EP0905558A1 - Emulsion photographique à l'halogénure d'argent - Google Patents

Emulsion photographique à l'halogénure d'argent Download PDF

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Publication number
EP0905558A1
EP0905558A1 EP98307192A EP98307192A EP0905558A1 EP 0905558 A1 EP0905558 A1 EP 0905558A1 EP 98307192 A EP98307192 A EP 98307192A EP 98307192 A EP98307192 A EP 98307192A EP 0905558 A1 EP0905558 A1 EP 0905558A1
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EP
European Patent Office
Prior art keywords
group
silver halide
sensitization
atom
formula
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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EP98307192A
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German (de)
English (en)
Inventor
Socman Ho
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Konica Minolta Inc
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Konica Minolta Inc
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Publication of EP0905558A1 publication Critical patent/EP0905558A1/fr
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/10—Organic substances
    • G03C1/12—Methine and polymethine dyes
    • G03C1/14—Methine and polymethine dyes with an odd number of CH groups
    • G03C1/18—Methine and polymethine dyes with an odd number of CH groups with three CH groups
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/0051—Tabular grain emulsions
    • G03C1/0053—Tabular grain emulsions with high content of silver chloride
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/10—Organic substances
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/34—Fog-inhibitors; Stabilisers; Agents inhibiting latent image regression
    • G03C1/346—Organic derivatives of bivalent sulfur, selenium or tellurium
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/09—Noble metals or mercury; Salts or compounds thereof; Sulfur, selenium or tellurium, or compounds thereof, e.g. for chemical sensitising
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/09—Noble metals or mercury; Salts or compounds thereof; Sulfur, selenium or tellurium, or compounds thereof, e.g. for chemical sensitising
    • G03C2001/096—Sulphur sensitiser
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/09—Noble metals or mercury; Salts or compounds thereof; Sulfur, selenium or tellurium, or compounds thereof, e.g. for chemical sensitising
    • G03C2001/097—Selenium
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/09—Noble metals or mercury; Salts or compounds thereof; Sulfur, selenium or tellurium, or compounds thereof, e.g. for chemical sensitising
    • G03C2001/098—Tellurium
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C2200/00—Details
    • G03C2200/01—100 crystal face

Definitions

  • the present invention relates to a silver halide emulsion, a method for processing a silver halide light sensitive photographic material having the emulsion and a photographing method by the use of the photographic material.
  • Shortening of processing time including developing, fixing, washing, drying, etc. is the key for faster processing of photographic materials. Shortening of the developing time alone, however, leads to a marked decrease of image density and sensitivity and deterioration of contrast. Shortening of only the fixing time leads to insufficient fixing, causing deterioration of image quality. Furthermore, shortening the time of each processing step results in incomplete dye leaching out of the processed material, causing stains due to residual dye. To overcome these problems, it is basically required to enhance developability and fixability of the photographic material, reduce the content of the dye and promote release or decoloring of the dye.
  • JP-A refers to unexamined and published Japanese Patent Application
  • JP-A discloses a technique of using, as a sensitizing dye, benzimidazolo-carbocyanines which are superior in decolorizability.
  • JP-A 5-61148 discloses a technique in which a combination of an oxacarbocyanine and benzimidazolocarbocyanine is used in a specific proportion, in a silver halide emulsion containing 1 mol% or less iodide and the silver halide emulsion is further chemically sensitized with a selenium compound and/or tellurium compound.
  • the dye stain reduction and rapid-processability can be improved by these techniques, but it is not insufficient to satisfy other desired levels. Specifically, sensitivity and safelight safety characteristics are still insufficient. Furthermore, another defect is that when aged under high temperature and high humidity, the decrease in sensitivity is marked.
  • an object of the present invention is to provide a photographic material superior in photographic characteristics, pressure resistance and storage stability, and without causing residual dye stain, even when continuously subjected to rapid processing at low effluents.
  • the object of the present invention can be accomplished by the following constitution:
  • a silver halide emulsion comprising reduction-sensitized silver halide grains and a compound represented by formula (1), (2) or (3); the silver halide emulsion grains having been further subjected to at least one chemical sensitization selected from sulfur sensitization, selenium sensitization and tellurium sensitization, in the presence of a spectral sensitizing dye represented by formula (4): formula (1) wherein X represents an atomic group necessary for forming a heterocyclic ring with a group selected from -SO 3 M, -COOM and -OM, which is attached directly or indirectly to the ring; M represents a hydrogen atom, a metal atom, a quaternary ammonium group or a phosphonium group, provided that a compound having, in part, the following structure is excluded: wherein R represents a hydrogen atom or a substituent, formula (2) formula (3) wherein (A 1 ) and (A 1 )' each represent -SO 3 M, -COOM, -OM or
  • the silver halide grains contained in the silver halide emulsion according to the invention may comprise silver chloride, silver iodochloride, silver iodochlorobromide, silver chlorobromide, silver bromide or silver iodobromide. Of these silver halides are preferred silver chloride, silver iodochloride silver bromochloride and silver bromide.
  • a preferred embodiment of silver halide grains according to the invention is those containing 10 mol% or more, preferably 50 mol% or more and more preferably 90 mol% or more chloride
  • the average overall iodide content is preferably 0.01 to 1.0 mol% and more preferably, 0.01 to 0.5 mol%.
  • the form of silver halide grains used in the invention it may be cube, octahedron, tetradecahedron, spherical form or tabular form. Of these are preferred tabular grains.
  • the iodide content of each grain and an average iodide content of overall grains can be determined by means of EPMA (Electron Probe Micro Analyzer).
  • EPMA Electro Probe Micro Analyzer
  • a sample which is prepared by dispersing silver halide grains so as not to be contact with each other is exposed to an electron beam to conduct X-ray analysis by excitation with the electron beam. Thereby, elemental analysis of a minute portion can be done.
  • halide composition of each grain can be determined by measuring intensities of characteristic X-ray emitted from each grain with respect to silver and iodide.
  • At least 50 grains are subjected to the EPMA analysis to determine their iodide contents, from which the average iodide content can be determined.
  • the tabular silver halide grains contained in the silver halide emulsion according to the invention have uniformly iodide contents among grains.
  • a relative standard deviation thereof i.e., a variation coefficient of the iodide content of grains
  • a relative standard deviation thereof i.e., a variation coefficient of the iodide content of grains
  • iodide contents among grains are preferably uniform.
  • a relative standard deviation i.e., coefficient of variation of the iodide content of grains
  • the iodide is preferably, internally contained. In this case, the iodide is contained more preferably in the central portion of the grain. It is also preferable that the iodide is made present in the surface portion of the grain.
  • the halide composition within a silver halide grain can be determined by cutting ultra-thinly slices from the grain and making observation and analysis of the grain by a transmission electron microscope with cooling.
  • a transmission electron microscope with cooling.
  • the grains are buried in a resin, which is cut at a thickness of ca. 60 nm with a diamond knife to prepare a slice sample.
  • the slice sample is observed and analyzed at various points with a transmission electron microscope provided with an energy-dispersion type X-ray analyzing apparatus to determine the halide composition within the grain (Inoue & Nagasawa, Abstracts of Annual Meeting of The Society of Photographic Science and Technology of Japan, 1987, page 62).
  • the iodide is present preferably in the outermost surface layer.
  • the iodide content in the outermost surface layer is preferably between 1 mol% and 10 mol%.
  • the iodide content in the outermost surface layer of the tabular silver halide grains refers to a silver iodide content of a portion in a depth from the surface of 50 nm, which can be determined by the XPS method (X-ray Photoelectron Spectroscopy). Thus, a sample is cooled to -110° C in super-vacuo of not more than 1x10 -8 torr.
  • the halide composition of the surface can be determined.
  • measurement errors resulted from destruction of the sample (i.e., decomposition of silver halide and diffusion of halide, specifically, iodide) when exposed to X-ray at room temperature are minimized, resulting in enhanced measurement accuracy.
  • sample destruction is minimized to a level which prevents problems in measurement.
  • the bromide is also present preferably in the outermost surface layer.
  • the bromide content in the outermost surface layer is preferably between 1 mol% and 10 mol%.
  • the tabular silver halide grains used in the invention have an average aspect ratio of 2 to 20, preferably not more than 8, more preferably less than 7, and still more preferably less than 5.
  • the tabular grains having (100) major faces account for preferably 50% or more, more preferably 70% or more, and still more preferably 90% or more of the total grain projected area of the emulsion layer.
  • the (100) major faces can be identified by X-ray diffractometry.
  • the major faces of the tabular silver halide grains is in the form of a rectangle (i.e., right-angled parallelogram) or one with rounded corners.
  • the edge ratio of the rectangle i.e., ratio of the long edge length to the short edge length
  • the edge length is defined as a distance between the intersection of an extended straight line of the edge and extended straight lines of adjacent edges.
  • An average grain diameter of the tabular silver halide grains of the invention is preferably 0.15 to 5.0 ⁇ m, more preferably 0.4 to 3.0 ⁇ and furthermore preferably 0.4 to 2.0 ⁇ m.
  • An average thickness of the tabular silver halide grains is preferably 0.01 to 1.0 ⁇ m, more preferably 0.02 to 0.40 ⁇ m and furthermore preferably 0.02 to 0.30 ⁇ m.
  • the grain diameter and thickness can be optimized so as make best sensitivity and other photographic characteristics. The optimal grain diameter and thickness depend upon sensitivity and other factors affecting photographic characteristics (thickness of a hydrophilic colloidal layer, hardening degree, chemical ripening conditions, designed speed of a photographic material, silver coating amount, etc.).
  • the tabular silver halide grains used in the invention are preferably monodisperse grains having a narrow grain size distribution.
  • a width of grain size (diameter) distribution is preferably 25% or less, more preferably 20% or less and furthermore preferably 15% or less:
  • the tabular silver halide grains used in the invention are preferably those having a narrow grain thickness distribution.
  • a width of grain thickness distribution is preferably 25% or less, more preferably 20% or less and furthermore preferably 15% or less:
  • the tabular silver halide grains used in the invention may have dislocation lines.
  • the dislocation lines can be directly observed by use of a transmission type electron microscope at low temperature, as described in J. F. Hamilton, Phot. Sci. Eng., 57 (1967) and T. Shiozawa, J. Soc. Phot. Sci. Japan, 35, 213 (1972).
  • silver halide grains which are carefully taken out from an emulsion without applying pressure to an extent of causing dislocation, are placed on a mesh for electron microscopic observation and observed by the transmission method, while being cooled to avoid damage due to electron beam.
  • the more is the grain thickness the less the transmission of the electron beam, so that clearer observation is achieved by use of a high voltage type electron microscope.
  • the process of preparing a silver halide emulsion is generally classified into grain formation, desalting, chemical sensitization and so on.
  • the grain formation is further classified into nucleation, ripening, growth and so on. Steps of the process are not necessarily performed in this order, but may be reversed or repeated.
  • Silver halide grains according to the invention are reduction sensitized.
  • the reduction sensitization can be applied to any one of these steps.
  • the reduction sensitization can be performed at the step of nucleation, physical ripening, or growth.
  • the reduction sensitization can be performed prior to chemical sensitization other than the reduction sensitization or after the chemical sensitization.
  • the chemical sensitization is applied in combination with gold sensitization, it is preferable to perform the reduction sensitization prior to the chemical sensitization so as not to cause unacceptable fog. It is more preferable to perform the reduction sensitization during the growth of silver halide grains.
  • the reduction sensitization includes a method of adding a known reducing agent into a silver halide emulsion, a method of growing or ripening grains under environments at a low pAg of 1 to 7 (so-called silver ripening), and a method of growing or ripening grains under environments at a high pH of 8 to 11 (so-called high pH ripening).
  • the method of adding a reduction sensitizer is preferable in terms of delicate adjustment of the reduction sensitization level.
  • the reduction sensitizer include stannous salts, amines or polyamines, hydrazine derivatives, formamidinesulfinic acid, silane compounds and borane compounds. These compounds can be employed singly or in combination.
  • Preferred reduction sensitizer includes stannous salts, thiourea dioxide, and dimethylamine borane.
  • the adding amount of the reduction sensitizer depending on conditions of emulsion preparation, is optimally between 10 -7 and 10 -3 mol per mol of silver halide.
  • Ascorbic acid and its derivatives can be employed as reduction sensitizer. Examples of ascorbic acid and its derivatives (hereinafter, also referred to as an ascorbic acid compound) are shown below.
  • the addition amount of ascorbic acid compounds is desirably larger than that of conventionally used reduction sensitizers.
  • JP-B 57-33572 (herein the term "JP-B" refers examined published Japanese patent) describes that the addition amount of a reducing agent conventionally does not exceed 0.75 milli-equivalent per lg of silver ion (8x10-4 mol/AgX mol); the amount of 1 to 10 mg per 1 kg of silver nitrate (ascorbic acid of 10 -7 to 10 -5 mol/AgX mol) is often effective.
  • U.S. Patent 2,487,850 described that a tin compound is added, as a reduction sensitizer, in an amount of 1x10 -7 to 44x10 -6 mol.
  • JP-A 57-179835 describes that the addition amount of thiourea dioxide or stannous chloride is optimally 0.01 to 2 mg or 0.01 to 3 mg per mol of silver halide, respectively.
  • the addition amount of the ascorbic compound used in the invention is preferably 5x10 -5 to 1x10 -1 , more preferably 5x10 -4 to 1x10 -2 , and still more preferably 1x10 -3 to 1x10 2 mol/AgX mol.
  • the reduction sensitizer can be dissolved in water or a solvent such as alcohols, glycols, ketones ,esters and amides and added during grain formation, before or after chemical sensitization.
  • the reduction sensitizer can be added at any step during the course of emulsion making and preferably added during the grain formation.
  • the reduction sensitizer may be previously added into a reaction vessel and preferably added at any time during the grain formation.
  • the reduction sensitizer is previously added to a silver salt or alkali halide aqueous solution, and the solution can be added during the grain formation.
  • the sensitizer solution can be added separately or continuously during the grain formation.
  • X represents an atomic group necessary for forming a heterocyclic ring having -SO 3 M, -COOM or -OM, which may be attached directly or indirectly, through a lincage group, to the ring.
  • the heterocyclic ring contains at least one of -SO 3 M, -COOM and -OM, or at least a group containing at least one of -SO 3 M, -COOM or -OM.
  • heterocyclic ring examples include an oxazole ring, a thiazole ring, a imidazole ring, a selenazole ring, a triazole ring, a tetrazole ring, a thiadiazole ring, an oxadiazole ring, a pentazole ring, a pyrimidine ring, a thiazine ring, a triazine ring, a thiazine ring, or a heterocyclic ring condensed with another carbon ring or heterocyclic ring, such as a benzothiazole ring, a benzotriazole ring, a benzimidazole ring, a benzooxazole ring, a benzoselenazole ring, a naphthooxazole ring, a triazaindolidine ring, a diazaindolidine ring or a tetraaza
  • imidazole ring a tetrazole ring, a thiazole ring, an oxazole ring, a benzimidazole ring, a benzthiazole ring, a benzoxazole ring and a triazole ring.
  • the compound represented by formula (1) does not include a compound having, in part, the following structure: wherein R represents a hydrogen atom or a substituent.
  • the compound represented by formula (1) is preferably represented by the following formula (1'): formula (1') wherein X 1 represents NR', O or S, in which R' represents a substituent; R represents a hydrogen atom or substituent; and X 2 is the same as defined in X of formula (1) described above.
  • the substituent represented by R or R' include an alkyl group or aryl group, each of which may be substituted.
  • (A 1 ) and (A 1 )' represent-SO 3 M, -COOM, -OM or a N-attached oxide group, in which M represents a metal, preferably, an alkali metal or a transition metal capable of bonding with sulfur, selenium or tellurium, such as silver, gold or palladium.
  • the electron-withdrawing group represented by (A 2 ) and (A 2 ) is preferably a fluorine atom, trifluoromethyl group, cyano group, nitro group, -SO 2 NH 2 , or -SO 2 CH 3 .
  • (A 3 ) and (A 3 )' is a functional group containing a sulfur atom, selenium atom or tellurium atom, which is capable of bonding with a silver ion.
  • the aliphatic hydrocarbon carbon group represented by Y preferably has 4 to 10 carbon atoms, including buty and pentyl.
  • the aromatic hydrocarbon ring grpup represented by Y is preferably a benzene ring or a naphthalene ring.
  • the compound represented by formula (2) or (3) may be substituted by a substituent , such as a halogen atom except for fluorine, hydroxy, amino, acylamino, alkylamino, alkyl, alkenyl, cycloalkyl, aryl, alkoxy, aryloxy, alkylthio, alkoxycarbonyl, carbamoyl, alkoxyalkyl, aminoalkyl, acylaminoalkyl, hydroxyalkyl, carboxyalkyl, sulfoalkyl or alkylsulfonamido.
  • substituent such as a halogen atom except for fluorine, hydroxy, amino, acylamino, alkylamino, alkyl, alkenyl, cycloalkyl, aryl, alkoxy, aryloxy, alkylthio, alkoxycarbonyl, carbamoyl, alkoxyalkyl, aminoalkyl, acylaminoal
  • the compound represented by formula (1), (2) or (3) can be added before, during or after chemical sensitization. When added before completion of chemical sensitization, enhanced effects can be obtained, and when added separately before and after completion of chemical sensitization, further enhanced effects can be obtained.
  • Each of the compound can be added, singly or in combination, and can also be added in combination with other inhibitors.
  • the compound can be added in the form of powder or through solution in water, a low boiling solvent such as methanol, ethanol or ethyl acetate, or a mixture of water and the low boiling solvent. To enhance solubility, a pH adjusting agent may be optionally added. In some cases, the compound is added in the form of a dispersion of fine solid particles, resulting in enhanced effects. In any cases, the addition amount is preferably 0.01 to 0.5 g, and more preferably 0.02 to 0.2 g per mol of silver halide.
  • the silver halide emulsion according to the invention is subjected to at least one of sulfur sensitization, selenium sensitization and tellurium sensitization, in the presence of a spectral sensitizing dye represented by formula (4).
  • a spectral sensitizing dye is adsorbed to silver halide grains and contributes to sensitization. It is preferred that when the sensitizing dye represented by formula (4) is allowed to adsorbed to silver halide emulsion grains and its reflection spectrum is measured, the maximum absorption wavelength of J-band is not more than 550 nm.
  • J-band is formed preferably in the same wavelength region as the green light emitted from the phosphor.
  • a spectral sensitizing dye so as to form the J-band having an absorption maximum in a range of 520 to 555 nm, preferably 530 to 553 nm and more preferably, 540 to 550 nm.
  • the alkyl group represented by R 1 and R 3 includes straight-chained or branched one (preferably, a lower alkyl group having 1 to 6 carbon atoms), such as ethyl, butyl or 3-methylbutyl.
  • the substituted alkyl group include 2-hydroxyethyl, 2-methoxyethyl, 2-ethoxyethyl, ethoxycarbonylethyl, phenethyl, methanesulfonylethyl and 3-oxobutyl.
  • Examples of the alkenyl group include vinyl and allyl.
  • the alkyl group represented by R 2 and R 4 includes straight-chained or branched one, such as methyl, ethyl, butyl or isobutyl.
  • the hydrophilic group contained in the alkyl group include sulfo group, carboxy group, methanesulfonylaminocarbonyl group, methanesulfonylamino-sulfonyl group, acetylaminosulfonyl group, sulfoamino group, trifluoroacetylaminosulfonyl group, acetylaminocarbonyl group, and N-methylsulfamoyl group.
  • Examples thereof include 2-sulfoethyl, 3-sulfopropyl, 3-sulfobutyl, 5-sulfopentyl, 2-N-ethyl-N-sulfoaminoethyl, carboxymethyl, carboxyethyl, 3-sulfoaminopropyl, 6-sulfo-3-oxahexyl, 10-sulfo-3,6-dioxadecyl, 6-sulfo-3-thiahexyl, o-sulfobenzyl, p-carboxybenzyl, methnesulfonylaminocarbonylmethyl and acetylaminosulfonyl-methyl.
  • Z 1 , Z 2 , Z 3 and Z 4 independently represent a hydrogen atom or a substituent.
  • substituents include a halogen atom, an alkyl group (e.g., a lower alkyl having 1 to 5 carbon atoms, such as methyl, ethyl propyl), an alkoxy group (e.g., methoxy, ethoxy proxy), a halogen-substituted alkoxy group (e.g., fluoromethyl, trifluoromethyloxy, 2,2,2-trifluoroethyloxy), an aryloxy group (e.g., phenoxy, p-bromophenoxy), an acyl group (e.g., acetyl, benzoyl), an acyloxy (e.g., acetyloxy, propionyloxy), an alkylthio group (e.g., methylthio, ethylthio), a halogen-substitute
  • X 1 - represents an ion necessary for neutralizing the charge within the spectral sensitizing dye, including an anion and a cation.
  • anion include a halide ion, perchlorate, ethylsulfatethiocyanate, p-toluenesulfonate and perfluoroborate.
  • Examples of the cation include a hydrogen ion, an alkali metal ion (e.g., lithium, sodium and potassium ions), alkali earth metal ion (e.g., magnesium and calcium ions), ammonium ion and an organic ammonium ion (e.g., triethylammonium, triethanolammonium, and tetramethylammonium ions).
  • an alkali metal ion e.g., lithium, sodium and potassium ions
  • alkali earth metal ion e.g., magnesium and calcium ions
  • ammonium ion and an organic ammonium ion e.g., triethylammonium, triethanolammonium, and tetramethylammonium ions.
  • spectral sensitizing dye represented by formula (4) Exemplary examples of the spectral sensitizing dye represented by formula (4) are shown below, but the dye is not limited to these examples.
  • spectral sensitizing dyes each can be employed in combination with other spectral sensitizing dyes.
  • Examples of the due employed in combination include a cyanine dye, a merocyanine dye, a complex cyanine dye, a complex merocyanine dye, a holopolar cyanine dye, a hemi-cyanine dye, a styryl dye and a hemioxonol dye.
  • a cyanine dye, merocyanine dye and a complex merocyanine dye are useful.
  • nuclei conventionally used including a pyrroline nucleus, a oxazoline nucleus, a pyrrol nucleus, a an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, imidazole nucleus, tetrazole nucleus and pyridine nucleus.
  • nuclei in which the nucleus described above is condensed with an aliphatic hydrocarbon ring including an indolenine, a benzindolenine nucleus, an indole nucleus, a benzoxazole nucleus, a naphthooxazole nucleus, a benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus and quinoline nucleus. These nuclei may be substituted.
  • a nucleus having a ketomethine structure is applicable, including 5 or 6-membered heterocyclic nucleus such as a pyrazoline-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidine-2,4-dione nucleus, a thiazoline-2,4-dione nucleus, a rhodanine nucleus and a thiobarbituric acid nucleus.
  • the dyes are described in German Patent 929,080; U.S.
  • the adding amount of the spectral sensitizing dye is preferably in such an amount as to be 30 to 90% of monomolecular layer coverage, and more preferably, 40 to 80%.
  • the monomolecular layer coverage refers to a relative value, based on that, when absorption isotherm at 50° C is prepared, a saturated absorbing amount is 100% of the coverage.
  • the optimal amount of the spectral sensitizing dye which is variable, depending on the total surface area of silver halide grains contained in an emulsion, is less than 600 mg and preferably less than 450 mg per mol of silver halide.
  • the proportion of the dye represented by formula (4) is preferably not less than 30% of the total dye to enhance sensitivity and improve residual dye stain.
  • a solvent for the sensitizing dye are usable conventionally employed water-miscible organic solvents, including alcohols, ketones, nitriles, and alkoxyalcohols.
  • examples thereof include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, ethylene glycol, propylene glycol, 1,3-propanediol, acetone, acetonitrile, 2-methoxyethanol and 2-ethoxyethanol.
  • Surfactants have been conventionally employed as a dispersing agent.
  • the invention is also usable any type of surfactants, including an anionic type, cationic type, nonionic type and amphoteric type.
  • sensitizing dye in the form of an acidic solution or a solid fine particle dispersion rather than in the form of an organic solvent solution.
  • At least one sensitizing dye is preferably added in the form of scarcely water-soluble, solid fine particles dispersed in water substantially free from an organic solvent and/or surfactant, allowing the dye to be adsorbed uniformly and effectively onto the surface of silver halide grains.
  • water substantially free from an organic solvent and/or surfactant refers to water containing impurities less than an extent of not exerting an unfavorable influence upon a silver halide emulsion. It is preferably deionized water or distilled water.
  • Solubility in water of the sensitizing dye used in the invention is preferably 2x10 -4 to 4x10 -2 , and more preferably 1x10 -3 to 4x10 -2 .
  • solubility is less than this range, sizes of dispersed particles become larger and inhomogeneous, leading to formation of precipitate of a dispersing material or to interference with adsorption of the sensitizing dye to silver halide, when the dispersion is added into a silver halide emulsion.
  • solubility is larger than this range, on the other hand, viscosity of the dispersion becomes larger than that needed and bubbles are incorporated, resulting in interference with dispersion, and when the solubility is still larger, the dispersion becomes impossible.
  • the solubility of the sensitizing dye can be determined in accordance with the following procedure.
  • the sensitizing dye used in the invention can be added in the process of chemical sensitization, preferably at the start of chemical sensitization. Addition of the dye during the course of nucleation of a silver halide emulsion to completion of washing results in a sensitive silver halide emulsion with enhanced spectral sensitization efficiency.
  • Sulfur sensitizers usable in the invention include those as described in U.S. Patent 1,574,944, 2,410,689, 2,278,947, 2,728,668, 3,501,313 and 3,656,955; German patent (OLS)1,422,869; JP-A 56-24937 and 55-45016.
  • Preferred examples thereof include thiourea derivatives such as 3-diphenylthiourea, triethylthiourea and 1-ethyl-3-(2-thiazolyl)thiourea; rhodanine derivatives, dithiacarbamates, polysulfide organic compounds and sulfur single body.
  • the sulfur single body is preferably rhombic ⁇ -sulfur.
  • the amount of the sulfur sensitizer to be added is 1x10 -9 to 1x10 -4 mol, and preferably 1x10 -8 to 1x10 -5 mol per mol of silver halide.
  • Selenium sensitizers usable in the selenium sensitization include a variety of selenium compounds, as described in U.S. Patent 1,574,944, 1,602,592 and 1,623,499; and JP-A 60-150046, 4-25832, 4-109240 and 4-147250.
  • colloidal selenium metal examples thereof include colloidal selenium metal, isoselenocyanates (e.g., allylisoselenocyanate), selenoureas (e.g., N,N-dimethylselenourea, N,N,N'-triethylselenourea, N,N,N'-trimethyl-N'-heptafluoroselenourea, N,N,N'-trimethyl-N'-heptafluoropropylcarbonylselenourea, N,N,N'-trimethyl-N'-4-nitrophenylcarbonylselenourea), selenoketones (e.g., selenoacetone, selenoacetophenone), selenoamides (e.g., selenoacetoamide, N,N-dimethylselenobenzamide), selenocarboxylic acids and selenoesters (e.g., 2-selenopropionic
  • the amount of the selenium sensitizer to be used is generally 10 -8 to 10 -4 mol per mol of silver halide.
  • the temperature of chemical sensitization with the selenium sensitizer is preferably 40 to 90° C and more preferably 45 to 80° C.
  • the pH and pAg is preferably 4 to 9 and 6 to 9.5, respectively.
  • tellurium sensitizers examples include telluroureas (e.g., N,N-dimethyltellurourea, tetramethyltellurourea, N-carboxyethyl-N,N'-dimethyltellurourea, N,N'-dimethyl-N'-phenyltellurourea), phosphine tellurides (e.g., tributylphosphine telluride, tricyclohexylphosphine telluride, triisopropylphosphine telluride, butyl-diisopropylphosphine telluride, dibutylphenylphosphine telluride), telluroamides (e.g., telluroacetoamide, N,N-dimethyltellurobenzamide), telluroketones, telluroesters and isotellurocyanates.
  • telluroureas e.g., N,N-dimethyltellurourea, t
  • Chemical sensitization other than the sulfur sensitization, selenium sensitization and tellurium sensitization can be employed in combination.
  • the condition in the process of chemical sensitization such as pH, pAg, temperature and time, and chemical sensitization is performed under conditions employed in the art.
  • the combined chemical sensitization includes reduction sensitization by the use of a reducing material and noble metal sensitization by the use of gold or other noble metals.
  • gold sensitization and reduction sensitization are preferable.
  • gold sensitizers include chloroauric acid, gold thiosulfate, gold thiocyanate, and gold complexes of various compounds such as thioureas and rhodanines.
  • the amount of the gold sensitizer to be used is the same as that of the sulfur sensitizer.
  • the sensitizer described above can be incorporated through solution in water, alcohols, or organic or inorganic solvents, or incorporated in the form of a dispersion employing water-insoluble solvents or a medium such as gelatin. Sensitization can be simultaneously applied, or separately and stepwise applied. It is also preferable to subject the grain surface to reduction sensitization by allowing to be stood under optimal reducing conditions.
  • preferable reducing agents include thiourea dioxide, ascorbic acid and its derivatives, polyamines such as hydrazine and diethylenetriamine, dimethylamine boranes and sulfites.
  • Z 5 represents an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring, including thiazoliums ⁇ e.g., thiazolium, 4-methylthiazolium, benzothiazolium, 5-methylbenzothiazolium, 5-chlorobenzothiazolium, 5-methoxybenzothiazolium, 6-methylbenzothiazolium, 6-methoxybenzothiazolium, naphtho[1,2-d]thiazolium, naphtho[2,1-d]thiazolium ⁇ , oxazoliums ⁇ e.g., oxazolium, 4-methyloxazolium, benzooxazolium, 5-chlorobenzooxazolium, 5-phenylbenzooxazolium, 5-methylbenzooxazolium, naph
  • the alkyl group represented by R 5 is preferably a lower alkyl group having 1 to 5 carbon atoms.
  • the alkenyl group represented by R 5 is preferably vinyl or allyl.
  • the lower alkyl group represented by R 6 is one having 1 to 5 carbon atoms.
  • the anion represented by X is preferably an acid anion, such as a hydrohalogenic acid anion (e.g., Cl - , Br - , I - ).
  • These compounds each can be employed in an amount of 10 to 5 g per mol of silver halide, and incorporated by directly dispersing in the emulsion or through solution in an appropriate solvent (e.g., water, methanol, ethanol, propanol, methyl cellosolve, acetone). Further the compound can also be incorporated in a manner similar to the sensitizing dye.
  • an appropriate solvent e.g., water, methanol, ethanol, propanol, methyl cellosolve, acetone.
  • Dyes usable in the photographic material according to the invention are preferably those which are substantially water-insoluble at a pH of 7 or less and water-soluble at a pH of not less than 8.
  • the addition amount, which is variable according to aided sharpness, is preferable 0.2 to 20 mg/m 2 , and more preferably 0.8 to 15 mg/m 2 . Examples thereof are described in German patent 616,007; British Patents 584,609 and 1,177,429; JP-B 26-7777, 39-22969 and 54-38129; JP-A 48-85130, 49-99620, 49-114420, 49-129537, 50-28827, 52-108115, 57-185038, 2-282244 and 4-307539; U.S.
  • a variety of photographic adjuvants can be employed in the photographic material relating to the invention.
  • the known adjuvants include compounds described in Research Disclosure No. 17643 (1978, December), ibid No. 18716 (1979, November), and ibid No. 308119 (1089, December).
  • the photographic material can contain, in an emulsion layer or other layers, a developing agent such as aminophenol, ascorbic acid, pyrocatechol, hydroquinone, phenylenediamine or 3-pyrazolidone.
  • Supports usable in the photographic material include those described in above-described RD-17643 at page 28, and RD-308119 at page 1009.
  • the surface of the support may be provided with a sub-layer or be subjected to corona discharge or UV exposure to improve adhesion property of coating layers.
  • the sub-layer preferably contain an antistatic agent such as a colloidal tin oxide sol.
  • the photographic material relating to the invention When the photographic material relating to the invention is employed for the use in X-ray photographing, enhanced sensitivity and sharpness and superior processability can be achieved by providing, on both sides of the support, a silver halide emulsion layer and a cross-over light cutting layer.
  • the total amount of gelatin used in the silver halide emulsion layer, a surface protective later and other layer(s), per one side, is preferably 0.5 to 3.5 g/m 2 , and more preferably 1.5 to 3.0 g/m 2 .
  • photographic latexes comprised of photographically inert surfaces having no interaction with various kinds of photographic additives, that is, the surfaces do not adsorb any dye or dyestuff, resulting in no stain and do not also adsorb any development accelerator or inhibitor, leading to no adverse effects on sensitivity or fog.
  • the silver halide photographic material relating to the invention can be processed by the use of a solid processing composition, such as powdered processing composition or solid processing compositions in the form of a tablet, a pellet or granules.
  • a solid processing composition such as powdered processing composition or solid processing compositions in the form of a tablet, a pellet or granules.
  • the powder is referred to an aggregate comprised of fine crystal particles.
  • the granules is referred to granular material prepared by subjecting the powder to granulating process, having particle sizes of 50-5000 ⁇ m.
  • the tablet is one prepared by subjecting the powder or granules to compression-molding to a given form.
  • the processing composition can be solidified in such a manner that the processing composition, in the form of a concentrated solution, fine powder or granules, is mixed with a water soluble bonding agent and then the mixture is molded, or the water soluble bonding agent is sprayed on the surface of temporarily-molded processing composition to form a covering layer.
  • the solid processing composition is preferably in the form of a tablet.
  • a preferred tablet-making process is to form a tablet by compression-molding after granulating powdery processing composition.
  • Granulation can be performed by the known method, such as rolling granulation, extrusion granulation, compression granulation, grinding granulation, stirring granulation, fluidized bed granulation and spray-drying granulation.
  • the average grain size of the granules is 100 to 800 ⁇ m and preferably 200 to 750 ⁇ m. In particular, 60% or more of the granules is with a deviation of ⁇ 100 to 150 ⁇ m.
  • Compression-molded (compression-tableted) solid processing composition may take any form and is preferably in a cylindrical form from the point of productivity, handleability and problems of powder dust in cases when used in user-side. It is further preferred to granulate separately each component, such as an alkali agent, reducing agent and preservative in the above process.
  • the solid processing composition can be used as not only a developer or fixer but also a photographic processing chemicals such as a rinsing agent. Particularly when used as a developer, effects of stabilizing photographic performance are marked.
  • the means for supplying a solid processing composition to a processing tank in the invention and in the case where the solid processing chemical is of the tablet type, for example, there are such a well-known means as described in Japanese Utility Model OPI Publication Nos. 63-137783/1988, 63-97522/1988 and 1-85732/1989, wherein, in short, any means may be used, provided that at least a function for supplying a tableted chemical to a processing tank can be performed. And, in the case where the solid processing chemical is of the granulated or powdered type, there are such a well-known means such as the gravity dropping systems described in JP OPI Publication Nos.
  • a solid processing composition of the invention may be added to any position inside a processing tank and, preferably, to a position communicated with a section for processing a light-sensitive material and circulating a processing solution between the processing tank and the processing section. It is also preferable to have such a structure that a certain amount of processing solution can be circulated therebetween so that a dissolved component can be moved to the processing section. It is further preferable that a solid processing chemical is added to a thermostatically controlled processing solution.
  • a X-ray photographic material prepared by the use of the silver halide emulsion according to the invention is advantageously employed in combination with an intensifying screen with a phosphor filling ratio of 68 to 90%.
  • Example 1 Preparation of Emulsion Em-1 Solution A1 Ossein gelatin 56.6 g 10% Ethanol solution of Compound (A) described below 0.36 ml Potassium bromide 48.2 g Water to make 8083 ml Solution B1 2.0 N Aqueous silver nitrate solution 1791 ml Solution C1 3.5 N Aqueous silver nitrate solution 11505 ml Solution D1 4.0 N Aqueous potassium bromide solution 10962 ml Solution E1 2.0 N Aqueous potassium bromide solution used for controlling the silver potential Solution F1 Ossein gelatin 245 g 10% Ethanol solution of Compound (A) described below 14.12 ml Water 2264 ml Solution G1 Thiosulfonic acid 1.556 g Water to make 156 ml Solution H1 Fine grain emulsion comprised of 3 wt.% gelatin and fine silver iodide grains (a
  • the silver iodide fine grain emulsion (H1) was prepared in the following manner. To 6.64 1 of 5.0 wt.% gelatin aqueous solution containing 0.06 mol of potassium iodide were added 2.0 l of a solution containing 7.06 mol of silver nitrate and 2.0 l of a solution containing 7.06 mol of potassium iodide over a period of 10 min, while the pH and temperature were maintained at 2.0 and 40° C. After completing addition, the pH was adjusted to 6.0.
  • solution A1 To solution A1 were added the total amount of solution B1 and 895 ml of solution D1 by the double jet precipitation method for a period of 3 min. 5 sec. to form nucleus grains, with stirring at 55° C by using a mixing stirrer as shown in JP-B 58-58288 and 58-58289. After completing addition of solutions B1 and D1, solution F1 was added thereto and the temperature was raised to 70° C in 30 min. and ripening was carried out. Further, solution C1 of 907 ml was added in 11 min., then 28 % ammonium aqueous solution was added and ripening was further carried out at a pH of 8.2 for 10 min.
  • Emulsion Em-2 was prepared in the same manner as Em-1, except that solutions I1 and J1 were not added.
  • the emulsions were each divided to a given amount, the temperature was raised to 55° C and fine silver iodide grains of 0.5 mol% was added. Thereafter, the compound represented formula (1), (2) or (3) as shown in Table 1, and spectral sensitizing dyes according to the invention and comparative dye (as shown in Table 1) in the form of solid particle dispersion were added thereto. Further, 10 mg of sodium thiosulfate and 2 mg of triphenylphosphine selenide in the form of fine solid particle dispersion were added, then 105 mg of ammonium thiocyanate and 12.5 mg of chloroauric acid were added and subsequently, ripening was carried out for 2 hr. in total.
  • Emulsion Em-3 Solution A2 Ossein gelatin 75.0 g KI 1.25 g NaCl 33.0 g Distilled water to make 15000 ml Solution B2 Silver nitrate 410 g Distilled water to make 684 ml Solution C2 Silver nitrate 11590 g Distilled water 19316 ml Solution D2 KI 4 g NaCl 140 g Distilled water to make 684 ml Solution E2 NaCl 3980 g Potassium hexachloroiridate (IV) 8x10 -6 mol Distilled water to make 19274 ml
  • the emulsion was divided to a given amount, the temperature was raised to 55° C and thiourea dioxide of 4.25 mg was added as a reduction sensitizer. Then, fine silver iodide grains of 0.5 mol% was further added. Thereafter, 2,2'-dithiobis-(pyridine)-N-oxide was added and spectral sensitizing dye (as shown in Table 2) was added in the form of solid particle dispersion.
  • the solid particle dispersion of the sensitizing dyes were prepared according to the method described in JP-A 5-297496. Thus, a given amount of the sensitizing dyes was added into water previously adjusted at 27° C and stirred by means of a high-speed stirrer (dissolver) at 3,500 rpm for 30 to 120 min. to obtain the dispersion.
  • a coating solution of an emulsion layer To the emulsion were added the following additives to prepare a coating solution of an emulsion layer. Coating solutions of a protective layer were also prepared, as below. Using these coating solutions, simultaneous double side coating was conducted by two slide-hopper type coating machines at a speed of 80 m/min. so that silver and gelatin coating amounts were respectively 1.6 g/m 2 and 2.5 g/m 2 of one side of a support, and coated web was dried over a period of 2 min. 20 sec. to obtain samples.
  • PET polyethylene terephthalate
  • Additives used in each layer are as follows, provided that the coating amount was expressed as per 1 m 2 of one side of the photographic material.
  • First layer Solid particle dispersion of dye (AHD) 180 mg/m 2 Gelatin 0.2 mg/ 2 Sodium dodecylbenzenesulfonate 5 mg/m 2
  • Compound (I) 5 mg/m 2 Sodium 2,4-dichloro-6-hydroxy-1,3,5-triazine 5 mg/m 2
  • Colloidal silica (av. size 0.014 ⁇ m) 10 mg/m 2
  • Second layer Solid particle dispersion of dye (AHD) 180 mg/m 2 Gelatin 0.2 mg/ 2 Sodium dodecylbenzenesulfonate 5 mg/m 2
  • Compound (I) 5 mg/m 2 Sodium 2,4-dichloro-6-hydroxy-1,3,5-triazine 5 mg/m 2
  • Colloidal silica (av. size 0.014 ⁇ m) 10 mg/m 2
  • Second layer
  • each sample was sandwiched between intensifying screens (high sensitive screen as described below), exposed to X-ray, through an aluminum wedge, to X-ray at tube voltage of 80 kVp and tube current of 100 mA for 0.05 sec.
  • intensifying screens high sensitive screen as described below
  • Solid developer composition used for 100 liters of a developing solution was prepared according to the following procedure.
  • Hydroquinone of 3,000 g, 1-phenyl-3-pyrazolidone of 400 g, N-actyl-D,L-penicillamine of 10 g and sodium glutaraldehyde bissulfite of 500 g each were pulverized up in a commercially available mill so as to have an average particle size of 10 ⁇ m.
  • sodium sulfite of 700 g and D-sorbit of 200 g were added and stirred in the mill for 30 min..
  • stirring granulator commercially available, the resulting mixture was granulated for 5 min. at room temperature by adding 30 ml of water.
  • the resulting granules were dried up at 40° C for 2 hr. in a fluidized bed drier so that the moisture content of the granules was almost completely removed off.
  • Potassium carbonate was added in such an amount as to have buffering capability of 0.16.
  • the buffering capability indicates pH variation when acetic acid of 0.1 mol/Lwp was added to a developing solution, the pH of which was adjusted to 10.0.
  • sodium bicarbonate of 1,000 g and KBr of 200 g each were pulverized up in a commercially available mill so as to have an average particle size of 10 ⁇ m. To the resulting fine particles, were added LiOH H 2 O of 200 g, DTPA.
  • Solid fixer composition used for 100 liters of a fixing solution was prepared according to the following procedure.
  • Ammonium thiosulfate/sodium thiosulfate (90/10 by weight) of 15,000 g was pulverized up in a commercially available mill so as to have an average particle size of 10 ⁇ m.
  • sodium sulfite 500 g
  • Na 2 S 2 O 5 750 g
  • binder Pineflow 1,300 g
  • the resulting mixture was granulated by adding 50 ml of water.
  • the resulting granules were dried up at 40° C in a fluidized bed drier so that the moisture content of the granules was almost completely removed off.
  • Boric acid of 400 g, aluminum sulfate octahydrate of 1,200 g, cinnamic acid of 1200 g and tartaric acid of 300 g were pulverized up in a commercially available mill so as to have an average particle size of 10 ⁇ m.
  • To the resulting fine particles was added D-mannit of 250 g, D-sorbit of 120 g and PEG #4000 of 160 g and the resulting mixture was granulated by adding 30 ml of water.
  • the resulting granules were dried up at 40° C in a fluidized bed drier so that the moisture content of the granules was almost completely removed off.
  • Each of the mixture was compression-tableted so as to have a filling amount of 10.2 g per tablet (C) and 11.2 g per tablet (D), by making use of a tableting machine that was modified model of Tough Press Collect 1527HU manufactured by Kikusui Mfg. Works, Inc.
  • prepared fixing compositions C and D in the form of a tablet were each packaged into a pillow bag containing aluminum for moisture-proof, in an amount for 4 liters of the fixing solution.
  • modified SRX-201 available from Konica Corp.
  • a starting developer solution in a developing tank was prepared so as to dissolve packaged tablets of developer composition-tablet in water using a modified chemical mixer. In this case, the tablets were completely dissolved and no precipitate was observed.
  • prepared developing solution of 7.8 l was introduced into the processor, modified SRX-201 and a starter having the composition as below was added thereto in amount of 33 ml/l to prepare a starting developing solution.
  • a fixing solution for use in the processor was prepared so as to dissolve packaged fixing composition-tablets C and D in water using the chemical mixer. In the thus prepared fixing solution, the tablets were completely dissolved and no precipitate was observed.
  • the fixing solution of 5.6 liters was introduced into a processor SRX-201 as a starting fixer solution.
  • Starter KBr 5.5 g HO(CH 2 ) 2 S(CH 2 ) 2 S(CH 2 ) 2 OH 0.05 g N-acetyl-D, L-penicilamine 0.10 g Sodium metabisulfite for pH-adjustment Water to make 35 ml
  • SRX-201 an inlets of a modified chemical mixer for supplying each of the developing and fixing solid compositions was provided and a built-in chemical mixer was modified for dissolving the solid processing composition.
  • An opened package of solid developing or fixing composition tablets was set at the inlet of modified chemical mixer and at the same time when the tablets was supplied into the tank, warm water (25 to 30° C) was also introduced to prepare the processing solution of 4.0 liter, with stirring and dissolving for 25 min. The resulting solution was used as a replenishing solution for developing or fixing solution.
  • the pH of the developing solution and fixing solution was respectively adjusted to 10.55 and 4.80 with acetic acid or potassium hydroxide.
  • the built-in chemical mixer was comprised of a supplying tank and an auxiliary tank, each having a volume of 4 liters.
  • the auxiliary tank was provided so as to supply a replenishing solution, without no supply of the replenishing solution, during the time a replenishing solution prepared in the supplying tank was exhausted during the running process and the solid processing compositions were being dissolved for a period of 25 min.
  • the starter was added and the pH of the developer stating solution was adjusted to 10.45.
  • Photographic material samples each were subjected to exposure giving a density of 1.0 and running process.
  • developer and fixer were replenished at a rate of 90 ml/m 2 and 90 ml/m 2 , respectively.
  • Fixing 36° C 3.5 sec.
  • Washing 35° C 2.5 sec.
  • Emulsion Dye (mg/Ag ⁇ mol) Compound (1),(2),(3) Remarks (mg/Ag ⁇ mol) (mg/Ag ⁇ mol) 1 Em-2 D-1 (450) - Comp. 2-1 Em-2 D-1 4-11 (225) (225) - Comp. 2-2 Em-2 D-1 4-11 (225) (225) 1-11 (4) 250 Comp. 3 Em-1 D-1 4-11 (225) (225) 1-11 (4) 250 Inv. 4 Em-1 D-1 4-23 (135) (315) 2-4 (4) 280 Inv. 5 Em-1 4-18 (450) 2-4 (5) 300 Inv. 6 Em-1 D-1 4-18 (45) (405) 3-12 (5) 300 Inv.
  • Em-1 was chemically sensitized in the same manner as in Example 1, except that after adding a spectral sensitizing dye, a compound represented by formula (5) was added, as shown in Table 3.
  • Photographic material samples were also prepared in the same manner as in Example 1, except that a compound represented by formula (1), (2) or (3) of 300 mg/ mol ⁇ Ag was added to the Emulsion layer coating solution, as shown in Table 3.
  • Samples prepared by the use of Em-2 were prepared in the same manner as in Example 1.
  • Samples by the use of Em-3 were prepared in the same manner as in Example 1, except that a compound represented by formula (1), (2) or (3) of 350 mg/ mol ⁇ Ag was added to the Emulsion layer coating solution, as shown in Table 3.
  • Each sample was sandwiched between intensifying screens, exposed to X-ray, through an aluminum wedge, to X-ray at tube voltage of 60 kVp and tube current of 200 mA for 0.05 sec.
  • the intensifying screen described below was employed.
  • the coating solution of the phosphor layer was coated in a thickness of 240 ⁇ m by using a doctor blade and dried, and subjected to compression.
  • the compression was conducted by means of a calendar roll at a pressure of 300 kgw/cm 2 and a temperature of 80° C.
  • a transparent protective layer was formed in accordance with the method described in Example 1 of JP-A 6-75097. There was thus obtained an intensifying screen with a thickness of 160 mm and a filling ratio of 68% and exhibiting sharpness (CTF) of 48%.
  • CTF sharpness
  • a screen (S-2) comprising a support, sublayer, phosphor layer and transparent protective layer was prepared in the same manner as the S-1 described above, except that the coating solution of the phosphor was coated in a thickness of 150 ⁇ m and the compression was not applied. There was thus obtained an intensifying screen with a thickness of 105 mm and a filling ratio of 65%.

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US8383819B2 (en) 2006-03-06 2013-02-26 Japan Tobacco Inc. Method for producing 4-oxoquinoline compound
US8420821B2 (en) 2006-03-06 2013-04-16 Japan Tobacco Inc. Process for production of 4-oxoquinoline compound

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US5565315A (en) * 1994-09-09 1996-10-15 Fuji Photo Film Co., Ltd. Silver halide emulsion and photographic material using the same
EP0768568A2 (fr) * 1995-10-13 1997-04-16 Konica Corporation Matèriau photographoque à l halogenure d argent sensille à la lumiere

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US5565315A (en) * 1994-09-09 1996-10-15 Fuji Photo Film Co., Ltd. Silver halide emulsion and photographic material using the same
EP0768568A2 (fr) * 1995-10-13 1997-04-16 Konica Corporation Matèriau photographoque à l halogenure d argent sensille à la lumiere

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8232401B2 (en) 2002-11-20 2012-07-31 Japan Tobacco Inc. 4-oxoquinoline compound and use thereof as HIV integrase inhibitor
EP1574899A3 (fr) * 2004-03-11 2007-05-02 FUJIFILM Corporation Emulsion à l'halogénure d'argent et matériau photographique couleur à l'halogénure d'argent sensible à la lumière
US7262002B2 (en) 2004-03-11 2007-08-28 Fuji Photo Film Co., Ltd. Silver halide emulsion and silver halide color photographic light-sensitive material
US7465534B2 (en) 2004-03-11 2008-12-16 Fujifilm Corporation Silver halide emulsion and silver halide color photographic light-sensitive material
CN1667504B (zh) * 2004-03-11 2010-11-24 富士胶片株式会社 卤化银乳剂和卤化银彩色照相感光材料
US8383819B2 (en) 2006-03-06 2013-02-26 Japan Tobacco Inc. Method for producing 4-oxoquinoline compound
US8420821B2 (en) 2006-03-06 2013-04-16 Japan Tobacco Inc. Process for production of 4-oxoquinoline compound

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