EP0573649A1 - Photographisches silberhalogenidmaterial - Google Patents

Photographisches silberhalogenidmaterial Download PDF

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Publication number
EP0573649A1
EP0573649A1 EP92901464A EP92901464A EP0573649A1 EP 0573649 A1 EP0573649 A1 EP 0573649A1 EP 92901464 A EP92901464 A EP 92901464A EP 92901464 A EP92901464 A EP 92901464A EP 0573649 A1 EP0573649 A1 EP 0573649A1
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EP
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Prior art keywords
silver halide
emulsion
silver
grains
sensitive material
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EP92901464A
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English (en)
French (fr)
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EP0573649A4 (de
EP0573649B1 (de
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Yasuo Kashi
Hirotomo Sasaki
Hiroyuki Mifune
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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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
    • G03C1/09—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
    • G03C1/0051—Tabular grain emulsions
    • 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
    • G03C1/16—Methine and polymethine dyes with an odd number of CH groups with one CH group
    • 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

Definitions

  • the present invention relates to a silver halide photographic light-sensitive material.
  • Tellurium sensitization is known as a chemicalsensitization described above, and is generally described in, for example, U.S. Patents 1,623,499, 3,320,069, 3,772,031, 3,531,289, and 3,655,394, British Patents 235,211, 1,121,496, 1,295,462, and 1,396,696, and Canadian Patent 800,958.
  • specific tellurium sensitizers are described in detail in a few publications only, such as British Patents 1,295,462 and 1,396,696, and Canadian Patent 800,958.
  • tabular grains which are one type of the silver halide grains described above, are described in, for example, U.S. Patents 4,434,226, 4,439,520, 4,414,310, 4,433,048, 4,414,306, and 4,459,353. These methods are known to achieve various advantages, such as increased sensitivity, including the color-sensitization efficiency increased by a sensitizing dye, an improved sensitivity/graininess ratio, increased sharpness owing to the optical properties specific to tabular grains, and increased covering power. As the recent sensitivity of tabular grains is not satisfactory, further improvement has been demanded.
  • the object of the present invention is to provide a silver halide photographic light-sensitive material containing a tabular silver halide grains which have been tellurium-sensitized, excel in sensitivity/graininess ratio, and have an improved pressure property.
  • tabular silver halide grains having an aspect ratio of 3 or more, but preferably less than 8, occupy at least 50% of the total projected area of all silver halide grains contained in the emulsion.
  • the term "tabular silver halide grains (tabular grains)" is a general name for silver halide grains having one twin face or two or more parallel twin planes.
  • a "twin plane” is a (111) face on both sides of which all ions at lattice points have a mirror-image relationship.
  • this tabular grain is viewed from the above, its shape is a triangle, a hexagon, or a rounded triangle or hexagon like circular.
  • the triangular grains have parallel triangular outer surfaces, the hexagonal grains have parallel hexagonal outer surfaces, and the circular grains have parallel circular outer surfaces.
  • an average aspect ratio of tabular grains is an average of the values (i.e., aspect ratios) of the tabular grains which have a thickness of less than 0.5 ⁇ m and a diameter of 0.3 ⁇ m or more, the value for each grain having been obtained by dividing the diameter of the grain by the thickness thereof.
  • the thickness of each grain can be easily determined in the following method. First, metal is vapor-deposited slantwise with respect to the grain, along with reference latex. Then, the grain and the latex are photographed under an electron photomicrography. Next, the length of the shadow of the grain observed in the photograph is measured. The thickness of the grain is calculated from the length of the shadow, with the length of the latex shadow as reference.
  • the diameter of each grain is the diameter of a circle which has the same area as the projected area of each parallel outer surface of the grain.
  • the projected are of the grain can be determined by measuring the projected area on an electron photomicrography of the grain, and then by correcting this projected area with the magnification at which the grain has been photographed.
  • the tabular grains of the invention have a diameter, thus defined, of 0.3 to 5.0 ⁇ m, and a thickness of 0.05 to 0.5 ⁇ m.
  • tabular grains occupy preferably 50% or more, more preferably 80% or more, of the total projected area of all silver halide grains contained in the emulsion, and, more preferably, the tabular grains which occupy said specific part of the total projected area have an average aspect ratio of 3 or more, but less than 8.
  • the tabular grains for use in the present invention can perpared by an appropriate combination of the methods known in the art.
  • seed crystals 40% or more by weight of which are tabular grains, are formed in a comparatively high pAg atmosphere having a pBr of 1.3, and then are grown while adding a silver salt solution and a halogen solution and while maintaining a similar or greater pBr value.
  • said silver salt solution and said halogen solution be added such that no new crystal nuclei are formed during the growth of grains being achieved by the addition of one or both of water soluble silver salt, such as, silver nitrate, and water soluble halogen.
  • the size of tabular silver halide grains can be adjusted, for example, by adjusting the temperature, selecting the type or amount of solvent, and controlling the speed of adding silver salt and halide used in grain growth.
  • JP-A means Published Unexamined Japanese Patent Application.
  • a silver halide solvent is useful.
  • an excessive amount of halogen ions may be introduced in the reaction vessel to accelerate the ripening. Therefore, it is clear that the ripening can be accelerated, merely by introducing an aqueous solution of a halide into the reaction vessel.
  • Other ripening agents can be used along with halogen ions. These ripening agents can be added, in their entirety, to the dispersion medium contained in the reaction vessel before silver salt and halide salt are introduced into the vessel, or can be introduced into the reaction vessel together with one or more halide salts, silver salt, or deflocculant. Alternatively, the ripening agents can be independently introduced at the stage of adding the halide salt and the silver salt.
  • ripening agents other than halogen ions there can be used ammonia, an amine compound, and a thiocyanate such as an alkali metal thiocyanate, especially sodium thiocyanate or potassium thiocyanate and ammonium thiocyanate.
  • a thiocyanate such as an alkali metal thiocyanate, especially sodium thiocyanate or potassium thiocyanate and ammonium thiocyanate.
  • thiocyanate as a ripening agent is disclosed in U.S. Patents 2,222,264, 2,448,534, and 3,320,069.
  • the known thioether ripening agents can be used, the examples of which are disclosed in U.S. Patents 3,271,157, 3,574,628, and 3,737,313.
  • thione compound of the type disclosed in JP-A-53-82408 and JP-A-53-144319 can be used.
  • various compounds can be used during the step of forming silver halide precipitate. thereby to control the properties of the silver halide grains. These compounds may be introduced into the vessel from the beginning, or may be added together with one or more salts by the ordinary method. More specifically, compounds of copper, iridium, lead, bismuth, cadmium, zinc, (chalcogens of sulfur, selenium and tellurium), and compounds of gold and precious metals of Group VIII can be sued during the step of forming silver halide precipitate, thereby controlling the properties of the silver halide grains, as is described in U.S. Patents 2,448,060, 2,628,167, 3,737,313 and 3,772,031, and Research Disclosure (hereinafter referred to as "R.D.”). vol. 134, 13452, June 1975.
  • the silver halide emulsion of the present invention is subjected to reduction sensitization during the forming of grains, after the forming of grains and before, during or after the chemical sensitization other than the reduction sensitization.
  • the reduction sensitization can be the method of adding a reduction sensitizer to the silver halide emulsion, the silver ripening method in which silver halide grains are grown or ripened in a low-pAg atmosphere having a pAg value of 1 to 7, or the high-pH ripening method in which silver halide grains are grown or ripened in a high-pH atmosphere having a pH value of 8 to 11. Alternatively, two of these methods can be used in combination.
  • the method of adding said reduction sensitizer to the silver halide emulsion is preferable in that it can/minutely control the level of reduction sensitization.
  • reduction sensitizers are, for example, stannate, ascorbic acid, a derivative thereof, amine, polyamine, hydrazine derivative, formamidinesulfinic acid, silane compound, and borane compound. Any reduction sensitizer selected from these known ones can be used in the present invention. Two or more compounds can be used in combination in the present invention. Preferable as reduction sensitizers for use in the present invention are stannous chloride, thiourea dioxide, dimethylaminehorane, ascorbic acid, and derivative thereof. The amount in which to added the reduction sensitization in the present invention should be determined from the conditions in which the emulsion is manufactured. The appropriate range of the amount is 10 ⁇ 7 to 10 ⁇ 3 mol per mol of silver halide.
  • the reduction sensitizer is dissolved in, for example, water, alcohol, gylcol, ketone, ester, or amide, thus forming a solution.
  • This solution is added during the forming of grains.
  • the solution can be introduced into the reaction vessel beforehand, the method of adding the solution at a proper time during the growth of silver halide grains.
  • the reduction sensitizer may be added to an aqueous solution of water-soluble silver salt or water-soluble alkali halide, and the resultant solution may be applied, thereby precipitating silver halide grains.
  • Another preferable method is to add the reduction sensitizer solution several times, in portions, or continuously over a long time, as while the silver halide grains are growing.
  • the treatment disclosed in, for example, European Patents 96,727Bl and 64,412Bl may be performed on the silver halide emulsion for use in the present invention, in order to round the grains contained in the emulsion.
  • the treatment disclosed in, for example, West German Patent 2,306,447C2 and JP-A-221320 may be conducted on the emulsion, in order to modify the surfaces of the grains.
  • the grains in the silver halide emulsion of the present invention generally have flat surfaces, but it is desirable that concavo-convex be formed in the surface of each grain.
  • Examples of such grains are those disclosed in JP-A-58-106532 and JP-A-60-221320, each of which has holes made in the apices or in the center portion of the surfaces, and ruffled grains which are disclosed in U.S. Patent 4,643,966.
  • the tabular grains in the emulsion for use in the present invention have at least one dislocation line each.
  • the dislocation line may be one extending straight in a specific crystal orientation, one curving, one introduced throughout the grain, one introduced in only a specified portion of the grain, e.g., the fringe thereof.
  • dislocation is displacement of a series of atoms which is observed at crystal lattices. Its general definition is described in, for example, Shuji Suzuki, “Introduction to Theory of Dislocation,” Agne Press, 1968. pp. 24-31.
  • Dislocation in silver halide grains can be observed by the methods described in, for example, Hamilton. Photgr. Sci. Eng., 11 , 57 (1967) and Shiozawa, J. Soc. Phot. Sci. Jap., 34 , 16 (1971) and 35 , 213 (1972).
  • the density of dislocation lines is the number of the dislocation lines existing in one grain. It is measured by the following method. First, a grain is rotated with respect to incident electron beams and is photographed every time it is tilted at a specific angle to the beams, thus obtaining photographs. The dislocation lines in each photograph are counted, thereby determining how many location lines the grain has. If the location lines observed on any photograph are too densely to count them, the grain is considered to have a great number of dislocation lines.
  • the distribution of the dislocation-line density, among the gains, is determined by examining 200 or more grains, preferably 300 or more grains, for their dislocation-line densities, and by recording the number of each group of grains which have dislocation-line densities falling within a specific range.
  • each silver halide grains contained in the emulsion for use in the present invention can be evaluated, for example, in terms of the equivalent-circle diameter of the grain calculated from the projected area measured by means of an electron microscope, the equivalent-sphere diameter of the grain calculated from the volume obtained from the projected area and thickness of the grain, or the equivalent-sphere diameter of the grain calculated from the volume determined by coaltar counter method.
  • Grains for use in the present invention can be selected from those of various sizes -- from very tiny grains having an equivalent-sphere diameter of 0.05 microns or less to large grains having an equivalent-sphere diameter of 10 microns or more.
  • grains having a diameter of 0.1 to 3 microns are used as light-sensitive silver halide grains.
  • Either a polydispersed emulsion, i.e., an emulsion containing silver halide grains of various sizes, or a monodispersed emulsion, i.e., an emulsion containing silver halide grains of limited sizes, can be used in accordance with the use.
  • the size distribution of silver halide grains is represented by the variation coefficient in terms of the equivalent-circuit diameter calculated from the projected area of each grain, or in terms of the equivalent-sphere diameter calculated from the volume of each grain.
  • a monodispersed emulsion is defined as one in which grains having a diameter deviating ⁇ 30% or less from the average diameter occupy 80% or more of all grains in terms of number or weight.
  • two or more monodispersed emulsions having different grain size can be coated in the form of a mixture to form an emulsion layer sensitive to a specific color, or can be coated independently to form two or more emulsion layers sensitive to substantially the same color.
  • two or more polydispersed emulsions or two or more monodispersed and polydispersed emulsions can be coated in the form of a mixture to form an emulsion layer or independently to form a plurality of emulsion layers.
  • the silver halide grains according to the present invention are made of silver bromide, silver chloride, silver iodide, silver chlorobromide, silver chloroiodide, silver bromoiodide, or silver bromochloroiodide.
  • the emulsion of the present invention may contain not only these silver halide grains, but also grains made of any silver salt, such as silver rhodanide, silver sulfide, silver selenide, silver carbonate, silver phosphate or silver salt of organic acid.
  • the emulsion may contain silver halide grains each containing any silver salt exemplified.
  • the silver halide grains have a high silver chloride content.
  • the silver halide grains contain silver iodide.
  • the optimum amount in which to use silver iodide depends on the type of the light-sensitive material.
  • the silver iodide content is 0.1 to 15 mol% for X-ray sensitive material, and 0.1 to 5 mol% for microfilm and graphic art film.
  • the silver iodide content ranges from 1 to 30 mol%, preferably 5 to 20 mol%, more preferably 8 to 15 mol%. In order to lessen lattice strain in each silver halide grain, it is recommendable that silver chloride be contained in the grain.
  • the silver halide emulsion has, in its grains, a distribution or a structure with respect to a halogen composition.
  • Typical example of such grains are those of double structure, each consisting of a core and shell which have different halogen compositions, as is disclosed in, for example, JP-B-43-13162, JP-A-61-215540, JP-A-60-222845, JP-A-60-143331, and JP-A-61-75337.
  • JP-B means Published Examined Japanese Patent Application.
  • Other examples of such grains are: those of triple structure, each formed of a core, a first shell and a second shell which have different halogen compositions, as is disclosed in JP-A-60-222844; and those consisting four or more layers.
  • Still another example is grains of double structure, each coated with a thin layer of silver halide which has a halogen composition different from those of the core and shell.
  • junction structure can be used in the present invention.
  • Various example of grains having the junction structure are disclosed in JP-A-59-133540, JP-A-58-108526, European Patent 199,290A2, JP-A-58-24772, JP-A-59-16254, and and some other references.
  • a junction-structure grain consists of a host crystal and a junction crystal which are different in composition from the host crystal and attached to the edge, corner or face parts of the host crystal.
  • the host crystal is one which is homogeneous in halogen composition or one which has a core-shell structure.
  • the host crystal and junction crystal forming a junction-structure grain can, of course, be made of different silver halides. Further, one of these crystals can be made of a silver chloride of non-halite structure, such as silver rhodanide and silver carbonate, provided that it can be attached to the crystal which is made of silver halide. If possible, one of these crystals can be made of a silver chloride of non-halide structure, such as lead oxide.
  • the core In the case of silver iodide grains having the core-shell structure, it is desirable that the core contain more silver iodide than the shell. In some cases, the core should better contain less silver iodide than the shell. As for silver iodide grains having the junction structure, it is desirable that the host crystal contains more silver iodide than the junction crystal in some cases, and less silver iodide than the junction crystal in other cases.
  • the two components can have a distinct boundary and an indistinct boundary. Alternatively, the boundary between the two components can have a composition which gradually changes from one component to the other.
  • the silver halide grains used are those formed of two or more silver halides which are present in the form of or mixed crystal or a core-shell structure, it is important to control the halogen distribution among the grains.
  • a method of measuring the halogen distribution is disclosed in JP-A-60254032. The more uniform the halogen distribution among the grains, the better.
  • An silver halide emulsion containing grains whose variation coefficient is 20% or less is particularly desirable.
  • Another preferable emulsion is one in which the grain size is correlated to the halogen composition of the grain, more specifically the iodine content of each grain is proportional to its size.
  • a silver halide emulsion can be used in which the iodide content of each grain is inversely proportional to the grain size, or in which the grain size and the content of any other halogen are correlated, in accordance with the use of the light-sensitive material. In view of this it would be recommendable that two or more emulsions having different composition be mixed and used.
  • the content of silver iodide or silver chloride in the near surface region should be increased to change the dye-adsorbing efficiency or developing speed of the grain. in accordance of the use of the light-sensitive material.
  • a layer can be formed, either covering the entire grain or covering only part of the grain. In the case of a tabular grain, for example, the halogen composition is changed in either one major surface or one side.
  • Gelatin is suitable for use in the emulsion of the present invention, as protective colloid and as binder in a layer made of any other hydrophilic colloid layer. Also, any other hydrophilic colloid can be used.
  • hydrophilic colloid examples include proteins such as graft polymer of gelatin and high-molecular substance, albumin, and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfate ester; sugar derivatives such as sodium arginate and starch derivative; and synthetic hydrophillc high-molecular substances such as monopolymer and copolymer (e.g., polyvinyl alcohol. polyvinyl partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole and polyvinylpyrazole).
  • proteins such as graft polymer of gelatin and high-molecular substance, albumin, and casein
  • cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfate ester
  • sugar derivatives such as sodium arginate and starch derivative
  • Gelatin can not only be lime-treated gelatin, but also acid-treated gelatin or such an enzyme-treated gelatin as is disclosed in Bull. Soc. Sci. Photo. Japan, No. 16, p. 30 (1966). Also, a substance obtained by hydrolyzing gelatin or by decomposing gelatin with an enzyme.
  • low molecular gelatin having a molecular weight of 70.000 or more be used during the forming of nuclei.
  • the emulsion of the present invention be washed with water to be desalted and then be dispersed in a protective colloid newly prepared.
  • the emulsion can be water washed at any temperature selected in accordance with its use, but preferably at 5°C to 50°C. It can be water-washed at any pH value selected for its application, but preferably at a pH value ranging from 2 to 10, more preferably at a pH value ranging from 3 to 8. Also, any value can be selected for the pAg at the time of the water-washing, in accordance with the use of the emulsion, but a preferable pAg value is 5 to 10.
  • the emulsion can be washed with water by any known method, such as noodle water-washing, dialysis, centrifugal separation, precipitation, or ion exchange.
  • noodle water-washing dialysis, centrifugal separation, precipitation, or ion exchange.
  • precipitation use can be made of a sulfate, an organic solvent, a water-soluble polymer, or a gelatin derivative.
  • the silver halide grains contained in the silver halide emulsion of the present invention is necessarily be subjected to chemical sensitization including tellurium sensitization.
  • Tellurium sensitizers for use in the present invention are, for example, the compounds which are described in U.S. Patents 1,623,499, 3,320,069 and 3,772,031, British Patents 235,211, 1,121,496, 1,295,462 and 1,396,696, Canadian Patent 800,958, Journal of Chemical Society Chemical Communication 635 (1980), ibid. 1102 (1979), ibid, 645 (1979), and Journal of Chemical Society Perkin Transaction 1, 2191 (1908).
  • tellurium sensitizers are: colloidal tellurium, telluroureas (e.g., allyl-tellurourea, N,N-dimethyl tellurourea, tetramethyl tellurourea, N-carboxyethyl-N',N'-dimethyltellurourea, and N,N'-diphenylethylene tellurourea), isotellurocyanates (e.g., allylisotellurocyanate), telluroketones (e.g., telluroacetone and telluroacetophenone), telluroamides (e.g., telluroacetoamide and N,N-dimethyl tellurobenzamide), tellurohydrazides (e.g., N,N',N'-trimethyl tellurobenzhydrazide), telluroester (e.g., t-butyl-t-hexyl telluroester).
  • colloidal tellurium e.g.,
  • phosphinetellurides e.g., tributyl phosphinetelluride, tricyclohexyl phosphinetelluride, triisopropyl phosphinetelluride, butyl-diisopropyl phosphinetelluride, and dibutylphenyl phosphine-telluride
  • tellurium compounds e.g., potassium telluride, potassium tellurocyanate, telluropentathionate sodium salt, allyltellurocyanate, and gelatin containing negatively charged telluride ions, as disclosed in British Patent 1,295,462).
  • R1, R2 and R3 represent aliphatic groups, aromatic groups, heterocyclic groups
  • R4, R7, and R11 represent aliphatic groups, aromatic groups, heterocyclic group, hydrogen atoms or cations
  • R5 and R6 represent aliphatic groups, aromatic groups, heterocyclic groups or hydrogen atoms
  • R8, R9 and R10 are aliphatic groups
  • X is a halogen atom.
  • R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, and R11 represent aliphatic groups, they are preferably those having 1 to 30 carbon atoms. Particularly preferable are alkyl group, alkenyl group, alkynyl group, and aralkyl group, each having 1 to 20 carbon atoms and present in the form of a straight chain, a branch, or a ring.
  • alkyl group, alkenyl group, alkynyl group and aralkyl group are: methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopentyl, cyclohexyl, allyl, 2-butenyl, 3-pentenyl, propargyl, 3-pentynyl, benzyl, and phenetyl.
  • R1, R2, R3, R4, R5, R6, R7, and R11 are aromatic groups, there are preferably those having 6 to 30 carbon atoms. Particularly preferred is aryl group having 6 to 20 carbon atoms and the form of a single ring or a condensed ring, such as phenyl group or naphthyl group.
  • R1, R2, R3, R4, R5, R6, R7, and R11 represent heterocyclic groups, they are saturated or unsaturated 3- to 10-membered heterocyclic groups, each having at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom. They can form a single ring, or can combine with an aromatic group or another heterocyclic group, thus forming a condensed ring.
  • 5-or 6 membered aromatic heterocyclic group such as pyridyl, furyl, thienyl, thiazolyl, imidazolyl, and benzimidazolyl.
  • R4, R7, and R11 represent cations, they are of alkali metal or ammonium.
  • X represents a halogen atom, it is, for example, a fluorine atom, a chlorine atom, a bromine atom, or a iodine atom.
  • the aliphatic groups, the aromatic groups, and the heterocyclic groups -- all specified above -- can be substituted.
  • substituent groups are: alkyl group, aralkyl group, alkenyl group, alkynyl group, aryl group, alkoxy group, aryloxy group, amino group, acylamino group, ureido group, urethane group, sulfonylamino group, sulfamoyl group, carbamoyl group, sulfonyl group, sulfinyl group, alkyloxycarbonyl group, aryloxycarbonyl group, acyl group, acyloxy group, phosphoric acid group, diacylamino group, imido group, alkylthio group, arylthio group, halogen atom, cyano group, sulfo group, carboxyl group, hydroxyl group, phosphono group, nitro group, and heterocyclic group. These groups can be substituted.
  • R1, R2, and R3 can combine together and with phosphor atoms, forming a ring.
  • R5 and R6 can combine, forming a nitrogen-containing heterocyclic ring.
  • R1, R2, and R3 are preferably aliphatic groups or aromatic groups. More preferably. they are alkyl groups or aromatic groups.
  • R11 represents aliphatic group, aromatic group, heterocyclic group or -NR13(R14)
  • R12 represents -NR15(R16), -N(R17)N(R18)R19 or -OR20
  • R13, R14, R15, R16, R17, R19 and R20 represent hydrogen atoms, aliphatic groups, aromatic groups, heterocyclic groups or acyl groups
  • R11 and R15, R11 and R17, R11 and R18, R11 and R20, R13 and R15, R13 and R17, R13 and R18, and R13 and R20 can combine, forming a ring.
  • R11, R13, R14, R15, R16, R17, R18, R19, and R20 represent aliphatic groups, they are preferably those having 1 to 30 carbon atoms. Particularly preferable are alkyl group, alkenyl group, alkynyl group, and aralkyl group, each having 1 to 20 carbon atoms and present in the form of a straight chain, a branch, or a ring.
  • alkyl group, alkenyl group, alkynyl group and aralkyl group are: methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopentyl, cyclohexyl, allyl, 2-butenyl, 3-pentenyl, propargyl, 3-pentynyl, benzyl, and phenetyl.
  • R11, R13, R14, R15, R16, R17, R18, R19, and R20 represent aromatic groups, they are preferably those having 6 to 30 carbon atoms. Particularly preferred is aryl group having 6 to 20 carbon atoms and present in the form of a single ring or a condensed ring, such as phenyl group or naphthyl group.
  • R11, R13, R14, R15, R16, R17, R18, R19, and R20 represent heterocyclic groups R20, they are saturated or unsaturated 3- to 10-membered heterocyclic groups, each having at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom. They can be each a single ring, or can combine with an aromatic group or another heterocyclic group, thus forming a condensed ring.
  • Preferable are 5- or 6 membered aromntic heterocyclic group such as pyridyl, furyl, thienyl, thiazolyl, imidazolyl, and benzimidazolyl.
  • R13, R14, R15, R16, R17, R18, R19, and R20 represent acyl groups, they have 1 to 30 carbon atoms. More preferably, they are acyl groups having 1 to 20 carbon atoms and present in the form of a straight chain or a branch. Examples of these acyl groups are acetyl, benzoyl, formyl, pivaloyl, and decanoyl.
  • the ring is, for example, alkylene group, arylene group, aralkylene group, or alkenylene group.
  • R11 represents preferably aliphatic group, aromatic group, or -NR13(R14), and R12 is -NR15(R16).
  • R13, R14, R15 and R16 represent aliphatic groups or aromatic groups.
  • R11 represents an aromatic group or -NR13(R14), R12 represents -NR15(R16).
  • R13, R14, R15 and R16 are alkyl groups or aromatic groups.
  • R11 and R15, and R13 and R15 are attached to each other through alkylene group, allylene group, aralkylene group, or alkenylene group.
  • the compounds of the formulas (I) and (II), which are used in the present invention, can be synthesized by the methods known in the art, as is disclosed in Journal of Chemical Society (A), 2927 (1969); Journal of Organometallic Chemistry, 4,320 (1965); ibid, 1,200 (1963); ibid, 113, C35 (1976); Phosphorus Sulfur 15, 155 (1983); Chemische Berichte, 109, 2996 (1976); Journal of Chemical Society Chemical Communication, 635 (1980); ibid; 1102 (1979); ibid, 645 (1979); ibid, 820 (1987); Journal of Chemical Society Perkin Transaction 1,2191 (1980); The Chemistry of Organo Selenium and Tellurium Compounds, Vol. 2, pp. 216-267 (1987).
  • tellurium sensitizers used in the tellurium sensitization of the present invention are compounds which form silver telluride in the surface or interior of a silver halide grain, which is considered to function as a sensitization nucleus.
  • the speed with which silver telluride is formed in the silver halide emulsion can be determined by the following test.
  • An emulsion which contains octahedral silver bro-mide grains having an average size of 0.5 ⁇ m (containing 0.75 mol of AgBr and 80 g of gelatin per kilogram) is maintained at 50°C, while holding pH and pAg at 6.3 and 8.3, respectively.
  • a telluride dissolved in an organic solvent e.g., methanol
  • the resultant emulsion is filled in a cell having a thickness of 1 cm.
  • the pseudo-first-order reaction rate constants of the tellurium sensitizers used in the present invention which have been obtained by performing the test described above, are as follows: Compound 7 k ⁇ 4 ⁇ 10 ⁇ 3 min ⁇ 1 Compound 10 k ⁇ 2 ⁇ 10 ⁇ 3 min ⁇ 1 Compound 12 k ⁇ 8 ⁇ 10 ⁇ 4 min ⁇ 1 Compound 18 k ⁇ 2 ⁇ 10 ⁇ 4 min ⁇ 1 compound 4 k ⁇ 7 ⁇ 10 ⁇ 5 min ⁇ 1
  • the silver telluride formed can be isolated from the unreacted tellurium sensitizer, to determine the quantity of the silver telluride.
  • the emulsion is immersed in an aqueous solution of a halogen salt or a water-soluble mercapto compound, thereby isolating the silver telluride from the unreacted tellurium sensitizer, and then a small amount of tellurium is quantitatively analyzed by means of atomic absorption spectrometry.
  • the reaction rate greatly varies by several orders, in accordance with not only the type of the compound but also the silver halide composition of the emulsion tested, the test temperature, the values of pAg and pH, and the like.
  • the tellurium sensitizers preferred for use in the present invention are compounds which can form silver telluride when reacted with a silver halide emulsion which has halogen compositions and crystal habit.
  • any compound is used in the present invention, that reacts with a silver halide emulsion at a temperature of 40 to 95°C, at a pH of 3 to 10, or at a pAg of 6 to 11.
  • a tellurium sensitizer is a compound which has a pseudo-first-order reaction rate constant k of 1 ⁇ 10 ⁇ 7 to 1 ⁇ 10 ⁇ 1 min ⁇ 1 if tested by the method specified above at a temperature of 40 to 95°C, at a pH of 3 to 10, or at a pAg of 6 to 11.
  • tellurium sensitizers are used in an amount of 10 ⁇ 8 to 10 ⁇ 2 mol per mol of silver halide, preferably 10 ⁇ 7 to 5 ⁇ 10 ⁇ 3 mol per mol of silver halide, depending on the type of silver halide grains used and the conditions of chemical sensitization performed.
  • the silver halide grains be chemically sensitized at a pAg of 6 to 11, preferably 7 to 10 and at a temperature of 40 to 95°C, preferably 50 to 85°C.
  • the silver halide emulsion is tellurium-sensitized in the presence of an compound which generates silver telluride at a temperature of 40 to 95°C, at a pH of 3 to 10, or at a pAg of 6 to 11.
  • Precious-metal sensitizers using gold, platinum, palladium, iridium or the like should preferably be used in the present invention, along with the tellurium sensitizers.
  • Specific example of precious-metal sensitizers are: chloroauric acid, potassium chloroaurate, potassium auric thiocyanate, gold sulfide, gold selenide, and the like. These precious-metal sensitizers can be used in an amount of about 10 ⁇ 7 to about 10 ⁇ 2 mol per mol of silver halide.
  • sulfur sensitizers it is also preferable to use sulfur sensitizers, too.
  • sulfur sensitizers are: thiosulfates (e.g., hypo), thioureas (e.g., diphenyl thiourea, triethyl thiourea, and allyl thiourea), and known unstable iodides (e.g., rhodanines). These sulfur sensitizers can be used in an amount of about 10 ⁇ 7 to about 10 ⁇ 2 mol per silver halide.
  • selenium sensitizers be used, too, in the present invention.
  • the unstable selenium sensitizer disclosed in JP-B-44-15748 is an preferable example.
  • Specific examples of selenium sensitizers are: colloidal selenium, selenoureas (e.g., N,N-dimethyl selenourea, selenourea, tetramethyl selenourea), selenoamides (e.g., selenoaceto amid, N',N'-dimethylselenobenzamide), selenoketones (e.g., slenoacetone, selenohenzenephenone), selenides (e.g., triphenyl phosphineselenide, dlethylselenide), selenophosphate (e.g., tri-p-triselenophosphate), selenocarboxylic acid, esters, and isoselenocyana
  • tellurium sensitization is carried out in the present invention, in the presence of a solvent for dissolving the silver halide.
  • this solvent are: thiocyanate (e.g., potassium thiocyanate), thioether compound (e.g., the compounds disclosed in U.S. Patents 3,021.215 and 3,271,157, JP-B-58-30571, and JP-A-60-136736, particularly 3,6-dithia-1,8-octadiol), and tetra-substituted thiourea compound (e.g., the compounds disclosed in JP-B-59 11892 and U.S. Patent 4,221,863, particularly tetramethyl thiourea).
  • thiocyanate e.g., potassium thiocyanate
  • thioether compound e.g., the compounds disclosed in U.S. Patents 3,021.215 and 3,271,157, JP-B-58-30571, and JP-A-60-136736, particularly 3,6-dithia-1,8-octadiol
  • the solvent examples include: the thion compounds disclosed in JP-B-60-11341, the mercapto compounds disclosed in JP-B-63029727, the mesoion compounds disclosed in JP-A-60-163042, the selenoether compounds disclosed in U.S. Patent 4,782,013, the telluoether compounds disclosed in JP-A-2-118566, and sulfides.
  • thiocyanate, thioether compendious, tetra-substituted thiourea compounds, and thione compounds are preferred.
  • the solvent can be used in an amount of about 10 ⁇ 5 to about 10 ⁇ 2 mol per mol of silver halide.
  • the present invention relates to a silver halide emulsion and a method of preparing the emulsion, too.
  • the characterizing features of the emulsion and the method are common to the silver halide photographic light-sensitive material. They can be understood by those skilled in the art, from the above description of the light-sensitive material.
  • Typical silver halide emulsions according to the present invention, and the methods of preparing these emulsions will be described below. Needless to say, these emulsions and methods can incorporate the technical concepts set forth in claim 2 and claims 4 et seq. of the present application.
  • the photographic emulsion for use in the invention can contain various compounds to prevent fogging from occurring during the manufacture, storage or processing of the light-sensitive material, and to stabilize the photographic properties of the light-sensitive material. More precisely, compounds known as antifoggants and stabilizing agents can be added to the emulsion.
  • thiazoles such as benzothiazolium salt; nitroimidazoles; nitrobenzimidazoles; chlorobenzimidazoles; bromobenzimidazoles; mercapto thiazoles; mercapto benzothiazoles; mercapto benzimidazoles; mercapto thiadiazoles; aminotriazoles; benzotriazoles; nitrobenzotriazoles; mercapto tetrazoles, particularly, 1-phenyl-5-mercapto tetrazole; mercapto pyrimidines; mercapto triazines; thioketo compounds such as oxadolinethione; azaindenes such as triazaindene and tetraazaindene (particularly, 4-hydroxy-substituted (1, 3, 3a, 7) tetraazaindenes); pentaazaindenes.
  • thiazoles such as benzothiazolium salt
  • the compounds disclosed in, for example, U.S. Patents 3,954,474 and 3,982,947 and JP-B-52-28660 can be used as antifoggants and stabilizing agents.
  • One of compounds which are preferahle for use in the invention is disclosed in JP-A-63-212932.
  • These antifoggants and stabilizing agents can be added before, during or after the forming of grains, during water-washing, during the dispersion process subsequent to the water-washing, before during or after chemical sensitization, or before coating process, in accordance with the purpose for which the antifoggants and the stabilizing agents are used.
  • the antifoggants and the stabilizing agents can be used, not only to prevent fogging and stabilize the photographic properties of the light-sensitive material, but also to control the crystal habit of the grains, reduce the grain size, decrease the solubility of the grain, control the chemical sensitization, and modify the arrangement of dye particles.
  • the photographic emulsion used in the present invention be spectrally sensitized with methine dyes or the like, thereby to achieve the advantages expected of the present invention.
  • the dyes used are: cyanine dye, melocyanine dye, composite cyanine dye, composite melocyanine dye, holopolar cyanine dye, hemicyanine dye, styryl dye, and hemioxonol dye.
  • cyanine dye, melocyanine dye, and composite melocyanine dye are particularly useful.
  • These dyes contains unclei which are usually used in cyanine dyes as basic heterocyclic nuclei.
  • nuclei each formed of any one of these nuclei and an alicylic hydrocarbon ring fused to the nucleus; and nuclei each formed of any one of these nuclei and an aromatic hydrocarbon ring fused to the nucleus, such as indolenine, henzindolenine, indole, benzoxazole, naphthoxazole, benzothiazole, naphthothiazole, benzoselenazole, benzimidazole, and quinoline.
  • These nuclei can be substituted at carbon atoms.
  • Melocyanine dye or composite melocyanine dye can be one which has nuclei of ketomethylene structure. Applicable as such nuclei are 5- or 6-membered heterocyclic nuclei of pyrazoline-5-on, thiohydantoin, 2-thiooxazoline-2,4-dione, thiazolidine-2,4 dione, rhodanine or thiobarbituric acid.
  • sensitizing dyes can be used, either singly or in combination. In many cases, they are used in combination, for achieving supersensitization, as is disclosed in U.S. Patents 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, 3,703,377, 3,769,301, 3,814,609, 3,837,862 and 4,026,707, British Patents 1,344,281 and 1,507,803, JP-B-43-4936, JP-B-53-12375, JP-A-52-110618, and JP-A-52-109925.
  • the emulsion can contain not only the sensitizing dye, but also a dye which has no sensitizing ability or a substance which absorbs virtually no visible light and has supersensitizing ability.
  • the sensitizing dye can be added at any time during the preparation of any emulsion that has been hitherto known as useful. In most cases, the dye is added after the chemical sensitization and before the coating of the emulsion. However, it can be added at the same time the chemical sensitizer is added, thereby to accomplish spectral sensitization and chemical sensitization at the same time, as is disclosed in U.S. Patents 3,628,969 and 4,225,666. Alternatively, it can be added before the chemical sensitization, to initiate spectral sensitization, as is described in JP-A-58-113928. Also, it can be added before the precipitation of silver halide grains, to initiate spectral sensitization.
  • the amount in which to add the sensitizing dye is 4 ⁇ 10 ⁇ 6 to 8 ⁇ 10 ⁇ 3 mol per mol of silver halide used.
  • the light-sensitive material of the present invention needs only to have at least one of silver halide emulsion layers, i.e., a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer, formed on a support.
  • the number or order of the silver halide emulsion layers and the non-light sensitive layers are particularly not limited.
  • a typical example is a silver halide photographic light-sensitive material having, on a support, at least one light-sensitive layers constituted by a plurality of silver halide emulsion layers which are sensitive to essentially the same color sensitivity but has different sensitivities.
  • the light-sensitive layers are unit light-sensitive layer sensitive to blue, green or red.
  • the unit light-sensitive layers are generally arranged such that red-, green-, and blue-sensitive layers are formed from a support side in the order named. However, this order may be reversed or a layer sensitive to one color may be sandwiched between layers sensitive to another color in accordance with the application.
  • Non light-sensitive layer such as various types of interlayers may be formed between the silver halide light-sensitive layers and as the uppermost layer and the lowermost layer.
  • the interlayer may contain, e.g., couplers and DIR compounds as described in JP-A-61-43748, JP-A-59-113438, JP-A-59-113440, JP-A-61-20037, and JP-A-61-20038 or a color mixing inhibitor which is normally used.
  • a two-layered structure of high- and low-sensitivity emulsion layers can be preferably used as described in West German Patent 1,121,470 or British Patent 923,045.
  • layers are preferably arranged such that the sensitivity is sequentially decreased toward a support, and a non light sensitive layer may be formed between the silver halide emulsion layers.
  • layers may be arranged such that a low-sensitivity emulsion layer is formed remotely from a support and a high-sensitivity layer is formed close to the support.
  • layers may be arranged from the farthest side from a support in an order of low-sensitivity blue-sensitive layer (BL)/high-sensitivity blue-sensitive layer (BH)/high-sensitivity green-sensitive layer (GH)/low-sensitivity green-sensitive layer (GL)/high sensitivity red sensitive layer (RH)/low sensitivity red-sensitive layer (RL), an order of BH/BL/GL/GH/RH/RL, or an order of BH/BL/GH/GL/RL/RH.
  • BL low-sensitivity blue-sensitive layer
  • BH high-sensitivity blue-sensitive layer
  • GH high-sensitivity green-sensitive layer
  • GL high sensitivity red sensitive layer
  • RH low sensitivity red sensitive layer
  • RL low sensitivity red sensitive layer
  • layers may be arranged from the farthest side from a support in an order of blue-sensitive layer/GH/RH/GL/RL.
  • layers may be arranged from the farthest side from a support in an order of blue-sensitive layer/GL/RL/GH/RH.
  • three layers may be arranged such that a silver halide emulsion layer having the highest sensitivity is arranged as an upper layer, a silver halide emulsion layer having sensitivity lower than that of the upper layer is arranged as an interlayer, and a silver halide emulsion layer having sensitivity lower than that of the interlayer is arranged as a lower layer, i.e., three layers having different sensitivities may be arranged such that the sensitivity is sequentially decreased toward the support.
  • these layers may be arranged in an order of medium-sensitivity emulsion layer/high-sensitivity emulsion layer/low-sensitivity emulsion layer from the farthest side from a support in a layer sensitive to one color as described in JP-A-59-202464.
  • an order of, for example, high-sensitivity emulsion layer/low-sensitivity emulsion layer/medium-sensitivity emulsion layer, or low sensitivity emulsion layer/medium-sensitivity emulsion layer/high-sensitivity emulsion layer may be adopted. Furthermore, the arrangement can be changed as described above even when four or more layers are formed.
  • a donor layer can be bonded to, or arranged adjacent to, a major light-sensitive layer BL, GL or RL.
  • the donor layer should have a spectral sensitivity distribution which is different from that of the major light-sensitive layer.
  • Donor layers of this type are disclosed in U.S. Patents 4,663,271, 4,705,744 and 4,707,436, JP-A-62-160448, and JP-A-63-89850.
  • Silver halide grains for use in the present invention other than the tabular grains described above, will be described.
  • a preferable silver halide contained in photographic emulsion layers of the photographic light-sensitive material of the present invention is silver bromoiodide, silver chloroiodide, or silver chlorobromoiodide, containing about 30 mol% or less of silver iodide.
  • the most preferable silver halide is silver bromoiodide or silver chlorobro-moiodide, containing about 2 mol% to about 10 mol% of silver iodide.
  • the silver halide grains contained in the photographic emulsion may be regular crystals such as cubic, octahedral or tetradecahedral crystals, irregular crystals such as spherical tabular crystals, crystals having defects such as crystal twin faces, or those having composite shapes thereof.
  • the silver halide grains may be fine grains having a grain size of about 0.2 ⁇ m or less or large grains having a projected-area diameter of up to 10 ⁇ m, and the emulsion may be either a polydispersed or mono dispersed emulsion.
  • the silver halide photographic emulsion which can be used in the present invention can be prepared by methods described in, for example, Research Disclosure (RD) No. 17,643 (December, 1978), pp. 22 to 23, "I. Emulsion preparation and types", RD No. 18,716 (November, 1979), page 648, and RD No. 307,105 (November, 1989), pp. 863 to 865; P. Glafkides, "Chemie et Phisique Photographique", Paul Montel, 1967: G.F. Duffin, "Photographic Emulsion Chemistry", Focal Press, 1966; and V.L. Zelikman et al., “Making and Coating Photographic Emulsion", Focal Press, 1964.
  • Monodispersed emulsions described in, for example, U.S. Patents 3,574,628 and 3,655,394 and British Patent 1,413,748 are also preferred.
  • tabular grains having an aspect ratio of about 3 or more can be used in the present invention.
  • the tabular grains can be easily prepared by methods described in, e.g., Gutoff, "Photographic Science and Engineering", Vol. 14, pp. 248 to 257 (1970); U.S. Patents 4,434,226, 4,414,310, 4,433,048, and 4,499,520, and British Patent 2,112,157.
  • the crystal structure which can used in the present invention, may be uniform, may have different halogen compositions in the interior and the surface thereof, or may be a layered structure.
  • a silver halide having a different composition may be joined by an epitaxial junction or a compound except for a silver halide such as silver rhodanide or zinc oxide may be joined.
  • a mixture of grains having various types of crystal shapes may be used.
  • the emulsion which can used in the present invention may be of any of a surface latent image type in which a latent image is mainly formed on the surface of each grain, an internal latent image type in which a latent image is formed in the interior of each grain, and a type in which a latent image is formed on the surface and in the interior of each grain.
  • the emulsion must be of a negative type.
  • the emulsion is of an internal latent image type, it may be a core/shell internal latent image type emulsion described in JP-A-63 264740. A method of preparing this core/shell internal latent image type emulsion is described in JP-A-59-133542.
  • the thickness of a shell of this emulsion changes in accordance with development or the like, it is preferably 3 to 40 nm, and most preferably, 5 to 20 nm.
  • a silver halide emulsion of the present invention is normally subjected to physical ripening, chemical ripening, and spectral sensitization steps before it is used. Additives for use in these steps are described in Research Disclosure Nos. 17,643, 18,716, and 307,105 and they are summarized in the table (later presented).
  • two or more types of emulsions different in at least one characteristic of a grain size, a grain size distribution, a halogen composition, a grain shape, and sensitivity can be mixed in one layer.
  • a surface-fogged silver halide grain described in U.S. Patent 4,082,553, an internally fogged silver halide grain described in U.S. Patent 4,626,498 or JP-A-59-214852, and colloidal silver can be preferably used in a light-sensitive silver halide emulsion layer and/or a substantially non light-sensitive hydrophilic colloid layer.
  • the internally fogged or surface-fogged silver halide grains are silver halide grains which can be uniformly (non-imagewise) developed in either a non-exposed portion or an exposed portion of the light-sensitive material.
  • a method of preparing the internally fogged or surface-fogged silver halide grain is described in U.S. Patent 4,626,498 or JP-A-59-214852.
  • a silver halide which forms the core of an internally fogged core/shell type silver halide grain may have the same halogen composition as or a different halogen composition from that of the other portion.
  • the internally fogged or surface-fogged silver halide are silver chloride, silver chlorobromide, silver iodobromide, and silver chloroiodobromide.
  • the grain size of these fogged silver halide grains is not particularly limited, an average grain size is 0.01 to 0.75 ⁇ m, and most preferably, 0.05 to 0.6 ⁇ m.
  • the grain shape is also not particularly limited but may be a regular grain shape.
  • the emulsion may be a polydispersed emulsion, it is preferably a monodispersed emulsion (in which at least 80% in weight or number of silver halide grains have a grain size falling within the range of ⁇ 30% of an average grain size).
  • fine non-light-sensitive silver halide grains are preferably used.
  • "Fine non-light-sensitive silver halide grains” are fine silver halide grains which are not sensitive upon imagewise exposure for obtaining a dye image and essentially not developed in development.
  • the fine non-light sensitive silver halide grains are preferably not fogged beforehand.
  • the fine silver halide grains contains 0 to 100 mol% of silver bromide. They may contain silver chloride and/or silver iodide as needed. Preferably, they contain 0.5 to 10 mol% of silver iodide.
  • An average grain size (an average value of equivalent-circle diameters of projected surface areas) of the fine grain silver halide is preferably 0.01 to 0.5 ⁇ m, and more preferably, 0.02 to 0.2 ⁇ m.
  • the fine silver halide grains can be prepared by a method similar to the method of preparing normal light-sensitive material silver halide. In this preparation, the surface of each silver halide grain need not be subjected to either optical sensitization or spectral sensitization. However, before the silver halide grains are added to a coating solution, a known stabllizer such as a triazole compound, an azaindene compound, a benzothiazolium compound, a mercapto compound, or a zinc compound is preferably added. A layer containing these fine silver halide grains may preferably contain a colloidal silver.
  • a coating silver amount of the light-sensitive material of the present invention is preferably 6.0 g/m2 or less, and most preferably, 4.5 g/m2 or less.
  • the light-sensitive material of the present invention contain the mercapto compounds disclosed in U.S. Patents 4,740,454 and 4,788,132, JP-A-62-18539, and JP-A-1-283551.
  • the light-sensitive material of the present invention contain compounds for releasing a fogging agent, a development accelerator, a silver halide solvent, or precursors thereof described in JP-A-1-106052, regardless of the amount of silver produced by the development.
  • the light-sensitive material of the present invention preferably contains dyes dispersed by methods described in International Disclosure WO 088/04794 and JP-A-1-502912 or dyes described in EP 317,308A, U.S. Patent 4,420,555, and JP-A-1-259358.
  • a yellow coupler Preferable examples of a yellow coupler are described in, e.g., U.S. Patents 3,933,501, 4,022,620, 4,326,024, 4,401,752, and 4,248,961, JP-B-58-10739, British Patents 1,425,020 and 1,476,760, U.S. Patents 3,973,968, 4,314,023, and 4,511,649, and European Patent 249,473A.
  • magenta coupler examples are preferably 5-pyrazolone and pyrazoloazole compounds, and more preferably, the compounds described in, e.g., U.S. Patents 4,310,619 and 4,351,897, European Patent 73,636, U.S. Patents 3,061,432 and 3,725,067, R.D. No. 24220 (June 1984), JP-A-60-33552, R.D. No. 24230 (June 1984), JP-A-60-43659, JP-A-61-72238, JP-A-60-35730, JP-A-55-118034, and JP-A-60-185951, U.S. Patents 4,500,630, 4,540,654, and 4,556,630, and International Disclosure WO No. 88/04795.
  • cyan coupler examples include phenol and naphthol couplers. Of these, preferable are those described in, e.g., U.S. Patents 4,052,212, 4,146,396, 4,228,233, 4,296,200, 2,369,929, 2,801,171, 2,772,162, 2,895,826, 3,772,002, 3,758,308, 4,343,011, and 4,327,173, West German Luid-open Patent Application 3,329,729, European Patents 121,365A and 249,453A, U.S.
  • the pyrazole-series couplers disclosed in JP-A-64-553, JP-A-64-554, JP-A-64-555 and JP-A-64-556, or the imidazole-series couplers disclosed in U.S. Patent 4,818,672 can be used.
  • a coupler capable of forming colored dyes having proper diffusibility are those described in U.S. Patent 4,366,237, British Patent 2,125,570 EP 96,570, and West German Laid-open Patent Application No. 3,234,533.
  • a colored coupler for correcting additional, undeslrable absorption of a colored dye are those described in R.D. No. 17643, VII-G, R.D. No. 307105, VII-G. U.S. Patent 4,163,670, JP-B-57-39413, U.S. Patents 4,004,929 and 4,138,258, and British Patent 1,146,368.
  • a coupler described in U.S. Patent 4,774,181, which corrects unnecessary absorption of a colored dye by virtue of a fluorescent dye released upon coupling, or a coupler described in U.S. Patent 4,777,120, which has, as a split-off group, a dye precursor group which can react with a developing agent to form a dye may preferably be used.
  • DIR couplers i.e., couplers releasing a development inhibitor are described in the patents cited in the above described RD No. 17643, VII-F, RD No. 307105, VII-F, JP-A-57-151944, JP-A-57-154234, JP-A-60-184248, JP-A-63-37346, JP-A-63-37350, and U.S. Patents 4,248,962 and 4,782,012.
  • the couplers which release a bleach accelerator and which are disclosed in R.D. No. 11449, R.D. No. 24241, and JP-A-61-201247 are effective for reducing the time of bleaching process. They are particularly effective if added to a light-sensitive material using the tabular silver halide grains described above.
  • a coupler for imagewise releasing a nucleating agent or a development accelerator during the development are the compounds described in British Patents 2,097,140 and 2,131,188, JP-A-59-157638, and JP-A-59-170840.
  • Examples of a coupler which can be used in the light-sensitive material of the present invention are competing couplers described in, e.g., U.S. Patent 4,130,427; poly-equivalent couplers described in, e.g., U.S.
  • the couplers for use in the present invention can be added to the light sensitive material by various known dispersion methods. Examples of these methods are an oil-in-water dispersion method and a latex dispersion method.
  • Examples of a high-boiling organic solvent to be used in the oil-in-water dispersion method are described in, for example, U.S. Patent 2,322,027.
  • Examples of a high-boiling organic solvent to be used in the oil-in-water dispersion method and having a boiling point of 175°C or more at atmospheric pressure are phthalate esters (e.g., dibutylphthalate, dicyclohexylphthalate, di-2-ethylhexylphthalate, decylphthalate, bis(2,4-di-t-amylphcnyl) phthulate, bis(2,4-di-t-amylphenyl) isophthalate, bis(1,1-di-ethylpropyl) phthalate); phosphate or phosphonate esters (e.g., triphenylphosphate, tricresylphosphate, 2-ethylhexyldiphenylphosphate,
  • An organic solvent having a boiling point of about 30°C or more, and preferably, 50°C to about 160°C can be used as an auxiliary solvent.
  • Typical examples of the auxiliary solvent are ethyl acetate, butyl acetate, ethyl propionate, methylethylketone, cyclohexanone, 2-ethoxyethylacetate, and dimethylformamide.
  • antiseptics and fungicides are preferably added to the color light-sensitive material of the present invention.
  • examples of the antiseptics and the fungicides are phenetyl alcohol, and 1,2-benzisothiazoline-3-one, n-butyl-p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxycthunol, and 2-(4-thiasolyl) benzimidazole described in JP-A-63-257747, JP-A-62-272248, and JP-A-1-80941.
  • the present invention can be applied to various color light-sensitive materials.
  • the material are a color negative film for a general purpose or a movie, a color reversal film for a slide or a television, color paper, a color positive film, and color reversal paper.
  • a support which can be suitably used in the present invention is described in, e.g., R.D. No. 17643, page 28, R.D. No. 18716, from the right column, page 647 to the left column, page 648, and R.D. No. 307105, page 879.
  • the sum total of film thicknesses of all hydrophilic colloidal layers at the side having emulsion layers is preferably 28 ⁇ m or less, more preferably, 23 ⁇ m or less, much more preferably, 18 ⁇ m or less, and most preferably, 16 ⁇ m or less.
  • a film swell speed T1/2 is preferably 30 sec, or less, and more preferably, 20 sec, or less.
  • the film thickness means a film thickness measured under moisture conditioning at a temperature of 25°C and a relative humidity of 55% (two days).
  • the film swell speed T1/2 can be measured in accordance with a known method in the art. For example, the film swell speed T1/2 can be measured by using a swell meter described in A.
  • the film swell speed T1/2 can be adjusted by adding a film hardening agent to gelatin as a binder or changing aging conditions after coating.
  • a swell ratio is preferably 150% to 400%.
  • the swell rat1o is calculated from the maximum swell film thickness measured under the above conditions in accordance with a relation: (maximum swell film thickness - film thickness)/film thickness.
  • hydrophillc colloid layers having a total dried film thickness of 2 to 20 ⁇ m are preferably formed on the side opposite to the side having emulsion layers.
  • the back layers preferably contain, e.g., the light absorbent, the filter dye, the ultraviolet absorbent, the antistatic agent, the film hardener, the binder, the plasticizer, the lubricant, the coating aid, and the surfactant described above.
  • the swell ratio of the back layers is preferably 150% to 500%.
  • the color photographic light-sensitive material according to the present invention can be developed by conventional methods described in R.D. No. 17643, pp. 28 and 29, R.D. No. 18716, the left to right columns, page 651, and R.D. No. 307105, pp. 880 and 881.
  • a color developer used in development of the light-sensitive material of the present invention is an aque-ous alkaline solution containing as a main component, preferably, an aromatic primary amine-based color developing agent.
  • an aromatic primary amine-based color developing agent preferably, an aminophenol-based compound is effective, a p-phenylenediamine-based compound is preferably used.
  • Typical examples of the p-phenylenediamine-based compound are: 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -hydroxyethylaniline, 3-methyl 4-amino-N-ethyl-N- ⁇ -methanesulfonamide ethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -methoxyethylaniline, and sulfates, hydrochlorides and p-toluenesulfonates thereof.
  • 3-methyl-4-amino-N-ethyl-N- ⁇ -hydroxyethyl aniline 4-amino-3-methyl-N-ethyl-N-(3-hydroxypropyl) aniline is preferred in particular.
  • These compounds can be used in a combination of two or more thereof in accordance with the application.
  • the color developer contains a pH buffering agent such as a carbonate, a borate, or a phosphate of an alkali metal, and a development restrainer or an antifoggant such as a chloride, a bromide, an iodide, a benzimidazole, a benzothiazole, or a mercapto compound.
  • a pH buffering agent such as a carbonate, a borate, or a phosphate of an alkali metal
  • an antifoggant such as a chloride, a bromide, an iodide, a benzimidazole, a benzothiazole, or a mercapto compound.
  • the color developer may also contain a preservative such as hydroxylamine, diethylhydroxylamine sulfites, a hydrazine such as N,N-biscarboxymethyl hydrazine, a phenylsemicar apelbanide, triethanolamine, or a catechol sulfonic acid; an organic solvent such as ethyleneglycol or diethyleneglycol; a development accelerator such as benzylalcohol, polyethyleneglycol, a quaternary ammonium salt or an amine; a dye-forming coupler; a competing coupler; an auxiliary developing agent such as 1-phenyl-3-pyrazolidone; a viscosity-imparting agent; and a chelating agent such as aminopolycarboxylic acid, an aminopolyphosphonic acid, an alkylphosphonic acid, or a phosphonocarboxylic acid.
  • a preservative such as hydroxylamine, diethylhydroxylamine sulfites,
  • the chelating agent examples include ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodi-acetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,N,N-tetramethylenephosphonic acid, and ethylenediamine di(o-hydroxyphenylacetic acid), and salts thereof.
  • black-and-white development is performed and then color development is performed.
  • black-and-white developer well-known black-and white developing agents, e.g., a dihydroxybenzene such as hydroquinone, a 3-pyrazolidone such as 1-phenyl-3-pyrazolidone, and an aminophenol such as N-methyl-p-aminophenol can be singly or in a combination of two or more thereof.
  • the pH of the color and black-and-white developers is generally 9 to 12.
  • the quantity of replenisher of the developer depends on a color photographic light-sensitive material to be processed, it is generally 3 liters or less per m2 of the light-sensitive material.
  • the quantity of replenisher can be decreased to be 500 ml or less by decreasing a bromide ion concentration in a replenisher.
  • a contact area of a processing tank with air is preferably decreased to prevent evaporation and oxidation of the solution upon contact with air.
  • the contact area of the solution with air in a processing tank can be represented by an aperture defined below.
  • Aperture [contact area (cm2) of processing solu tion with air]/[volume (cm3) of the solution]
  • the above aperture is preferably 0.1 or less, and more preferably, 0.001 to 0.05.
  • a shielding member such as a floating cover may be provided on the surface of the photographic processing solution in the processing tank.
  • a method of using a movable cover described in JP-A-1-82033 or slit developing method descried in JP-A-63-216050 may be used.
  • the aperture is preferably reduced not only in color and black-and-white development steps but also in all subsequent steps, e.g., bleaching, bleach-fixing, fixing, washing, and stabilizing steps.
  • the quantity of replenisher can be reduced by using a means of suppressing storage of bromide ions in the developing solution.
  • a color development time is normally 2 to 5 minutes.
  • the processing time can be shortened by setting a high temperature and a high pH and using the color developing agent at a high concentration.
  • the photographic emulsion layer is generally subjected to bleaching after color development.
  • the bleaching may be performed either simultaneously with fixing (bleach-fixing) or independently thereof.
  • bleach-fixing may be performed after bleaching.
  • processing may be performed in a bleach-fixing bath having two continuous tanks, fixing may be performed before bleach-fixing, or bleaching may be performed after bleach-fixing, in accordance with the application.
  • the bleaching agent are a compound of a multivalent metal, e.g., iron(III), peroxides; quinones; and a nitro compound.
  • Typical examples of the bleaching agent are an organic complex salt of iron(III), e.g., a complex salt of an aminopolycarboxylic acid such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediamine-tetraacetic acid, methyliminodiacetic acid, and 1,3-diaminopropanetetraacetic acid, and glycoletherdiaminetetraacetic acid; or a complex salt of citric acid, tartaric acid, or malic acid.
  • an aminopolycarboxylic acid such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediamine-tetraacetic acid, methyliminodiacetic acid, and 1,3-diaminopropanetetraacetic acid, and glycoletherdiaminetetraacetic acid
  • a complex salt of citric acid, tartaric acid, or malic acid e
  • an iron(III) complex salt of aminopolycarboxylic acid such as an iron(III) complex salt of ethylenediaminetetraacetic acid or 1,3-diaminopropanetetraacetic acid is preferred because it can increase a processing speed and prevent an environmental contamination.
  • the iron(III) complex salt of aminopolycarboxylic acid is useful in both the bleaching and bleach-fixing solutions.
  • the pH of the bleaching or bleach-fixing solution using the iron(III) complex salt of aminopoly carboxylic acid is normally 4.0 to 8. In order to increase the processing speed, however, processing can be performed at a lower pH.
  • a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution, and their pre-bath, if necessary.
  • Useful examples of the bleaching accelerator are: compounds having a mercapto group or a disulfide group, described in, e.g., U.S.
  • Patent 3,893,858 West German Patents 1,290,812 and 2,059,988, JP-A-53-32736, JP-A-53-57831, JP-A-53-37418, JP-A-53-72623, JP-A 53-95630, JP-A 53-95631, JP-A-53-104232, JP-A-53-124424, and JP-A-53-141623, and JP-A-53-28426, and R.D. No.
  • 17129 July, 1978; a thiazolidine derivative described in JP-A-50-140129; thiourea derivatives described in JP-B-45-8506, JP-A-52-20832, JP-A-53-32735, and U.S.
  • a compound having a mercapto group or a disulfide group is preferable since the compound has a large accelerating effect.
  • Patent 3,893,858, West German Patent 1,290,812, and JP-A-53-95630 are preferred.
  • a compound described in U.S. Patent 4,552,834 is also preferable.
  • These bleaching accelerators may be added in the light-sensitive material. These bleaching accelerators are useful especially in bleach-fixing of a photographic color light-sensitive material.
  • the bleaching solution or the bleach-fixing solution preferably contains, in addition to the above compounds, an organic acid in order to prevent a bleaching stain.
  • the most preferable organic acid is a compound having an acid dissociation constant (pKa) of 2 to 5, e.g., acetic acid, propionic acid, or hydroxy acetic acid.
  • Examples of the fixing solution or the bleach-fixing solution are thiosulfate, a thiocyanate, a thioether-based compound, a thiourea and a large amount of an iodide.
  • a thiosulfate especially, ammonium thiosulfate can be used in the widest range of applications.
  • a combination of thiosulfate and a thiocyanate, a thioether-based compound, or thiourea is preferably used.
  • a sulfite, a bisulfite, a carbonyl bisulfite adduct, or a sulfinic acid compound described in EP 294,769A is preferred.
  • various types of aminopolycarboxylic acids or organic phosphonic acids are preferably added to the solution.
  • 0.1 to 10 mol/l of a compound having a pKa of 6.0 to 9.0 are preferably added to the fixing solution or the bleach-fixing solution in order to adjust the pH.
  • a compound having a pKa of 6.0 to 9.0 are preferably added to the fixing solution or the bleach-fixing solution in order to adjust the pH.
  • the compound are imidazoles such as imidazole, 1-methylimidazole, 1-ethylimidazole, and 2-methylimidazole.
  • the total time of desilvering step is preferably as short as possible as long as no desilvering defect occurs.
  • a preferable time is 1 to 3 minutes, and more preferably, one to two minutes.
  • a processing temperature is 25°C to 50°C, and preferably, 35°C to 45°C. Within the preferable temperature range, a de silvering speed is increased, and generation of a stain after the processing can be effectively prevented.
  • stirring should be performed as strongly as is possible.
  • a method of intensifying the stirring are a method of colliding a jet stream of the processing solution against the emulsion surface of the light-sensitive material described in JP-A-62-183460, a method of increasing the stirring effect using rotating means described in JP-A-62-183461, method of moving the light-sensitive material while the emulsion surface is brought into contact with a wiper blade provided in the solution to cause disturbance on the emulsion surface, thereby improving the stirring effect, and a method of increasing the circulating flow amount 1n the overall processing solution.
  • Such a stirring improving means is effective in any of the bleaching solution, the bleach-fixing solution, and the fixing solution.
  • the above stirring improving means is more effective when the bleaching accelerator is used, i.e., significantly increases the accelerating speed or eliminates fixing interference caused by the bleaching accelerator.
  • An automatic developing machine for processing the light-sensitive material of the present invention preferably has a light-sensitive material conveyer means described in JP-A-60-191257, JP-A-60-191258, or JP-A-60-191259.
  • this conveyer means can significantly reduce carry-over of a processing solution from a pre-bath to a post-bath, thereby effectively preventing degradation in performance of the processing solution. This effect significantly shortens especially a processing time in each processing step and reduces the quantity of replenisher of a processing solution.
  • the photographic light-sensitive material of the present invention is normally subjected to washing and/or stabilizing steps after desilvering.
  • An amount of water used in the washing step can be arbitrarily determined over a broad range in accordance with the properties (e.g., a property determined by the substances used, such as a coupler) of the light-sensitive material, the application of the material, the temperature of the water, the number of water tanks (the number of stages), a replenishing scheme representing a counter or forward current, and other conditions.
  • the relationship between the amount of water and the number of water tanks in multi-stage counter-current scheme can be obtained by a method described in "Journal of the Society of Motion Picture and Television Engineering", Vol. 64, pp. 248 - 253 (May, 1955).
  • a germicide such as an isothiazolone compound and cyabendazole described in JP-A-57-8542, a chlorine based germicide such as chlorinated sodium isocyanurate, and germicides such as benzotriazole described in Hiroshi Horiguchi et al., "Chemistry of Antibacterial and Antifungal Agents", (1986), Sankyo Shuppan, Eiseigijutsu-Kai ed., “Sterilization, Antibacterial, and Antifungal Techniques for Microorganisms", (1982), Kogyogijutsu-Kai, and Nippon Bokin Bokabi Gakkai ed., “Dictionary of Antibacterial and Antifungal Agents", (1986), can be used.
  • the pH of the water for washing the photographic light-sensitive material of the present invention is 4 to 9, and preferably, 5 to 8.
  • the water temperature and the washing time can vary in accordance with the properties and applications of the light-sensitive material. Normally, the washing time is 20 seconds to 10 minutes at a temperature of 15°C to 45°C, and preferably, 30 seconds to 5 minutes at 25°C to 40°C.
  • the light sensitive material of the present invention can be processed directly by a stabilizing agent in place of washing. All known methods described in JP-A-57-8543, JP-A-58-14834, and JP-A-60-220345 can be used in such stabilizing processing.
  • stabilizing is performed subsequently to washing.
  • An example is a stahilizing bath containing a dye stabilizing agent and a surface-active agent to be used as a final bath of the photographic color light-sensitive material.
  • the dye stabilizing agent are formalin, an aldehyde such as glutaraldehyde, an N-methylol compound, hexamethylenetetramine, and an adduct of aldehyde sulfite.
  • Various cheleting agents and fungicides can be added to this stabilizing bath.
  • An overflow solution produced upon washing and/or replenishment of the stabilizing solution can be reused in another step such as a desilvering step.
  • the silver halide color light-sensitive material of the present invention may contain a color developing agent in order to simplify processing and increases a processing speed.
  • a color developing agent for this purpose, various types of precursors of a color developing agent can be preferably used.
  • the precursor are an indoaniline based compound described in U.S. Patent 3,342,597, Schiff base compounds described in U.S. Patent 3,342,599 and R.D. Nos. 14,850 and 15,159, an aldol compound described in RD No. 13,924, a metal salt complex described in U.S. Patent 3,719,492, and an urethane based compound described in JP-A-53-135628.
  • the silver halide color light-sensitive material of the present invention may contain various 1-phenyl-3-pyrazolidones in order to accelerate color development, if necessary.
  • Typical examples of the compound are described in, for example, JP-A-56-64339, JP-A-57-144547, and JP-A-58-115438.
  • Each processing solution in the present invention is used at a temperature of 10°C to 50°C. Although a normal processing temperature is 33°C to 38°C, processing may be accelerated at a higher temperature to shorten a processing time, or image quality or stability of a processing solution may be improved at a lower temperature.
  • the light-sensitive material according to the present invention can be used as monochrome or color photographic material, as material for making printing plates, as material for laser recording, and as recording material for various uses.
  • the silver halide photographic light-sensitive material of the present invention can be applied to the thermal developing light sensitive materials disclosed in, for example, U.S. Patent 4,500,626, JP-A-60-133449, JP-A-59-218443, JP-A-61-238056, and European Patent 210,660A2.
  • Emulsion Em-A contained tabular grains which had an average aspect ratio of 11.2, an equivalent sphere diameter of 1.08 ⁇ , and a variation coefficient of 24%.
  • Em-B to Em-G were prepared by the same method as Emulsion Em-A, except that the silver potential was held at various values other than -25 mV during the growth of grains.
  • These emulsions. which will be referred to as "Emulsions B, C, D, E, F and G,” contained tabular grains having average aspect ratios of 9.5, 7.8, 6.5, 5.0, 3.1, and 2.5, respectively.
  • Em-A to Em-F were subjected to gold-sulfur sensitization. More specifically, each of these emulslons was heated to 64°C. Next, 7.2 ⁇ 10 ⁇ 4 mol/mol Ag of sensitizing dye A specified in Table B (later presented), 1.0 ⁇ 10 ⁇ 4 mol/mol Ag of antifoggant A specified in Table B, 8.5 ⁇ 10 ⁇ 6 mol/mol Ag of sodium thiosulfate, 1.0 ⁇ 10 ⁇ 5 mol/mol Ag of chloroauric acid, and 1.0 ⁇ 10 ⁇ 3 mol/mol Ag of potassium thiocyanate were sequentially added to the emulsion, thereby performing optimal chemical sensltization on each emulsion.
  • the term "optimal chemical sensitization” means a chemical sensitization which makes the emulsion have a maximum sensitivity when exposed to light for 1/100 second.
  • Em-A to Em-F were subjected to gold-sulfurtellurium sensitization. More specifically. each of these emulsions was heated to 64°C. Next, 7.2 ⁇ 10 ⁇ 4 mol/mol Ag of sensitizing dye A specified in Table B (later presented), 1.0 ⁇ 10 ⁇ 4 mol/mol Ag of antifoggant A specified in Table B, 7.1 ⁇ 10 ⁇ 6 mol/mol Ag of sodium thiosulfate, 1.5 ⁇ 10 ⁇ 5 mol/mol Ag of chloroauric acid, 2.5 ⁇ 10 ⁇ 3 mol/mol Ag of potassium thiocyanate, and 2.2 ⁇ 10 ⁇ 6 mol/mol Ag of butyl-diisopropyl phosphinetelluride were sequentially added to the emulsion, thereby performing optimal chemical sensitization on each emulsion.
  • composition of the emulsion layer and that of the protective layer were as follows: (1) Emulsion Layer Emulsion selected (silver: 2.1 ⁇ 10 ⁇ 2 mol/m2) Coupler (Table B) (1.5 ⁇ 10 ⁇ 3 mol/m2) Tricresylphosphate (1.10 g/m2) Gelatin (2.30 g/m2) (2) Protective Layer 2,4-dichloro-6-hydroxy-S-triazine sodium salt (0.08 g/m2) Gelatin (1.80 g/m2)
  • Samples 101 to 114 were left to stand for 14 hours at 40°C and relative humidity of 70%. Then, they were exposed to light for 1/100 second. said light applied through a gelatin filter (i.e., filter SC50 made by Fuji Film) and also through a continuous wedge. Samples 101 to 114 were color-developed under the conditions which will be specified below. The developed samples were subjected to density measurement by using a green filter. Processing Step Time Temperature Color developing 2 min. 00 sec. 40°C Bleaching 3 min. 00 sec. 40°C Water-washing (1) 20 sec. 35°C Water-washing (2) 20 sec. 35°C Stabilizlng 20 sec. 35°C Drying 50 sec. 65°C
  • the sensitivity of each sample was evaluated in a relative value, with that (100) of Sample 101 used as reference, said relative value being the reciprocal of the exposure amount represented in terms of lux-second which imparted density of fog +0.2.
  • the pressure property of each sample was evaluated in the following method.
  • the sample was wound around a rod having a diameter of 6 mm, with its emulsion-coated surface turned inwards, and maintained in this condition for 10 seconds. Thereafter, the sample was wedge-exposed for 1/100 second under the same conditions as described above. The density of the sample was then measured, with the density (100) of Sample 101 not wound, used as reference.
  • the graininess of each sample was evaluated in the following way. The sample was uniformly exposed to light until it gained density of fog +0.5, and developed in the same method as described above. The RMS graininess of the sample was measured by the method disclosed in "The Theory of the Photographic Process," Macmillan, page 619, with that (100) of Sample 101 used as reference. The smaller the numerical value, the better the graininess.
  • the tellurium sensitization according to this invention serves to provide an emulsion which has high sensitivity and excels in graininess. It is also understood that an emulsion containing tabular grains having an aspect ratio of 3 or more had not only high sensitivity and excellent graininess, but also improved pressure property.
  • Em-A, Em-C, Em F, and Em-G gold-sulfur-tellurium sensitization was performed on Em-A, Em-C, Em F, and Em-G. More specifically, each of these emulsions was heated to 68°C, and 4.2 ⁇ 10 ⁇ 4 mol/mol Ag of sensitizing dye B, 1.4 ⁇ 10 ⁇ 4 mol/mol Ag of sensitizing dye C, 2.3 ⁇ 10 ⁇ 4 mol/mol Ag of sensitizing dye D, 1.2 ⁇ 10 ⁇ 4 mol/mol Ag of antifoggant A, 7.4 ⁇ 10 ⁇ 6 mol/mol Ag of sodium thiosulfate, 2.0 ⁇ 10 ⁇ 5 mol/mol Ag of chloroauric acid, 2.0 ⁇ 10 ⁇ 3 mol/mol Ag of potassium thiocyanate, and 2.0 ⁇ 10 ⁇ 6 mol/mol Ag of N,N-dimethyl tellurourea were sequentially added to the heated emulsion, thus chemically sensitizing the emulsion optimally.
  • Example 201 A plurality of layers having the following compositions were coated on an undercoated triacetylcellulose film support, forming a multilayered color light-sensitive material hereinafter referred to as "Sample 201".
  • Numerals corresponding to each component indicates coating amount represented in units of g/m2.
  • the coating amount of a silver halide is represented by the coating amount of silver.
  • the coating amount of a sensitizing dye is represented in units of moles per mole of a silver halide in the same layer.
  • Layer 1 (Antihalation layer) Black colloidal silver silver 0.20 Gelatin 1.40
  • Layer 2 (Interlayer) 2,5-di-t-pentadecylhydroquinone 0.18 EX-1 0.18 EX-3 0.020 EX-12 2.0 ⁇ 10 ⁇ 3 U-1 0.060 U-2 0.080 U-3 0.10 HBS-1 0.10 HBS-2 0.020 Gelatin 1.04
  • Layer 3 (1st red-sensitive emulsion layer) Emulsion I silver 0.30 Emulsion II silver 0.20 Sensitizing dye I 6.5 ⁇ 10-5 Sensitizing dye I 1.8 ⁇ 10 ⁇ 5 Sensitizing dye III 2.7 ⁇ 10 ⁇ 4 EX-2 0.17 EX-10 0.020 EX-4 0.17 U-1 0.070 U-2 0.050 U-3 0.070 HBS-1 0.060 Gelatin 0.87
  • Layer 4 (2nd red-sensitive emulsion layer)
  • Emulsion VI 1.20 Sensitizing dye I 5.1 ⁇ 10 ⁇ 5 Sensitizing dye II 1.4 ⁇ 10
  • Sample 1 contained W-1, W-2, B-4, B-5, F-1, F-2, F-3, F-4, F-5, F-6, F-7, F-8, F-9, F-10, F-11, F-12, F-13, iron salt, lead salt, gold salt, platinum salt, iridium salt, and rohdium salt, so that they may have improved storage stability, may be more readily processed, may be more resistant to pressure, more antibacterial and more antifungal, may be better protected against electrical charging, and may be more readily coated.
  • Samples 202 to 208 were made by the same method as Sample 201, except that Em-2 to Em-8 were used in place of Em-1 used in Sample 201.
  • Samples 201 to 208 were exposed to light and processed by an automatic developing machine, in the method specified below, until the quantity of replenisher reached three times the volume of the mother solution tank. Processing Method Process Time Temp. Quantity* of replenisher Tank volume Color development 3 min. 15 sec. 37.8°C 25 ml 10l Bleaching 45 sec. 38°C 5 ml 4l Bleach-fixing (1) 45 sec. 38°C -- 4l Bleach-fixing (2) 45 sec. 38°C 30 ml 4l Washing (1) 20 sec. 38°C -- 2l Washing (2) 20 sec. 38°C 30 ml 2l Stabilization 20 sec. 38°C 20 ml 2l Drying 1 min. 55°C *Note: The quantity of replenisher is per meter of a 35-mm wide sample.
  • the bleach-fixing steps and the washing steps were carried out in counter flow.
  • the step (1) was performed after the step (2).
  • the over-flowing part of the bleaching solution was all used in the bleach-fixing (2).
  • This overflowing part of the bleaching solution amounted to 2 ml per meter in the case of the 35-mm wide sample.
  • compositions of the solutions used in the color-developing process are as follows:
  • the mother solution and the replenisher were of the same composition.
  • the sensitivity of each sample was measured in terms of relative value of the fog density determined from a cyan-image characteristic curve and the relative value of the reciprocal of the exposure amount which imparted a density 0.1 higher than the fog density.
  • the sensitivity was evaluated in terms of a relative value, with the density (100) of Sample 201 used as reference.
  • the samples were tested in the same way as in Example 1, for their graininesses and pressure properties.
  • the graininess of each sample was represented in a relative value, with the graininess (100) of Sample 201 used as reference.
  • the sensitivity of each sample was represented in a relative value, using as reference the sensitivity (100) of Sample 201 not bent.
  • a silver nitrate aqueous solution (AgNO3, 136.3g) and a halogen aqueous solution (containing KI in an amount of 4.2 mol% based on KBr) were added to the solution over 51 minutes, by double-jet method at an accelerated flow rate. During this addition, the silver potential was held at 0 mV with respect to the saturated calomel electrode employed. The solution was cooled to 40°C. Then, a silver nitrate aqueous solution (AgNO3, 28.6g) and a KBr aqueous solution were added to the solution over 5.35 minutes by means of double-jet method, thereby forming an emulsion.
  • Em-H1 contained tabular grains which had an equivalent circle diameter of 1.14 ⁇ m, an average thickness of 0.189 ⁇ m, an average aspect ratio of 5.9, and a variation coefficient of 28% in terms of equivalent-circle diameter.
  • Emulsion Em-H2 was prepared in the same way as Em-H1, until the second portion of silver nitrate aqueous solution was added to the solution, then the solution was cooled to 40°C. Next, a silver nitrate aqueous solution (AgNO3, 3.0g) and an KI aqueous solution (KI, 2.5g) were added to the solution over 5 minutes. Then, a silver nitrate aqueous solution (AgNO3, 25.4g) and a KBr aqueous solution were added to the solution over 5.35 minutes by means of double-jet method. During this addition, the silver potential was held at -50 mV with respect to the saturated calomel electrode.
  • Em-H1 contained tabular grains which had an equivalent-circle diameter of 1.12 ⁇ m, an average thickness of 0.19 ⁇ m, an average aspect ratio of 5.9, and a variation coefficient of 29% in terms of equivalent-circle diameter.
  • Em-H1 and Em-H2 were examined at liquid-nitrogen temperature by means of a 200 kV transmission electron microscope.
  • Em-H1 was found to contain grains, most of which had no dislocation lines.
  • Em-H2 was found to contain grains, each of which had many dislocation lines in its entire periphery. Although the dislocation lines each grain in Em-H2 had could not counted, it was obvious that each grain had ten or more dislocation liens.
  • Figs. 1 and 2 are photographs representing Em-H1 and Em-H2, respectively. As can be clearly seen in Figs. 1 and 2, dislocation lines existed in Em-H2, whereas no dislocation lines had been introduced into Em-H1.
  • Em-I1, Three emulsions were prepared by the same method as Em-H1, except that the silver potential was held at various values other than -50 mV during the growth of grains.
  • These emulsions which will be referred to as "Em-I1,” “Em-J1,” and “Em-K1,” respectively, contained tabular grains having average aspect ratios of 7.9, 3.8, and 2.7, respectively.
  • Em-I2 Three emulsions were prepared by the same method as Em-H2, except that the silver potential was held at various values other than -50 mV during the growth of grains.
  • These emulsions which will be referred to as "Em-I2,” “Em-J2,” and “Em-K2,” respectively, contained tabular grains having average aspect ratio of 7.9, 3.8 and 2.7, respectively.
  • Emulsions Em-H1, Em-I1, and Em-K1, thus prepared were subjected to gold-sulfur sensitization. More specifically, each of these emulsions was heated to 72°C. Next, 7 ⁇ 10 ⁇ 5 mol/mol Ag of antifoggant A used in Example 1, 1.1 ⁇ 10 ⁇ 5 mol/mol Ag of sodium thiosulfate, 1.0 ⁇ 10 ⁇ 5 mol/mol Ag of chloroauric acid, and 8.0 ⁇ 10 ⁇ 4 mol/mol Ag of potassium thiocyanate were sequentially added to the emulsion, in the presence of the sensitizing dye A used in Example 1, thereby performing optimal chemical sensitization on each emulsion.
  • optical chemical sensitization means a chemical sensitization in which the sensitizing dye was used in such an amount and the solution was sensitized for such a time, that the resultant emulsion will have a maximum sensitivity when exposed to light for 1/100 second.
  • Emulsions Em-H2, Em-I2, and Em-K2 were subjected to gold-sulfur-tellurium sensitization. More specifically, each of these emulsions was heated to 72°C. Next, 1.0 ⁇ 10 ⁇ 4 mol/mol Ag of antifoggant A used in Example 1, 1.0 ⁇ 10 ⁇ 5 mol/mol Ag of sodium thiosulfate, 1.5 ⁇ 10 ⁇ 5 mol/mol Ag of chloroauric acid, 2.4 ⁇ 10 ⁇ 3 mol/mol Ag of potassium thiocyanate, and 1.0 ⁇ 10 ⁇ 5 mol/mol Ag of butyl-diisopropyl phosphine-telluride were sequentially added to the emulsion, in the presence of the sensitizing dye A used in Example 1, thereby performing optimal chemical sensitization on each emulsion.
  • the sensitivity of each sample was indicated in a relative value, using as reference the sensitivity (100) of Sample 301 not bent.
  • the graininess of each sample was represented in a relative value, with the graininess (100) of Sample 301 used as reference.
  • the emulsions of the present invention which had been tellurium-sensitized, had a high sensitivity and excelled in graininess, and had an improved pressure property.
  • the emulsion, into which dislocation had been introduced had its pressure property greatly improved by virtue of the tellurium sensitization according to the present invention.
  • the present invention greatly helps to provide a silver halide photo graphic light-sensitive material which excels in sensitivity/graininess ratio and had an improved pressure property.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
EP92901464A 1991-12-18 1991-12-18 Photographisches silberhalogenidmaterial Expired - Lifetime EP0573649B1 (de)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP1991/001731 WO1993012460A1 (en) 1991-12-18 1991-12-18 Silver halide photographic material

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EP0573649A1 true EP0573649A1 (de) 1993-12-15
EP0573649A4 EP0573649A4 (de) 1994-11-02
EP0573649B1 EP0573649B1 (de) 1999-04-07

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1162503A2 (de) * 2000-06-09 2001-12-12 Fuji Photo Film Co., Ltd. Verfahren zur Verarbeitung eines farbphotographischen lichtempfindlichen Silberhalogenidmaterials

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1602591A (en) * 1924-06-06 1926-10-12 Eastman Kodak Co Photographic light-sensitive material containing tellurium and process of making the same
US1623499A (en) * 1925-06-16 1927-04-05 A corpora
CA800958A (en) * 1965-06-17 1968-12-10 Eastman Kodak Company Sensitization of photographic systems
JPS6365438A (ja) * 1986-09-06 1988-03-24 Konica Corp 圧力かぶりが改良されたハロゲン化銀写真感光材料
EP0458278A1 (de) * 1990-05-21 1991-11-27 Fuji Photo Film Co., Ltd. Photographisches Silberhalogenidmaterial
EP0542306A1 (de) * 1991-11-15 1993-05-19 Fuji Photo Film Co., Ltd. Photographisches Silberhalogenidmaterial

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6167845A (ja) * 1984-09-11 1986-04-08 Konishiroku Photo Ind Co Ltd ハロゲン化銀写真感光材料
JPS61277942A (ja) * 1985-06-01 1986-12-08 Konishiroku Photo Ind Co Ltd 写真要素
JPH03236043A (ja) * 1990-02-14 1991-10-22 Fuji Photo Film Co Ltd ハロゲン化銀カラー写真感光材料
JPH03260640A (ja) * 1990-03-12 1991-11-20 Fuji Photo Film Co Ltd ハロゲン化銀写真乳剤、その製造方法、及びそれを含む感光材料

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1602591A (en) * 1924-06-06 1926-10-12 Eastman Kodak Co Photographic light-sensitive material containing tellurium and process of making the same
US1623499A (en) * 1925-06-16 1927-04-05 A corpora
CA800958A (en) * 1965-06-17 1968-12-10 Eastman Kodak Company Sensitization of photographic systems
JPS6365438A (ja) * 1986-09-06 1988-03-24 Konica Corp 圧力かぶりが改良されたハロゲン化銀写真感光材料
EP0458278A1 (de) * 1990-05-21 1991-11-27 Fuji Photo Film Co., Ltd. Photographisches Silberhalogenidmaterial
EP0542306A1 (de) * 1991-11-15 1993-05-19 Fuji Photo Film Co., Ltd. Photographisches Silberhalogenidmaterial

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO9312460A1 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1162503A2 (de) * 2000-06-09 2001-12-12 Fuji Photo Film Co., Ltd. Verfahren zur Verarbeitung eines farbphotographischen lichtempfindlichen Silberhalogenidmaterials
EP1162503A3 (de) * 2000-06-09 2002-07-24 Fuji Photo Film Co., Ltd. Verfahren zur Verarbeitung eines farbphotographischen lichtempfindlichen Silberhalogenidmaterials
US6555299B2 (en) 2000-06-09 2003-04-29 Fuji Photo Film Co., Ltd. Method of processing silver halide color photographic light-sensitive material

Also Published As

Publication number Publication date
EP0573649A4 (de) 1994-11-02
EP0573649B1 (de) 1999-04-07
WO1993012460A1 (en) 1993-06-24
DE69131105D1 (de) 1999-05-12
DE69131105T2 (de) 1999-08-26

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