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
  • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
• • 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
• • 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
  • G03C1/07—Substances influencing grain growth during silver salt formation
• • 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
  • G03C2001/03511—Bromide 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
  • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
  • G03C2001/03517—Chloride 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
  • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
  • G03C2001/03529—Coefficient of variation
• • 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
  • G03C2001/03535—Core-shell 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
  • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
  • G03C2001/0357—Monodisperse emulsion
• • 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
  • G03C2001/0836—Copper compounds
• • 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
  • G03C2001/0845—Iron compounds
• • 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
  • G03C2001/093—Iridium
• • 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
  • G03C2001/094—Rhodium

Definitions

• the present invention relates to a light-sensitive silver halide photographic material, and, more particularly, to a light-sensitive silver halide photographic material having excellent pressure resistance and suitable for rapid processing.
• the color images are usually formed, after imagewise exposure, by reacting an oxidized p-phenylenediamine type color developing agent with a dye image-forming coupler.
• a color reproduction process employing a subtractive color process, according to which dye images of cyan, magenta and yellow corresponding to red, green and blue are each formed in the respective light-sensitive layers.
• 1-aryl-3-pyrazolidones are particularly preferably used.
• Japanese Patent O.P.I. Publication No. 89739/1981 discloses that 1- aryl-3-pyrazolidone is added to a light-sensitive silver halide color photographic material having on a support a silver halide emulsion layer wherein the grain size percentage of silver halide grains is different by 50 % or more.
• the light-sensitive silver halide color photographic material disclosed in this publication and containing 1-aryl-3-pyrazolidone is used for intensification processing in the presence of an intensifier such as a cobalt complex salt, and, when processed as a material for usual color developing processing, the development-accelerating effect can be only achieved very insufficiently.
• an intensifier such as a cobalt complex salt
• Japanese Patent O.P.I. Publication No. 64339/1981 also discloses a method in which a 1-aryl-3-pyrazolidone of particular structure is added to a light-sensitive silver halide color photographic material
• Japanese Patent O.P.I. Publications No. 144547/1982, No. 50532/1983, No. 50533/1983, No. 50534/1983, No. 50535/1983 and No. 50536/1983 each disclose that 1-aryl-3-pyrazolidones are added to a light-sensitive silver halide color photographic material and processing is carried out in a very short developing time.
• chloride-rich silver halide emulsions have remarkably speedy developing performance as compared with silver bromide emulsions or silver iodobromide emulsions, they have low sensitivity and tend to be fogged, disadvantageously, thereby raising a great problem in putting them into practical use.
• Japanese Patent O.P.I. Publication No. 135832/1980 and British Patent No. 1,495,753 disclose a method in which a metal ion is combined with chloride-rich silver halide grains
• Japanese Patent O.P.I. Publications No. 95736/1983 and No. 222844/1985, No. 222845/1985 disclose a method in which a laminated chloride-rich silver halide emulsion provided with a layer chiefly comprising silver bromide is used
• Japanese Patent O.P.I. Publications No. 95340/1983 and No. 107531/1983 disclose a method in which a chloride-rich silver halide emulsion is combined with a sensitizing dye.
• chloride-rich silver halide emulsions have a disadvantage of poorer pressure resistance as compared with other silver bromide emulsions or silver iodobromide emulsions.
• a plasticizer such as polymer
• a method in which the ratio of silver halide to gelatin is made smaller etc.
• British Patent No. 738,618 discloses a method in which an alkylphthalate is used; British Patent No. 738,639, a method in which an alkyl ester is used; U.S. Patent No. 2,960,404, a method in which a polyhydric alcohol is used; U.S. Patent No. 3,121,060, a method in which a carboxyalkyl cellulose is used; Japanese Patent O.P.I. Publication No. 5017/1974, a method in which paraffin and a carbonate are used; and Japanese Patent Examined Publication No. 28086/1978, a method in which an alkyl acrylate and an organic acid are used.
• Japanese Patent Examined Publication No. 23248/1982 discloses a method in which a mercapto compound and a water soluble iridium compound are added at the time of forming silver halide grains
• U.S. Patent No. 3,622,318 discloses a method in which a surface-sensitized modified emulsion is used.
• the pressure resistance effect is lowered as the high sensitivity or the grain size of silver halide grains increase.
• any of the conventional techniques can achieve only insufficient effects for improving the pressure characteristic in both the dry state and wet state, and further improvement has been sought after.
• An object of the present invention is to provide a light-sensitive silver halide photographic material having excellent pressure resistance in both the dry state and the wet state, and suitable for rapid processing. Other objects of the present invention will be made apparent from the following descriptions.
• a light-sensitive silver halide photographic material having at least one light-sensitive silver halide emulsion layer on a support, by providing a light-sensitive silver halide photographic material characterized in that said at least one silver halide emulsion layer contains 10 -8 to 10 -5 mole of a metal ion per mole of silver halide, and a silver chloride-rich grain having silver chloride content of 80 to 99 mole % and having a silver bromide-rich phase.
• the silver halide grain contained in at least one silver halide emulsion layer is a silver halide grain having silver chloride content of 80 mole % to 99 mole %, and having a silver chloride-rich phase constituting the greater part of a grain and a silver bromide-rich phase locally present in the inside or the surface of said grain.
• the "locally present" herein mentioned means that the above silver halide grain, when analyzed by X-ray diffraction, show a diffraction pattern in which a peak assigned to the above silver bromide-rich phase can be clearly distinguished from a peak assigned to the silver chloride-rich phase other than the above silver bromide-rich phase.
• the silver bromide-rich phase preferably have the silver bromide composition of 70 mole % or more, and more preferably 90 mole % or more. Also, the proportion of the silver bromide-rich phase held in one silver halide grain is preferably 0.5 to 20 mole %, more preferably 1 to 10 mole %.
• the silver halide grain having the above silver bromide-rich phase as a localized phase may be of the laminated structure comprising the above silver bromide-rich phase and the above silver chloride-rich phase, or a grain in which the silver bromide-rich phase has been epitaxially grown on the crystal surface of the grain after the formation of silver halide grain comprising the silver chloride-rich phase and in such a form that the crystal surface is not entirely covered.
• the above silver bromide-rich phase may comprise two or more localized phases in one silver halide grain.
• the composition may also be discontinuously varied, or continuously varied, at the boundary between the silver bromide-rich phase and the silver chloride-rich phase.
• silver halide grain of the present invention having the localized silver bromide-rich phase may be used alone or as a mix with other silver halide grains.
• the ratio of the projected area held by the silver halide grain of the present invention to the projected area held by all the silver halide grains in a silver halide emulsion layer containing the silver halide grain of the present invention is preferably 50 % or more, and more preferably 75 % or more.
• Such a silver halide grain can be formed following, for example, the procedures disclosed in Japanese Patent O.P.I. Publications No. 162540/1984, No. 48755/1984, No. 222844/1985, No. 222845/1985, No. 136735/1985, etc.
• the silver halide grain of the present invention may have any shape.
• One of preferable examples thereof is a cube having ( 100 ⁇ face as a crystal surface.
• grains having crystal forms such as an octahedron, a tetradecahedron and a dodecahedron which can be prepared according to the procedures disclosed in the specifications of U.S. Patents No. 4,183,756, No. 4,225,666, Japanese Patent O.P.I. Publication No. 26589/1980 and Japanese Patent Examined Publication No. 42737/1980, and papers such as The Journal of Photographic Science, 21, 39 (1973).
• Grains having a twin crystal face may be also used.
• the silver halide grain of the present invention may be grains comprising a grain of a single shape, or may be grains comprising mixture of grains having various shapes.
• the grain size of the silver halide grain of the present invention is preferably in the range of 0.1 to 1.6 ⁇ m, more preferably 0.25 to 1.2 ⁇ m.
• the above grain size can be measured according to a variety of methods generally used in the present technical field. Typical methods are disclosed in Loveland, "Method of Analysis of Grain Size", A.S.T.M. Symposium on Light Microscopy, 1955, pp.94-122, or "The Theory of the Photographic Process” written by Meath and James, Macmillan Publishing Co. Inc. (1966), Chapter II.
• This grain size can be measured by using a projected area of a grain, or a diametrical approximate value thereof.
• grain size distribution can be expressed as the diameter or projection area in a considerably precise manner.
• the grain size distribution may be polydisperse or monodisperse.
• the variation coefficient is a coefficient showing the width of grain size distribution, and can be defined by the following formula:
• ri represents the grain size of each grain
• ni represents the number thereof.
• the grain size herein mentioned refers to its diameter in the case of silver halide grains having a spherical shape, or, in the case of grains having a cubic shape or a shape other than the spherical shape, the diameter determined by calculating the projected area thereof as a round image having the corresponding area.
• a metal ion is further added in amount of 10 -8 to 10 -5 mole per mole of silver halide.
• metal ion used in the present invention may be preferably used cadmium, lead, copper, zinc, rhodium, palladium, iridium, platinum, thallium, iron, etc.
• metal ions may be preferably used in the form of a metal salt or a metal complex salt.
• the amount to be added may range from 10 -8 to 10 mole per mole of silver halide as mentioned above, and optimum amount may be suitably selected within this range depending on the size, or crystal habit, of silver halide grains, and also the combination with sensitizing dyes and other additives.
• the amount less than 10 -8 can not be useful for sufficiently exhibiting the effect of the present invention, and the amount more than 10-5 may sometimes result in such an adverse influence to other photographic performances as desensitization.
• the above metal ions used in the present invention may be used at any stage of the nucleus formation, grain growth and physical ripening of the silver halide grain of the present invention, or may be added in a divided manner. These metal ions are used in the form of a metal salt or a metal complex salt, but these compounds are added by dissolving them in water or other suitable solvents.
• iridium preferred is iridium, and specific compound thereof may include iridium trichloride, iridium tetrachloride, potassium hexachloroiridate (III), potassium hexachloroiridate (IV), ammonium hexachloroiridate (III), etc.
• the silver halide grains of the present invention may be obtained by any of an acidic method, a neutral method and an ammoniacal method.
• the grains may be allowed to grow in one time or to grow after seed grains have been formed.
• the method for the formation of the seed grains and the method for the growth may be the same or different.
• the manner of reacting a soluble silver salt and a soluble halogen salt may be any of an ordinary mixing method, a reversed mixing method, a simultaneous mixing method and a combination of any of these, but preferred are grains obtained by the simultaneous mixing method.
• a manner of the simultaneous mixing method there can be also used the pAg controlled double jet method as disclosed in Japanese Patent O.P.I. Publication No. 48521/1979, etc.
• silver halide solvents such as thioether, or crystal habit- controlling agents such as compounds having the silver ion solubility product of 1 x 10-10 or less and sensitizing dyes.
• the useful sensitizing dyes that can be used in the present invention may include, for example, those disclosed in West German Patent No. 929,080, U.S. Patents No. 2,231,658, No. 2,493,748, No. 2,503,776, No. 2,519,001, No. 2,912,329, No. 3,656,959, No. 3,672,897, No. 3,694,217, 4,025,349, and No. 4,046,572, British Patent No. 1,242,588, Japanese Patent Examined Publication No. 14030/1969 and No. 24844/1977, etc.
• Typical examples of the useful sensitizing dyes may include cyanine dyes, merocyanine dyes or composite cyanine dyes as disclosed, for example, in U.S. Patents No. 1,939,201, No. 2,072,908, No. 2,739,149 and No. 2,945,763, British Patent No. 505,979, etc.
• Other typical examples of the useful sensitizing dyes may include cyanine dyes, merocyanine dyes or composite cyanine dyes as disclosed, for example, in U.S. Patents No. 2,269,234, No. 2,270,378, No. 2,442,710, No. 2,454,629 and No.2,776,280, etc.
• cyanine dyes merocyaninedyes or composite cyanine dyes as disclosed, for example, in U.S. Patents No. 2,213,995, No. 2,493,748 and No. 2,519,001, West German Patent No. 929,080, etc.
• the above nitrogen-containing heterocyclic compounds and sensitizing dyes may be dissolved in solvents of the same or different kinds, and these solvents may be mixed before the addition to a silver halide emulsion or may be added separately. When they are added separately, the order, time and interval can be determined arbitrarily depending on the purpose.
• the time at which the nitrogen-containing heterocyclic compounds and sensitizing dyes used in the present invention are added to the emulsion is particularly preferably such that they are added so as to be contained in the inside of the silver bromide-rich silver halide phase in the above outermost shell portion.
• they can be added at any time before a nucleus of a silver chloride-rich grain having a silver chloride content of 80 to 99 mole % is formed and until the silver bromide-rich silver halide phase is formed. or, alternatively, they may be added in a divided form. They may be preferably added at the time starting from the completion of the formation of the silver chloride-rich silver halide grain and ending with the formation of the silver bromide-rich silver halide phase, in other words, added to the surface of the silver chloride-rich silver halide phase.
• the silver halide grains of the present invention may be grains such that a latent image is chiefly formed on the surface thereof, or grains such that the latent image is chiefly formed in the inside thereof.
• the silver halide grains of the type in which the latent image is chiefly formed in the inside thereof are not used after silver halide grains have been formed, i.e., in the state where no chemical sensitization has been carried out, or after silver halide grains have been finally formed, in the case where the chemical sensitization is carried out in the course of the formation of silver halide grains.
• evaluations may be carried out following the method disclosed in Japanese Patent Examined Publication No. 34213/1977.
• the emulsion to be evaluated is applied on a polyethylene-coated support with a silver coating amount of 300 to 400 mg/ft 2 .
• the specimen obtained is divided into two fractions, and each of them is set in a light-intensity scale and exposed for a fixed time of 1 x 10-2 to 1 second with use of a tungsten lamp of 500 W.
• One of the specimens is developed at 18.3°C for 5 minutes in Developing Solution Y ( an "internal type” developing solution) shown below, and the other of them is developed at 20 0 C for 6 minutes in Developing Solution X (a "surface type” developing solution) shown below.
• silver halide grains wherein [maximum density after internal development/maximum density after surface development] in that occasion is 5 or less, more preferably 2 or less.
• the aforesaid silver halide emulsion containing the silver halide grain of the present invention and 10 -8 to 10 -5 mole of the above metal ion per mole of silver halide may be either one from which unnecessary soluble salts have been removed after completion of the growth of silver halide grains, or one from which they remain unremoved. When the salts are removed, they can be removed according to the method disclosed in Research Disclosure No. 17643.
• the silver halide emulsion of the present invention may be chemically sensitized according to conventional methods. Namely, a sulfur sensitization method using a compound containing sulfur capable of reacting with silver ions, and active gelatin, a selenium sensitization method using a selenium compound, a reduction sensitization method using a reducing substance, and a noble metal sensitization method using noble metal compounds such as gold and so forth can be used alone or in combination.
• sulfur sensitizer known compounds can be used.
• it may include thiosulfate, allythiocarbamide thiourea, allylisothiocyanate, cystine, p-toluenethiosulfonate, rhodanine, etc.
• sulfur sensitizers disclosed in U.S. Patents No. 1,574,944, No. 2,410,689, No. 2,278,947, No. 2,728,668, No. 3,501,313 and No. 3,656,955, German Patent No. 14 22 869, Japanese Patent O.P.I. Publications No. 24937/1981 and No. 45016/1980, etc.
• the sulfur sensitizers may be added in an amount that can effectively increase the sensitivity of an emulsion. This amount may vary in a considerably wide range depending on the various conditions such as the amount of nitrogen-containing heterocyclic compounds, pH, temperature and size of silver halide grains, but, as a standard, may be approximately 0.5 to 2.0 mg, preferably 0.7 to 1.5 mg, per mole of silver halide.
• gold compounds can be used, including any of those having the oxidation number of +1 or +3. Typical examples thereof may include chloroaurate, potassium chloroaurate, auric trichloride, potsassium auric thiocyanate, potassium iodoaurate, tetracyanoauric acid, ammonium aurothiocyanate, pyridyltrichlorogold.
• the amount of the gold sensitizer may vary dependingon the various conditions, but, as a standard, may be approximately 0.1 to 10 mg, preferably 1.5 x 10 to 4.0 x 10 mg, per mole of silver halide.
• the silver halide grains according to the present invention may be preferably subjected to chemical sensitization in the presence of a nitrogen-containing heterocyclic compound which forms a complex compound with silver.
• the heterocyclic ring may include a pyrazole ring, a pyrimidine ring, a 1,2,4-triazole ring, a 1,2,3-triazole ring, a 1,3,4-thiazole ring, 1,2,3-thiadiazole ring, a 1,2,4-thiadiazole ring, a 1,2,5-thiadiazole ring, a 1,2,3,4-tetrazole ring, a pyridazine ring, a 1,2,3-triazine ring, a 1,2,4-triazine ring, a 1,3,5-triazine ring, a ring comprising combination of two or three of these rings, for example, a triazolotriazole ring, a diazaindene ring, a triazaindene ring, a tetrazaindene ring, a pentazaindene ring, etc
• heterocyclic ring formed by condensation of a heterocyclic ring comprising a single ring with an aromatic ring, for example, a phthaladine ring, a benzimidazole ring, an indazole ring, a benzothiazole ring, etc.
• the silver halide emulsion of the present invention can be optically sensitized to a desired wavelength region by using a dye known as a sensitizing dye in the field of photography.
• the sensitizing dye may be used alone, or may be used in combination of two or more of the dye.
• a dye having itself no action of spectral sensitization, or a supersensitizing agent which is a compound substantially absorbing no visible light and capable of strengthening the sensitizing action of the sensitizing dye may be contained in the emulsion.
• the silver halide emulsion of the present invention is used as a blue-sensitive emulsion, it is preferable to carry out spectral sensitization with use of any of sensitizing dyes represented by General Formula (A) shown below.
• Z 11 and Z 12 each represent a group of atoms necessary for the formation of a benzoxazole nucleus, a naphthoxazole nucleus, a benzoselenazole nucleus, a naphthoselenazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzimidazole nucleus, a naphthoimidazole nucleus, a pyridine nucleus or a quinoline nucleus, and these heterocyclic rings may include those having a substituent.
• the substituent of the hetero rings formed by Z 11 and Z 12 may include a halogen atom, a hydroxyl group, a cyano group, an aryl group, an alkyl group, an alkoxycarbonyl group, etc., and preferable substituent among these substituents is a halogen atom, a cyano group, an aryl group, or an alkyl group or alkoxy group having 1 to 6 carbon atoms.
• Particularly preferable substituent includes a halogen atom, a cyano group, a methyl group, an ethyl group, a methoxy group or an ethoxy group.
• R 21 and R 22 each represent an alkyl group, an alkenyl group or an aryl group; preferably represent an alkyl group; more preferably represent an alkyl group substituted with a carboxyl group or a sulfo group; and most preferably represent a sulfoalkyl group having 1 to 4 carbon atoms.
• R23 is selected from a hydrogen atom, a methyl group and an ethyl group.
• X ⁇ represents an anion; and l represents 0 or 1.
• sensitizing dyes represented by General Formula (A) particularly useful dyes are sensitizing dyes represented by General Formula (A') shown below:
• Y 1 and Y 2 each represent a group of atoms necessary for the completion of a benzene ring or naphthalene ring which may have a substituent.
• the benzene ring and the naphthalene ring formed by Y and Y 2 may include those having a substituent, which substituent may preferably include a halogen atom, a hydroxyl group, a cyano group, an aryl group, an alkyl group, an alkoxy group and an alkoxycarbonyl group.
• More preferable substituent may include a halogen atom, a cyano group, an aryl group and an alkyl group or alkoxy group having 1 to 6 carbon atoms, and particularly preferable substituent may include a halogen atom, a cyano group, a methyl group, an ethyl group, a methpxy group and an ethoxy group.
• R 21 , R 22 , R 23 , X ⁇ and have the same meaning as those shown in General Formula (A).
• Z 11 and Z 12 each represent a group of atoms necessary for the formation of a benzene ring or naphthalene ring condensed to oxazoles.
• the heterocyclic nucleus to be formed may be substituted with a variety of substituents, which substituents may preferably include a halogen atom, an aryl group, an alkyl group and an alkoxy group. More preferable substituents may include a halogen atom, a phenyl group and a methoxy group, and most preferable substituents may include a phenyl group.
• Z 11 and Z 12 both represent benzene rings each condensed to an oxazole ring, and at least one of these benzene rings is substituted with a phenyl group at the 5- position thereof, or one of the benzene rings is substituted with a phenyl group at the 5-position thereof and the other benzene ring is substituted with a halogen atom at the 5-position thereof.
• R 21 and R 22 each represent an alkyl group, an alkenyl group or an aryl group, and preferably represent an alkyl group. More preferably, R 21 and R 22 each represent an alkyl group substituted with a carboxyl group or a sulfo group, most preferably a sulfoalkyl group having 1 to 4 carbon atoms, and further most preferably a sulfoethyl group.
• R 23 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and preferably represents a hydrogen atom or an ethyl group.
• X 1 ⁇ represents an anion, including, for example, anions such as halide ions of chlorine, bromine or iodine, CH 3 S0 4 and C 2 H 5 SO 4 .
• Symbol n represents 1 or 0, provided, however, that n represents 0 when the compound forms a intramolecular salt.
• the silver halide emulsion of the present invention is used as a red-sensitive emulsion, it is preferable to carry out spectral sensitization with use of any of sensitizing dyes represented by General Formula (C) or sensitizing dyes represented by General Formula (D) shown below.
• C sensitizing dyes represented by General Formula (C)
• D sensitizing dyes represented by General Formula (D) shown below.
• R represents a hydrogen atom or an alkyl group
• R I to R 4 each represent an alkyl group or an aryl group
• Z 1 , Z 2 , Z 4 and Z 5 each represent a group of atoms necessary for the formation of a benzene ring or naphthalene ring condensed to a thiazole ring or selenazole ring
• Z 3 represents a group of hydrocarbon atoms necessary for the formation of a 6-membered ring
• Z represents a sulfur atom or a selenium atom
• X ⁇ represents an anion.
• the alkyl group represented by R may include a methyl group, an ethyl group and a propyl group, and R is preferably a hydrogen atom, a methyl group or an ethyl group. Particularly preferably, it is a hydrogen atom or an ethyl group.
• R 1 , R 2r R 3 and R 4 each represent a group selected from a straight chain or branched alkyl group, which alkyl group may have a substituent (including, for example, methyl, ethyl, propyl, chloroethyl, hydroxyethyl, methoxyethyl, acetoxyethyl, caboxymethyl, carobxyethyl, ethoxycarbonylmethyl, sulfoethyl, sulfopropyl, sulfobutyl, ⁇ -hydroxy- ⁇ -sulfopropyl, sulfate propyl, aryl, benzyl, etc.), and an aryl group, which aryl group may have a substituent (including, for example, phenyl, carboxyphenyl, sulfophenyl, etc.); and the heterocyclic nucleus to be formed by Z 1 , Z 2 , Z 4 and Z 5 may have
• X represents an anion (for example Cl, Br, I, CH 3 SO 4 and C 2 H 5 SO 4 ); and l represents 1 or 2, provided, however, that l represents 1 when the compound forms an intramolecular salt.
• sensitizing dyes represented by General Formula (C) or (D) preferably used in the present invention are shown below:
• the sensitizing dyes may be added by using a method well known in the present industrial field.
• these sensitizing dyes can be added in the form of a solution obtained by dissolving them in a water soluble solvent such as pyridine, methyl alcohol, ethyl alcohol, methyl cellosolve and acetone (or a mixture of these solvents), by diluting them with water in some case, or, also in some case, by dissolving them in water. It is also advantageous to use ultrasonic vibration for dissolving them.
• a water soluble solvent such as pyridine, methyl alcohol, ethyl alcohol, methyl cellosolve and acetone (or a mixture of these solvents)
• ultrasonic vibration for dissolving them.
• the sensitizing dyes used in the present invention there can be also used a method in which a dye is dissolved in a volatile organic solvent, and the resulting solution is dispersed in a hydrophilic colloid, and then the resulting dispersion is added, as disclosed in U.S. Patent No.
• the sensitizing dyes to be contained in the silver halide emulsion of the present invention may be dissolved in solvents of the same or different kinds, and then added by mixing these solvents before addition to the silver halide emulsion, or separately. When they are added separately, the order, time and interval of the addition can be arbitrarily determined depending on the purposes. As for the time to add the sensitizing dyes used in the present invention, they may be added at any time in the course of the production of the emulsion, but preferably in the course of chemical ripening or after chemical ripening, and, more preferably, they are added in the course of chemical ripening.
• a compound known as an antifoggant or a stabilizer can be added in the course of chemical ripening and/or at the time of the completion of chemical ripening and/or after completion of chemical ripening, for the purpose of preventing fog from being generated in the course of the production, storage or photographic processing of light-sensitive materials and/or keeping stable the photographic performances.
• Z 0 represents a heterocyclic residual group
• the heterocyclic residual group represented by Z 0 in the above General Formula (I) may have a substituent, which substituent may include, for example, an alkyl group, an aryl group, an alkenyl group, a sulfamoyl group, a carbamoyl group, an acyl group, etc.
• Z 0 1 represents a group of atoms necessary for the formation of a heterocyclic ring such as an imidazoline ring, an imidazole ring, an imidazolone ring, a pyrazoline ring, a pyrazole ring, a pyrazolone ring, an oxazoline ring, an oxazole ring, an oxazolone ring, a thiazoline ring, a thiazole ring, a thiazolone ring, a selenazoline ring, a selenazole ring, a selenazolone ring, an oxadiazole ring, a thiazole ring, a triazole ring, a tetrazole ring, a benzimidazole ring, a benztriazole ring, an indazole ring, a benzoxazole ring, an benzthiazole ring, an
• the heterocyclic residual group represented by: of General Formula (I-a) may have a substituent including the same substituents as those represented by Z 0 in General Formula (I) set out above.
• mercapto heterocyclic compounds represented by General Formula (I-a) more preferred are mercapto triazole type compounds comprising a triazole ring.
• the mercapto heterocyclic compounds represented by General Formula (I) and preferably used in the present invention are disclosed, for example, in Japanese Patent Examined Publications No. 42974/1973 and No. 51666/1982, Japanese Patent O.P.I. Publication No. 102621/1973, French Patents No. 701,053, No. 701,301 and No. 1,563,019, U.S. Patent No. 3,457,078 and The Journal of Photographic Science, 19. pp.83-87.
• the mercapto heterocyclic compounds preferably used in the present invention are added in an amount widely ranging depending on the conditions for the silver halide emulsion, for example, silver chloride content, grain size, crystal form, etc., but may be added approximately in an amount of 1 x 10 -6 to 1 x 10 -2 mole, preferably 1 x -5 -3 10 to 1 x 10 , to obtain good results.
• the method for addition they may be added to the silver halide emulsion according to a method of adding ordinary photographic additives, for example, by dissolving them in water, an acidic or alkaline aqueous solution having a suitable pH value, or an organic solvent such as methanol and ethanol.
• the mercapto heterocyclic compounds preferably used in the present invention may be used alone or in combination of two or more kinds, and there may be further additionally added, without any inconvenience, other compounds known as antifoggants or stabilizers in the filed of photographic industry.
• heterocyclic compounds preferably used in the present invention can be effectively added to any of the silver halide photographic emulsion layers of the present invention and/or the other photographic constituent layers, but preferably used in the silver halide emulsion layers.
• the compounds may be preferably added in the time after completion of chemical sensitization and right before the coating of a silver halide emulsion, during which they may be added in one time or may be added in a divided form without any inconvenience.
• the light-sensitive silver halide photographic material of the present invention may include, for example, color negative films, color positive films, color photographic paper and so forth, but, in particular, the effect of the present invention can be effectively exhibited when used in the color photographic paper used for direct appreciation.
• the light-sensitive silver halide photographic material of the present invention may be for use in monochrome or multicolor.
• the light-sensitive material has usually such structure that silver halide emulsion layers containing magenta couplers, yellow couplers and cyan couplers, respectively, as couplers for photography are laminated on a support in a suitable number and order of the layers to effect subtractive color reproduction, but the number and order of the layers may be appropriately varied depending on what are important performances and what the materials are used for.
• the constitution of the silver halide emulsion layers i.e., the order of layers of a blue-sensitive silver halide emulsion layer, a green-sensitive emulsion layer and a red-sensitive emulsion layer may be arbitrarily selected, and non-light-sensitive layers other than the protective layer of the present invention (for example, an intermediate layer, a filter layer, an irradiation preventive layer, etc.) may be also in arbitrary order.
• preferable specific layer constitution is such that a yellow dye image-forming layer, a first intermediate layer, a magenta dye image-forming layer, a second intermediate layer containing an ultraviolet absorbent, a cyan dye image-forming layer, an intermediate layer containing an ultraviolet absorbent, and a protective layer are provided on a support in this sequence from the support.
• Yellow dye-forming couplers used in the present invention may preferably include known acylacetoanilide type couplers. Of these, advantageous are benzoylacetoanilide type and pivaloylacetonitrile type compounds. Specific examples of usable yellow couplers are those disclosed in British Patent No. 1,077,874, Japanese Patent Examined Publication No. 40757/1970, Japanese Patent O.P.I. Publications No.1031/1972, No. 26133/1972, No. 94432/1973, No. 87650/1975, No. 3631/1976, No. 115219/1977, No. 99433/1979, No. 133329/1979 and No. 30127/1981, U.S. Patents No. 2,875,057, No.
• Yellow dye-forming couplers used in the present invention are preferably represented by General Formula (Y) shown below:
• R 1 represents a halogen atom or an alkoxy group.
• R represents a hydrogen atom, a halogen atom, or an alkoxy group which may have a substituent.
• R 3 represents an acylamino group, alkoxy carbonyl group, alkylsulfamoyl group, arylsulfamoyl group, arylsulfonamide group, alkylureido group, arylureido group, succinimide group, alkoxy group or aryloxy group which may have a substituent.
• Z 1 represents a group eliminable through the coupling reaction with an oxidized product of a color developing agent.
• magenta dye-forming couplers the couplers represented by General Formulas (M-1) and (M-2) can be preferably used.
• Ar represents an aryl group
• R I represents a hydrogen atom or a substituent
• R 2 represent a substituent
• Y represents a group eliminable through the reaction with an oxidized product of a color developing agent
• W represents -NH-, -NHGO- (where the nitrogen atom is attached to a carbon atom in the pyrazolone ring) or -NHCONH-
• m is an integer of 1 or 2.
• Z a represent a group of non- metallic atoms necessary for the formation of a nitrogen-containing heterocyclic ring, and the ring to be formed by the Z a may have a substituent.
• X represents a hydrogen atom or a substituent eliminable through the reaction with an oxidized product of a color developing agent.
• R 1 represents a hydrogen atom or a substituent.
• the substituent represented by the above R 1 may include, for example, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an acyl group, a sulfonyl group, a sulfinyl group, a phosphonyl group, a carbamoyl group, a sulfamoyl- group, a cyano group, a spiro compound residual group, an organic hydrocabon compound residual group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, a siloxy group, an acyloxy group, a carbamoyloxy group, an amino group, an acylamino group, a sulfonamide group, an imide group, an ureido group, a sulfamoyla
• the cyan dye-forming couplers may typically include four equivalent type or two equivalent type phenol or naphthol cyan dye-forming couplers, and Specific examples are disclosed in U.S. Patents No. 2,306,410, No. 2,356,475, No. 2,362,598, No. 2,367,531, No. 2,369,929, No. 2,423,730, No. 2,474,293, No. 2,476,008, No. 2,498,466 No. 2,545,687, No. 2,728,660, No. 2,772,162, No. 2,895,826, No. 2,976,146, No. 3,002,836, No. 3,419,390, No. 3,446,622, No. 3,476,563, No. 3,737,316, No.
• Cyan dye-forming couplers preferably used may include the couplers represented by General Formula (C-1) and (C-2) shown below:
• R 1 represents an aryl group, a cycloalkyl group or a heterocyclic group.
• R 2 represents an alkyl group or a phenyl group.
• R 3 represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group.
• Z 1 represents a hydrogen atom, a halogen atom or a group eliminable through the reaction with an oxidized product of an aromatic primary amine type color developing agent.
• R 4 represents an alkyl group (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a nonyl group, etc.).
• R 5 represents an alkyl group, (for example, a methyl group, an ethyl group, etc.).
• R represents a hydrogen atom, a halogen atom (for example, fluorine, chlorine, bromine, etc.) or an alkyl group (for example, a methyl group, an ethyl group, etc.).
• Z z represents a hydrogen atom, a halogen atom or a group eliminable through the reaction with an oxidized product of an aromatic primary amine type color developing agent.
• hydrophilic compounds such as dye-forming couplers which are not required to be absorbed on the surface of silver halide crystals
• hydrophilic compounds such as dye-forming couplers which are not required to be absorbed on the surface of silver halide crystals
• a variety of methods such as a solid dispersion method, a latex dispersion method and and an oil-in-water emulsification dispersion method. This can be suitably selected depending on the chemical structure of the hydrophobic compounds such as couplers.
• an oil-in-water emulsification dispersion method a conventionally known method for dispersing hydrophobic additives such as couplers can be applied.
• the method may be carried out by dissolving the couplers in a high boiling organic solvent having a boiling point of 150°C or more optionally together with a low boiling and/or water soluble organic solvent, and carrying out emulsification dispersion in a hydrophilic binder such as an aqueous gelatin solution by use of a surface active agent and by use of a dispersing means such as a stirrer, a homogenizer, a colloid mill, a flow jet mixer, an ultrasonic device, followed by adding the dispersion to an intended hydrophilic colloid layer. There may be inserted a step of removing the dispersing solution or, at the same time of the dispersion, the low boiling organic solvent.
• a hydrophilic binder such as an aqueous gelatin solution
• a dispersing means such as a stirrer, a homogenizer, a colloid mill, a flow jet mixer, an ultrasonic device
• the high boiling solvent to be used may include organic solvents having a boiling point of 150°C or more such as phenol derivatives, phthalates, phosphates, citrates, benzoates, alkyl amides, aliphatic acid esters and trimesic acid esters which do not react with an oxidized product of a developing agent.
• the low boiling or water soluble organic solvent that can be used together with, or in place of, the high boiling solvent may include those disclosed in U.S. Patent No. 2,801,171 and No. 2,949,360.
• the low boiling and substantially water insoluble organic solvent may include ethyl acetate, propyl acetate, butyl acetate, butanol, chloroform, carbon tetrachloride, nitromethane, nitroethane, benzene, etc.
• the water soluble organic solvent may include, for example, acetone, methyl isobutyl ketone, p-ethoxyethyl acetate, methoxy glycol acetate, methanol, ethanol, acetonitrile, dioxane, dimethylformamide, dimethylsulfoxide, hexamethyl phosphoryl amide, diethylene glycol monophenyl ether, phenoxy ethanol, etc.
• the latex dispersion method may preferably include the methods disclosed, for example, in U.S. Patents No. 4,199363, No. 4,214,047, No. 4,203,716 and No. 4,247,627, Japanese Patent O.P.I. Publications No. 74538/1974, No. 59942/1976, No. 59943/1976 and No. 32552/1979, etc.
• the surface active agent used as a dispersion auxiliary may preferably include, for example, anionic surface active agents such as alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfonates, alkyl sulfuric acid esters, alkyl phosphoric acid esters, sulfosuccinic acid esters and sulfoalkyl polyoxyethylene alkyl phenyl ether; nonionic surface active agents such as steroid type saponines, alkylene oxide derivatives and glycidol derivatives; amphoteric surface active agents such as amino acids, aminoalkylsulfonic acids and alkylbetainic acids; and cationic surface active agents such as quaternary ammonium salts. Specific examples of these surface active agents are disclosed in "Handbook of Surface Active Agents", Sangyo Tosho, 1966, and "Data for Studies and Techniques on Emulsifying Agents and Emulsifying Apparat
• gelatin As a binder (or a protective colloid) for the silver halide emulsion of the present invention, it is advantageous to use gelatin, but it is also possible to use hydrophilic colloids such as gelatin derivatives, a graft polymer of gelatin with other macromolecules, proteins, sugar derivatives, cellulose derivatives and synthetic hydrophilic high molecular substances such as homopolymer or copolymer.
• hydrophilic colloids such as gelatin derivatives, a graft polymer of gelatin with other macromolecules, proteins, sugar derivatives, cellulose derivatives and synthetic hydrophilic high molecular substances such as homopolymer or copolymer.
• Photographic emulsion layers and other hydrophilic colloid layers of the light-sensitive material in which the silver halide emulsion of the present invention is used can be hardened by using one or more kinds of hardening agents that can crosslink binder (or protective colloid) molecules to enhance the film strength.
• the hardening agents can be added in such an amount that a light-sensitive material can be hardened to the extent that no hardening agent is required to be added in a processing solution. It, however, is also possible to add the hardening agent in the processing solution.
• the compound represented by General Formula (II) shown below or the compound represented by General Formula (III) shown below is preferably used as the hardening agent.
• R 1 represents a chlorine atom, a hydroxyl group, an alkyl group, an alkoxy group, an alkylthio group, a group of -OM (M is a monovalent metallic atom), a group of -NR'R" (R' and R" each represents a hydrogen atom, an alkyl group or an aryl group) or a group of -NHCOR"'(R"' represents a hydrogen atom, an alkyl group or an aryl group); R 2 represents a group having the same meaning as for the above R except that it represents a chlorine atom.
• R 3 and R 4 each represent a chlorine atom, a hydroxyl group, an alkyl group, an alkoxy group or a group of -OM (M represents a monovalent metallic atom).
• Q and Q' each represent a linking group showing -O-, -S-or -NH-;
• L represents an alkylene group or an arylene group;
• an l and m each represent 0 or 1.
• the alkyl group component in the groups mentioned as the alkyl group, the alkoxy group and the alkylthio group in General Formulas (II) and (III) may include an alkyl group having 1 to 3 carbon atoms, including, for example, a methyl group, an ethyl group, a methoxy group, an ethoxy group, a methylthio group, an ethylthio group, etc.
• the M representing a monovalent metallic atom in the group -OM represented by R 1 may include, for example, sodium, potassium, ammonium, etc.
• the alkyl group represented by R' and R" in the group -NR'R" may include an alkyl group having 1 to 3 carbon atoms, for example, a methyl group, an ethyl group, etc., and the aryl group may include a phenyl group.
• the alkyl group and the aryl group represented by R"' in the group -NHCOR"' represented by R may include the groups having the same meaning as for the alkyl group and the aryl group represented by R' and R" in the above, respectively.
• R 2 is a group having the same meaning as that for the above R 1 ' excluding a chlorine atom as mentioned above.
• the groups represented by R 3 and R 4 represent the same groups as the groups represented by the above R 1 .
• the alkylene group represented by L may include an alkylene group having 1 to 3 carbon atoms, for example, a methylene group, an ethylene group, etc.
• the arylene group may include, for example, a phenylene group.
• the compounds represented by General Formulas (II) and (III) used in the present invention may be used alone or by mixing tow or more of them, and in an amount of 0.5 to 100 mg, preferably 2 to 50 mg per 1 g of coated gelatin.
• the above compounds may be dissolved in water or alcohols such as methanol and ethanol, and then added.
• the addition may be carried out according to any of a batch system or an in-line system.
• a plasticizer can be added to the silver halide emulsion layers and/or other hydrophilic colloid layers of the light-sensitive material in which the silver halide emulsions of the present invention are used, for the purpose of enhancing flexibility.
• a dispersion (latex) of a water insoluble or hardly soluble synthetic polymer can be contained in the photographic emulsion layers and other hydrophilic colloid layers in which the silver halide emulsions of the present invention are used.
• a color fog preventive agent can be used in order to prevent color turbidity from being caused by the migration of an oxidized product or an electron migrator of a developing agent between emulsion layers (between the same color sensitive layers and/or different color sensitive layers) of the light-sensitive material of the present invention, or prevent the deterioration of sharpness or prevent overly conspicuous graininess.
• the color fog preventive agent may be contained in the emulsion layers per se, or may be contained in an intermediate layer by providing the intermediate layer between adjacent emulsion layers.
• An image stabilizing agent for preventing the deterioration of color images can be used in the color light-sensitive material in which the silver halide emulsions of the present invention are used.
• Hydrophilic colloid layer such as protective layers and intermediate layers of the light-sensitive material of the present invention may contain an ultraviolet absorbent in order to prevent the fog due to the discharge caused by static charge by friction or the like of light-sensitive materials and prevent the deterioration due to ultraviolet light.
• the light-sensitive silver halide material using the silver halide emulsion of the present invention can be provided with auxiliary layer such as a filter layer, an anti-halation layer and an ant-irradiation layer.
• auxiliary layer such as a filter layer, an anti-halation layer and an ant-irradiation layer.
• These layers and/or the emulsion layers may contain a dye that may be flowed out of the light-sensitive material, or bleached, during the development processing.
• a matte agent can be added for the purposes of decreasing the gloss of the light-sensitive material, improving the writing performance, and preventing mutual sticking of light-sensitive materials.
• a lubricant can be added to the light-sensitive material using the silver halide emulsion of the present invention, in order to decrease sliding friction.
• An antistatic agent aiming at preventing static charge can be added to the light-sensitive material using the silver halide emulsion of the present invention.
• the antistatic agent may be used in an antistatic layer provided on the side of a support at which no emulsion layer is laminated, or may be used in an emulsion layer and/or a protective colloid layer other than the emulsion layers provided on the side of a support on which emulsion layers are laminated.
• a variety of surface active agents can be used for the purpose of improving coating performance, preventing static charge, improving slidability, emulsification dispersion, preventing adhesion, and improving photographic performances (such as development acceleration, hardening and sensitization).
• the light-sensitive material using the silver halide emulsion of the present invention can be applied on flexible reflective supports made of baryta paper, paper laminated with -olefin polymers or synthetic paper; films comprising semisynthetic or synthetic high molecular compounds such as cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate and polyamide; rigid bodies such as glass, metals and ceramics; etc.
• the light-sensitive silver halide material of the present invention may be applied, as occasion calls, after having been subjected to corona discharging, ultraviolet irradiation, flame treatment and so forth, directly on the surface of the support or through interposition of one or more subbing layers for improving adhesion, antistatic performance, dimensional stability, abrasion resistance, hardness, anti-halation performance, friction characteristics and/or other characteristics of the surface of the support.
• a thickening agent may be used in order to improve the coating performance.
• Particularly useful coating method may include extrusion coating and curtain coating by which two or more layers can be simultaneously coated.
• the light-sensitive material of the present invention can be exposed by use of electromagnetic wave having the spectral region to which the emulsion layers constituting the light-sensitive material of the present invention have the sensitivity.
• a light source there can be used any known light sources including natural light (sunlight)., a tungsten lamp, a fluorescent lamp, a mercury lamp, a xenon arc lamp, a carbon arc lamp, a xenon flash lamp, a cathode ray tube flying spot, every kind of laser beams, light from a light-emitting diode, light emitted from a fluorescent substance energized by electron rays, X-rays, gamma-rays, alpha-rays, etc.
• the exposure time it is possible to make exposure, not to speak of exposure of 1 millisecond to 1 second usually used in cameras, of not more than 1 microsecond, for example, 100 microseconds to 1 microsecond by use of a cathode ray tube or a xenon arc lamp, and it is also possible to make exposure longer than 1 second. Such exposure may be carried out continuously or may be carried out intermittently.
• the light-sensitive silver halide photographic material of the present invention can form images by carrying out color development known in the art.
• the color developing agent used for a color developing solution in the present invention includes known ones widely used in the various color photographic processes. These developing agents include aminophenol type and p-phenylenediamine type derivatives. These compounds, which are more stable than in a free state, are used generally in the form of a salt, for example, in the form of a hydrochloride or a sulfate. Also, these compounds are used generally in concentration of about 0.1 to 30 g per 1 liter of a color developing solution, preferably in concentration of about 1 to 15 g per 1 liter of a color developing solution.
• the aminophenol type developing agent may include, for example, o-aminophenol, p-aminophenol, 5-amino-2- oxytoluene, 2-amino-3-oxy-toluene, 2-oxy-3-amino-1,4-dimethyl-benzene, etc.
• Most useful primary aromatic amine type color developing agent includes N,N'-dialkyl-p-phenylenediamine compound, wherein the alkyl group and the phenyl group may be substituted with any substituent.
• examples of particularly useful compounds may include N-N'-dimethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, N,N'-dimethyl-p-phenylenediamine hydrochloride, 2-amino-5-(N-ethyl-N-dodecylamino)-toluene, N-ethyl-N- ⁇ -methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, N-ethyl-N- ⁇ -hydroxyethylaminoaniline, 4-amino-3-methyl-N,N l- diethylaniline, 4-amino-N-(2-methoxyethyl
• known compounds for developing solution components can be added to the color developing solution used in the processing of the light-sensitive silver halide photographic material of the present invention.
• alkali agents such as sodium hydroxide, sodium carbonate and potassium carbonate, alkali metal sulfites, alkali metal bisulfites, alkali metal thiocyanates, alkali metal halides, benzyl alcohol, water softeners, thickening agents, etc.
• This color developing solution may have usually the pH of 7 or more, most usually about 10 to 13.
• the light-sensitive silver halide photographic material according to the present invention may contain these color developing agents in the hydrophilic colloid layer as the color developing agents per se or a precursor thereof, and can be processed in an alkaline activated bath.
• the precursor of the color developing agent is a compound capable of forming the color developing agent under an alkaline condition, and may include a Schiff base type precursor with an aromatic aldehyde derivative, a polyvalent metallic ion complex precursor, a phthalimide derivative precursor, phosphoric acid amide derivative precursor, a sugar-amine reaction product precursor and an urethane type precursor.
• These precursors of the aromatic primary amine color developing agents are disclosed, for example, in U.S. Patents No. 3,342,599, No. 2,507,114, No.
• aromatic primary amine color developing agents or the precursors thereof are required to be added in an amount only by which a sufficient color can be obtained when an activated processing is carried out. This amount may considerably vary depending on the type of light-sensitive materials, but may approximately range between 0.1 mole and 5 moles, preferably 0.5 mole and 3 moles, per mole of silver halide. These color developing agents or the precursors thereof may be used alone or in combination.
• ком ⁇ онентs may be added by dissolving them in a suitable solvent such as water, methanol, ethanol and acetone, or may be added as an emulsified dispersion using a high boiling organic solvent such as dibutyl phthalate, dioctyl phthalate and tricrezyl phosphate. It is also possible to add them by impregnating a latex polymer therewith as disclosed in Research Disclosure No. 14850.
• the light-sensitive silver halide photographic material is, after color developing, subjected to bleaching and fixing.
• the bleaching may be carried out simultaneously with the fixing.
• a bleaching agent a variety of compounds can be used, particularly including polyvalent metallic compounds such as iron (III), cobalt (III) and copper (II); in particular, complex salts of these polyvalent metallic cations with organic acids, for example, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetate and N-hydroxyethyl ethylenediaminebiacetic acid; metal complex salts of malonic acid, tartaric acid, malic acid, diglycolic acid, dithioglycolic acid, and so forth; or ferricyanic acid salts, dicromates, etc., which can be used alone or in suitable combination.
• polyvalent metallic compounds such as iron (III), cobalt (III) and copper (II)
• organic acids for example, aminopolycarboxylic acids such as
• a fixing agent there may be used a soluble complexing agent that can solubilize a silver halide as a complex salt.
• This soluble complexing agent may include, for example, sodium thiosulfate, ammonium thiosulfate, potassium thiocyanate, thiourea, thioether, etc.
• stabilizing may be carried out as a substitute for the washing, or both of them may be used in combination.
• a stabilizing solution used in the stabilizing may contain a pH regulator, a chelating agent, an antifungal agent and so forth. Specific conditions for these processings are available by making reference to Japanese Patent O.P.I. Publication No. 134636/1983.
• the present invention can provide a light-sensitive silver halide photographic material having goodness in sensitivity and fog, excellent in pressure resistance in both the dry state and the wet state, and feasible for rapid processing.
• an aqueous solution containing potassium chloride and potassium bromide and an aqueous solution of silver nitrate were simultaneously mixed in an aqueous solution of inert gelatin, at 50°C over a period of 60 minutes with vigorous stirring to obtain a silver chloride-rich emulsion containing 2 mole % of silver bromide.
• Characteristics fo the resulting silver chloride-rich emulsion were measured according to the method described in the foregoing to reveal that it comprised silver chloride-rich grains having an average grain size of 0.8 ⁇ m and a variation coefficient of 0.10. The ratio of maximum density (internal development/surface development) was further measured according to the method described above to find that it was 1.2. Subsequently, precipitation washing was carried out, and thereafter sodium thiosulfate was added to this silver chloride-rich grains to carry out chemical sensitization. At the stage of completion of the chemical sensitization, a blue-sensitive sensitizing dye represented by the aforesaid exemplary compound A-23 and a stabilizer were added thereto to prepare a blue-sensitive silver chloride-rich emulsion.
• a silver chloride-rich emulsion comprising grains having an average grain size of 0.8 ⁇ m, a variation coefficient of 0.1 and a maximum density ratio of 1.3 was prepared in the same manner as that for Emulsion A except that 2 x 10 -6 mole of K 2 IrCl 6 per mole of silver halide was added 30 minutes after start of the addition of the aqueous solution containing potassium chloride and potassium bromide and the aqueous solution of silver nitrate.
• An aqueous solution containing potassium bromide and potassium chloride and an aqueous solution of silver nitrate were simultaneously mixed in an aqueous solution of inert gelatin, at 70°C over a period of 120 minutes with vigorous stirring while controlling pAg to 6 to obtain a silver chlorobromide emulsion containing 90 mole % of silver bromide and comprising grains having an average grain size of 0.8 pm, a variation coefficient of 0.11 and a maximum density ratio of 1.0.
• a blue-sensitive silver bromide emulsion was also prepared in the same manner as that for Emulsion A.
• aqueous solution containing potassium bromide and potassium chloride and an aqueous solution of silver nitrate were simultaneously added to an aqueous solution of inert gelatin, at 50 0 C with vigorous stirring while controlling pAg to 6. Subsequently, an aqueous solution of potassium bromide and an aqueous solution of silver nitrate were further added simultaneously. Pouring time was 60 minutes. By these procedures, obtained was a silver chloride-rich emulsion comprising grains whose outermost layer is constituted of a silver bromide phase, and containing 2 mole % of silver bromide.
• the emulsion thus obtained comprised grains having an average grain size of 0.8 ⁇ m, a variation coefficient of 0.10 and a maximum density ratio of 1.2.
• a blue-sensitive silver chloride-rich emulsion was also prepared in the same manner as that for Emulsion A.
• a blue-sensitive silver chloride-rich emulsion comprising grains having an average grain size of 0.8 pm, a variation coefficient of 0.10 and a maximum density ratio of 1.5 was prepared in the same manner as that for Emulsion D except that 2 x 10 -6 mole of K 2 IrCl 6 per mole of silver halide was added 30 minutes after start of the addition of the aqueous solution containing potassium bromide and potassium chloride and the aqueous solution of silver nitrate.
• Emulsion E was analyzed according to X-ray diffraction to reveal that the peak assigned to the silver bromide-rich phase showed a diffraction pattern clearly distinguishable from the peak assigned to the silver chloride-rich phase other than the silver bromide-rich phase.
• yellow coupler 80 g of yellow coupler were dissolved in a mixed solution comprising 30 g of dinonyl terephthalate as a high boiling organic solvent and 100 ml of ethyl acetate as a low boiling organic solvent.
• a mixed solution comprising 30 g of dinonyl terephthalate as a high boiling organic solvent and 100 ml of ethyl acetate as a low boiling organic solvent.
• 300 ml of an aqueous 5 % gelatin solution containing sodium dodecylbenzenesulfonate were added, and thereafter the mixture was dispersed by using an ultrasonic homogenizer to prepare a yellow coupler dispersion.
• a ball-point needle of 0.1 mm in ball diameter was vertically stood on end on the surface of a sample and parallelly moved on the surface at a speed of 1 cm/sec while simultaneously applying a load to the ball-point needle.
• ⁇ DD (Density at pressure-applied portion) - (Density at no pressure-applied portion)
• Table 1 tells the following: It is seen from Samples No. 1 and No. 3 that the silver chloride-rich emulsion shows very poor pressure resistance as compared with the silver bromide-rich emulsion. It is also seen from Samples No. 2 and No. 4 that a combination of the silver chloride-rich grains and the metal ion, or the emulsion of the present invention but containing no metal ion, shows little improvement in the pressure resistance. In contrast thereto, however, Sample No. 5 constituted according to the present invention shows improved pressure resistance, achieving the object of the invention.
• Emulsion F Same as Emulsion E except that this contains 5 x 10 -6 mole of cadmium per mole of silver halide.
• Emulsion G Same as Emulsion E except that this contains 5 x 10 -6 mole of rhodium per mole of silver halide.
• Emulsion H Same as Emulsion E except that this is a silver chloride-rich emulsion whose outermost layer comprises a silver chlorobromide phase containing 80 mole % of silver bromide, and containing 5 mole of silver bromide.
• Samples No. 31 and No. 32 which are in accordance with the constitution of the present invention show excellent pressure resistance similar to Examples 1 and 2 even when multi-layered. It is also seen from Sample 31 that the mercapto compound preferably used in the present invention can improve the pressure resistance when additionally used in the constitution of the present invention, to bring about desirable results.
• An aqueous solution of silver nitrate and an aqueous solution containing the compound represented by 1-19 and sodium chloride were mixed with vigorous stirring in an aqueous solution of inert gelatin at a temperature of 45°C, controlling pAg to 7.0, over a period of 60 minutes according to a double jet method, provided that an aqueous solution containing 1 x 10 mole of K 2 IrCl 6 per mole of silver halide was added 30 minutes after initiation of the addition, and, right before completion of the addition, a 0.1 % methanol solution of the sensitizing dye represented by A-23 was added.
• aqueous solution of silver nitrate and an aqueous solution of potassium bromide were further added simultaneously.
• a silver chloride-rich emulsion containing 1 mole % of silver bromide and having an outermost layer comprising a silver bromide phase.
• the resulting emulsion was comprised of grains having an average grain size of 0.7 um and a variation coefficient of 0.09, and, as a result of analysis by X-ray diffraction, the peak assigned to the silver bromide-rich phase showed a diffraction pattern clearly distinguishable from the peak assigned to the silver chloride-rich phase other than the silver bromide-rich phase.
• Emulsion G and Emulsion H were prepared, provided that the compound B-4 was used in place of A-23 as for Emulsion G, having an average grain size of 0.4 ⁇ m, and the compound C-9 was used in place of A-23 as for Emulsion F, having an average grain size of 0.45 um.
• the constitution of the present invention has made it possible to provide a light-sensitive silver halide photographic material for use in rapid processing, having excellent pressure resistance in both the dry state and the wet state as aimed in the present invention.

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• 1986
  • 1986-04-26 JP JP61097506A patent/JPH0711681B2/ja not_active Expired - Fee Related
• 1987
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