WO2004046813A1 - Materiau photosensible aux couleurs a base d'halogenure d'argent - Google Patents

Materiau photosensible aux couleurs a base d'halogenure d'argent Download PDF

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Publication number
WO2004046813A1
WO2004046813A1 PCT/JP2002/012110 JP0212110W WO2004046813A1 WO 2004046813 A1 WO2004046813 A1 WO 2004046813A1 JP 0212110 W JP0212110 W JP 0212110W WO 2004046813 A1 WO2004046813 A1 WO 2004046813A1
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WIPO (PCT)
Prior art keywords
silver halide
emulsion
silver
halide emulsion
tabular
Prior art date
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Ceased
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PCT/JP2002/012110
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English (en)
Japanese (ja)
Inventor
Hiroshi Takada
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Konica Minolta Inc
Konica Minolta Photo Imaging Inc
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Konica Minolta Inc
Konica Minolta Photo Imaging Inc
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Priority to PCT/JP2002/012110 priority Critical patent/WO2004046813A1/fr
Priority to CNA028299116A priority patent/CN1695086A/zh
Publication of WO2004046813A1 publication Critical patent/WO2004046813A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/3022—Materials with specific emulsion characteristics, e.g. thickness of the layers, silver content, shape of AgX grains
    • 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
    • G03C2001/0055—Aspect ratio of tabular grains in general; High aspect ratio; Intermediate aspect ratio; Low aspect ratio
    • 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
    • G03C2001/0056—Disclocations
    • 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
    • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
    • G03C2001/03558—Iodide content
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/09—Noble metals or mercury; Salts or compounds thereof; Sulfur, selenium or tellurium, or compounds thereof, e.g. for chemical sensitising
    • G03C2001/097—Selenium

Definitions

  • the present invention relates to a silver halide emulsion photographic light-sensitive material using a silver halide emulsion having high sensitivity, excellent granularity, excellent latent image stability, and excellent storage stability.
  • sensitization techniques relate to the manufacturing method of silver halide emulsions, to chemical sensitivity of silver halide emulsions, to spectral sensitivity of silver halide emulsions, to silver halide emulsions.
  • Various methods are known, such as a method for designing a color photographic material and a method for developing a silver halide color photographic material.
  • the most preferable and essential method is silver halide.
  • the aim is to reduce the inefficiency of the crystal during the photosensitization process and improve the quantum efficiency.
  • emulsion a technology to improve the sensitivity / particle size ratio per silver halide grain in a silver halide emulsion (hereinafter simply referred to as emulsion) is being studied. Have been.
  • silver halide grains contained in silver halide emulsions are known to have various shapes. For example, cubic, octahedral, and tetradecahedral normal silver halide grains, tabular silver halide grains having one or more twin twin planes, non-parallel There are tetrapod-like and rod-like silver halide particles having twin planes.
  • tabular silver halide grains (hereinafter, also simply referred to as tabular grains) have a color characteristic that is relatively high in photographic sensitivity as compared with intrinsic sensitivity.
  • the silver halide photographic light-sensitive material has various advantages, such as improvement in sharpness (sharpness), scatter of light due to particles, and high-resolution images can be obtained.
  • Japanese Patent Application Laid-Open No. 6-23049 discloses an aspect ratio of 8 to 1 in which the silver iodide content in the fringe 0 region is 1.5 to 50 times that of the silver iodide content in the central region. 0 tabular grains are disclosed.
  • Japanese Patent Application Laid-Open No. 6-235988 describes a multi-structure grain comprising at least an inner shell, an intermediate shell and an outermost shell, wherein the intermediate shell has a region with a high silver iodide content of 5 to 5 regions.
  • Tabular grains having an aspect ratio of 3 to 100 are disclosed.
  • the outermost shell having a low silver iodide content and having a high silver iodide outer portion arranged outside the region having a high silver iodide content has a large particle fraction, the development of tabular grains having a high aspect ratio is high. It was not possible to solve problems such as deterioration of granularity caused by the acceleration.
  • capri is a technology that suppresses the generation of capri, and furthermore, the development of sensitization technology that minimizes capri during storage and sensitivity fluctuation. Had been rare.
  • JP-A-5-53234, JP-A-5-27360, JP-A-5-19395, and JP-A-5-17540 disclose various combinations of inhibitors. Not all problems have been solved.
  • JP-A-2-837 discloses a capri prevention agent for tabular grains and a low-light-intensity failure improving agent
  • JP-A-4-16838 discloses a capri prevention for selenium sensitization.
  • An agent is disclosed.
  • JP-A-6-19024, JP-A-6-19026, and JP-A-6-19037 disclose that a reaction-inactive chalcogen compound is effective in preventing capri.
  • capri there are two problems with capri: the final capri (absolute capri) of the silver halide emulsion itself introduced into the silver halide color photographic light-sensitive material and the progress of capri during the process of optimal chemical ripening. is there. From the viewpoint of production stability, it is preferable that the progression of capri is slow, and from the viewpoint of photographic performance, a silver halide emulsion having a low absolute value of capri is considered to be ideal, but it has not reached a level satisfying both.
  • a silver halide photosensitive material having high sensitivity and excellent force fray stability using a silver halide emulsion having a specific structure during selenium sensitization using a haptic silver halide emulsion. It has been proposed (see, for example, Patent Document 1).
  • the grain growth in the direction perpendicular to the main grain plane of the base emulsion grains was performed using the grain-to-grain distance control method.
  • a silver halide emulsion containing tabular silver silver halide particles having a specific silver halide composition distribution has been proposed (for example, Patent Document 2).
  • a silver halide color photographic material having at least one red-sensitive layer, green-sensitive layer, blue-sensitive layer and non-light-sensitive layer on a support, wherein at least one of the photosensitive layers
  • the layer contains a monodispersed silver halide emulsion having an average silver iodide content of 2.0 to 4.0 mo 1%, an average aspect ratio of 8.0 or more, and having dislocation lines.
  • the silver halide emulsion is chemically ⁇ by selenium sensitizer, and the addition amount of ⁇ Se Ren ⁇ agent, ⁇ Haguchi Gen halide emulsion per mole, at 5.
  • 0 X 1 0- 6 molar or A silver halide color photographic light-sensitive material characterized in that:
  • the addition ratio of the selenium sensitizer and the sulfur sensitizer to the silver halide emulsion is 0.6 or more.
  • the silver halide color photographic light-sensitive material of the present invention is a silver halide color photographic light-sensitive material having at least one layer of a red light-sensitive layer, a green light-sensitive layer, a blue light-sensitive layer and a non-light-sensitive layer on a support. Wherein at least one of the photosensitive layers has an average silver iodide content of 2.0 to 4.0 m 0 1%, an average aspect ratio of 8.0 or more, and has dislocation lines.
  • a monodispersed silver silver halide emulsion, the silver halide emulsion is chemically sensitized by a selenium sensitizer, and the added amount of the selenium sensitizer is: 5. it is characterized is 0 X 1 0- 6 mol or more.
  • a monodispersed silver halide milk according to the present invention having an average silver iodide content of 2.0 to 4.0 m 0 1%, an average aspect ratio of 8.0 or more, and having dislocation lines. The agent will be
  • the silver halide emulsion according to the present invention is tabular silver halide grains having an average aspect ratio of 8.0 or more (hereinafter, also simply referred to as tabular grains), and the tabular grains are crystallographically twinned. are categorized.
  • a twin is a crystal having one or more twin planes in one grain. This is described in detail in “P hotographishe K orrespondenz”, Vol. 99, p. 99, and vol. 100, p.
  • the tabular silver halide grains according to the present invention preferably have two or more twin planes parallel to each other in the grains. These twin planes are almost parallel to the plane having the largest area among the planes forming the surface of the tabular grains (called the main plane).
  • a particularly preferred embodiment according to the present invention is a case where it has two twin planes parallel to the main plane.
  • the number of silver halide particles having two twin planes parallel to the main plane is preferably at least 70%, more preferably at least 80%, particularly preferably at least 90%. preferable.
  • the tabular silver halide grains according to the present invention are silver halide grains having an aspect ratio determined by the following method of 8 or more, and preferably have an average aspect ratio of 8 to 500. And more preferably 10 to 500.
  • the aspect ratio of silver halide grains can be obtained by the following formula by determining the grain size and the grain thickness of each silver halide grain by the following method.
  • Aspect ratio particle size / particle thickness
  • the tabular silver halide grains according to the present invention are preferably tabular silver halide grains having two (11 1) main planes having two twin planes parallel to the main plane.
  • the average particle size of the tabular silver halide grains is preferably from 0:! To 50 m, more preferably from 0.1 to 20 m, and from 1.0 to 20 m. m is most preferred.
  • the average particle size is an arithmetic average of the particle size ri.
  • the grain size ri referred to here is the main size of the tabular silver halide grains. It is the diameter (projected area circle equivalent particle diameter) when the projected image viewed from the direction perpendicular to the plane is converted into a circular image of the same area.
  • the particle size ri can be obtained by photographing and printing silver halide particles with an electron microscope at a magnification of 10,000 to 70,000, and printing, and then measuring the particle diameter or the projected area on the print. Can be.
  • the average thickness of the tabular silver halide grains is preferably not more than 0.25 m, and is preferably from 0.05 to 0.20 m. Is more preferable, and it is particularly preferable that it is 0.005 to 0.10 ⁇ m.
  • the projected area and thickness of each grain for calculating the above-described silver halide grain diameter ratio can be determined by the following method.
  • a sample was prepared by coating a latex ball with a known particle size as an internal standard on a support and silver halide particles with the main plane oriented parallel to the substrate, and carbon vapor deposition was performed from a certain angle.
  • a replica sample is prepared by the normal replica method.
  • An electron micrograph of the sample is taken, and the projected area and thickness of each particle are determined using an image processing device or the like.
  • the projected area of the particle can be calculated from the projected area of the internal standard
  • the thickness of the particle can be calculated from the internal standard and the length of the shadow of the particle.
  • the tabular silver halide silver halide grains according to the present invention are characterized by being monodisperse.
  • the particle size distribution (coefficient of variation of particle size) is defined by the following equation, the particle size distribution is less than 30%. And more preferably less than 15%.
  • Particle size distribution (%) (Standard deviation of particle size / Average particle size) X 100
  • the average particle size and standard deviation shall be determined from the particle size ri defined above.
  • the silver halide emulsion according to the present invention contains an average silver iodide content of silver halide grains.
  • One of the features is that the prevalence is 2.0 to 4.0 mol%.
  • the silver iodide content of the silver halide grains can be determined by the EPMA method (ElectronProbeMicRocAna1yzer method). Specifically, a sample in which silver halide grains are well dispersed so that they do not contact each other is prepared, and irradiated with an electron beam while cooling to below 10 o ° c with liquid nitrogen. By determining the characteristic X-ray intensity of the emitted silver and iodine, the silver iodide content of each silver halide grain can be determined. In the present invention, the average silver iodide content of the silver halide grains determined for 100 or more silver halide grains by the above method is defined as the average silver iodide content.
  • the tabular silver halide silver halide grains according to the present invention has a dislocation line, and the form of the dislocation line can be appropriately selected.
  • a dislocation line that exists linearly with respect to a specific direction of the crystal orientation of the grain or a dislocation line that is bent can be selected. Further, it is present over the entire particle or only at a specific part of the particle. For example, the dislocation line exists only at the fringe portion (outer periphery) of the particle, Therefore, it is possible to select from a mode in which dislocation lines are present or a mode in which dislocation lines are concentrated near the vertex.
  • dislocation lines are preferably present at least in the fringe portions of the grains, and preferably have 10 or more dislocation lines in the fringe portion, and more preferably 20 or more. Is more preferable.
  • the dislocation lines of the silver halide grains are, for example, JF Hamilton, P hot o. S ci. Eng. 11 (1967) 57, and T. Shi hi o awa, J. Soc. P hot .S ci .J apan 35 (1972) 2 1 3 Observation can be made by a direct method using a transmission electron microscope at a low temperature. That is, the silver halide grains taken out from the silver halide emulsion so as not to apply enough pressure to generate dislocations on the grains are placed on a mesh for an electron microscope and damaged by an electron beam (such as a printout). Observe by the transmission method in a state where the sample is cooled so as to prevent bleeding.
  • the thicker the particles, the more difficult it is for the electron beam to penetrate so that a clearer observation can be obtained by using a high acceleration voltage electron microscope.
  • the number and location of dislocation lines in each particle can be known from the particle photographs obtained by such a method.
  • 50% preferably has 10 or more dislocation lines in the fringe portion, more preferably 70% or more, in terms of the number ratio of grains.
  • the number ratio of tabular silver halide grains having a fringe dislocation line is preferably 50 to 100% by number, more preferably 60 to 100% by number, and 70 to 1%. More preferably, it is 100% by number.
  • the tabular silver halide grains having dislocation lines in the fringe portion in the present invention means that there are at least 10 dislocation lines per grain near the outer periphery, near the ridgeline, or near the vertex of the tabular grains. is there.
  • the fringe part is a line segment that connects the center of the main plane of the tabular grain (the center of gravity when the main plane is regarded as a two-dimensional figure) and the vertex, observing the tabular grain perpendicular to the main plane.
  • the length of L is L, the area outside the figure connecting the points whose distance from the center is 0.50 L for each vertex is indicated.
  • a method for introducing dislocation lines into silver halide grains for example, a method of adding an aqueous solution containing iodide ions such as potassium iodide and a water-soluble silver salt solution by double jet, or silver iodide
  • a method of adding fine particles a method of adding only a solution containing iodide ions, and a method as described in JP-A-6-11781
  • a known method such as a method using an iodide ion releasing agent can be used to form a dislocation at a desired position as a source of a dislocation line.
  • a method in which an aqueous solution containing iodine and a water-soluble silver salt solution are added by double jet, a method in which silver iodide fine particles are added, and a method in which an iodide ion releasing agent is used are preferable.
  • the iodide ion releasing agent referred to in the present invention is a compound represented by the following general formula (1), which releases iodide ion by reaction with a base or a nucleophile.
  • R represents a monovalent organic group.
  • R is, for example, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group, a heterocyclic group, an acyl group, a carbamoyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyl group, It is preferably an arylsulfonyl group or a sulfamoyl group.
  • R is preferably an organic group having 30 or less carbon atoms, more preferably 20 or less, and even more preferably 10 or less.
  • R preferably has a substituent, and the substituent may be further substituted with another substituent.
  • Preferred examples of the substituent include a halide, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group, a heterocyclic group, an acyl group, an acyloxy group, a carbamoyl group, an alkyloxycarbonyl group, and an aryloxycarbonyl group.
  • iodine ion releasing agent represented by the general formula (1) include chlorides, chlorides, chlorides, chlorides, and derivatives thereof. Halogen alcohols and derivatives thereof are more preferred, and the amides substituted with a heterocyclic group are more preferred, and the most preferred example is (hydroxyacetamide) benzenesulfonate.
  • examples of the nucleophile include hydroxide ion, sulfite ion, thiosulfate ion, sulfinate, and carboxylate.
  • the nucleophile include hydroxide ion, sulfite ion, thiosulfate ion, sulfinate, and carboxylate.
  • Ammonia, amines, alcohols, ureas, thioureas, phenols, hydrazines, sulfides, hydroxamic acids, etc. can be used.
  • Thiosulfate, sulfinate, carboxylate, ammonia, and amines are preferred, and hydroxide ion and sulfite ion are more preferred.
  • the reaction temperature is preferably 8 (TC to 30 ° C, more preferably 70 ° (: to 40 ° C.
  • the p Ag immediately before the introduction of dislocation lines is 7.0 or more and 10.0 or less.
  • the amount of the iodide ion releasing agent to be added is 1 to 5 mol% based on the total amount of silver halide after completion of grain growth.
  • the pH at the time of the iodine ion releasing reaction is preferably in the range of 7.0 to 11.0, more preferably 8.0 to 10.0.
  • the amount of the nucleophile is preferably 0.25 times or more and 2.0 times or less the amount of the iodide ion releasing agent.
  • the temperature at which the fine grain emulsion containing silver iodide is added is preferably 80 ° C to 30 ° C, more preferably 7 ° C (more preferably TC to 40 ° C.
  • Fine grain emulsion containing silver iodide to be added Is preferably 1 to 5 m 0 1% based on the total amount of silver halide after completion of grain growth.
  • the silver halide emulsion according to the present invention contains at least one of a polyvalent metal atom, a polyvalent metal atom ion, a polyvalent metal atom complex and a polyvalent metal atom complex ion inside or on the surface of silver halide grains. Is preferred.
  • the polyvalent metal atom, polyvalent metal atom ion, polyvalent metal atom complex or polyvalent metal atom complex ion includes Fe, Co, Ni, Ru, Rh, Pd, Re, Os, Ir, Pt, Mg, Al, Ca, Sc, Ti, V, Cr, Mn, Cu, Zn, Ga, Ge, As, Se, Sr , Y, Mo, Zr, Nb, Cd, In, Sn, Sb, Ba, La, W, Au ⁇ Hg, Tl, Pb, Bi, Ce and U, etc.
  • Metal atoms, ions, their complexes and their salts (including complex salts) from the 3rd to 7th period (most commonly the 4th to 6th period) of the Periodic Table of Elements, and other compounds containing these At least one member selected from the group consisting of a single salt and a metal complex can be used.
  • a metal complex When a metal complex is selected, a six-coordinate complex, a five-coordinate complex, a four-coordinate complex, and a two-coordinate complex are preferable, and an octahedral six-coordinate complex and a planar four-coordinate complex are more preferable.
  • Ligands for constituting the complex CN-, CO, N0 2 - , 1, 10- Fouesnant trolley down, 2, 2 'over bipyridine, S 0 3 -, Echirenjiami down, NH 3, pyridine H 2 0, NC S—, NC O- ⁇ 0 3 ⁇ S 0 4 2 — ⁇ OH— ⁇ N 3 —, S 2 —FC 1 —, Br—, I, etc. can be used.
  • ResealcDiscslosure (hereinafter abbreviated as RD), Vol. 367, January 1994, Item 36736, provides an easy-to-understand explanation of the criteria for selecting shallow electron trapped pumps.
  • RD ResealcDiscslosure
  • M is a charged frontier orbital polyvalent metal ion, preferably Fe 2+ , Ru 2+ , 0 s 2 Co 3+ , Rh 3+ , Ir 3+ , P d 4+ or P t it is 4+;
  • L 6 represents an 6 coordination complex ligands which can be selected independent, provided that at least four ligands are Anionrigando, at least one ligand (at least three are properly preferred And optimally at least four) are more electronegative than any halide ligand; and ⁇ represents 2-, 3- or 4-.
  • at least one selected from the group consisting of a polyvalent metal atom, an ion thereof, and a complex thereof is used, but Ir, Ru, Os, Fe, Rh, Co, In, G
  • Each atom of a, Ge, (1 or? 1 :, etc., its ion and its complex are particularly preferably used.
  • the concentration of at least one selected from the group consisting of the polyvalent metal atom, its ion, its complex, and its ion used in the present invention is generally from 1 ⁇ 10 to 7 to 1 ⁇ 10- 2 mols are suitable, more preferably 1 X 10- 6 ⁇ : in the range of LX 10 one 3 moles, 2 X 10 one 6 ⁇ 1 X 10_ 4 mols is particularly preferred.
  • the silver halide emulsion according to the present invention is preferably silver bromide, silver iodobromide, or silver iodobromochloride, and particularly preferably silver iodobromide or silver iodobromochloride.
  • the silver chloride content is preferably 0 to 50 mol%, more preferably 0 to 30 mol%, and still more preferably 0 to 10 mol%.
  • Gelatin and hydrophilic colloid are mentioned as a dispersion medium which can be preferably used in the silver halide emulsion according to the present invention.
  • the gelatin usually, an alkali-treated gelatin or an acid-treated gelatin having a molecular weight of about 100,000, an oxidized gelatin, or a Bull. Soc. S ci. P hot o. Ja ano 16.
  • P30 Enzyme-treated gelatin as described in (1966) can be preferably used.
  • hydrophilic colloids include gelatin derivatives, graft polymers of gelatin and other macromolecules, proteins such as albumin and casein; hydroxyxethyl cellulose, carboxymethyl cellulose, and cell monoester sulfates.
  • Derivatives such as cellulose derivatives, sodium alginate, starch derivatives, etc .; polyvinyl alcohol, polyvinyl alcohol partial acetal, Various kinds of synthetic hydrophilic polymer materials such as mono- or copolymers such as N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, and polyvinylazole can be used. .
  • the desalting step is to wash the silver halide emulsion with water to remove soluble salts.
  • the desalting step it is possible to refer to Research Disclosure (hereinafter abbreviated as RD) No. 17643, item II, and to use inorganic salts, anionic surfactants or anionic polymers-(for example, It can be preferably carried out by a flocculation method using polystyrene sulfonic acid).
  • the desalting step is preferably performed at a time point of less than 10% by volume, more preferably at a time point of less than 5% by volume, based on the volume after the growth of the silver halide grains.
  • the silver halide emulsion according to the present invention may be reduced.
  • Reduction sensitization is carried out by adding a reducing agent to an aqueous solution of a protective colloid in which silver halide grains grow, or by adding an aqueous solution of a protective colloid in which silver halide grains grow to a low p
  • the silver halide grains can be applied by ripening or growing the grains under Ag conditions or high pH conditions of pH 7.0 or higher. These methods may be appropriately combined.
  • a jet method a double-jet method, a triple-jet method, or a method of supplying fine silver halide particles
  • PH and pAg in the liquid phase where silver halide is formed are adjusted to the growth rate of silver halide.
  • the control method can be used together.
  • the formation of silver halide grains is preferably performed under conditions close to the critical growth rate.
  • a seed emulsion can also be used.
  • the silver halide grains in the seed emulsion may have a regular crystal structure such as cubic, octahedral, or tetradecahedral, or may have a spherical or plate-like shape. It may have an irregular crystal form. In these particles, any ratio can be used for the (100) plane and the (111) plane.
  • the crystal grains may be a composite of these crystal forms, and grains of various crystal forms may be mixed, but the silver halide grains in the seed emulsion used are twin halogenated grains having twin planes. Silver grains are preferred, and twin silver halide grains having two opposed parallel twin planes are particularly preferred.
  • a silver halide solvent known in the art can be used.However, if possible, the use of the silver halide solvent during the formation of base tabular grains is not required. However, it is better to avoid it except ripening after nucleation.
  • any of the acidic method, the neutral method and the ammonia method can be used, but the acidic method or the neutral method is preferred.
  • a halide ion and a silver ion may be mixed simultaneously, or one of them may be mixed in the presence of the other.
  • halide ions and silver ions can be added sequentially or simultaneously while controlling pAg and pH in a mixing vessel.
  • the halogen composition of the silver halide grains may be changed using a conversion method. .
  • the silver halide fine particles are used.
  • the grains may be prepared in advance of the preparation of the silver halide grains according to the present invention, or may be prepared in parallel with the preparation of the silver halide grains. When the latter is prepared in parallel, as described in JP-A-11-183417, JP-A-2-44335, etc., silver halide fine particles are reacted to form silver halide grains according to the present invention. It can be manufactured by using a mixer provided separately outside the container.However, a preparation container is provided separately from the mixer, and the silver halide fine particles once prepared by the mixer are mixed with the silver halide used here. It is preferable that the particles are arbitrarily prepared so as to be suitable for the growth environment in the reaction vessel in which the particles are prepared and then supplied to the reaction vessel.
  • the silver halide emulsion according to the present invention it is preferable to carry out a concentration operation of the silver halide emulsion by an ultrafiltration method in at least a part of the growing step.
  • a concentration operation of the silver halide emulsion by an ultrafiltration method in at least a part of the growing step.
  • a dilution environment is preferable. Therefore, the ultrafiltration method is preferably applied in order to improve productivity.
  • a silver halide emulsion production facility disclosed in JP-A-10-339923 can be preferably used.
  • the present invention is characterized in that a selenium sensitizer is used in an amount of 5.0 ⁇ 10 16 mol or more per 1 mol of the silver halide emulsion, together with the silver halide emulsion having the characteristics specified in the present invention as described above. one of.
  • an unstable selenium compound which can react with silver nitrate in an aqueous solution to form a silver selenide precipitate is preferably used.
  • an unstable selenium compound which can react with silver nitrate in an aqueous solution to form a silver selenide precipitate is preferably used.
  • Useful selenium sensitizers include colloid selenium metal, isoselenosocyanates (eg, aryliselenosinate), selenoureas (eg, N, N-dimethylselenourea, N, N, N ′).
  • selenium sensitizers are selenoureas, selenoamides, and selenides. Specific examples of techniques for using these selenium sensitizers are disclosed in the following patents.
  • At least one chalcogen sensitizer together with the selenium sensitizer when chemically sensitizing a silver halide emulsion having the characteristics defined in the present invention.
  • the chalcogen ⁇ sensitizer referred to in the present invention is, in addition to the selenium sensitizer described above, It is a general term for well-known sulfur sensitizers and tellurium sensitizers.
  • a sulfur sensitizer as a chalcogen sensitizer, and it is further preferable to use a selenium sensitizer and a sulfur sensitizer.
  • sulfur sensitizer examples include thiourea derivatives such as 1,3-diphenylthiourea, triethylthiourea, 1-ethyl-3- (2-thiazolyl) thiourea, rhodanine derivatives, Preferred are dithicarbamic acids, polysulfide organic compounds, thiosulfates, and simple sulfur.
  • thiourea derivatives such as 1,3-diphenylthiourea, triethylthiourea, 1-ethyl-3- (2-thiazolyl) thiourea, rhodanine derivatives
  • dithicarbamic acids examples include dithicarbamic acids, polysulfide organic compounds, thiosulfates, and simple sulfur.
  • simple substance of sulfur ⁇ -sulfur belonging to the orthorhombic system is preferable.
  • a noble metal salt such as gold, platinum, palladium, and iridium described in RD Vol. 307, No. 307105, etc.
  • gold sensitizers include, for example, chloroauric acid, gold thiosulfate, gold thiocyanate, and the like, as well as U.S. Patent Nos. 2,597,856 and 5,049,485; And organic gold compounds disclosed in JP-A No. 5748, JP-A Nos. 1-147537, 4-70650 and the like.
  • an auxiliary agent such as thiosulfate, thiocyanate or thioether may be used. It is preferable to use a ligand in combination, and it is particularly preferable to use a thiocyanate.
  • the above-mentioned various sensitizers can be added by dissolving them in water or an organic solvent such as methanol alone or in a mixed solvent, or by mixing them in advance with a gelatin solution
  • a method disclosed in JP-A-4-14739 that is, a method of adding in the form of an emulsified dispersion of a mixed solution with an organic solvent-soluble polymer may be used.
  • JP-A-7-78685 or the like can be used.
  • the silver halide color photographic light-sensitive material of the present invention preferably has a specific photographic sensitivity of 200 or more, more preferably 200 to 5000, and 200 to 5000.
  • Particularly preferred is 3200.
  • the specific photographic sensitivity of the silver halide color photographic light-sensitive material used in the present invention is determined in accordance with a test method established in accordance with JIS K 7614-1981, which is established in accordance with the method of measuring ISO sensitivity.
  • Test conditions Perform the test in a room at a temperature of 20 ⁇ 5 and a relative humidity of 60 ⁇ 10%. Leave the photosensitive material to be tested in this state for at least 1 hour before use.
  • the illuminance change on the exposed surface is performed using an optical wedge.
  • the optical wedge used has a variation in spectral transmission density of 360 to 700 400 nm in the nm wavelength range
  • the area of less than 10% should be used within 10%, and the area of 400 nm or more should be used within 5%.
  • the exposure time is 1 / 10'0 second.
  • the concentration is expressed as L 0 g 1Q (00/0).
  • 00 is an illumination light flux for density measurement
  • ⁇ is a transmitted light flux of the measured portion.
  • the geometric conditions for density measurement are based on the fact that the illumination light flux is a parallel light flux in the normal direction, and that the total light flux transmitted as a transmitted light flux and diffused into a half space is used as a reference. Perform correction using standard density strips.
  • the emulsion film surface shall face the light receiving device side. Density measurement was performed with blue, green, and red status M densities.
  • the spectral characteristics of the light source, optical system, optical filter, and light receiving device used in the thermometer were described in Japanese Patent Application Laid-Open No. Hei 6-67350. Paragraph number [0036] Make the value described.
  • the specific photographic sensitivity is determined in the following procedure. For each of the minimum densities of blue, green, and red, the exposure amount corresponding to 0.15 higher density is expressed in lux-seconds, and is defined as HB, HO, and HR, respectively. The larger of HB and HR (lower sensitivity) is designated as HS.
  • the specific photographic sensitivity S is calculated according to the following equation.
  • RD ResealcDiSc1osure
  • Halogen composition is not uniform 993 I-1 B
  • Couplers can be used in the photosensitive layer according to the present invention, and specific examples thereof are described in the above RD. The relevant sections are described below.
  • Each of the above-mentioned additives can be added 5 by a dispersion method described in RD308119 XIV.
  • the silver halide color photographic light-sensitive material of the present invention may be provided with an auxiliary layer such as a filter layer or an intermediate layer described in the aforementioned RD 308 1 19VII-K.
  • the silver halide color photographic light-sensitive material of the present invention may have various layer constitutions such as a forward layer, a reverse layer, and a unit constitution described in RD 308 1 19VII-K10.
  • X-01 solution 1.25 mol ZL potassium bromide aqueous solution 205.7 ml
  • G-01 solution alkali-treated inert gelatin (average molecular weight 100,000) 1 20.5 g and the following surfactant A 10% by weight methanol solution containing 8.8 m 1 292 1 m 1 aqueous solution
  • Surfactant A HO (CH 2 CH 2 0) m [CH (CH 3) CH 2 0] 2.
  • the emulsion thus obtained was a tabular emulsion having a cubic equivalent average particle size of 0.27 m, an average aspect ratio of 12.0, and a variation coefficient of particle size of 14.2%. This is designated as tabular seed emulsion 1.
  • Tabular seed emulsion 1 was continuously grown according to the following procedure to prepare a tabular silver halide emulsion Em-1.
  • X-11 solution aqueous solution containing 3.45 mol / L of potassium bromide and 0,05 mol / L of potassium iodide 2059 ml
  • phase B After the formation of phase A, add the following solution I-111 and solution Z-111, adjust the pH to 9.7 with aqueous hydrating water solution, hold for 6 minutes, and then adjust the pH to 5 with acetic acid aqueous solution. 2.0, pAg was adjusted to 9.8 with an aqueous solution of bromide power. Subsequently, the following S- 12 solution and the following X- 12 solution were added while accelerating the addition flow rate (the ratio of the addition flow rate at the start to the end was about 2.2 times) to form the B phase. .
  • 1-1-1 solution Aqueous solution containing 57.7 g of sodium p-acetoamide benzene sulphonate
  • Z-11 solution Aqueous solution containing 20.0 g of sodium sulfite
  • X-12 solution 3.36 mol aqueous solution containing ZL potassium bromide and 0.14 mol / L potassium iodide 726 ml
  • the outermost phase was formed by adding the following S-13 solution and the following X-13 solution while accelerating the flow rates (the ratio of the flow rates at the start and end was about 1.4 times).
  • Em-1 a tabular silver halide emulsion, revealed that the average grain size in cubic terms was 1.0 m, the average aspect ratio was 13.3, the variation coefficient of grain size was 14%, and the average iodine of the grains was 1. Tabular grains having a silver halide content of 3.4 mol% were obtained.
  • Em-1 a tabular silver halide emulsion, has five or more dislocation lines on each side. Tabular grains were present at 82% of the total projected area.
  • a tabular silver halide emulsion was prepared in the same manner except that the following liquid X-12 'was used in place of the liquid X-12 used for forming the B phase.
  • a silver halide emulsion Em-2 was prepared.
  • Em-2 Analysis of Em-2, a tabular silver halide emulsion, revealed that the average grain size in cubic terms was 1.0 m, the average aspect ratio was 12.9, the variation coefficient of grain size was 15%, and the average iodine of the grains was Tabular grains having a silver halide content of 4.2 mol% were obtained.
  • a tabular silver halide emulsion tabular grains having 5 or more dislocation lines on each side are present at ⁇ 7% of the total projected area. confirmed.
  • a tabular silver halide emulsion Em-1 was prepared in the same manner except that the liquids I-11 and Z-11 used for the formation of the B phase were omitted. 3 was prepared.
  • Em-3 a tabular silver halide emulsion, revealed that the average particle size in terms of cubic was 1.0 m, the average aspect ratio was 12.3, the variation coefficient of the particle size was 15%, and the average particle size Tabular grains having a silver iodide content of 3.4 mol% were obtained.
  • Em-3 a tabular silver halide emulsion, does not have tabular grains having dislocation lines.
  • the average aspect ratio was A tabular silver halide emulsion Em-4 was prepared in the same manner except that the A phase, the B phase, and the p Ag at the time of forming the outermost layer were appropriately adjusted so as to obtain 6.8.
  • Some of the tabular silver halide emulsion Em 1 was dissolved by heating at 55, the silver halide per mole ⁇ dye SD- 4 1. 0 X 10- 4 mole, the SD- 5 3. 5 X 10- 5 mol, SD- 6 and 6. 0 X 10 moles was added, after 20 minutes while maintaining the 55 ° C, as a chemical ⁇ agents, Chio sulfate Natoriumu pentahydrate 1. 1 X 10- 5 mol, the salt gold acid 3. 2 X 10- 5 moles and Chioshian oxide helium 3. 5 X 10- 4 mole mixture, 1Z100 seconds sensitivity were added at 2 minute intervals was ripened so as to optimize.
  • the stabilizer ST-1 was added, the temperature was lowered, and the mixture was cooled and solidified to obtain a green photosensitive emulsion G-1.
  • the details of SD-4, SD-5, SD-6 and ST-11 used in the above preparation will be described later.
  • Se triphenylphosphine selenide
  • S sodium thiosulfate pentahydrate
  • Au chloroauric acid
  • a silver halide color photographic light-sensitive material was prepared by sequentially forming each layer having the following composition from the support side on a 125-m-thick triacetyl cell orifice film support provided with an undercoat layer. 101 was produced.
  • Silver iodobromide emulsion b 0.11 Silver iodobromide emulsion d 0.17 Silver iodobromide emulsion e 0.17
  • coating aids SU-2, SU-3, dispersion aid SU-4 Viscosity modifier V-1, Stabilizer ST-1, Weight average molecular weight: 10,000 and weight average molecular weight: 100,000
  • AF-1, AF-2 polyvinylpyrrolidone
  • calcium chloride inhibitor AF-3, AF-4, AF-5, AF-6, AF-7
  • hardeners H-1, H-2 and preservative Ase-1 were added as appropriate.
  • the characteristics of each silver iodobromide emulsion other than the green photosensitive emulsion G-1 used in the preparation of Sample 101 are shown in the table below.
  • the average grain size is the diameter (average value) of a circle corresponding to the same projected area for silver iodobromide emulsions c, d, e, g, and h.
  • silver iodobromide emulsions a, b, and i Is represented by one side length (average value) of the cube.
  • the specific photographic sensitivity was 200 as a result of measurement according to the method specified in Japanese Industrial Standard JIS K7614-1981, which was established in accordance with the above-mentioned
  • the reciprocal of the exposure required to obtain a density of +0.10 from the minimum density is defined as the sensitivity, and the sample 101 The relative sensitivity was determined with the sensitivity being 100.
  • each sensitivity was measured according to the above method, and the sensitivity of reference sample 2 of each sample was set to 100, and the difference in sensitivity of forcedly degraded sample 2 to this ⁇ S ⁇ the sensitivity of reference sample 2 (1 00) —Sensitivity of forcedly degraded sample 2).
  • the constitution of the present invention relates to a silver halide color photographic light-sensitive material using a silver halide emulsion having high sensitivity, excellent granularity, excellent latent image stability, and excellent storage stability.

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  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)

Abstract

Cette invention se rapporte à un matériau photosensible aux couleurs à base d'halogénure d'argent, qui comprend une émulsion d'halogénure d'argent ayant une photosensibilité élevée, d'excellentes caractéristiques de granularité et de stabilité des images latentes et une bonne caractéristique de stabilité de conservation. Ce matériau comporte un support et, sur ce support, au moins une couche photosensible au rouge, au moins une couche photosensible au vert, au moins une couche photosensible au bleu et au moins une couche non photosensible, ce matériau se caractérisant en ce qu'au moins l'une desdites couches photosensibles contient une émulsion d'halogénure d'argent monodispersée ayant une teneur en iodure d'argent moyenne comprise entre 2,0 et 4,0 % en mole, un rapport d'aspect moyen égal ou supérieur à 8,0 et une ligne de dislocation, en ce que l'émulsion d'halogénure d'argent est sensibilisée chimiquement par un sensibilisateur au sélénium, et en ce que la quantité de sensibilisateurs au sélénium ajouté est égale ou supérieure à 5,0 x 10-6 mol par mole d'émulsion d'halogénure d'argent.
PCT/JP2002/012110 2002-11-20 2002-11-20 Materiau photosensible aux couleurs a base d'halogenure d'argent Ceased WO2004046813A1 (fr)

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CNA028299116A CN1695086A (zh) 2002-11-20 2002-11-20 卤化银彩色照相感光材料

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09179227A (ja) * 1995-12-21 1997-07-11 Konica Corp ハロゲン化銀写真乳剤及びハロゲン化銀写真感光材料
JP2001264909A (ja) * 2000-03-17 2001-09-28 Konica Corp ハロゲン化銀乳剤及びハロゲン化銀カラー写真感光材料
JP2001318443A (ja) * 2000-05-11 2001-11-16 Konica Corp ハロゲン化銀写真乳剤及びハロゲン化銀写真感光材料
JP2002072395A (ja) * 2000-08-29 2002-03-12 Fuji Photo Film Co Ltd ハロゲン化銀写真乳剤、およびこれを用いたハロゲン化銀写真感光材料
JP2002099060A (ja) * 2000-09-22 2002-04-05 Konica Corp ハロゲン化銀カラー写真感光材料
JP2002214731A (ja) * 2001-01-22 2002-07-31 Fuji Photo Film Co Ltd ハロゲン化銀写真乳剤
JP2002287282A (ja) * 2001-03-28 2002-10-03 Fuji Photo Film Co Ltd ハロゲン化銀写真感光材料

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09179227A (ja) * 1995-12-21 1997-07-11 Konica Corp ハロゲン化銀写真乳剤及びハロゲン化銀写真感光材料
JP2001264909A (ja) * 2000-03-17 2001-09-28 Konica Corp ハロゲン化銀乳剤及びハロゲン化銀カラー写真感光材料
JP2001318443A (ja) * 2000-05-11 2001-11-16 Konica Corp ハロゲン化銀写真乳剤及びハロゲン化銀写真感光材料
JP2002072395A (ja) * 2000-08-29 2002-03-12 Fuji Photo Film Co Ltd ハロゲン化銀写真乳剤、およびこれを用いたハロゲン化銀写真感光材料
JP2002099060A (ja) * 2000-09-22 2002-04-05 Konica Corp ハロゲン化銀カラー写真感光材料
JP2002214731A (ja) * 2001-01-22 2002-07-31 Fuji Photo Film Co Ltd ハロゲン化銀写真乳剤
JP2002287282A (ja) * 2001-03-28 2002-10-03 Fuji Photo Film Co Ltd ハロゲン化銀写真感光材料

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