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WO1993012460A1 - Materiau photographique a base d'halogenure d'argent - Google Patents

Materiau photographique a base d'halogenure d'argent Download PDF

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Publication number
WO1993012460A1
WO1993012460A1 PCT/JP1991/001731 JP9101731W WO9312460A1 WO 1993012460 A1 WO1993012460 A1 WO 1993012460A1 JP 9101731 W JP9101731 W JP 9101731W WO 9312460 A1 WO9312460 A1 WO 9312460A1
Authority
WO
WIPO (PCT)
Prior art keywords
silver halide
silver
emulsion
group
tellurium
Prior art date
Application number
PCT/JP1991/001731
Other languages
English (en)
Japanese (ja)
Inventor
Yasuo Kashi
Hirotomo Sasaki
Hiroyuki Mifune
Original Assignee
Fuji Photo Film Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fuji Photo Film Co., Ltd. filed Critical Fuji Photo Film Co., Ltd.
Priority to DE69131105T priority Critical patent/DE69131105T2/de
Priority to EP92901464A priority patent/EP0573649B1/fr
Priority to PCT/JP1991/001731 priority patent/WO1993012460A1/fr
Publication of WO1993012460A1 publication Critical patent/WO1993012460A1/fr

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Classifications

    • 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 sensation is known as the chemical sensitization method.
  • German Patent Nos. 1,295,462 and 1,396,696 and Canadian Patent 800,958 are known, as are British Patent Nos. 1,295,462 and 1,396,696 and Canadian Patent 800,958.
  • tabular silver halide grains are described, for example, in US Pat. Nos. 4,434,226 and 4,439,520; No. 4,414,310, No. 4,433,048, No. 4,414,306, No. 4,459,353 disclose its manufacturing method and use technology, and have various advantages, for example, Improvement of sensitivity including improvement of color sensitization efficiency by dye, improvement of sensitivity Z granularity ratio, improvement of sharpness due to specific optical properties of tabular grains, covering no. No. 1 improvement is known. However, the sensitivity reached by the tabular grains is not at a satisfactory level, and further improvement is desired.
  • tabular grains often have an increased sensitivity due to their shape, but their pressure properties may deteriorate.Therefore, there is a need for a technique for improving the sensitivity within a range that does not deteriorate the pressure properties.
  • An object of the present invention is to provide a silver halide photographic light-sensitive material containing tabular silver halide grains having a tellurium sensation, excellent sensitivity Z granularity, and improved pressure characteristics.
  • a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, at least 50% of the total projected area of silver halide grains contained in the emulsion layer is ascord.
  • a silver halide photographic light-sensitive material characterized in that the silver halide grains are occupied by tabular grains having a cut ratio of 3 or more, and the silver halide grains have been subjected to a chemical feeling including a tellurium feeling.
  • the tabular silver halide grains have the following general formula
  • R, R 2 and R are an aliphatic group, an aromatic group, a heterocyclic group, OR 4 , NR 5 (R 6 ) SR 7 , OS i R 8 (R 9 )
  • R 10 T e R n , X or a hydrogen atom.
  • R 4, R 7 and R u represents an aliphatic group, an aromatic group, a heterocyclic group, a hydrogen atom or represents a cation
  • R 5 and R 6 represents an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom Stands for R.
  • R 9 and R 1Q are fat X represents a halogen atom
  • X represents a halogen atom
  • R u is an aliphatic group, an aromatic group, a heterocyclic group, or - NR
  • N (R lg ) represents R 10 or 0 R 20 ; R i3 , H .15 ,
  • R 16 , R 17 , R 1R , R 1Q and R 9n are a hydrogen atom, an aliphatic group
  • R 15, R ll and ⁇ , ⁇ "11 ⁇ R 18 ⁇ R 11 ⁇ R 20, R 13 C" R 15 ⁇ R i3 and R 17, R i3 and R 18 and R and R 2 () is combined with A ring may be formed.
  • tabular silver halide grains having an aspect ratio of 3 or more, and preferably less than 8, are present in all of the silver halide grains contained in the emulsion. It accounts for at least 50% of the projected area.
  • tabular silver halide grains are a general term for silver halide grains having one twin plane or two or more parallel twin planes.
  • the twin plane is the (1 1 1) plane when ions at all lattice points on both sides of the (1 1 1) plane are in a mirror image relationship.
  • These tabular grains have a triangular, hexagonal or rounded circular shape when the grains are viewed from above, with the triangular being triangular and the hexagonal being hexagonal.
  • the average aspect ratio of the tabular grains refers to the tabular grains having a grain thickness of less than 0.5 m and a grain diameter of 0.3 ra or more. It is the average of the values (aspect ratio) divided by.
  • a metal was deposited from an oblique direction of the particles together with a reference lattice, the length of the shadow was measured on an electron micrograph, and the length of the shadow of the reference lattice was measured. This can be easily done by calculating with reference.
  • the particle diameter in the present invention is the diameter of a circle having an area equal to the projected area of the parallel outer surface of the particle.
  • the projected area of a particle can be obtained by measuring the area on an electron micrograph and correcting the photographing magnification.
  • the diameter of the tabular grains of the present invention thus determined is preferably from 0.3 to 5.0 in. Further, the thickness of the tabular particles is preferably from 0.05 to 0.5 m.
  • the proportion of the tabular grains in the emulsion is preferably 50%, particularly preferably 80% or more, of the projected area of all silver halide grains in the emulsion. Further, the average aspect ratio of the tabular grains occupying these fixed areas is preferably 3 or more and less than 8.
  • the tabular grains used in the present invention can be produced by appropriately combining methods known in the art.
  • a tabular grain forms a seed crystal in which 40% or more exists by weight. Or higher by adding a silver salt solution and a halogen solution while keeping the pBr value higher than that, and growing the seed crystal.
  • the silver salt solution and the halogen solution may be added so that new crystal nuclei are not generated during the grain growth process by adding a water-soluble silver salt, for example, silver nitrate and / or a water-soluble halogen. Desirable.
  • the size of the tabular grains can be adjusted, for example, by controlling the temperature, selecting the type and amount of the solvent, and controlling the addition speed of the silver salt and halide used during grain growth.
  • a silver halide solvent is useful for accelerating ripening of silver halide grains.
  • it is known to have excess halogen ions present in the reactor to promote ripening. Therefore, it is clear that ripening can be promoted simply by introducing an aqueous halide solution into the reactor.
  • other ripening agents can be used. These ripening agents can be incorporated in their entirety in the dispersion medium in the reactor before adding the silver salt and the halide salt, or one or more halide salts, silver salts or silver salts can be added.
  • a salt or peptizer may be added and introduced into the reactor.
  • the ripening agent can also be introduced independently at the stage of adding the haematogenide salt and the silver salt.
  • ripening agent other than the above-mentioned halogen ions ammonia, amine compounds, thiosinates, for example, alkali metal thiosinates, particularly sodium and potassium sulphate salts, and ammonium thiosinates Agate salts can be used.
  • thiocyanate ripening agents is taught in U.S. Pat. Nos. 2,222,264, 2,448,534 and 3,320,069.
  • well-known thioether ripening agents as described in U.S. Pat. Nos. 3,271,157, 3,574,628 and 3,737,313 can be used.
  • thione compounds as disclosed in JP-A-53-82408 and JP-A-53-144319 can be used.
  • the properties of silver halide grains can be controlled by the presence of various other compounds in the process of silver halide precipitation.
  • a compound may be initially present in the reaction vessel, or may be added together with one or more salts according to a conventional method.
  • reduction sensitization refers to a method in which a reduction sensitizer is added to a silver halide emulsion, a method in which silver halide grains are grown or ripened in an atmosphere having a low pAg of pAg 1 to 7, which is called silver ripening. Either growth or ripening in a high pB atmosphere with a pE of 8 to 11 called pH ripening can be selected. Also, two or more of these methods can be used in combination.
  • the above method of adding a reducing sensitizer is a preferable method because the level of reduction sensitization can be finely adjusted.
  • Known reduction sensitizers include, for example, stannous salts, ascorbic acid and its derivatives, amides and polyamines, hydrazine derivatives, formamidine sulfinic acid, silane compounds, and borane compounds. .
  • these known reduction sensitizers can be selected and used, and two or more compounds can be used in combination.
  • Preferred compounds as reduction sensitizers used in the present invention are stannous chloride, thiourea dioxide, dimethylamborane, ascorbic acid and derivatives thereof.
  • the addition amount of the reduction sensitizer in the present invention it is necessary to be selected depending on the emulsion manufacturing conditions, a preferable range of 1 0 _7 ⁇ 1 0 one 3 moles per mole of silver halide equivalent Ri.
  • the reduction sensitizer is dissolved in a solvent such as water or alcohols, glycols, ketones, esters, and amides and added during grain growth. It is good to add to the reaction vessel in advance The method of adding at an appropriate time during the growth of the silver halide grains is preferred.
  • a reducing sensitizer may be added in advance to an aqueous solution of a water-soluble silver salt or a water-soluble alkali halide, and these aqueous solutions may be used to precipitate silver halide particles. It is also preferable to add the solution of the reducing sensitizer in several portions as the silver halide grains grow, or to continuously add the solution for a long time.
  • the silver halide emulsion used in the present invention may be, for example, a treatment for imparting roundness to grains as disclosed in European Patent Nos. 96,727 B1 and 64,412 B1 or a West German patent.
  • the surface may be modified as disclosed in Japanese Patent No. 2,306,447 C2 and JP-A-60-221320.
  • the grain surface generally has a flat structure, but intentionally forming irregularities is sometimes preferable.
  • a portion of the crystal described in JP-A-58-1 06532 and JP-A-60-221320, for example, a particle having a hole at the vertex or the center of the surface, or US Pat. No. 4,643, Raffle particles described in 966 are an example.
  • the tabular grains in the emulsion used in the present invention have at least one dislocation.
  • Such dislocations can include dislocations introduced linearly in a particular direction of the crystallographic orientation of the grain, distorted dislocations, dislocations introduced throughout the grain, or introduced only in a particular part of the grain, For example, it can be selected from dislocations introduced only in the fringe portion of the particle.
  • a dislocation is a displacement (displacement) of a series of atomic arrangements in the crystal lattice, and its general definition is, for example, Shuji Suzuki, Introduction to Dislocation Theory, Agnesha, 1968, p. Specified on 24-31.
  • Dislocations (lines) existing in the crystal can be observed by electron microscopy, and changes in contrast due to sample tilt etc. are described in Hirsch et al. (Electron Microscopy of Thin Crystals, P 169-18.8, Butterworts, London, 1965).
  • dislocation lines observed in silver halide grains include Hami 1 ton (P hotgr. Sci. Eng., 11, 57 (1967), Shiozawa (Nissha, 16 (171), 3_ 5_, 2 1 3 (1 972)).
  • Dislocation line images can be distinguished Dislocation line density measurement method and method for measuring dislocation line density distribution between particles Dislocation line density is the number of dislocation lines present in one particle It is assumed that The measurement is performed as follows.
  • a series of particle photographs with different tilt angles with respect to the incident electrons are taken for each particle to confirm the existence of dislocation lines. At this time, if the number of dislocation lines can be counted, the number is also counted. When dislocation lines exist in a dense manner and the number of dislocation lines per particle cannot be counted, it is counted that there are many dislocation lines.
  • the distribution of dislocation line densities between particles is determined by measuring dislocation line densities of 200 or more particles, more preferably 300 or more particles, and creating a frequency distribution.
  • the silver halide grain size of the emulsion used in the present invention may be, for example, a circle equivalent diameter of a projected area using an electron microscope, a sphere equivalent diameter of a grain volume calculated from a projected area and a grain thickness, or a Coulter counter. It can be evaluated by the sphere equivalent diameter of the volume by the method. In the present invention, it can be used by selecting from ultrafine particles having a sphere equivalent diameter of 0.05 micron or less to coarse particles exceeding 10 micron. Preferably, grains having a size of 0.1 micron or more and 3 micron or less are used as photosensitive silver halide grains.
  • a so-called polydisperse emulsion having a wide size distribution of silver halide grains or a monodisperse emulsion having a narrow size distribution can be selected according to the purpose.
  • the coefficient of variation of the projected area circle equivalent diameter of a grain or the sphere equivalent diameter of a volume is used as a measure of the size distribution of silver logenide grains.
  • a monodisperse emulsion may be defined as an emulsion having a size distribution such that the number of grains or a grain diameter of 80% or more of all grains by weight falls within ⁇ 30% of the average grain diameter.
  • two or more kinds of monodisperse silver halide emulsions having different grain sizes in the emulsion layer having substantially the same color sensitivity are mixed or separated in the same layer. Layers can be overcoated.
  • two or more kinds of polydispersed silver halide emulsions or a combination of a monodispersed emulsion and a polydispersed emulsion can be used in the same layer as a mixture or in a multi-layer coating.
  • the silver halide grains according to the present invention are silver bromide, silver chloride, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, and silver chloroiodobromide.
  • Other silver salts for example, silver rhodan, silver sulfide, silver selenide, silver carbonate, silver phosphate, and organic acid silver may be contained as separate grains or as a part of silver halide grains.
  • silver halide grains containing a large amount of silver chloride are preferred. In order to appropriately suppress the development, it is preferable to contain silver iodide.
  • the preferred silver iodide content depends on the intended light-sensitive material. For example, 0.1 to 15 mol% is preferred for X-ray sensitive materials, and 0.1 to 5 mol% is preferred for graphic arts and microsensitive materials. Silver iodide content. In the case of a photographic light-sensitive material represented by a color negative, a silver halide containing 1 to 30 mol% of silver iodide is preferably used, more preferably 5 to 20 mol%, particularly preferably. For silver halide, silver halide containing 8 to 15 mol% of silver iodide can be used. It is. It is preferable that silver iodobromide grains further contain silver chloride because lattice strain is reduced.
  • the silver halide emulsion according to the present invention preferably has a distribution or structure with respect to the halogen composition in the grains.
  • Typical examples thereof include, for example, Japanese Patent Publication No. 3-13162, Japanese Patent Application Laid-Open No. 61-215540, Japanese Patent Application Laid-Open No. 60-222845, Japanese Patent Application No. 60-143331, and Japanese Patent Application No. 61-75337 is a core-shell type or double-structure type particle having a different halogen composition between the inside of the particle and the surface layer.
  • a triple structure type particle as disclosed in Japanese Patent Application Laid-Open No. 60-222484, or a multilayer structure type particle having more than that a core-surprising double
  • the grains may have a structure in which silver halides having different compositions are thinly applied to the surfaces of the grains having the structure.
  • the grains having a structure inside as the silver halide grains according to the present invention include not only the above-described wrapping structure but also grains having a so-called junction structure. Examples of these are disclosed, for example, in JP-A-59-133540, JP-A-58-108526, European Patent No. 199,290 A2, JP-A-58-24772, and JP-A-59-16254. Issue.
  • the host crystal has a composition different from that of the host crystal. It can be generated by bonding to the edges, corners, or faces of the surface.
  • the crystal having such a junction structure either a crystal having a uniform host crystal with respect to the halogen composition or a crystal having a core-shell structure can be used.
  • the combination of silver halides is naturally possible, but a joint structure in which a silver salt compound having no rock salt structure, for example, rhodium silver or silver carbonate is combined with silver halide can also be used.
  • a non-silver salt compound such as lead oxide may be used as long as the bonding structure is possible.
  • the core portion has a higher silver iodide content than the shell portion.
  • grains having a low silver iodide content in the core portion and a high silver iodide content in the shell portion are preferred.
  • the grain having the above-mentioned bonding structure may be a grain having a high silver iodide content of the host crystal and a relatively low silver iodide content of the bonding crystal, or a grain having the opposite relation. It may be.
  • the boundary portions of the grains having these structures having different halogen compositions may be clear boundaries or unclear boundaries.
  • a preferred embodiment is one in which a continuous change in the halogen composition is positively applied to the grains.
  • halogen distribution between grains is uniform This is a desirable characteristic.
  • highly uniform emulsions having a coefficient of variation of 20% or less are preferred.
  • Another preferred form is an emulsion which correlates grain size with halogen composition. For example, there is a correlation in which large particles have a higher eode content, while small particles have a lower eode content.
  • halogen composition near the surface of the silver halide grains It is important to control the halogen composition near the surface of the silver halide grains according to the present invention.
  • Increasing the silver iodide content in the vicinity of the grain surface or increasing the silver chloride content is selected according to the purpose because it changes the adsorptivity of the dye and the developing speed.
  • a structure that wraps the entire particle or a structure that adheres only to a part of the particle can be selected. For example, a state where the composition of one of the main plane and the side of the tabular grain is changed is selected.
  • Gelatin is advantageously used as a protective colloid used in the preparation of the silver halide emulsion according to the present invention, and as another binder for the hydrophilic colloid layer.
  • Hydrophilic colloids can also be used.
  • hydrophilic colloid examples include proteins such as gelatin derivatives, graft polymers of gelatin and other macromolecules, albumin, and casein; cellulose derivatives such as hydroxyxethyl cellulose, carboxymethyl cellulose, and cellulose sulfate. Esters; sugar derivatives, for example, sodium alginate, powdered derivatives; single or various synthetic hydrophilic polymer substances such as copolymers, for example, polyvinyl alcohol, polyvinyl alcohol partial acetal, and poly (vinyl alcohol).
  • Vinylpyrrolidone polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylvinylazole can be used ⁇
  • the silver halide emulsion according to the present invention is preferably washed with water for desalting to obtain a newly prepared protective colloid dispersion.
  • the washing temperature can be selected according to the purpose, but it is preferable to select a temperature in the range of 5 to 50 ° C.
  • the pB at the time of washing can be selected according to the purpose, but is preferably selected in the range of 2 to 10. More preferably, it is in the range of 3 to 8.
  • the pAg at the time of washing can be selected according to the purpose, but is preferably selected in the range of 5 to 10.
  • the method of washing can be selected from the following: noodle washing, dialysis using a semipermeable membrane, centrifugation, coagulation sedimentation, and ion exchange.
  • coagulation sedimentation for example, a method using a sulfate, a method using an organic solvent, a method using a water-soluble polymer, and a method using a gelatin derivative You can choose from different methods
  • the silver halide grains contained in the silver halide emulsion of the present invention be subjected to a chemical feeling including a tellurium feeling.
  • the tellurium sensitizers used in the present invention include, for example, U.S. Pat. Nos. 1,623,499, 3,320,069, and 3,772,031. , UK Patent Nos. 2, 3, 2 11, 1, 1 2, 1 496, 1, 2 95, 4 62, 1, 3 96, 6 96, Canadian Patent No. 800,958, Journal * Ob ⁇ Chemical Society-Chemical Communications (J. Chem. S0c. Chem. Commun.) 63 5 (1980), ibid 1102 (19779), ibid 645 (19779), journal ⁇ Ob-Chemicals * Society-Perkin-Transaction ( J. Chem. Soc. Perkin Trans.) 1, 2191 (1980).
  • tellurium sensitizers include, for example, colloidal tellurium, tellurium ureas (for example, aryl urea urea, N, N-dimethyl tereurea, tetramethyl tereurea, N-carboxyethyl-N ', N'-dimethyl terium urea, N, N'-dimethyl ethylene ter urea, N, N 'diphenyl ethylene terlourea, isotel cyanates (e.g., arylysotellurocyanate), telluroket (E.g., tellurium acetate, telluroacetofphenon), telomers (e.g.
  • colloidal tellurium for example, aryl urea urea, N, N-dimethyl tereurea, tetramethyl tereurea, N-carboxyethyl-N ', N'-dimethyl terium urea, N
  • the compounds represented by the general formulas (I) and (II) are preferable.
  • R 2 and R 3 are an aliphatic group, an aromatic group, a heterocyclic group, OR NR s CR ⁇ SR-0 S ⁇ R g (R.) (R 10 ), Te R u, represents X or a hydrogen atom.
  • R 4, R 7 and R u represents an aliphatic group, an aromatic group, heterocyclic group, a hydrogen atom or a cation, and R 6 represents fat aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom, R.
  • R 9 and R 1Q represent an aliphatic group, and X represents a halogen atom.
  • alkyl group, alkenyl group, alkynyl group, and aralkyl group examples include methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopentyl, and cyclohexyl.
  • R 7 and R u represent respectively a heterocyclic group, the heterocyclic group nitrogen atom, an oxygen atom And a 3- to 10-membered saturated or unsaturated heterocyclic group containing at least one of a sulfur atom and a sulfur atom. These may be monocyclic or may form a condensed ring with another aromatic or heterocyclic ring.
  • the heterocyclic group is preferably a 5- to 6-membered aromatic heterocyclic group, and specific examples thereof include pyridyl, furyl, chenyl, thiazolyl, imidazolyl, and benzimidazolyl.
  • R 7 and R u represent respectively cation, examples of the cation, alkali metals, Anmoniumu.
  • X in the general formula (I) represents a halogen atom
  • examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
  • substituents include, for example, an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group, an acylamino group, a perido group, a urethane group, and a sulfonylamino group.
  • R 2 , and R 5 may be bonded to each other to form a ring together with a phosphorus atom, and R 5 and R 6 may be bonded to each other to form a nitrogen-containing heterocyclic ring.
  • R ⁇ , R 2 and R 3 represent an aliphatic group or an aromatic group, more preferably an alkyl group or an aromatic group.
  • R n represents an aliphatic group, an aromatic group, a heterocyclic group or —NR (R 14 ), and R 12 represents one NR 15 (R 16 ), -N (R 17 ) N (R 18 ) represents R or one OR 20 .
  • R 13, R 14, R 15 , R, R 17, R 18, R 19 and R represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, or Ashiru group.
  • R u , R 13 s R, R 15 , R 16 , R, R 18 , R 19 and R 2 each represent an aliphatic group
  • the aliphatic group is It is preferably a compound having 1 to 30 carbon atoms, particularly a linear, branched or cyclic alkyl group, alkenyl group, alkynyl group or aralkyl group having 1 to 20 carbon atoms.
  • alkyl group, alkenyl group, alkynyl group and aralkyl group examples include, for example, methyl, ethyl, n-propyl, isopyl, t-butyl, n-octyl, n-decyl, n-hexadecyl , Cyclopentyl, cyclohexyl, aryl, 2-butenyl, 3-pentenyl, propargyl, 3-pentynyl, benzyl and phenyl.
  • R u, R 13, R 14, R 15, R 16, R, if R 18, R 19 and R 2Q represent each an aromatic group
  • aromatic group lay preferred Has 6 to 30 carbon atoms, particularly a monocyclic or condensed aryl group having 6 to 20 carbon atoms, and examples thereof include phenyl and naphtinolene.
  • R n , R, R 14 , R 15 When R 1, R 2 , R 3, R 1 and R 2 () each represent a heterocyclic group, the heterocyclic group has 3 to 10 members including at least one of a nitrogen atom, an oxygen atom and a sulfur atom It is a saturated or unsaturated heterocyclic group of the ring. These may be monocyclic or may form a condensed ring with another aromatic or heterocyclic ring. Specific examples of the heterocyclic group preferably include a 5- to 6-membered aromatic heterocyclic group, for example, pyridyl, furyl, chenyl, thiazolyl, imidazolyl, and benzimidazolyl.
  • R 13 , R 14 , R 15 , R 16 , R 17 , R i8 , R 19 and R 2Q each represent an acyl group
  • the acyl group preferably has 1 carbon atom.
  • R ll and R 15, 11 and R 17, R ll and 18, R ll and R 20, R 13 and R 11:, R 13 and R 17, R 13 and R 18 and R 13 and R 20 are forming
  • the divalent group formed by this bond is, for example, an alkylene group, an arylene group, an aralkylene group or an alkenylene group.
  • R u represents an aliphatic group, an aromatic group or a NR (R 1 / f)
  • R 12 is - NR 15 represents a (R 16).
  • R 13 , R 14 s R 15 and R are aliphatic groups Or represents an aromatic group.
  • R u or aromatic group - NR 13 represents (R 14)
  • R 12 is - NR 15 represents a (R 16).
  • R 13 , R 14 , R 15 and R 16 represent an alkyl group or an aromatic group.
  • combined binding R u and R 15 and R 13 and R 15 may form a ring, alkylene group, Ariren group, it is also more preferable arbitrary as the Araruki alkylene or alkenylene group.
  • Table A below shows specific examples 1 to 38 of the compounds represented by the general formulas (I) and (II) in the present invention, but the present invention is not limited thereto.
  • the compounds represented by the general formulas (I) and (H) of the present invention can be synthesized according to a known method.
  • Journal of Chemical Society J. Chem. Soc.) (A) 1969, 2992; Journal of Organic Metallic Chemistry Story (J. Oranomet. Chem.) 4, 320 (1965); ibid, J ⁇ , 200 (1963); ibid, 113, C3 Phosphorus sulfur (Phosphorus Sulfur) 15, 15 5 (1 983); Hemisch-Berrichte (Chem. Ber.) 10 (5) 9, 2997 (1976); Journal of Chemicals, Society, Chemistry and Communication (J. Chem. Soc. Chem.
  • the tellurium sensitizer used in the tellurium sensitization of the present invention is a compound that forms silver telluride which is presumed to be a sensitizing nucleus on the surface of silver halide emulsion grains or inside the grains.
  • the following test can be performed for the formation rate of silver telluride in a silver halide emulsion.
  • the amount of silver sulfide formed in a silver halide emulsion was determined from the infinite reflectivity of the emulsion in the visible region (520 nm) using the Kubea-Munk equation. twenty five
  • the relative silver telluride formation rate can be easily obtained in the same manner as that obtained by using the above method.
  • this reaction is apparently close to a first-order reaction, a pseudo-first-order reaction rate constant can also be obtained.
  • the pseudo-first-order reaction constants of the tellurium sensitizer of the present invention according to the test method are as follows.
  • the generated silver telluride can be separated and quantified from the unreacted tellurium sensitizer.
  • a trace amount of Te is quantitatively analyzed by an atomic absorption method or the like. This reaction rate varies greatly within several digits depending on the silver halide composition of the emulsion to be tested, the temperature to be tested, pAg and pH, as well as the type of compound.
  • the tellurium sensitizer preferably used in the present invention is a compound capable of forming silver telluride with respect to a specific silver halide emulsion having a halogen composition and crystal habit to be used.
  • a compound capable of forming silver telluride with respect to a silver halide emulsion at a temperature of 40 to 95 and a pH of 3 to 10 or a pAg of 6 to ll is the present invention.
  • a compound in which the pseudo-first-order reaction rate constant k according to the above test method falls within the range of 1 X 10 _7 to: LX 10 _ ⁇ min -1 is a tellurium sensitizer. As more preferred.
  • the amount of tellurium ⁇ agent used in these present invention, the silver halide grains to use will vary with the chemical ripening condition and the like, generally, per mol of silver halide 10 _8 ⁇ 10 _ 2 moles, preferable properly It is about 10-7 to 5 x 10-3 mol.
  • the conditions of the chemical sensitivity in the present invention are not particularly limited, but pAg is 6 to 11, preferably 7 to: L0, and the temperature is 40 to 95 ° C, preferably. Is between 50 and 85 ° C.
  • the temperature is 40 to 95.
  • C, pH 3 ⁇ : L0, pAg 6 ⁇ : L1 This is a preparation method in which a silver halide emulsion is tellurium-sensitive in the presence of a compound which forms silver telluride.
  • the silver halide emulsion of the present invention has a silver halide in which at least 50% of the total projected area of the silver halide grains is occupied by tabular silver halide grains having an aspect ratio of 3 or more.
  • a noble metal sensitizer such as gold, platinum, palladium or iridium in combination.
  • a gold sensitizer in combination, and specific examples include chloroauric acid, potassium chromate, potassium thioate, gold sulfide, and gold selenide. . , Per mol of silver halide, it can be used 1 0 _7 to 1 0_ 2 moles.
  • a sulfur sensitizer in combination.
  • Specific examples thereof include known thiosulfates (eg, hypo), thioureas (eg, diphenylthiourea, triethylthiourea, and arylthiourea), and known unstable compounds such as rhodanines. 1 mole of silver halide 1 0 one 7 to 1 0 - 2 moles per can Mochiiruko.
  • the unstable selenium sensitizer described in JP-B-44-15748 is preferably used.
  • the unstable selenium sensitizer described in JP-B-44-15748 is preferably used.
  • Specific examples thereof include colloidal selenium, selenoureas (eg, N, N-dimethylselenourea, selenourea, tetramethylselenourea), and selenoamides (eg, selenoacetate, N, N —Dimethyl-selenobenzamide), selenoketons (eg, selenoaceton, selenobenzophenone), selenides (eg, triphenylphosphineselenide, getylselenide), selenophosphate Doo compound (such as Application Benefits - p - DOO drill selenophosphate), selenocarboxylic acids and esters, Lee Sosereno Shiane preparative acids and the like, per mol of silver s
  • the above-described reduction sensitizer may be used in combination.
  • halogenated solvent examples include thiocyanates (for example, potassium thiocyanate), thioether compounds
  • thiocyanates thioether compounds, tetrasubstituted thiourea compounds and thione compounds can be preferably used.
  • the amount used can have 1 0 _5 ⁇ 1 0 one 2 moles Mochiiruko per mol of silver halide.
  • the present invention also relates to a silver halide emulsion and a method for preparing the same. Its characteristic part is common to the silver halide photographic light-sensitive material described above, and is obvious to those skilled in the art. Representative silver halide emulsions and their preparation are described below. It goes without saying that these inventions can add the limitations of the subordinate concepts described in claims 2 and 4 and below.
  • the photographic emulsion used in the present invention may contain various compounds for the purpose of preventing force blur during the production process, storage or photographic processing of the photographic material, or stabilizing photographic performance. That is, thiazoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazols, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, and mercaptobenazole Nzimidazoles, mercaptothia asiazo , Aminothriazoles, benzotriazoles, dibenzobenzotriazoles, mercaptothe torazols (especially 11-phenyl-2-mercaptote torazole); menolecapto pyrimidines; mercapto Triazines; thioketo compounds such as oxadrinthion; azaindenes, such as triazaindenes, tetraazaindenes (especially
  • the compounds described in U.S. Pat. Nos. 3,954,474, 3,982,947, and JP-B-5-286660 can be used. it can.
  • One of the preferred compounds is the compound described in JP-A-63-121932.
  • the anti-friction agent and stabilizer are used before particle formation, during particle formation, after particle formation, in the washing step, during dispersion after water washing, before chemical sensitization, during chemical sensitization, after chemical sensitization, and before coating. It can be added at various times according to the purpose.
  • These anti-capri agents or stabilizers are added during emulsion preparation to exhibit the original anti-fogging and stabilizing effects, and also reduce the particle size for various purposes, such as controlling the crystal wall of the particles. It can be used to reduce particle solubility, control chemical sensitization, and control dye alignment.
  • the silver halide emulsion used in the present invention may be spectrally sensitized by methine dyes or the like.
  • Dyes used include cyanine dye, merocyanine dye, complex cyanine dye, complex Includes merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes.
  • Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei generally used for cyanine dyes as basic heterocyclic nuclei can be applied to these dyes.
  • the merocyanine dye or the complex merocyanine dye includes, as nuclei having a ketomethylene structure, pyrazolin-15-one nucleus, thiohydantoin nucleus, 2-thioxazolidin-12,4-dione nucleus, thiazolidin-12, A 5- to 6-membered heterocyclic nucleus such as 4-dione nucleus, rhodanine nucleus and thiobarbituric acid nucleus can be applied.
  • sensitizing dyes may be used alone or in combination. Combinations of sensitizing dyes are often used, particularly for the purpose of intense color sensation.
  • a representative example is U.S. Pat. No. 2,688,54. Nos. 5, 2, 977, 229, 3, 397, 060, 3, 522, 052, 3, 522, 641, 3 , 6 17, 29 3, 3, 628, 964, 3, 66,
  • a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and which exhibits supersensitization may be contained in the emulsion.
  • These dyes may be added to the emulsion at any stage in the preparation of the emulsion which has hitherto been known to be useful. Most commonly, this is done after completion of the chemical reaction and before application, but as described in U.S. Pat. Nos. 3,628,969 and 4,225,666. It can be carried out simultaneously with the sensitizer or prior to the chemical sensitization as described in JP-A-58-113, 928. It can be added before the completion of the step to start spectral sensitization. Furthermore, these compounds are added separately as taught in U.S. Pat. No.
  • the amount of the dye to be added may be 4 ⁇ 10 -6 to 8 xl0 -3 mol per mol of silver halide.
  • the light-sensitive material of the present invention only needs to have at least one of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer of a silver halide emulsion layer on a support.
  • the number and order of the silver emulsion layer and the non-photosensitive layer are not particularly limited.
  • a typical example is that the support has at least one color-sensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities.
  • a silver halide photographic light-sensitive material wherein the light-sensitive layer is a unit light-sensitive layer having color sensitivity to any one of blue light, green light, and red light;
  • the arrangement of the unit light-sensitive layers is arranged in the order of red-sensitive layer, green-sensitive layer, and blue-sensitive layer from the support side.
  • the above-mentioned order of installation may be reversed, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layers.
  • a non-light-sensitive layer such as an intermediate layer of each layer may be provided between the silver halide light-sensitive layers and as the uppermost layer and the lowermost layer.
  • Examples of the intermediate layer include those described in JP-A-61-43748, JP-A-59-1111338, JP-A-59-111340, JP-A-61-20037, and JP-A-61-120038. And a DIR compound as described in (1), and may contain a color mixing inhibitor as usually used.
  • the plurality of silver halide emulsion layers constituting each unit light-sensitive layer are preferably a high-sensitivity emulsion layer as described in German Patent No. 1,121,470 or British Patent No. 923,045. A two-layer structure of a low-speed emulsion layer can be used.
  • a non-photosensitive layer may be provided between the halogen emulsion layers.
  • a low-sensitivity emulsion layer is provided on the side away from the support.
  • a sensitive emulsion layer may be provided on the side closer to the body.
  • the layers can be arranged in the order of blue-sensitive layer / GHZRHZGLZRLL from the side farthest from the support. Further, as described in JP-A-56-25738 and JP-A-62-63936, the blue-sensitive layers ZGL / RLZGHZRH can be arranged in this order from the farthest side from the support.
  • the upper layer is the silver halide emulsion layer with the highest sensitivity
  • the middle layer is the silver halide emulsion layer with a lower sensitivity
  • the lower layer is the silver halide emulsion layer with a lower sensitivity than the middle layer.
  • the layers may be arranged in the order of layer Z high-sensitivity emulsion layer Z low-sensitivity emulsion layer.
  • the high-speed emulsion layer, the low-speed emulsion layer, the medium-speed emulsion layer, the low-speed emulsion layer, the medium-speed emulsion layer, and the high-speed emulsion layer may be arranged in this order. Also, in the case of four or more layers, the arrangement may be changed as described above.
  • silver halide grains other than the tabular grains used in the present invention will be described.
  • Preferred silver halides contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention include silver iodobromide, silver iodochloride, containing about 30 mol% or less of silver iodide. Is silver iodochlorobromide. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 10 mol% of silver iodide.
  • Silver halide grains in photographic emulsions include those having regular crystals such as cubic, octahedral, and tetrahedral, those having regular crystal forms such as spheres and plates, and those having twin planes. It may have a crystal defect or a combination thereof.
  • the silver halide may be fine grains having a grain size of about 0.2 or less or large grains having a projected area diameter of about 10 / m, and may be a polydisperse emulsion or a monodisperse emulsion.
  • Silver halide photographic emulsions usable in the present invention include, for example, Lisa Ichi * Disclosure (RD) No. 17643 (January 1978), pp. 22-23, "I. Emulsion Production” (Emu1sionpreparationndtypes and No. 187 16 (January 19, 1997)), p. 648, No. 31071 05 (January 19, 989), 863- Pp.
  • Monodisperse emulsions described in 394 and British Patent 1,413,748 are also preferred.
  • Tabular grains having an aspect ratio of about 3 or more can also be used in the present invention. Tabular grains are described in Gatoff, Photographic Science and Engineering ⁇ Engineering (Gutoff, Photographic Science and Engineering), Vol. 14, pp. 248-257 (1970). Year); U.S. Pat. Nos. 4,434,226,
  • the crystal structure of the silver halide grains used in the present invention may be uniform, may have a different halogen composition between the inside and the outside, may have a layered structure, and may have an epitaxy junction.
  • silver halides having different compositions may be joined together, or may be joined to a compound other than silver halide such as, for example, silver rhodane or lead oxide.
  • a mixture of particles of various crystal forms may be used.
  • the silver halide emulsion which can be used in the present invention is a surface latent image type in which a latent image is mainly formed on a surface, an internal latent image type in which a latent image is formed inside a grain, or a type having a latent image on both the surface and the inside. Any of Good, but must be a negative emulsion.
  • core / shell type internal latent image type emulsions described in JP-A-63-264740 may be used.
  • the method for preparing the core Z-silver type internal latent image type emulsion is described in JP-A-59-133354.
  • the thickness of the shell of this emulsion is preferably 3 to 40 DID, and more preferably 5 to 20 nm, depending on the development process and the like.
  • the silver halide emulsion used in the present invention is usually subjected to physical ripening, chemical ripening and spectral sensitization. Additives used in such a process are described in R.D.No.17643, No.18771 and No.307105, and The relevant sections are summarized in the table below.
  • the light-sensitive material of the present invention contains two or more types of emulsions having at least one characteristic different from each other in the grain size, grain size distribution, halogen composition, grain shape, and sensitivity of the photosensitive silver halide emulsion. It can be mixed and used in one layer.
  • the silver halide grains fogged inside the grains described in S52 and silver colloid are preferably used in a photosensitive silver halide emulsion layer and a substantially non-photosensitive hydrophilic colloid layer.
  • a silver halide emulsion having a fogged inside or surface is a silver halide emulsion that can be uniformly (non-imagewise) developed regardless of the unexposed and exposed portions of the photosensitive material. Say. Halogen covered inside or on the particle
  • the method for preparing silver halide grains is described in U.S. Pat. No. 4,626,498 and JP-A-59-214852.
  • the silver halide forming the inner nucleus of the core / silver-type silver halide grains whose inside is fogged may have the same halogen composition as the outer silver halide or a different halogen composition.
  • silver halide having the inside or surface of the grain fogged any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used.
  • the grain size of these fogged silver halide grains but the average grain size is 0.01 to 0.75 ⁇ 111, especially 0.05 to 0.6 / iin. Is preferred.
  • the grain shape is not particularly limited, and may be regular grains, or may be a polydisperse emulsion, but the grain size distribution is monodisperse (at least the weight or the number of silver halide grains is small). 80% having a particle diameter within ⁇ 30% of the average particle diameter).
  • Non-photosensitive fine grain silver halides are silver halide grains that are not exposed during imagewise exposure to obtain a dye image, and are not substantially developed in the development process. It is better not to do so.
  • the fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may contain silver chloride and / or silver iodide as needed. Preferably, it contains 0.5 to 10 mol% of silver iodide.
  • the fine grain silver halide has an average grain size (equivalent to a circle of the projected area). (Diameter average value) is 0.01 to 0.5; iD is preferable, and 0.02 to 2 uin is more preferable.
  • the fine grain silver halide can be prepared in the same manner as in the case of ordinary photosensitive silver halide. In this case, the surface of the silver halide grains does not need to be optically sensed, and no spectral sensitivity is required. However, prior to adding this to the coating solution, a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, or mercapto-based compound or a zinc compound is added in advance. Is preferred. Colloidal silver can be preferably contained in the fine grain silver halide grain-containing layer.
  • the coated silver amount of the light-sensitive material of the present invention is preferably at most 6. O gm 2 , and most preferably at most 4.5 g Zm.
  • the light-sensitive material of the present invention contains a mercapto compound described in U.S. Pat. Nos. 4,740,454, 4,788,132, JP-A-62-18539, and JP-A-1-283551. It is preferable to let them.
  • the photosensitive material of the present invention contains a dye dispersed or dispersed by the method described in International Publication WO88Z04794, JP-T-Hei5-1201912 or EP317, 308A. It is preferable to include the dyes described in U.S. Pat. No. 4,420,555 and JP-A-11-25935S.
  • color couplers can be used in the present invention, and specific examples thereof are RD Nos. 17643, VII-CG, and No. 307110. -G are described in the patents.
  • Yellow couplers include, for example, U.S. Pat. Nos. 3,933,501, 4,022,620, 4,326,024, and No. 4,401,752, No. 4,248,961, Japanese Patent Publication No. 58-10773, British Patent No. 1,425,020, No. Nos. 1, 476, 760; U.S. Pat.Nos. 3,973, 968; 4,314,023; 4,511,
  • magenta coupler 5-pyrazolone and pyrazoazole compounds are preferable.
  • cyan couplers examples include phenol couplers and naphthol couplers.
  • Typical examples of polymerized dye-forming couplers include, for example, U.S. Patent Nos. 3,451,820; 4,080,211; 4,367,282; 409, 320, No. 4,576,910, British Patent 2,102,137 and EP 341,188A.
  • Coupled couplers for capturing unwanted absorption of color-forming dyes are described in RD No. 17643, VII-G, RD No. 307 105, VII-G, US Pat. No. 4,163,670, The compounds described in JP-B-57-39413, U.S. Pat. Nos. 4,004,929 and 4,138,258, and British Patent 1,146,368 are preferred. Further, a coupler described in U.S. Pat. No. 4,774,181 for capturing unnecessary absorption of a coloring dye by a fluorescent dye released at the time of force ringing, and a coupler described in U.S. Pat. No. 4,777,120. It is also preferable to use a coupler having, as a leaving group, one dye precursor capable of forming a dye by reacting with a developing agent.
  • DIR couplers that release a development inhibitor include the above-mentioned patents described in RD 17643, Sections VII-F and No. 307 105, and VI I-F described in JP-A-57-151944. Nos. 57-154234, 60-184248, 63-37346, 63-37350, U.S. Pat.Nos. 4,248,962 and 4,782,012 Is preferred.
  • the bleaching accelerator releasing couplers described in RD Nos. 1 1449 and 24241 and JP-A-6-201247 are effective in shortening the time of a processing step having bleaching ability.
  • the effect is great when added to a light-sensitive material using the above-mentioned tabular silver halide grains.
  • couplers that release a nucleating agent or development accelerator in the form of an image during development include UK Patent Nos. 2,097,140, 2,131,188, and Tokukai Sho 59 — The compounds described in Nos. 1 57638 and 59-170840 are preferred. Further, by the redox reaction with an oxidized developing agent described in JP-A-60-107029, JP-A-60-252340, JP-A-1-44940 and JP-A-11-45687, for example, Also preferred are compounds that release agents, development accelerators, and silver halide solvents.
  • Other compounds that can be used in the light-sensitive material of the present invention include, for example, competitive couplers described in U.S. Pat. No. 4,130,427, for example, U.S. Pat. No. 4,283,472, No. 4,338,393 and No. 4,310,618, the multi-equivalent couplers described in, for example, JP-A-60-185950 and JP-A-62-24252.
  • DIR Redox Compound Release Coupler DIR Coupler Release Coupler, DIR Force Release Redox Compound or DIR Redox Release Redox Compound, EP 173,302 A, No. 3 No. 13,308A, couplers capable of releasing dyes that recolor after release, for example, ligand releasing couplers described in U.S. Pat. No. 4,555,477 and described in JP-A-63-75747.
  • the coupler used in the present invention can be introduced into a light-sensitive material by various known dispersion methods. Examples include the oil-in-water dispersion method and the latex dispersion method.
  • high boiling point solvent used in the oil-in-water dispersion method examples include phthalic acid esters (for example, dibutyl phthalate, dicyclohexyl phthalate).
  • esters of phosphoric acid or phosphonic acid eg, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclo
  • Hexyl phosphate tri-2-ethyl hexyl phosphate
  • tridodecyl phosphate tributoxyshethyl phosphate Trichloropropyl phosphate, di-2-ethylhexylphenylphosphonate
  • benzoates eg, 2-ethylhexylbenzoate, dodecinolebenzoate, 2-ethynolehexyl
  • An organic solvent having a temperature of not less than C and not more than about 160 ° C can be used, and typical examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, and 2-ethoxy. Shetyl acetate and dimethylformamide. Specific examples of the latex dispersing process, the effects and the latex for impregnation are described in U.S. Pat. No. 4,199,363 and West Unique Patent Application (OLS) Nos. 2,541,274 and 2nd. , 541, 230.
  • the color light-sensitive material of the present invention includes, for example, 1,2-benzisothiazoline-3 described in Funetyl alcohol, JP-A-63-257747, JP-A-62-272248, and JP-A-1-80941.
  • the light-sensitive material of the present invention can be applied to various color light-sensitive materials. Typical examples include power or negative film for general use or movie, color reversal film for slide or TV, color paper, color positive film and color reversal paper.
  • Suitable supports that can be used in the light-sensitive material of the present invention include, for example, the above-mentioned R, D. No. 17643, page 28; It is described on page 8 on the left, and on page 879 of No. 3 0 7 10 5.
  • the total thickness of all hydrophilic colloid layers on the side having the emulsion layer is preferably 2 or less.
  • the film swelling speed T 1/2 is preferably 30 seconds or less, more preferably 20 seconds or less.
  • the film thickness means a film thickness measured at 25 ° C. and a relative humidity of 55% under humidity control (2 days).
  • the film swelling rate ⁇ 1/2 can be measured according to a method known in the art. it can. For example, A. Green et al., Photographic Research ⁇ Science and Engineering (Photogr. Sci. Eng.) Vol. 19, No. 2, 124-129 It can be measured by using a serometer (swelling meter) of the type described on page.
  • T 1/2 is the saturated film thickness of 90% of the maximum swelling film thickness reached when the photosensitive material is processed at 30 ° C. for 3 minutes and 15 seconds with a color developing solution. It is defined as the time to reach 1 Z 2 of.
  • the film swelling speed ⁇ 1/2 can be adjusted by adding a hardener to gelatin as a binder or by changing the temporal conditions after coating.
  • the swelling ratio is preferably from 150 to 400%. The swelling ratio is calculated from the maximum swelling film thickness under the conditions described above according to the formula: (maximum swelling film thickness-film thickness) film thickness.
  • the light-sensitive material of the present invention preferably has a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 ⁇ ra to 20 / m on the side opposite to the side having the emulsion layer.
  • a back layer contains, for example, the aforementioned light absorbers, filter dyes, ultraviolet absorbers, antistatic agents, hardeners, binders, plasticizers, lubricants, coating aids, and surfactants. It is preferable to let them.
  • the swelling ratio of this backing layer is preferably 150 to 500%.
  • the photographic light-sensitive material according to the present invention is described in RD No. 17643, pp. 28-29, RD No. 18716, 651, left column to right column, and RD No. 307105, 880- Development can be carried out by the usual method described on page 881.
  • the color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution mainly containing an aromatic primary amine color developing agent.
  • Aminophenol compounds are also useful as the color developing agent, but p-phenylenediamine compounds are preferably used, and a typical example thereof is 3-methyl-4-amine.
  • the color developing solution may be a pH buffer such as an alkali metal carbonate, borate or phosphate, a chloride, a bromide, an iodide, a benzimidazole, or a benzothiazole. Or it usually contains a development inhibitor or an antifoggant such as a mercapto compound.
  • the color developing solution may be, if necessary, hydrazines such as hydroxylamin, getinolehydroxylamin, sulfites, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides, and thiolamine.
  • Various preservatives such as liethanolamine and catechol sulfonic acids, organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, and development acceleration such as amines Agents, dye-forming couplers, competing couplers, capture aids such as 1-phenyl-2-virazolidone Developers, viscosity enhancers, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, phosphonocarboxylic acids Various chelating agents such as ethylenediamine 4 Acid, the two-door re-opening triacetate, diethylene door Riami down pentaacetic acid, Kisanjia Mi emissions tetra-acetic acid to the city black, human Dorokishechirui Mi Bruno di vinegar Acid, 1-hydroxylethylene 1,1-diphosphonic acid, tri-N-N, N, N-trimethylenephosphonic acid, ethylene diamine N, N, N
  • This black-and-white developer may include, for example, dihydroxybenzenes such as hydroquinone, 3-virazolidones such as 1-pheninole-3-pyrazolidone, or N-methyl-p-a Known black-and-white developing agents such as aminophenols such as minophenol can be used alone or in combination.
  • the color developing solution and the black-and-white developing solution generally have a pH of 9 to 12.
  • the amount of replenishment of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per square meter of the light-sensitive material. By doing so, it can be reduced to 500 ml or less.
  • the replenishment rate is reduced, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the processing tank with air.
  • the contact area between the photographic processing solution and air in the processing tank can be represented by the aperture ratio defined below.
  • the above-mentioned aperture ratio is preferably 0.1 or less, more preferably 0.001 to 0.05.
  • a shield such as a floating lid is provided on the photographic processing liquid surface of the processing tank, and a method using a movable lid described in JP-A-1-82033,
  • the slit development method described in JP-A-63-210650 can be mentioned. Reducing the aperture ratio should be applied not only to both color development and black-and-white development, but also to all subsequent steps, such as bleaching, bleach-fixing, fixing, washing, stabilization. Is preferred.
  • the amount of trapping can be reduced.
  • the time required for color development processing is usually set to 2 to 5 minutes, and the processing time can be further reduced by using a high temperature and high pH and using a high concentration of a color developing agent.
  • the photographic emulsion layer after color development is usually bleached.
  • the bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed separately.
  • a bleach-fixing process may be performed after the bleaching process.
  • processing in a continuous bleach-fixing bath in two tanks, fixing before bleach-fixing, or bleaching after bleach-fixing can be arbitrarily performed according to the purpose.
  • the bleaching agent for example, a compound of a polyvalent metal such as iron ( ⁇ ), peracids, quinones, and nitro compounds are used.
  • Typical bleaching agents are organic complex salts of iron ( ⁇ ), for example, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexadiaminetetraacetic acid, methyliminodiacetic acid, 1,3-diamido.
  • Aminopolycarboxylic acids or citric acid such as nopropanetetraacetic acid, glycoletherdiamintetraacetic acid, Complex salts such as tartaric acid and lingic acid are mentioned.
  • the iron (II) complex salts of aminopolycarbonate such as the iron (II) complex salt of ethylenediaminetetraacetate and the iron (111) complex salt of 1,3-diaminopropanetetraacetate
  • the iron (111) complex salt of an aminopolycarboxylate is particularly useful in a bleaching solution and a bleach-fixing solution.
  • the pH of the bleaching solution or bleach-fixing solution using these aminopolycarboxylate iron (II) complex salts is usually 4.0 to 8, but it should be treated at a lower pH to speed up the processing. You can also.
  • a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and the prebath thereof, if necessary.
  • useful bleaching accelerators include, for example, U.S. Pat. No. 3,893,858, West German Patent Nos. 1,290,812, 2,059,988 and JP-A-53-988. No. 32736, No. 53-578831, No. 53-374 178, No. 53-72623, No. 53-9563, No. 53-95631, No. 53-1 04232, No. 53-1 Compounds having a mercapto group or a disulfide group described in Nos. 24424, 53-141623, 53-28426 and RD No.
  • the bleaching solution and the bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleaching stain, in addition to the above compounds.
  • organic acids are compounds having an acid dissociation constant (pKa) of 2 to 5, and specifically, acetic acid, propionic acid, and hydroxyacetic acid.
  • Examples of the fixing agent used in the fixing solution or the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas, and a large amount of iodide salts.
  • thiosulfates is common, and in particular, ammonium thiosulfate can be used most widely. It is also preferable to use a combination of a thiosulfate and a compound such as a thiocyanate, a thioether-based compound, or a thiourea.
  • Sulfites, bisulfites, carbonyl bisulfite adducts or the sulfinic acid compounds described in EP 294,769 A are preferred. Further, it is preferable to add various aminopolycarboxylic acids or organic phosphonic acids to the fixing solution or the bleach-fixing solution for the purpose of stabilizing the solution.
  • the fixing solution or the bleach-fixing solution contains a compound having a pKa of 6.0 to 9.0, preferably imidazole, 1-methylimidazole, and 1-ethylethyl for adjusting pB. It is preferable to add imidazoles such as midazole and 2-methylimidazole in an amount of 0.1 to 10 mol / liter.
  • the total time of the desilvering step in the development process is short as long as the desilvering failure does not occur.
  • the preferred time is 1 to 3 minutes, more preferably 1 to 2 minutes.
  • the processing temperature is 25 ° C to 50 ° C, preferably 35 ° C. C ⁇ 45. C. In the preferred temperature range, the desilvering rate is improved and post-processing stains are effectively prevented.
  • the stirring is strengthened as much as possible.
  • a method described in JP-A-62-183460 in which a jet of a processing solution is made to impinge on the emulsion surface of a photographic material and a method described in JP-A-62-183464 can be used.
  • There is a method of improving the effect and a method of increasing the circulation flow rate of the entire processing liquid.
  • Such means for improving agitation include bleaching solutions, bleach-fixing It is effective for both liquid and fixer. It is believed that improved agitation speeds up the supply of bleach and fixer into the emulsion film, which in turn increases the desilvering speed.
  • the means for improving the stirring is more effective when a bleaching accelerator is used, and can remarkably increase the accelerating effect or eliminate the fixing inhibiting effect of the bleaching accelerator.
  • the silver halide photographic light-sensitive material of the present invention generally undergoes a washing and / or stabilizing step after desilvering.
  • the amount of water to be washed in the washing process depends on the characteristics of the photosensitive material (for example, the material used such as a coupler), the purpose of use, and also the washing water temperature, the number of washing tanks (number of stages), for example, replenishment methods such as countercurrent and forward flow. It can be set widely according to various other conditions. Of these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is described in Journa 1 of the Society of Motion Picture and Television Enginers, Vol. 64, pp. 248-253 (1955--5). Month issue).
  • the ability to significantly reduce the amount of washing water for example, the increase in the residence time of water in the tank causes the propagation of bacteria, and the generated suspended matter adheres to the photosensitive material.
  • the method of reducing calcium ions and magnesium ions described in Japanese Patent Application Laid-Open No. 62-288,388 can be used very effectively.
  • isotizazolone compounds and siabendazoles described in JP-A-57-8,542 chlorinated bactericides such as sodium chlorinated sodium isocyanurate, and other bases.
  • the pH of the washing water in the processing of the light-sensitive material of the present invention is from 4 to 9, and preferably from 5 to 8.
  • the washing temperature and washing time can also be variously set depending on the characteristics of the photosensitive material, the application, and the like, but are generally 15 to 45.
  • the range is 20 seconds to 10 minutes at C, and preferably 30 seconds to 5 minutes at 25 to 40 ° C.
  • the light-sensitive material of the present invention can be processed directly with a stabilizing solution instead of the above-mentioned water washing. In such a stabilization treatment, all the known methods described in JP-A-57-8543, JP-A-58-14834, and JP-A-60-220345 can be applied.
  • a stabilization process may be performed after the water washing process.
  • a treatment with a stabilizing bath containing a dye stabilizer and a surfactant can be used.
  • the dye stabilizing agent include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenelenteamine and aldehyde sulfite adducts.
  • Various chelating agents and fire retardants can also be added to this stable bath.
  • the overflow solution accompanying the above-mentioned washing and replenishment of Z or the stabilizing solution can be reused in other steps such as a desilvering step.
  • the silver halide photographic light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up the processing. It is preferable to use various precursors of a color developing agent for the incorporation.
  • a color developing agent for the incorporation.
  • Base compounds aldol compounds described in JP-A-13,924, metal salt complexes described in U.S. Pat. No. 3,711,492, and urethane-based compounds described in JP-A-53-135628 can be mentioned. it can.
  • the silver halide photographic light-sensitive material of the present invention may contain, if necessary, various kinds of 11-phenyl-2-pyrazolidones for the purpose of accelerating color development.
  • Typical compounds include, for example, JP-B-56-64339, JP-B-57-144547, and No. 58-1115438.
  • the various processing solutions in the present invention are used at 10 ° C to 50 ° C. Normally, a temperature of 33 ° C to 38 ° C is standard, but higher temperatures accelerate processing and reduce processing time, and lower temperatures improve image quality and improve the stability of processing solutions. Can be achieved.
  • the light-sensitive material of the present invention can be used as a black-and-white or color photograph, a printing plate-making material, a laser recording material and a wide variety of recording materials.
  • the silver halide photographic light-sensitive material of the present invention is described in, for example, U.S. Pat. No. 4,500,626, JP-A-60-133449, JP-A-59-218443, and 61-238056. It can also be applied to the photothermographic materials described in European Patent No. 210,660 A2. BRIEF DESCRIPTION OF THE FIGURES
  • FIG. 1 is an electron micrograph of typical silver halide grains of the emulsion Em-H1 prepared in Example 13.
  • FIG. 2 is an electron micrograph of typical silver halide grains of the emulsion Em—H 2 prepared in Example 13. State
  • emulsions B, C, D, E, F and G were referred to as emulsions B, C, D, E, F and G, respectively.
  • Em-A to Em-F were subjected to a gold-sulfur sensation, which is a comparison with the present invention, as follows. Raise each emulsion to 64 Raised, ⁇ dyes shown in Table B given later - A a 7. 2 xl O_ 4 moles Z moles A g, similarly Capri inhibitor one A shown in Table B 1. O x 1 0 _4 mol mol A g, Chio sulfate Na Application Benefits um 8. 5 x 1 0 one 6 mol / mol g, chloroauric acid 1.
  • optical sensitization means performing chemical sensitization such that sensitivity after exposure for 100 seconds is highest after chemical sensitization.
  • each of Em-A to Em-F was subjected to gold-sulfur-tellurium sensation as follows.
  • the emulsion was heated to 64 ° C, before Symbol ⁇ dye one A of 7. 2 X 1 0 _ 4 mol mol A g, 1.
  • Coating samples were prepared by sequentially providing each layer having the following formulation on a triacetyl cellulose support from the support side.
  • Samples 101 to 114 were prepared using the emulsion having the above-mentioned chemical feeling applied to the emulsion layer.
  • the treated sample was concentrated and measured with a green filter.
  • H-type strongly acidic cation exchange resin Amber Light IR-120 B manufactured by Michi-Island
  • Amber Light IR-400 H-type Anion exchange resin
  • Water is passed through a mixed-bed column to adjust the calcium and magnesium ion concentrations to 3 mg / liter or less. 20 mg of sodium isocyanurate and 1.5 g of sodium sulfate were added to obtain a water washing solution.
  • the pH of this solution is in the range of 6.5-7.5.
  • Ethylenediaminetetraphosphate sodium salt 0.05 Add water to add 1.0 liter pH 5.0-8.0 The sensitivity of each sample is displayed in lux-seconds giving a concentration of 0.2 on the capri And the relative value of the reciprocal of the exposure amount. The sensitivity was evaluated by a relative value with the sensitivity of sample 101 being 100.
  • the evaluation of the pressure characteristics of each sample was performed as follows. Immediately, wrap the sample around a cylindrical rod with a diameter of 6mra0 so that the emulsion surface is on the inside, and hold it for 10 seconds. Thereafter, edge exposure was performed for 1Z100 seconds under the same exposure conditions as described above, and after performing the same development processing, the density was measured. The sensitivity was shown as a relative value where the sensitivity of the sample obtained without bending the sample 101 without bending was 100.
  • Table 1 below shows the results of each evaluation for Samples 101 to 114.
  • the tellurium-sensitive method according to the present invention can provide an emulsion having high sensitivity and excellent granularity.
  • Em-A, C, F and G prepared in Example 1 were subjected to a gold-sulfur sensation as a comparison of the present invention as follows.
  • the emulsion temperature was raised to 68, the ⁇ dye one B shown in Table C given later 1.
  • 4 X 1 0 _4 mol / mol A g the same ⁇ dye one C 4.
  • 1 X 1 0 one 5 Molar Z mole Ag same dye
  • 6.lxl CT 4 mole Z mole Ag, antifoggant A A 1.2 x 10 — 4 mole / mole Ag, sodium thiosulfate Li um 8.
  • 1 X 1 0 _6 mol / mol g salt gold acid 1.
  • Em-A, C, F and G were sensitized with gold-sulfur-tellurium as follows.
  • the temperature of the emulsion was raised to 68 ° C, and 4.2 x 10 _4 mol / mol Ag of the color sensitive element B and 4 x 10- 4 mol Z moles A g, a sensitizing dye one D 2. 3
  • each layer having the composition shown below was applied in multiple layers to prepare a sample 201 as a multilayer color photosensitive material.
  • the number corresponding to each component indicates a coating amount represented in GZm 2 units, the silver halide, the coating amount is shown in terms of silver. However, for the sensitizing dye, the coating amount is shown in mol units per mol of silver halide in the same layer.
  • Emulsion I silver 0.30 Emulsion ⁇ silver 0 20 ⁇ Sensitive dye I 6.5 1 0 -5 Sensitizing dye 11 18 X 0 ⁇ 5 ⁇ Sensitive dye III 27 X 0 • 4 • EX-20.
  • Emulsion I silver 0.5 Emulsion II silver 0.5 Sensitizing dye IV 3.0 X 0 -5 Sensitizing dye V 0 X 0 Sensitizing dye V 13.8 X 10
  • Emulsion I Silver 0.080 Emulsion ⁇ Silver 0.07 0 Emulsion V Silver 0.07 0 ⁇ Sensitive dye ⁇ 3.5 X 10 -4
  • Emulsion VI Silver 0.4 ⁇ Dye VII 2, 1 X 10 -4
  • HBS-10.0 50 Gelatin 0.78 3rd layer (3rd blue emulsion layer)
  • Samples using Em-2 to Em-8 instead of Em-1 in Sample 201 were referred to as Samples 202 to 208, respectively.
  • the amount of the bleach-fix solution brought into the washing step in the above processing was 2 ml per lm of a 35-width photosensitive material.
  • composition of the processing solution used for each processing is shown below.
  • Ammonia bromide 84.0 1 2 0 0 Ammonia nitrate 17.5 2 50 Ammonia water (27%) 1 0.08 Acetic acid (98%) 51. 173.0 Water added] 0 liter. 0 liter H 4.3.3.4
  • H-type strongly acidic cation exchange resin (Amberlight IR-120B manufactured by Mouth Haus Co., Ltd.) and 0 H-type strongly basic anion exchange resin (Amberlite IRA-400).
  • Water is passed through a mixed-bed column to treat the calcium and magnesium concentrations to 3 mgZ liter or less, and then this solution is added to sodium diisosocyanurate 2 OmgZ liter and sodium sulfate. 150 m / liter was added. The pH of this solution was in the range of 6, 5-7.5.
  • This sensitivity was evaluated by a relative value with the sensitivity of Sample 201 being 100.
  • the granularity and pressure characteristics of each sample were evaluated in the same manner as in Example 1.
  • the granularity is shown as a relative value when the granularity of sample 201 is 100.
  • the sensitivity is the sensitivity of sample 201 without bending.
  • Gelatin 1 0. 5 g was stirred maintaining the B r 3. solution 1 00 OML containing O g to 58 e C.
  • Aqueous silver nitrate solution (A g N 0 3 8 2 s) and an aqueous halide solution (KB r 5. 7 g. KI 0. 2 8 g) was added via double jet over 1 minute.
  • the temperature was raised to 75 ° C. It was added over silver nitrate aqueous solution (A gN 0 3 136. 3 g ) and (4 KI against KB r, 2 mol% comprising) a halogen aqueous solution double jet at a flow rate pressurized Hayashi and 51 minutes.
  • the silver potential was kept at OraV with respect to the saturation electrode. Temperature was lowered to 40 ° C silver nitrate aqueous solution (A g N 0 3 28. 6 g) the KB r aqueous solution was added over double Rujini' preparative 5. 35 min. At this time, the silver potential was kept at 150 nV with respect to the saturation force Romel electrode. The resulting emulsion was desalted by flocculation method, gelatin was added, and then adjusted to pH 5.5 and pAg 8.8. Em-HI was a tabular grain emulsion having an average equivalent circle diameter of 1.14 m, an average thickness of 0.189 ra, an average aspect ratio of 5.9, and a variation coefficient of 28% equivalent circle diameter.
  • Em-H1 In the preparation of Em-H1, the same procedure was performed until the second stage aqueous silver nitrate solution was added and the temperature was lowered to 40 ° C. Aqueous silver nitrate solution (A g N0 3 3. 0 g ) and KI aqueous solution (KI 2. 5 g) was added over 5 minutes. It was then added over 5.3 5 minutes and the KB r aqueous solution double jet silver nitrate aqueous solution (A g N 0 3 25. 4 g). At this time, the silver potential was kept at 150 mV with respect to the saturation port mel electrode. After the flocculation, the procedure was performed in the same manner as in Em-H1.
  • Em-H2 was tabular grains with an average equivalent circle diameter of 1.12 m, an average thickness of 0.19 m, an average aspect ratio of 5.9, and a coefficient of variation of the equivalent circle diameter of 29%.
  • Observation of Em-Hl and H2 at liquid nitrogen temperature with a 200 kV transmission electron microscope revealed that most of Em-HI had no dislocation lines.
  • many dislocation lines were observed in the entire periphery of tabular grains in Em-H2.
  • E m—H 2 the exact average number of dislocation lines per particle cannot be counted, but more than 10 were clearly present.
  • Figures 1 and 2 show representative photographs of Em-H1 and Em-H2. It can be observed that dislocation lines are clearly present in E m -H 2, whereas no dislocation lines are introduced in E m -H 1.
  • Emulsions Em-Hl to Em-K1 were subjected to gold-sulfur sensation as follows.
  • the emulsion temperature was raised to 72, ⁇ dye used in Example 1 - in the presence of A, Capri inhibitor A used in Example 1 7 X 1 0 _5 mole Z mol A g and Chio sulfate Na DOO Li um 1.
  • lx 1 CT 5 mole Z moles A g chloroauric acid 1.
  • 0 X 1 0 _5 mole Z moles A g Chioshiashi oxide Li um 8.
  • 0 X 1 CT 4 mol mol A g was sequentially added to each of them to perform optimal chemical sensitization.
  • “optimal chemical sensitization” refers to chemical sensitization in which the amount of the sensitizing dye and the time are set so that the sensitivity at the time of exposure to 1 Z 100 seconds after chemical sensitization is the highest. .
  • Emulsions Em—H2 to Em—K2 were sensitized with gold / sulfur / tellurium as follows.
  • the emulsion was heated to 72 ° C, and the antifoggant A used in Example 1 was used in the presence of the dye Dye A used in Example 1 for 1 XI 0 _4 mol Z mol Ag and sodium thiosulfate Lithium 1.0 X 1 CT 5 mol Z mol Ag, chloroauric acid 1.5 _ 5 mol Z mol A g, potassium thiocyanate 2.4 X 1 CT 3 mol / mol Ag:
  • Puchirujii Sopuro Piruhosufi Nteruri de 1. subjected to 0 x 1 0 _ 5 mol Z moles a g sequentially added to each optimum chemical sensitization.
  • coating samples 301 to 316 were prepared by the method described in Example 1, and the performance was evaluated.
  • the sensitivity was shown as a relative value with the sample before bending of Sample 301 set to 100.
  • the granularity was shown as a relative value with the granularity of sample 301 being 100.
  • the pressure-sensitive property was significantly improved by the tellurium-sensitive method according to the present invention, particularly for emulsions into which dislocations were introduced. Came.
  • the present invention has a remarkable effect in providing a silver halide photographic light-sensitive material having an excellent sensitivity / granularity ratio and an improved pressure-sensitive property.
  • CH 2 CH-S0 2 CH: -CONH-CH
  • CH 2 CH-S0 2 — CH: -CONH-CH:

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Abstract

L'invention se rapporte à un matériau photographique à base d'halogénure d'argent, qui comprend au moins une couche d'émulsion d'halogénure d'argent formée sur un support et dans lequel au moins 50 % de la superficie de projection totale des particules d'halogénure d'argent contenues dans la couche d'émulsion est occupée par des particules d'aspect plat ayant un rapport longueur/largeur de trois ou plus, et les particules d'halogénure d'argent d'aspect plat sont soumises à une sensibilisation par le tellure au moyen d'au moins un agent sensibilisateur contenant du tellurure de butyldi-isopropylphosphine et à une sensibilisation chimique ultérieure.
PCT/JP1991/001731 1991-12-18 1991-12-18 Materiau photographique a base d'halogenure d'argent WO1993012460A1 (fr)

Priority Applications (3)

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DE69131105T DE69131105T2 (de) 1991-12-18 1991-12-18 Photographisches silberhalogenidmaterial
EP92901464A EP0573649B1 (fr) 1991-12-18 1991-12-18 Materiau photographique a base d'halogenure d'argent
PCT/JP1991/001731 WO1993012460A1 (fr) 1991-12-18 1991-12-18 Materiau photographique a base d'halogenure d'argent

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JP2001350236A (ja) * 2000-06-09 2001-12-21 Fuji Photo Film Co Ltd ハロゲン化銀カラー写真感光材料の処理方法

Citations (4)

* 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

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Publication number Priority date Publication date Assignee Title
US1574943A (en) * 1924-06-06 1926-03-02 Eastman Kodak Co Art of light-sensitive photographic materials
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
JP3049335B2 (ja) * 1990-05-21 2000-06-05 富士写真フイルム株式会社 ハロゲン化銀写真感光材料
JP2756520B2 (ja) * 1991-11-15 1998-05-25 富士写真フイルム株式会社 ハロゲン化銀写真感光材料

Patent Citations (4)

* 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

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP0573649A4 *

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EP0573649A1 (fr) 1993-12-15
EP0573649A4 (fr) 1994-11-02
DE69131105D1 (de) 1999-05-12
DE69131105T2 (de) 1999-08-26
EP0573649B1 (fr) 1999-04-07

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