number of from not smaller than 0 to not greater than 4 required to neutralize the electric charge in the molecule; and R71 and R72 each represent a substituted or unsubstituted alkyl, aryl or heterocyclic group.
wherein X and R are the same as defined in the general formula (I); L81, L82, L83, L84, L85, L86 and L87 each represent a methine dye; p8 represents 0 or 1; n81 and n82 each represent 0, 1, 2, 3 or 4; Y81 and Y82 each represent an atomic group required to form a 5- or 6-membered nitrogen-containing heterocyclic group and may have substituents, with the proviso that Y82maybe further condensed with other carbon rings or heterocyclic rings; M8 represents a counter ion; m8 represents a number of from not smaller than 0 to not greater than 4 required to neutralize the electric charge in the molecule; and R81 and R82 each represent a substituted or unsubstituted alkyl, aryl or heterocyclic group.
The 5- or 6-membered nitrogen-containing heterocyclic group represented by Y51, Y72 or Y82 in the general formula (V), (VI), (VII) or (VIII) may be further condensed to other 5- or 6-membered carbon rings or heterocyclic rings. Examples of the carbon ring employable herein include benzene ring, and naphthalene ring. Examples of the heterocyclic ring employable herein include furan ring, and thiophene ring. Specific examples of these carbon or heterocyclic rings include those described as examples of Z11, Z12, Z13, Z14 and Z16 in U.S. Pat. No. 5,340,694, columns 23-24.
Y61 represents an atomic group required to form a non-cyclic or cyclic acidic nucleus and may be in the form of any acidic nucleus of ordinary melocyanine dye. In a preferred embodiment, a thiocarbonyl group or carbonyl group is disposed adjacent to the methine chain connecting site in Y61.
The term xe2x80x9cacidic nucleusxe2x80x9d as used herein is defined in, e.g., T. H. James, xe2x80x9cThe Theory of the Photographic Processxe2x80x9d, 4th Edition, Macmillan Publishing Inc., 1977, page 198. For the details of the definition of acidic nucleus, reference can be made to U.S. Pat. Nos. 3,567,719, 3,575,869, 3,804,634, 3,837,862, 4,002,480, and 4,925,777, Japanese Patent Application (Laid-Open) No. 167546/1991, etc.
Preferred examples of the acidic nucleus which constitutes a 5- or 6-membered heterocyclic group carbon atom, nitrogen atom and chalcogen atom (representative examples: oxygen, sulfur, selenium and tellurium) include nuclei such as 2-pyrazoline-5-one, pyrazolidine-3,5-dione, imidazoline-5-one, hydantoin, 2-thiohydantoin, 4-thiohydantoin, 2-iminooxazolidine-4-one, 2-oxazoline-5-one, 2-thiooxazoline-2,4-dione, isooxazoline-5-one, 2-thiazoline-4-one, thiazolidine-4-one, thiazolidine-2,4-dione, rhodanine, thiazolidine-2,4-dithione, isorhodanine, indane-1,3-dione, thiphene-3-one, thiophene-3-one-1,1-dioxide, indoline-2-one, indoline-3-one, 2-oxoindazolinium, 3-oxoindazolinium, 5,7-dioxo-6,7-dihydrothiazolo[3,2-a]pyrimidine, cyclohexane-1,3-dione, 3,4-dihydroisoquinoline-4-one, 1, 3-dioxane-4, 6-dione, barbituric acid, 2-thiobarbituric acid, chroman-2,4-dione, indazoline-2-one, pyrido[l,2-a]pyrimidine-1,3-dione, pyrazolo[l,5-b]quinazolone, pyrazolo[1,5-a]benzimidazole, pyrazolopyridone, 1,2,3,4-tetrahydroquinoline-2,4-dione, 3-oxo-2,3-dihydrobenzo[d]thiophene-1,1-dioxide and 3-dicyanomethylene-2,3-dihydrobenzo[d]thiophene-1,1-dioxid e, and nuclei having an exomethylene structure obtained by substituting carbonyl group or thiocarbonyl group constituting these nuclei by an active methylene compound having a structure such as ketomethylene and cyanomethylene at the active methylene position.
Preferred among the groups represented by Y61 are hydantoin, 2-thiohydantoin, 4-thiohydantoin, 2-oxazoline-5-one, 2-thiooxazoline-2,4-dione, thiazolidine-2,4-dione, rhodanine, thiazolidine-2,4-dithione, barbituric acid, and 2-thiobarbituric acid. Even more preferred among these groups are hydantoin, 2-thiohydantoin, 4-thiohydantoin, 2-oxazoline-5-one, rhodanine, barbituric acid, and 2-thiobarbituric acid. Particularly preferred among these groups are 2-thiohydantoin, 4-thiohydantoin, 2-oxazoline-5-one, rhodanine, and barbituric acid.
The 5- or 6-membered nitrogen-containing heterocyclic group formed by Y71 or Y81 is obtained by removing oxo group or thioxo group from the heterocyclic ring represented by Y61. Preferred examples of the 5- or 6-membered nitrogen-containing heterocyclic group formed by Y71 or Y81 include those obtained by removing oxo group or thioxo group from hydantoin, 2-thiohydantoin, 4-thiohydantoin, 2-oxazoline-5-one, 2-thiooxazoline-2,4-dione, thiazolidine-2,4-dione, rhodanine, thiazolidine-2,4-dithione, barbituric acid, and 2-thiobarbituric acid. Even more preferred among these 5- or 6-membered nitrogen-containing heterocyclic groups are those obtained by removing oxo group or thioxo group from hydantoin, 2-thiohydantoin, 4-thiohydantoin, 2-oxazoline-5-one, rhodanine, barbituric acid, and 2-thiobarbituric acid. Particularly preferred among these 5- or 6-membered nitrogen-containing heterocyclic groups are those obtained by removing oxo group or thioxo group from 2-thiohydantoin, 4-thiohydantoin, 2-oxazoline-5-one, and rhodanine.
The substituent (referred to as xe2x80x9cR61xe2x80x9d if any) on the nitrogen atom in R51, R71, R72, R81, R82 and acidic nucleus Y61 each represent a substituted or unsubstituted alkyl, aryl or heterocyclic group which is preferably a group described as an example of R in the methine dye of the general formula (I).
Preferred among R51, R61, R71, R72, R81 and R82 is a substituted or unsubstituted alkyl group, more preferably an alkyl group substituted by a group having acidic group or dissociative proton, further more preferably a substituted alkyl group containing any of carboxyl group, sulfo group, xe2x80x94CONHSO2xe2x80x94, xe2x80x94SO2NHSO2xe2x80x94, xe2x80x94CONHCOxe2x80x94, and xe2x80x94SO2NHCOxe2x80x94, particularly carboxylmethyl group, 2-sulfoethyl group, 3-sulfopropyl group, 3-sulfobutyl group, 4-sulfobutyl group or methanesulfonylcarbamoylmethyl group.
L51, L52, L53, L54, L55, L61, L62, L71, L72, L73, L74, L75, L76, L77, L81, L82, L83, L84 L85, L86 and L87 each independently represent a methine group. These methine dyes each may have substituents. Examples of the substituents on the substituted methine group include the various substituents represented by V.
These methine groups may form a ring with other methine groups or Y51, Y61, Y71, Y72, Y81 or Y82.
L54, L55, L76, L77, L86 and L87 each are preferably an unsubstituted methine group.
The suffixes n5, n6, n71, n72, n81 and n82 each represent 0, 1, 2, 3 or 4. When n5, n6, n71, n72, n81 and n82 each are 2 or more, the methine group is repeated. However, these methine groups may not be the same. The suffixes n5, n6, n71 and n72 each are preferably 0, 1, 2 or 3, more preferably 0, 1 or 2, particularly 0 or 1. The suffixes n72 and n81 each are preferably 0 or 1, more preferably 0.
The suffixes p5, p7 and p8 each independently represent 0 or 1, preferably 0.
M5, M6, M7 and M8 each represent a counter ion, preferably the same as M. The suffixes m5, m6, m7 and m8 each represent a number of not smaller than 0 required to neutralize the electric charge in the molecule. When an intramolecular salt is formed, m5, m6, m7 and m8 each are 0. The suffixes m5, m6, m7 and m8 each are preferably a number of from not smaller than 0 to not greater than 4.
Most desirable among these methine dyes is cyanine dye represented by the general formula (V), particularly a cyanine dye represented by the general formula (II). The dye represented by the general formula (II) will be further described hereinafter.
In the general formula (II), X1 and X2 each represent an oxygen atom, sulfur atom, selenium atom or NR3 in which R3 represents a substituted or unsubstituted alkyl, aryl or heterocyclic group. X1 and X2 each are preferably an oxygen atom or sulfur atom.
The condensed ring represented by Y1 is an aromatic or non-aromatic hydrocarbon ring or heterocyclic ring or a polycyclic condensed ring having these rings in combination. Examples of these condensed rings include benzene ring, naphthalene ring, anthracene ring, phenathrene ring, fluorene ring, triphenylene ring, naphthacene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imdiazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indolidine ring, indole ring, benzofuran ring, benzotiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, isoquinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, carbazole ring, phenanthridine ring, acridine ring, phenanthroline ring, thianthrene ring, chromene ring, xanthene ring, phenoxathiin ring, phenothiazine ring, and phenazine ring. Preferred among these condensed rings are benzene ring, naphthalene ring, furan ring, thiophene ring, pyrrole ring, benzofuran ring, benzothiophene ring, and indole ring. Even more desirable among these condensed rings are benzene ring and naphthalene ring.
Examples of the substituents on Y1 include the various substituents represented by V. Preferred among these substituents are alkyl group (e.g., methyl), aryl group (e.g., phenyl), aromatic heterocyclic group (e.g., 1-pyrrolyl), alkoxy group (e.g., methoxy), alkylthio group (e.g., methylthio), cyano group, and halogen atom (e.g., fluorine, chlorine, bromine, iodine). Even more desirable among these substituents is halogen atom, particularly chlorine atom or bromine atom.
Examples of the alkyl, aryl or heterocyclic group represented by R1, R2 or R3 include those described as preferred examples of R with reference to the general formula (I). R1, R2 and R3 each are preferably a group substituted by a group having an acidic group or dissociative proton {e.g., carboxyl group, sulfo group, phosphonate group, boronate group, xe2x80x94CONHSO2xe2x80x94, xe2x80x94SO2NHSO2xe2x80x94, xe2x80x94CONHCOxe2x80x94, xe2x80x94SO2NHCOxe2x80x94}, more preferably an alkyl group substituted by the group having an acidic group or dissociative proton, even more preferably a substituted alkyl group containing any of carboxyl group, sulfo group, alkylsulfonylcarbamoyl group (e.g., methanesulfonylcarbonyl), acylcarbamoyl group (e.g., acetylcarbamoyl), acylsulfamoyl group (e.g., acetylsulfamoyl), and alkylsulfonylsulfamoyl group (e.g., methanesulfonyl sulfamoyl). Particularly preferred among these groups are carboxymethyl group, 2-sulfoethyl group, 3-sulfopropyl group, 3-sulfobutyl group, 4-sulfobutyl group, and methane sulfonyl carbamoyl methyl group.
The two sensitizing dyes to be incorporated in the same emulsion layer of the present invention each preferably have at least two dissociative groups. More preferably, these dissociative groups are incorporated in R1, R2 or R3in the general formula (II). One of the two dissociative groups is preferably a sulfo group (xe2x80x94SO3H) and the other is preferably a dissociative group other than sulfo group. The dissociative group other than sulfo group is selected from the group consisting of xe2x80x94COOH, xe2x80x94CONHSO2Z, xe2x80x94SO2NHCOZ, xe2x80x94SO2NHSO2Z and xe2x80x94CONHCOZ in which Z represents an alkyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, heterocyclyloxy group or amino group, preferably a lower alkyl group (e.g., methyl, ethyl).
The methine group represented by L1, L2 or L3 may be unsubstituted or substituted. Examples of the substituents on the substituted methine group include the various substituents represented by V. When n1 is 2 or more, the plurality of L2""s or L3""s may be the same or different. Preferably, n1 is 0 or 1. L1 and L3 each are preferably an unsubstituted methine group, and L2 is preferably a methine group substituted by an unsubstituted alkyl group.
Examples of M1 include the various ions described with reference to M in the methine dye of the general formula (I). In particular, M1 is preferably a cation. Preferred examples of the cation include sodium ion, potassium ion, triethylammonium ion, pyridinium ion, and N-ethylpyridinium ion.
The suffix m1 represents a number of not smaller than 0 required to neutralize the electric charge in the molecule. When an intramolecular salt is formed, m1 is 0. The suffix m1 is preferably 0, 1, 2 or 3.
More preferably, the two sensitizing dyes to be incorporated in the same emulsion layer of the present invention are cyanine dyes having the same number of methine chains. It is particularly preferred that the two sensitizing dyes have the same n1 in the general formula (II).
In the present invention, it is particularly preferred that a sensitizing dye represented by the general formula (III) be used. In the general formula (III), the alkyl group represented by R11 or R12 may be the same as described as a preferred example of R with reference to the general formula (I). R11 and R12 each are preferably an alkyl group substituted by a group having an acidic group or dissociative proton. At least one of R11 and R12 is substituted by a dissociative group other than sulfo group (particularly preferably by a xe2x80x94COOH group).
More preferably, one of R11 and R12 is a sulfoalkyl group (e.g., 2-sulfoethyl group, 3-sulfopropyl group, 3-sulfobutyl group, 4-sulfobutyl group) and the other is a substituted alkyl group (particularly carboxymethyl group or methanesulfonylcarbamoylmethyl group) containing any of carboxyl group, alkylsulfonylcarbamoyl group (e.g., methanesulfonylcarbonyl), acylcarbamoyl group (e.g., acetylcarbamoyl), acylsulfamoyl group (e.g., acetylsulfamoyl), and alkylsulfonylsulfamoyl group (e.g., methanesulfonyl sulfamoyl).
X11 and X12 each represent an oxygen atom or sulfur atom. One of X11 and X12 which has a group substituted by the dissociative group other than sulfo group is preferably a sulfur atom.
Y 11 represents a condensed naphthalene ring which may have substituents. Examples of the substituents on the substituted condensed naphthalene ring include the various substituents described with reference to the substituent V. Y11 is preferably naphtho[1,2-d]azole-condensed and is preferably free of substituents.
The suffix n11 represents 0 or 1, preferably 1.
A1 is preferably an unsubstituted alkyl group, more preferably a methyl group or ethyl group, particularly an ethyl group.
Examples of M11 include the various ions described with reference to M in the methine dye of the general formula (I). In particular, M11 is preferably a cation. Preferred examples of the cation include sodium ion, potassium ion, triethylammonium ion, pyridinium ion, and N-ethylpyridinium ion.
The suffix m11 represents a number of not smaller than 0 required to neutralize the electric charge in the molecule. When an intramolecular salt is formed, m11 is 0. The suffix m11 is preferably 0, 1, 2 or 3, more preferably 0 or 1.
Particularly preferred examples of the combination of two sensitizing dyes to be used in the present invention include the combination of a dye of the general formula (III) and a dye of the general formula (IV).
In the general formula (IV), the alkyl group represented by R21 or R22 maybe the same as described as a preferred example of R with reference to the general formula (I). R21 and R22 each are preferably an alkyl group substituted by a group having an acidic group or dissociative proton. At least one of R21 and R22 is substituted by a dissociative group other than sulfo group.
More preferably, one of R21 and R22 is a sulfoalkyl group (e.g., 2-sulfoethyl group, 3-sulfopropyl group, 3-sulfobutyl group, 4-sulfobutyl group) and the other is a substituted alkyl group (particularly carboxymethyl group or methanesulfonylcarbamoylmethyl group) containing any of carboxyl group, alkylsulfonylcarbamoyl group (e.g., methanesulfonylcarbonyl), acylcarbamoyl group (e.g., acetylcarbamoyl), acylsulfamoyl group (e.g., acetylsulfamoyl), and alkylsulfonylsulfamoyl group (e.g., methanesulfonyl sulfamoyl).
X21 and X22 each represent an oxygen atom or sulfur atom. One of X21 and X22 which has a group substituted by the dissociative group other than sulfo group is preferably a sulfur atom. More preferably, both X21 and X22 are a sulfur atom.
Y21 represents a condensed benzene ring which may have substituents. Examples of the substituents on the substituted condensed benzene ring include the various substituents described with reference to the substituent V. However, these substituents are not connected to each other to form a condensed ring. Examples of these groups include alkyl group (e.g., methyl), aryl group (e.g., phenyl), aromatic heterocyclic group (e.g., 1-pyrrolyl), alkoxy group (e.g., methoxy), alkylthio group (e.g., methylthio), cyano group, and halogen atom (e.g., fluorine, chlorine, bromine, iodine). Preferred among these substituents is halogen atom, particularly chlorine atom or bromine atom.
The suffix n21 represents a number of 0 or 1, preferably the same as n11. More preferably, both n11 and n21 are 1.
A2 is preferably an unsubstituted alkyl group, more preferably a methyl group or ethyl group, particularly an ethyl group.
Examples of M21 include the various ions described with reference to M in the methine dye of the general formula (I). In particular, M21 is preferably a cation. Preferred examples of the cation include sodium ion, potassium ion, triethylammonium ion, pyridinium ion, and N-ethylpyridinium ion.
The suffix m21 represents a number of not smaller than 0 required to neutralize the electric charge in the molecule. When an intramolecular salt is formed, m21 is 0. The suffix m21 is preferably 0, 1, 2 or 3. More preferably, the suffix m21 is 0 or 1.
Specific examples of the sensitizing dye of the present invention will be given below, but the present invention should not be construed as being limited thereto.
The synthesis of the compound represented by the general formula (I) (including dyes of lower concept) can be accomplished by the method described in F. M. Hamer, xe2x80x9cHeterocyclic Compounds-Cyanine Dyes and Related Compoundsxe2x80x9d, John Wiley and Sons, New York, London, 1964, D. M. Sturmer, xe2x80x9cHeterocyclic Compounds-Special Topics in Heterocyclic Chemistryxe2x80x9d, Chapter 18, Article 14, pp. 482-515, John Wiley and Sons, New York, London, 1977, xe2x80x9cRodd""s Chemistry of Carbon Compoundsxe2x80x9d, 2nd Ed. vol. IV., part B, 1977, Chapter 15, pp. 369-422, Elsevier Science Publishing Company Inc., New York, etc.
The proportion of the amount of the two sensitizing dyes of the general formula (I) of the present invention to be incorporated in the emulsion is arbitrary. The molar ratio of the two sensitizing dyes to be added depends on the use and purpose but is preferably from 1,000/1 to 1/1,000, more preferably from 100/1 to 1/100, even more preferably from 10/1 to 1/10.
In the most desirable embodiment wherein one sensitizing dye of the general formula (III) of the present invention and one sensitizing dye of the general formula (IV) of the present invention are used, the molar ratio of the dye of the general formula (III) and the dye of the general formula (IV) is preferably from 10/1 to 1/100, more preferably from 5/1 to 1/30, even more preferably from 2/1 to 1/10.
In addition to the incorporation of at least two sensitizing dyes of the general formula (I) of the present invention in the same emulsion, these sensitizing dyes may be used in the same emulsion in combination with other sensitizing dyes falling outside the present invention. Preferred examples of these sensitizing dyes employable herein include cyanine dye, melocyanine dye, rhodacyanine dye, trinuclear melocyanine dye, tetranuclear melocyanine dye, allopolar dye, hemicyanine dye, and styryl dye. Preferred among these sensitizing dyes are cyanine dye, melocyanine dye, and rhodacyanine dye. Particularly preferred among these sensitizing dyes is cyanine dye. For the details of these dyes, reference can be made to F. M. Hamer, xe2x80x9cHeterocyclic Compounds-Cyanine Dyes and Related Compoundsxe2x80x9d, John Wiley and Sons, New York, London, 1964, D. M. Sturmer, xe2x80x9cHeterocyclic Compounds-Special Topics in Heterocyclic Chemistryxe2x80x9d, Chapter 18, Article 14, pp. 482-515, etc.
Preferred examples of these dyes include those of the general formulae shown in U.S. Pat. No. 5,994,051, pp. 32-44, U.S. Pat. No. 5,747,236, pp. 30-39, and those exemplified in these patents.
Preferred examples of the general formula of cyanine dye, melocyanine dye and rhodacyanine dye include the general formulae (XI), (XII) and (XIII) shown in U.S. Pat. No.5,340,694, columns 21-22 (with the proviso that n12, n15, n17 and n18 are not restricted but each are an integer of not smaller than 0 (preferably not greater than 4)).
These sensitizing dyes may be used singly or in combination of two or more thereof. A combination of sensitizing dyes is often used for the purpose of supersensitizing. Representative examples of such a combination of sensitizing dyes are described in U.S. Pat. Nos. 2,688,545, 2,977,229, 3,397,060, 3,522,052, 3,527,641, 3,617,293, 3,628,964, 3,666,480, 3,672,898, 3,679,428, 3,303,377, 3,769,301, 3,814,609, 3,837,862 and 4,026,707, British Patents 1,344,281 and 1,507,803, Japanese Patent Publication No. 49336/1968, Japanese Patent Publication No. 12375/1978, Japanese Patent Application (Laid-Open) No. 1977-110618, and Japanese Patent Application (Laid-Open) No. 1977-109925.
The emulsion may contain a dye which doesn""t have a spectral sensitizing effect itself or a material which doesn""t substantially absorb visible light but exerts supersensitizing effect in combination with sensitizing dyes.
For the details of supersensitizers useful in spectral sensitization in the present invention (e.g., pyrimidylamino compound, triazinylamino compound, azolium compound, aminostyryl compound, aromatic organic acid-formaldehyde condensate, azaindene compound, cadmium salt) and combination of supersensitizer and sensitizing dye, reference can be made to U.S. Pat. Nos. 3,511,664, 3,615,613, 3,615,632, 3,615,641, 4,596,767, 4,945,038, 4,965,182, 4,965,182, 2,933,390, 3,635,721, 3,743,510, 3,617,295, and3,635,721. For preferred examples of their uses, too, reference can be made to these patents.
The silver halide photographic material of the present invention will be further described hereinafter.
The time at which the methine dye of the present invention is added to the silver halide emulsion may be any step during the preparation of emulsion which has heretofore been considered useful (This can apply also to other sensitizing dyes and supersensitizers). As disclosed in U.S. Pat. Nos. 2,735,766, 3,628,960, 4,183,756 and 4,225,666, Japanese Patent Application (Laid-Open) No. 1983-184142, and Japanese Patent Application (Laid-Open) No. 1985-196749, the methine dye of the present invention may be added at any time during the formation of silver halide grains and/or before desalting or any time during desalting and/or between desalting and the beginning of chemical ripening. As disclosed in Japanese Patent Application (Laid-Open) No. 1983-113920, the methine dye of the present invention may be added at any time shortly before or during chemical ripening or between chemical ripening and application of emulsion. Alternatively, as disclosed in U.S. Pat. No. 4,225,666 and Japanese Patent Application (Laid-Open) No. 1983-7629, the same compound may be added singly or in combination with compounds of foreign structure, e.g., at any time during the formation of grains and during or after completion of chemical ripening or at any time before or during chemical ripening and after chemical ripening. The kind of compound to be added separately and combination of compounds to be added may be varied.
The amount of the methine dye of the present invention to be added depends on the shape and size of the silver halide grains but is normally from 1xc3x9710xe2x88x926 to 8xc3x9710xe2x88x923 mols per mol of silver halide (This applies also to other sensitizing dyes and supersensitizers). For example, when the size of silver halide grains is from 0.2 xcexcm to 1.3 xcexcm, the amount of the methine dye of the present invention to be added is preferably from 2xc3x9710xe2x88x926 to 3.5xc3x9710xe2x88x923 mols, more preferably from 7.5xc3x9710xe2x88x926 to 1.5xc3x9710xe2x88x923 mols per mol of silver halide.
The methine dye of the present invention may be dispersed directly in the emulsion (This applies also to other sensitizing dyes and supersensitizers). Alternatively, the methine dye of the present invention may be added to the emulsion in the form of solution in a proper solvent such as methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, water, pyridine and mixture thereof. In this case, additives such as base, acid and surface active agent may coexist in the emulsion. The dissolution of the methine dye of the present invention and additives in the solvent can be accomplished with the aid of ultrasonic wave. Examples of the method for adding the methine dye of the present invention to the emulsion include a method disclosed in U.S. Pat. No. 3,469,987 which comprises dissolving the compound in a volatile organic solvent, dispersing the solution in a hydrophilic colloid, and then adding the dispersion to the emulsion, a method disclosed in Japanese Patent Publication No. 24185/1961 which comprises dispersing the compound in a water-soluble solvent, and then adding the dispersion to the emulsion, a method disclosed in U.S. Pat. No. 3,822,135 which comprises dissolving the compound in a surface active agent, and then adding the solution to the emulsion, a method disclosed in Japanese Patent Application (Laid-Open) No. 1976-74624 which comprises dissolving the compound in a red-shifting compound, and then adding the solution to the emulsion, and a method disclosed in Japanese Patent Application (Laid-Open) No. 1975-80826 which comprises dissolving the compound in an acid substantially free of water, and then adding the solution to the emulsion. Besides these methods, the addition of the compound to the emulsion can be accomplished by the method disclosed in U.S. Pat. Nos. 2,912,343, 3,342,605, 2,996,287 and 3,429,835.
Examples of the organic solvent in which the sensitizing dye of the present invention is dissolved include methyl alcohol, ethyl alcohol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, benzyl alcohol, fluoroalcohol, methyl cellosolve, acetone, pyridine, and mixture thereof.
During the dissolution of the sensitizing dye in water, the foregoing organic solvent or mixture thereof, a base is preferably added. As such a base there may be used either an organic base or inorganic base. Examples of these bases include amine derivatives (e.g., triethylamine, triethanolamine), pyridine derivatives, sodium hydroxide, potassium hydroxide, sodium acetate, and potassium acetate. A preferred method for dissolving the sensitizing dye of the present invention in the solvent is a method which comprises adding the dye to a mixture of water and methanol, and then adding triethylamine to the solution in an amount equimolecular with the dye.
As the granular silver halide to be incorporated in the silver halide emulsion of the present invention there may be used any of silver chloride, silver bromide, silver bromochloride, silver bromoiodide, silver chloroiodide and silver bromochloroiodide. For example, if used for color photographic paper, the silver halide emulsion preferably is a silver bromochloride emulsion for the purpose of expediting and simplifying processing. As such a silver bromochloride emulsion there is preferably used a silver chloride, silver bromochloride or silver bromochloroiodide emulsion having a silver chloride content of not smaller than 95 mol-%. In particular, silver bromochloride or silver chloride substantially free of silver iodide is preferably used to reduce the development time. Alternatively, if used for color picture taking film (negative and reversal), the silver halide emulsion preferably is a silver bromoiodide emulsion. As such a silver bromoiodide emulsion there is preferably used silver bromide, silver bromoiodide or silver bromochloroiodide emulsion having a silver bromide content of not smaller than 95 mol-%.
The average size of silver halide grains to be incorporated in the silver halide emulsion of the present invention is preferably from 0.1 xcexcm to 2 xcexcm as calculated in terms of number-average of diameter of circles having the same area as the projected area of grains.
The distribution of grain sizes is preferably as so-called monodisperse as not greater than 20%, preferably not greater than 15%, more preferably not greater than 10% as calculated in terms of coefficient of variation (obtained by dividing the standard deviation of grain size distribution by the average grain size). In this case, for the purpose of obtaining a wide latitude, the foregoing monodisperse emulsions are preferably incorporated in the same layer in admixture or applied in a multi-layer coating process.
The shape of the silver halide grains to be incorporated in the photographic emulsion may be a regular crystal form such as cube, octahedron and tetradecahderon, irregular crystal form such as sphere and plate or mixture thereof. The emulsion of the present invention preferably comprises grains having the foregoing regular crystal form in an amount of not smaller than 50%, more preferably not smaller than 70%, even more preferably not smaller than 90%.
The preparation of the emulsion to be used in the present invention can be accomplished by the method disclosed in P. Glafkides, xe2x80x9cChimie et Phisique Photographiquexe2x80x9d, Paul Montel, 1967, G. F. Duffin, xe2x80x9cPhotographic Emulsion Chemistryxe2x80x9d, Focal Press, 1966, V. L. Zelikman et al, xe2x80x9cMaking and Coating Photographicn Emulsionxe2x80x9d, Focal Press, 1964, etc. In some detail, any of acid method, neutral method and ammonia method may be used. The reaction of the soluble silver salt with the soluble halogen salt can be accomplished by single jet method or double jet method, singly or in combination. A method involving the formation of grains in the atmosphere of excess silver ions (so-called reverse mixing method) may be used. As one of double jet methods there may be used a method which comprises keeping the pAg value of the liquid phase in silver halide is produced constant, i.e., so-called controlled double jet method. The use of this method makes it possible to obtain a silver halide emulsion having a regular crystal form and a substantially uniform grain size.
The emulsion of the present invention preferably comprises tabular grains having an aspect ratio of not smaller than 2 (preferably not larger than 1,000) in an amount of not smaller than 50%, more preferably not smaller than 70%, even more preferably not smaller than 80% based on the total projected area of silver halide grains incorporated therein.
In general, a tabular grain is in the form of tablet having two parallel planes. Thus, the xe2x80x9cthicknessxe2x80x9d of a tabular grain is represented by the distance between the two parallel planes constituting the tabular grain. The diameter of a silver halide grain is defined by the diameter of the circle having the same area as the projected area of the grain as viewed in its electron microphotograph. The ratio of diameter to thickness is called aspect ratio.
The aspect ratio of the silver halide grain of the present invention is preferably from 4 to 100, more preferably from 6 to 80, particularly from 8 to 60. For example, if the silver halide emulsion is used for color photographic paper, a tabular silver bromochloride grain is preferably used. If the silver halide emulsion is used for color picture taking film, a tabular silver bromoiodide grain is preferably used.
Referring further to the tabular silver bromochloride grain for color photographic paper, it has a silver chloride content of not smaller than 80 mol-%. Even more preferably, the tabular silver bromochloride grain is a high silver chloride grain having a silver chloride as high as not smaller than 95%.
The silver bromochloride grain preferably comprises a core portion and a shell portion (outermost layer) having a higher iodide content than the core portion. The core portion preferably is formed by silver chloride in an amount of not smaller than 90%. The core portion may comprise two or more portions having different halogen compositions. The shell portion preferably accounts for not greater than 50%, particularly not greater than 20%, of the total volume of particle. The shell portion preferably has a silver iodide content of from 0.5 to 13 mol-%, particularly from 1 to 6 mol-%. The content of silver iodide in all silver halide grains is preferably from 0.1 to 5 mol-%, particularly from 0.1 to 2 mol-%. The silver iodide content of the core portion is preferably not greater than 1 mol-%, particularly 0%.
The silver bromide content may differ from the core portion to the shell portion. The silver bromide content is preferably from 0 to 20 mol-%, particularly from 0.1 to 5 mol-% based on the total amount of silver.
The diameter of high silver chloride tabular grain is preferably from 0.2 xcexcm to 1.0 xcexcm. The thickness of high silver chloride tabular grain is not greater than 0.2 xcexcm, preferably not greater than 0.15 xcexcm, particularly not greater than 0.1 xcexcm. The aspect ratio of high silver chloride tabular grain is preferably from 3 xcexcm to 20 xcexcm, more preferably from 5 xcexcm to 15 xcexcm.
The distribution of size of high silver chloride tabular grains may be either polydisperse or monodisperse, preferably monodisperse. The coefficient of dispersion of grain sizes is preferably from 5% to 25%, particularly from 5% to 20%.
The coefficient of dispersion of grain thicknesses is preferably from 5% to 25%, particularly from 5% to 15%.
In order to form 111 plane as an outer surface in the high silver chloride tabular grain for color photographic paper, a crystal phase controller is used. The formation of a tabular grain can be accomplished by producing two parallel twinning planes. The formation of twinning planes is governed by the temperature, dispersant (gelatin), halogen concentration, etc. Therefore, these conditions need to be properly predetermined. In the case where a crystal phase controller is present during nucleation, the gelatin concentration is preferably from 0.1% to 10%. The concentration of chloride is not smaller than 0.01 mol/l, preferably not smaller than 0.03 mol/l.
For the details of the crystal phase controller (i.e., the crystal habit-controlling agent) to be used and the method for forming 111 high silver chloride tabular grain using this crystal phase controller, reference can be made to Japanese Patent Application (Laid-Open) No. 2000-29156.
The tabular grain of the present invention maybe a tabular grain having (100) plane as a main plane. The shape of the main plane is a rectangular parallelogram, a triangle, rectangle or pentagon obtained by removing one corner from the rectangular parallelogram (the corner to be removed is a right-angled triangle formed by the corner as apex and two sides forming the corner) or a rectangle, pentagon, hexagon, heptagon or octagon having 2 to 4 such lost portions.
For the details of method for forming a tabular silver halide grain having (100) main plane, reference can be made to Japanese Patent Application (Laid-Open) No. 1994-301129, Japanese Patent Application (Laid-Open) No. 1994-347929, Japanese Patent Application (Laid-Open) No. 1997-34045, Japanese Patent Application (Laid-open) No. 1997-96881, Japanese Patent Application (Laid-Open) No. 1996-122954, and Japanese Patent Application (Laid-Open) No. 1997-189977. The tabular silver bromide grain to be incorporated in the color picture taking film is preferably silver bromoiodide, silver chloroiodide or silver bromoiodide having a silver iodide content of not greater than 30 mol-%. In particular, silver bromoiodide or silver bromochloroiodide having a silver iodide content of from 2 to 10 mol-% is preferred. The tabular silver bromide grain may contain silver chloride. The silver chloride content of the silver bromide grain is preferably not greater than 8 mol-%, more preferably not greater than 3 mol-% or 0 mol-%.
The tabular silver bromoiodide grain preferably has a diameter of from 0.3 xcexcm to 5.0 xcexcm and a thickness of 0.05 to 0.5 xcexcm. The tabular silver bromoiodide grain preferably has an aspect ratio of from 3 to 50, more preferably from 4 to 30, even more preferably from 5 to 25.
The silver halide emulsion to be used in the present invention is normally subjected to chemical sensitization. Examples of the chemical sensitization process employable herein include so-called gold sensitization process with a gold compound (as disclosed in U.S. Pat. Nos. 2,448,060 and 3,320,069), sensitization process with a metal such as iridium, platinum, rhodium and palladium (as disclosed in U.S. Pat. Nos. 2,448,060, 2,566,245 and 2,566,263), sulfur sensitization process with a sulfur-containing compound (as disclosed in U.S. Pat. No. 2,222,264), selenium sensitization process with a selenium compound, tellurium sensitization process with a tellurium compound, and reduction sensitization with a stannous salt, thiourea dioxide, polyamine or the like (as disclosed in U.S. Pat. Nos. 2,487,850, 2,518,698 and 2,521,925). These sensitization processes may be used singly or in combination.
The emulsion of the present invention is preferably subjected to chemical sensitization with a selenium sensitizer.
As such a selenium sensitizer there may be used any selenium compound disclosed in conventional known patents. In some detail, the emulsion is normally stirred at a high temperature, preferably not lower than 40xc2x0 C., with a labile selenium compound and/or non-labile selenium compound. As the labile selenium compound there is preferably used a compound described in Japanese Patent Publication No. 15748/1969, Japanese Patent Publication No. 13489/1968, Japanese Patent Application (Laid-Open) No. 1992-25832, and Japanese Patent Application (Laid-Open) No. 1992-109240. Specific examples of the labile selenium sensitizer employable herein include isoselenocyanates (e.g., aliphatic isoselenocyanate such as allylisoselenocyanate), selenoureas, selenoketones, selenoamides, selenocarboxylic acids (e.g., 2-selenopropionic acid, 2-selenobutyric acid), selenoesters, diacylselenides (e.g., bis(3-chloro-2,6-dimethoxybenzoyl)selenide), selenophosphates, phosphineselenides, and colloidal metal selenium.
Preferred types of labile selenium compound have been described hereinabove, but the present invention should not be construed as being limited thereto. It is generally understood by those skilled in the art that the structure of a labile selenium compound as a sensitizer for photographic emulsion is not so important so far as selenium is labile and the organic moiety of the selenium sensitizer molecule has no functions other than supporting selenium and allowing it to be present in the emulsion in a labile form. In the present invention, a labile selenium compound having such a wide concept can be used to advantage.
As the non-labile selenium compound employable herein there may be used a compound disclosed in Japanese Patent Publication No. 4553/1971, Japanese Patent Publication No. 34492/1977 and Japanese Patent Publication No. 34491/1977. Examples of the non-labile selenium compound employable herein include selenous acid, potassium selenocyanide, selenazoles, quaternary salt of selenazoles, diaryl selenide, diaryl diselenide, dialkyl selenide, dialkyl diselenide, 2-selenazolidinedion, 2-selenooxazolidinethione, and derivatives thereof.
Preferred among these selenium compounds are those of the general formulae (VII) and (VIII) disclosed in Japanese Patent Application (Laid-Open) No. 1999-15115. These selenium sensitizers are added during chemical sensitization in the form of solution in water or an organic solvent such as methanol and ethanol, singly or in admixture. Preferably, these selenium sensitizers are added before the beginning of chemical sensitization. The number of selenium sensitizers to be used is not restricted to one. Two or more of the selenium sensitizers may be used in combination. The combined use of a labile selenium compound and a non-labile selenium compound is desirable.
The amount of the selenium sensitizers to be added depends on the activity of the selenium sensitizers used, the kind and size of silver halide, the temperature and time of ripening, etc. but preferably is not smaller than 1xc3x9710xe2x88x928 mols, more preferably from 1xc3x9710xe2x88x927 to 5xc3x9710xe2x88x925 mols per mol of silver halide in the emulsion. The temperature of chemical ripening with a selenium sensitizer is preferably not lower than 45xc2x0 C., more preferably from 50xc2x0 C. to 80xc2x0 C. The pAg and pH values of the selenium sensitizer are arbitrary. When the pH value of the selenium sensitizer falls within the range of from 4 to 9, the effect of the present invention can be exerted.
The silver halide emulsion to be used in the present invention may comprise various compounds or precursors thereof incorporated therein for the purpose of inhibiting fogging during the preparation, storage or photographic processing of photographic light-sensitive material or stabilizing the photographic properties. Specific examples of these compounds include those described in the above cited Japanese Patent Application (Laid-Open) No.1987-215272, pp.39-72. Further, 5-arylamino-1,2,3,4-thiatriazole compounds (the aryl residue has at least one electron attractive group) disclosed in EP0447647 are preferably used.
The silver halide emulsion prepared according to the present invention can be incorporated in both color photographic light-sensitive material and black-and-white photographic light-sensitive material. Examples of the color photographic light-sensitive material to which the silver halide emulsion of the present invention can be applied include color photographic paper, color picture taking film, and color reversal film. Examples of the black-and-white photographic light-sensitive material to which silver halide emulsion of the present invention can be applied include X-ray film, ordinary picture taking film, and film for printing photographic light-sensitive material.
The silver halide photographic material of the present invention may comprise at least one light-sensitive layer provided on a support. Typically, the silver halide photographic material of the present invention comprises at least one light-sensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different light sensitivities provided on a support. In the case where the silver halide photographic material of the present invention is a multi-layer color photographic light-sensitive material, there are provided a blue-sensitive layer (BL), a green-sensitive layer (GL) and a red-sensitive layer (RL). The order of disposition of these color-sensitive layers as viewed from the support may differ with the purpose of the light-sensitive material. The order of disposition of these color-sensitive layers in the ordinary picture taking color-sensitive material as viewed from the support is RL-GL-BL. The order of disposition of these color-sensitive layers in the printing color photographic light-sensitive material (photographic paper) as viewed from the support is BL-GL-RL in most cases. A light-insensitive layer may be provided interposed between these light-sensitive silver halide emulsion layers and on the uppermost or lowermost layer.
In order to improve color reproducibility, a donor layer with an interlayer effect having a spectral sensitivity distribution different from that of the main light-sensitive layer such as BL, GL and RL as disclosed in U.S. Pat. Nos. 4,663,271, 4,705,744 and 4,707,436, Japanese Patent Application (Laid-Open) No. 1987-160448 and Japanese Patent Application (Laid-Open) No. 1988-89850 is preferably provided adjacent to or in the vicinity of the main light-sensitive layer.
The silver halide photographic material of the present invention may comprise the foregoing various additives incorporated therein but may further comprise other various additives incorporated therein depending on the purpose.
For the details of these additives, reference can be made to Research Disclosure, Item 17643 (December 1978), Item 18716 (November 1979) and Item 308119 (December 1989). The sites of disclosure will be tabulated below.
For the details of the emulsion of the present invention, technique for arrangement of layers in the photographic light-sensitive material comprising the emulsion, the silver halide emulsion, the functional couplers such as dye-forming coupler and DIR coupler, various additives, and development, reference can be made to EP0565096A1 (disclosed on Oct. 13, 1993) and patents cited therein. These technical items and the sites of disclosure thereof will be tabulated below.
1. Layer constitution: Lines 23-35, p. 61; line 41, p. 61xe2x80x94line 14, p. 62
2. Interlayer: Lines 36-40, p. 61
3. Interlayer effect-providing layer: Lines 15-18, p. 62
4. Halogen formulation of silver halide: Lines 21-25, p. 62
5. Crystal habit of silver halide grain: Line 26-30, p. 62
6. Size of silver halide grain: Lines 31-34, p. 62
7. Process for the preparation of emulsion: Lines 35-40, p. 62
8. Distribution of size of silver halide grains: Lines 41-42, p. 62
9. Tabular grain: Lines 43-46, p. 62
10. Internal structure of grain: Lines 47-53, p. 62
11. Type of formation of latent image in emulsion: Line 54, p. 62xe2x80x94line 5, p. 63
12. Physical ripening/chemical sensitization of emulsion:
Lines 6-9, p. 63
13. Combined use of emulsions: Lines 10-13, p. 63
14. Fogging emulsion: Lines 14-31, p. 63
15. Light-insensitive emulsion: Lines 32-43, p. 63
16. Coated amount of silver: Lines 49-50, p. 63
17. Formaldehyde scavenger: Lines 54-57, p. 64
18. Mercapto-based fog inhibitor: Lines 1-2, p. 65
19. Fogging agent-releasing agent: Lines 3-7, p. 65
20. Dye: Lines 7-10, p. 65
21. Color coupler (general): Lines 11-13, p. 65
22. Yellow, magenta and cyan couplers: Lines 14-25, p. 65
23. Polymer coupler: Lines 26-28, p. 65
24. Diffusive dye-forming coupler: Lines 29-31, p. 65
25. Colored coupler: Lines 32-38, p. 65
26: Functional coupler (general): Lines 39-44, p. 65
27. Bleach accelerator-releasing agent: Lines 45-48, p. 65
28. Development accelerator-releasing coupler: Lines 49-53, p. 65
29. Other DIR couplers: Line 54, p. 65xe2x80x94line 4, p. 66
30. Method for dispersing coupler: Lines 5-28, p. 66
31. Preservative/mildewproofing agent: Lines 29-33, p. 66
32. Kind of photographic light-sensitive material: Lines 34-36, p. 66
33. Thickness and swelling rate of light-sensitive layer: Line 40, p. 66xe2x80x94line 1, p. 67
34. Back layer: Lines 3-8, p. 67
35. Development (general): Lines 9-11, p. 67
36. Developer and developing agent: Lines 12-30, p. 67
37. Additive to developer: Lines 31-44, p. 67
38. Reversal processing: Lines 45-56, p. 67
39. Percentage opening of processing tank: Line 57, p. 67xe2x80x94line 12, p. 68
40. Development time: Lines 13-15, p. 68
41. Blix, bleaching, fixing: Line 16, p. 68xe2x80x94line 31, p. 69
42. Automatic developing machine: Lines 32-40, p. 69
43. Water washing, rinsing, stabilization: Line 41, p. 69xe2x80x94line 18, p. 70
44. Replenishment and reuse of processing solution: Lines 19-23, p. 70
45. Incorporation of developing agent in photographic light-sensitive material: Lines 24-33, p. 70
46. Development temperature: Lines 34-38, p. 70
47. Use in film with lens: Lines 39-41, p. 70


Disclosed are a method and device for controlling low grayscale white balance. The method comprises: calculating a total color difference ΔE(nmax−0) between a grayscale 0 and a grayscale threshold value nmax, according to measured tristimulus values of the grayscale 0 and the grayscale threshold value nmax; determining a color difference relation between various grayscales from the grayscale 0 to the grayscale threshold value nmax, according to the total color difference ΔE(nmax−0) between the grayscale 0 and the grayscale threshold value nmax, wherein the color difference relation enables human eyes to observe a gradual and smooth change from the grayscale 0 to the grayscale threshold value nmax; and controlling white balance according to the color difference relation between various grayscales from the grayscale 0 to the grayscale threshold value nmax. By means of the method, the present invention can automatically adjust white balance, and the transition between low grayscales can be smooth and natural when observed by human eyes.

Since the factors driving the characteristics of the LCD panel, the white balance gray color performance differences have a considerable degree of color shift. In order to display a certain color correctness and consistency, therefore, it must be carried out one by one to monitor gray white balance (Grayscale white balance) adjustment.
Gray white balance adjustment method of the prior art is to make the display pixel displays white images in all gray, and then adjust the red, green and blue image intensity gain value (Gain), so that a white image is displayed chrominance and luminance values close to the color value and the brightness value of a target value of white, the white image is adjusted within a certain color temperature (Color temperature) and color deviation (Color derivation) range. Wherein, testing low grayscale is difficult. For the low grayscale, the present method of white balance for no better treatment methods, it is often to manual testing the white balance by a R/G/B lookup table designed by eyes subjectivity in feeling after a higher grayscale is calculated. There is also an algorithm to automatic adjustment low grayscale white balance.
However, the manual testing method increases workload of development and design staff and has a large error by different subjective feelings between people. The formula of the automatic method is tedious, complex and large computation. However, the low grayscale is transition unsmoothness when the white balance is calculated and eyes are observing subjectivity.

Method and apparatus for controlling low grayscale white balance

Shenzhen China Star Optoelectronics Technology Co., Ltd.


Methodology, with a programmable-processor imaging system, for control and determination of breast lesion viscoelastic properties with the use of a creep-like test. Two dimensional reconstruction maps are used for different parameters of a linear viscoelastic model. Description of different aspects of the test used on live subjects and suitability of a 1-D inversion model in capturing different viscoelasticity parameters. An automated methodology for the selection of a region of interest derived only from the appearance of the breast lesion on pre-compressed B-mode images. Based on the ROI and estimated viscoelasticity parameters, contrast values are determined that facilitate the enhanced differentiation of breast mass. Employing the methodology in a large group of patients provides better understanding of variations of different viscoelasticity parameters in different types of breast lesion and helps to identify new biomarkers for enhanced differentiation of benign from malignant cases.

Pathologic changes in tissues can manifest as changes in mechanical properties of the tissues. In non-invasive quasi-static strain elastography, an axial compression is applied to the tissue, and tissue deformation is visualized by analyzing the pre-compression and post-compression ultrasonic data. In maps, constructed based on such data and referred to as "elastograms", softer parts of the tissue show higher levels of deformation (strain) as compared to the stiffer parts. In breast tissue, while analysis of the elasticity alone can predict architectural changes in tissue to some extent, the complexity of tissue biomechanics requires a more comprehensive model to predict a wider range of pathologies. In breast tumors, particularly, finding a mechanical property that not only shows sensitivity to malignancy, but also shows sensitivity to benign changes can be extremely beneficial as it can potentially enhance diagnosis specificity which in turn may reduce a significant number of unnecessary, painful and costly biopsies.
Recent studies have aimed at extending the notion of elastography to more comprehensive models that account for the biphasic nature of the tissue. These works have resulted in models based on viscoelasticity, poroelasticity, and poroviscoelasticity, and have shown that two major components play important roles in governing tissue deformation under external compression: a) the drained matrix viscoelasticity (which is mostly defined by the fiber density, orientation and cross-linking density), and b) the interstitial fluid motion that creates retardation in the deformation rate via frictional forces. However, a comprehensive methodology that describes tissue biomechanics at a wide range of frequencies is still desired. For example, the studies conducted with the use of magnetic resonant elastography (MRE) suggestsed that a single model simply cannot simultaneously explain tissue behavior in different frequency ranges. Hence, a unified approach to separate the dynamics of the two phases (i.e. a viscoelastic deformable solid response and a hydraulic fluid motion) in tissue-like materials remains an open problem, as was recognized by, for example, M. Galli et al. (Journal of Materials Research, vol. 24, pp. 973-979, 2009/003/001 2009) and M. L. Oyen (Current Opinion in Solid State and Materials Science, vol. 19, pp. 317-323, 2015). To address these shortcoming, alternative approaches (which describe tissue deformation as purely poroelastic or purely viscoelastic solids) are favored.
Unlike quasi-static strain elastography, which relies only on pre- and post-deformation states of the tissue, these alternative methods require continuous observation of the tissue response under an external stimulation. For example, methods based on poroelasticity imaging require observation of the tissue dynamic deformation during hundreds of seconds while a constant surface compression is maintained. The methods based on viscoelastic models, on the other hand, have shown to predict mechanical properties in shorter time scales, which is more favorable for in vivo applications. Tissue deformations at these time scales reside in a frequency range of less than 1 Hz. Stress-relaxation and creep-compliance tests are two standard mechanical testing methods suitable for this range of frequency. While stress-relaxation may not be feasible for in vivo scenarios (due to lack of accurate estimate of the stress distribution), with appropriate assumptions creep-like tests can be performed with the help of a force-control mechanism that mimics a ramp-and-hold stress excitation and monitoring internal strain field via ultrasonic strain tracking algorithms.
While malignant and benign masses may present different viscoelastic characteristic as a result of a creep-like test with limited force feedback information, the added noise (caused by manual operation, lack of an accurate estimate of the excreted force (to ensure operation in linear regime and maintaining a constant force), and dependency of the interpretation of imaging contrasts based on different viscoelastic parameters on the operator limits the utility and reproducibility of such method for patient studies.

Automated time-domain determination of tissue viscoelasticity in a sub-hertz frequency range

Mayo Foundation for Medical Education and Research


Thermally conductive thermoplastic resin compositions are provided containing thermoplastic resin and thermally conductive filler and fibrous filler, along with articles made therefrom. In certain instances when the thermally conductive filler and fibrous filer are more restricted, and other ingredients are present, the thermally conductive composition exhibits an improved volume resistibility and is suitable for fabricating a chassis for LCD display. Also described are the thermally conductive resin compositions, especially when the polymer is LCP. Such compositions are useful for items such as electrical and electronic housings requiring highly thermally conduciveness.

Many electrical and electronic devices such as a light emitting package in a structure such as a mold frame, a chassis structure or a metal bottom cover. These can be used as a light source for a backlight unit of an LCD or as a light unit in an illumination field backlight unit. In general, there are edge-type backlight units and direct-type backlight units, depending on the position of a light source. Because of their excellent mechanical and electrical insulation properties, thermoplastic polymeric resin compositions are used to manufacture articles of various sizes and shapes, including without limitation chassis components, and housings. In many cases, because of the design flexibility and their low cost, polymer resin compositions have replaced metal in these applications. However, many of these applications require that the parts be in the vicinity of or in contact with heat sources such as electrical lights. It is therefore desirable to form these parts from materials that are sufficiently thermally conductive to dissipate the heat generated. While metal parts thermally conductive, they are also often electrically conductive, which can be undesirable in certain applications.
Thermoplastic resin compositions are generally thermally insulating and typically electrically insulating unless they contain large amounts of electrically conductive additives. Thus, a thermally conductive, electrically insulating thermoplastic resin composition would be desirable and could replace metals, and in particular, aluminum, in many applications.
U.S. Pat. No. 6,487,073 describes a case for dissipating heat from an electronic device, comprising a housing of a net-shaped moldable thermally conductive composite material of a polymer base matrix with thermally conductive filler, and in thermal communication with an electronic component with heat dissipating from a heat generating electronic component and therethrough. No mention is made of using particular thermal conductive fillers with thermoplastic polymer.

Thermally conductive thermoplastic resin compositions and related applications


A method of copying a body of source data is shown, with rapid creation of an a backup dataset inventory. While write operations to the source data are temporarily suspended, a backup manager conducts an instant virtual copy of the source data creating a backup copy. Also while write operations are being suspended, the backup manager captures contents of a source dataset inventory cross-referencing datasets in the source data and locations in the body of source data where the datasets are stored. After the copy operation completes and writes to the source data resume, the backup manager adds the captured backup contents to a backup dataset inventory cross-referencing datasets in the backup copy and locations where the backup copy datasets are stored in the backup copy.

1. Field of the Invention
The present invention relates to the copying of source data that resides in one or more direct access storage devices (DASDs). More particularly, the invention concerns a copy method that, while write operations to source data are suspended, performs an instant virtual copy of the source data and also captures contents of a source dataset inventory. Later, the captured contents are used to create and/or update an analogous inventory for backup datasets.
2. Description of the Related Art
A number of DASD subsystems are capable of performing xe2x80x9cinstant virtual copyxe2x80x9d operations, also referred to as xe2x80x9cfast replicate functions.xe2x80x9d Instant virtual copy operations work by modifying metadata such as relationship tables or pointers to treat a source data object as both the original and copy. In response to a host""s copy request, the storage subsystem immediately reports creation of the copy without having made any physical copy of the data. Only a xe2x80x9cvirtualxe2x80x9d copy has been created, and the absence of any physical copy is completely unknown to the host.
Later, when the storage system receives updates to the original or copy, the updates are stored separately and cross-referenced to the updated data object only. At this point, the original and copy data objects begin to diverge. The initial benefit is that the instant virtual copy occurs almost instantaneously, completing much faster than a normal physical copy operation. This frees the host and storage subsystem to perform other tasks. The host or storage subsystem may even proceed to create an actual, physical copy of the original data object during background processing, or at another time.
With such benefits, instant virtual copy has been an important development in modern DASD subsystems, and a number of different embodiments have surfaced. As one example, International Business Machines Corporation (IBM) has developed the xe2x80x9cFLASH COPYxe2x80x9d technique, as described in different publications including U.S. application Ser. No. 09/347,344, filed on Jul. 2, 1999 and entitled xe2x80x9cMethod, System, and Program for Maintaining Electronic Data as of a Point-In-Time.xe2x80x9d A different fast replicate technique is the xe2x80x9cSNAPSHOTxe2x80x9d technique disclosed in U.S. Pat. No. 5,410,667 entitled xe2x80x9cData Record Copy System for a Disk Drive Array Data Storage Subsystem,xe2x80x9d which issued on Apr. 25, 1995. The foregoing references are hereby incorporated herein by reference.
Instant virtual copy techniques have been developed, at least in part, to quickly create a duplicate copy of data without interrupting or slowing foreground processes. A natural extension of this function has been the creation of a physical xe2x80x9cbackupxe2x80x9d copy of the source data, to aid in disaster recovery. Under one such technique, an operation such as xe2x80x9cFLASH COPYxe2x80x9d or xe2x80x9cSNAPSHOTxe2x80x9d operation is used to perform an instant virtual copy operation; this creates a virtual target volume identical to the source volume in all respects. Then, the target volume is taken off-line, which may occur automatically as a result of the instant virtual copy operation or manually at the direction of a system administrator.
Although the foregoing technique is useful in some respects, there are still certain challenges. Normal instant virtual copy operations can involve tens of thousands of files. Under these circumstances, it can be difficult to locate a particular dataset on a backup volume since the backup datasets are not catalogued. The usual procedure is to identify the source dataset on a source volume and then utilize other directories to identify the backup volume counterpart to that source volume. Then, the backup dataset is located by reviewing an inventory such as a volume table of contents (VTOC) aboard the backup volume. In another embodiment, an independent background process reviews contents of the backup volumes and creates an appropriate backup dataset inventory. This process, however, is consumptive of time and processing resources. Furthermore, if the source volume fails before the lengthy backup dataset inventory is compiled, the effort expended toward compiling this inventory is completely wasted.
For the foregoing reasons, then, known backup processes based on the instant virtual copy technique are not completely adequate for some applications due to certain unsolved problems.
A process of copying a body of source data is shown, where a backup manager quickly creates an accurate backup dataset inventory. While write operations to the source data are temporarily suspended, the backup manager performs an instant virtual copy upon the source data to create a backup copy. Also during this time, the backup manager captures contents of a source dataset inventory cross-referencing datasets in the source data and locations where those datasets are stored. The capture operation is especially rapid, and may be performed by reading the source dataset inventory into memory, performing an instant virtual copy of data including the source dataset inventory, copying the inventory into nonvolatile storage, etc. After the copy operation completes and writing of the source data resumes, the backup manager incorporates the captured source dataset inventory into a backup dataset inventory cross-referencing the names of datasets in the backup copy and their locations in the backup copy. Later, when a request occurs to access a particular backup dataset, the backup manager accesses the backup dataset inventory to locate the specified dataset in the backup copy, and ultimately accesses the specified dataset from that storage location.
Optionally, this process may be further enhanced in a number of different ways. For instance, where the source data is stored on a number of different storage media, an additional step may be performed before starting the backup operations. Namely, each source storage medium is paired with a counterpart backup storage medium having predetermined characteristics that match characteristics of the source storage medium. This effectively reserves the backup storage media before creating the backup copy.
Another optional enhancement concerns the use of copy pools. The invention may receive operator input of a xe2x80x9ccopy poolxe2x80x9d providing a shorthand reference for a specific group of source volumes. This shorthand eases the burden on operators to painstakingly specify multiple volumes for each time a storage operation involving those volumes is performed. Furthermore, when the copy pool definition is amended, this automatically applies whenever the copy pool is used in any future storage operations.
The foregoing features may be implemented in a number of different forms. For example, the invention may be implemented to provide a backup copy method. In another embodiment, the invention may be implemented to provide an apparatus such as a storage system or backup manager component configured to perform backup copy operations as discussed herein. In still another embodiment, the invention may be implemented to provide a signal-bearing medium tangibly embodying a program of machine-readable instructions executable by a digital data processing apparatus to perform backup copy operations. Another embodiment concerns logic circuitry having multiple interconnected electrically conductive elements configured to perform backup copy operations.
The invention affords its users with a number of distinct advantages. For example, the invention eases and speeds the process of locating a particular backup dataset because the backup datasets are inventoried. The invention also provides a number of other advantages and benefits, which should be apparent from the following description of the invention.

Instant virtual copy technique with expedited creation of backup dataset inventory from source dataset inventory