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
  • G03C1/46—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein having more than one photosensitive layer
• • 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
  • G03C1/34—Fog-inhibitors; Stabilisers; Agents inhibiting latent image regression
  • G03C1/346—Organic derivatives of bivalent sulfur, selenium or tellurium

Definitions

• This invention relates to a silver halide light-­sensitive photographicmaterial which is high in both sensitivity and image-quality and excellent in processing stability and, more particularly, to a silver halide light-sensitive photographic material which is high in sensitivity, excellent in both relation of fogginess to sensitivity and graininess and stable in development processes.
• a monodisperse type emulsion could be advantageous for effectively achieving a high sensitivity, keeping low fogginess in the course of the so-called chemical sensiti­zation process for sensitizing a silver halide emulsion, which will be detailed later.
• a monodisperse type emulsion is extremely effective for improving quantum efficiency during a light absorption and achieving low fogginess during a chemical sensitization.
• monodisperse type emulsions themselves intrinsically have. More concretely, with narrowly grain-distributed and uniformly chemical-sensitized emulsion grains, all the latent image nuclei formed on and/or in each grain are of the order of the same size and every grain, therefore, starts to develop at the same time when the emulsion is developed.
• Japanese Patent Publication open to Public Inspection (hereinafter called Japanese Patent O.P.I. Publication) Nos. 53-99938/1978 and 59-170839/1984, and U.S. Patent Nos. 3,892,572 and 4,153,460 each describe methods in each of which a fine-grained and non-light-sensitive silver chloride emulsion is used in combination with a DIR compound. In those methods, however, not only may the desired sensitivity not be obtained, but also only the limited kinds of couplers may be contained in a light-sensitive emulsion layer subject to a high sensitization are limited.
• Japanese Patent O.P.I. Publication No. 59-160135/1984 describes a layer arrangement where a relatively non-light-­sensitive silver halide grain-containing layer is arranged adjacent to and between two light-sensitive emulsion layers having sensitivities different from each other. Also in this layer arrangement, the light-sensitive emulsion layers arranged adjacent to the non-light-sensitive silver halide grain-containing layer are limited to be of the same color-sensitivity and the fogginess cannot be inhibited from increasing satisfactorily.
• Japanese Patent O.P.I. Publication Nos. 59-180555/1984 and 60-194450/1985 each disclose techniques in which high sensitization, excellent contrast or processing stability may be achieved by combining a specific inverted layer structure with fine-grained non-light-sensitive silver halide grains. Even in those techniques, the layer arrangements are limited to some peculiar arrangements and are not satisfactory for achieving a high sensitization.
• Japanese Patent O.P.I. Publication No. 61-246739/1986 describes a method in which a high sensiti­zation may be achieved by combining core/shell type silver halide grains having a plurality of shells with non-light-­sensitive silver halide fine grains, while keeping low fogginess. This method is still unsatisfactory from the viewpoint of making high sensitivity.
• Another object of the invention is to provide a silver halide light-sensitive photographic material capable of displaying also a high processing stability in the course of development.
• a silver halide light-sensitive photographic material comprising a support having thereon a silver halide emulsion layer and a non-light-sensitive layer adjacently provided to said emulsion layer, wherein at least one of the silver halide emulsion layer and the non-light-sensitive layer contains substantially non-light-sensitive fine-grained silver halide having a silver chloride content of not less than 20 mol% and the silver halide emulsion layer contains monodisperse light-sensitive silver halide grains sub­stantially consisting of silver bromide or silver iodo­bromide.
• this invention is characterized by the following points.
• the light-sensitive emulsions relating to the invention which are used in light-sensitive emulsion layers, sub­stantially comprise silver bromide and/or silver iodobromide.
• the expression, '--- substantially comprise ---' mentioned herein, means that they are allowed to contain any silver halides other than silver bromide or silver iodobromide, such as silver chloride, provided that the other silver halide does not hinder the effects of the invention. More precisely, in the case of silver chloride, it is contained desirably in a proportion of not more than 1 mol%.
• the light-sensitive silver halide emulsions relating to the invention which are contained in light-sensitive emulsion layers, are of the monodisperse type.
• the term, 'mono­dispersive' means that the grain size distribution of the silver halide grains constituting an emulsion is not more than 20% in terms of the grain size variation coefficient.
• the variation coefficient should preferably be not more than 15%.
• such a variation coefficient is defined by the following equation:
• Such a variation coefficient is a scale for indicating the degrees of monodispersiveness.
• Light-sensitive silver halide grains to be contained in the light-sensitive emulsion layers are allowed to take any form, such as a regular crystal form, a twinned crystal form, a tabular-grain form, an octahedral form, a cubic form, a dodecahedral form, a rhombic dodecahedral form, a tetra­cosahedral form, the mixed crystal forms thereof and so forth, and those forms may be so selected as to meet an application.
• the halogen composition of the above-mentioned light-sensitive silver halide grains may be either uniform inside the grains or of the so-called core/shell type structure including the multilayered core/shell type structure having two or more shells. These grains may be prepared in well known methods. They may be of the so-called conversion type, such as those described in, for example, British Patent No. 635,841 and U.S. Patent No. 3,622,318.
• the light-sensitive emulsion contained in the above-mentioned light-sensitive emulsion layer a single kind of monodisperse type emulsion only may be used and the mixture of two or more kinds of monodisperse type emulsions may also be used.
• non-light-­sensitive silver halide fine grains having a chloride content of not less than 20 mol%, preferably, not less than 50 mol% and, more preferably, not less than 70 mol%.
• the non-­light-sensitive silver halide fine-grains are allowed to have any halogen composition such as silver chloride, silver chlorobromide, silver chloroiodobromide and so forth and, among these compositions, silver chloride and silver chlorobromide are more preferably used.
• the substantially non-light-sensitive silver halide fine grains hereinafter called simply non-light-sensitive silver halide fine grains, relating to the invention are allowed to have monodispersiveness or polydispersiveness. In order to achieve the objects of the invention more effectively, monodisperse type grains are preferably used.
• the average grains sizes of the non-light-sensitive silver halide fine grains may freely be selected to meet the requirements for an application. However, a preferable average grain size is within the range of from 0.03 ⁇ m to 0.5 ⁇ m.
• the non-light-sensitive silver halide fine grains may be used in any amount.
• these grains are used in a proportion of, preferably, from 5 to 30% by weight and, more preferably, from 5 to 25% by weight in terms of silver to the light-sensitive silver halide grains contained in the emulsion used.
• the grains are used in a proportion of, preferably, from 0.5mg to 20mg/dm2 and, more preferably, from 1mg to 10mg/dm2 in terms of the silver content of the non-light-sensitive silver halide layer.
• the non-light-sensitive silver halide fine grains relating to the invention may be used in a single kind or in the mixture of two or more kinds thereof. It is also allowed to use the different kinds of the non-light-sensitive silver halide fine grains in different layers. In addition, it is further allowed to jointly use the other non-light-sensitive silver halide fine grains than those of the invention, such as silver bromide or silver iodobromide. These non-light-­sensitive silver halide fine grains may be prepared in any of the well known methods.
• substantially non-light-sensitive ---' mentioned herein means that the grains are not substantially developed in a developer. However, the grains are allowed to have a low light-sensitivity to the extent that an image is not substantially affected by development.
• the objects of the invention can more effectively be achieved by containing at least one of the compounds represented by the following Formula A into at least one layer of the above-mentioned light-sensitive silver halide emulsion layer and the above-mentioned non-light-sensitive silver halide layer adjacently provided to the silver halide emulsion layer.
• Z represents a group consisting of atoms necessary to complete a 5- or 6-membered heterocyclic ring, provided that the atoms are selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom and a selenium atom, and that the heterocyclic ring is allowed to have a condensed carbon ring.
• the heterocyclic rings include, for example, those of pyridine, pyrimidine, imidazole, benzoimidazole, naphtho­imidazole, oxazole, benzoxazole, naphthoxazole, thiazoline, thiazole, benzothiazole, naphthothiazole, selenazole, benzoselenazole, naphthoselenazole, triazole, oxadiazole, thiadiazole, triazine, tetrazole, purine, azaindene or the like.
• heterocyclic rings may also be substituted with, for example, an aromatic group, an aliphatic group, a hydroxy group, an alkoxy group, an aryloxy group, an amino group, a nitro group, a halogen atom, carboxyl group or the salts thereof, a sulfo group or the salts thereof, a mercapto group, an alkylmercapto group, an acylamino group, a sulfamoyl group, a sulfoamino group, a carbamoyl group or the like groups.
• the compounds represented by the following Formulas B through D are particularly preferable.
• Ar represents a phenyl group, a naphthyl group or a cyclohexyl group
• R1 represents a group capable of being a substituent of the group represented by Ar or a hydrogen atom
• M is synonymous with that denoted in Formula A.
• Z′ represents a sulfur atom, an oxygen atom, a selenium atom or - -
• R2 represents a group capable of being a substituent of a benzene ring or a hydrogen atom
• M is synonymous with that denoted in Formula A.
• Z ⁇ represents a sulfur atom, an oxygen atom, a selenium atom or in which R4 represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an aralkyl group, -COR5, -SO2-R5, -NHCOR6 or -NHSO2-R6;
• R5 represents an alkyl group, an aryl group, a cycloalkyl group, an aralkyl group or -NH2;
• R6 represents an alkyl group, an aryl group, a cycloalkyl group or an aralkyl group;
• R3 represents a hydrogen atom, an alkyl group, an aryl group, a cycloalkyl group, an aralkyl group, an alkenyl group, an amino group or a heterocyclic group; and M is synonymous with that denoted in Formula A.
• the above-given compounds may be prepared in the methods described in, for example, Japanese Patent Examined Publication No. 40-28496/1965; Japanese Patent O.P.I. Publication No. 50-89034/1975; U.S. Patent No. 2,824,001; Journal of Organic Chemistry, 1965, 39, 2469; Journal of Chemical Society, 1952, 4237; or in any other methods correspondingly equivalent to the above-given methods.
• Examples of the compounds represented by Formula D are examples of the compounds represented by Formula D
• the compound is used in an amount of preferably from 1x10 ⁇ 6 mol to 3x10 ⁇ 3 mol per mol of the light-sensitive silver halide emulsion used and, more preferably from 1x10 ⁇ 5 mol to 2x10 ⁇ 3 mol.
• the compound is used in an amount of preferably from 1x10 ⁇ 8 mol to 1x10 ⁇ 4 mol/dm2 per layer and more preferably from 1x10 ⁇ 7 mol to 1x10 ⁇ 5 mol/dm2.
• the silver halide grains applicable to the invention may be prepared in the methods respectively described in, for example, P. Glafkides, Chimie et Physique Photographique, Paul Montel, 1967; G.F. Daffin, Photographic Emulsion Chemistry, The Focal Press, 1966; V.L. Zelikman et al, Making and Coating Photographic Emulsion, The Focal Press, 1964; and so forth.
• Those methods include, for example, an acid-­method, a neutral- method, an ammoniacal method.
• As the methods of reacting a soluble silver salt with a soluble halide salt it is also allowed to use any of a single-jet precipitation method, a double-jet precipitation method and the combination thereof.
• a controlled double-jet precipitation method in which a pAg value is kept constant in a liquid phase where silver halides are produced.
• a silver halide emulsion regular in crystal form and nearly uniform in grain size may be prepared.
• a light-sensitive emulsion applicable to the invention has the so-called core/shell type structure or the multilayered core/shell type structure
• the shells thereof may be provided in such a manner that an ordinary halogen-conversion method or a method of newly coating silver halide is applied to the internal nuclei prepared in the foregoing method of preparing silver halide grains, after carrying out a desalting treatment, if required.
• halogen-conversion methods include, for example, those described in U.S. Patent Nos. 2,592,250 and 4,075,020; Japanese Patent O.P.I. Publication No. 55-127549/1980; and so forth.
• the methods of newly coating silver halides may be carried out in accordance with those described in, for example, Japanese Patent O.P.I. Publication Nos. 53-22408/1978 and 58-14829/1983; Japanese Patent Examined Publication No. 43-13162/1968; Journal of Photographic Science, 24, 198, 1976; and so forth.
• Japanese Patent O.P.I. Publication Nos. 53-22408/1978 and 58-14829/1983 Japanese Patent Examined Publication No. 43-13162/1968
• Journal of Photographic Science, 24, 198, 1976 and so forth.
• it is allowed to similarly use the above-mentioned method of providing each of the internal nuclei of the emulsion grains with a shell.
• a method popularly applied to ordinary type emulsions such as a noodle-washing method method; a dialyzing method; a sedimentation method utilizing an inorganic salt, an anionic surface active agent, anionic polymers such as polystyrene­sulfonic acid, or gelatin derivatives such as acylated gelatin, carbamoylated gelatin and so forth; a floccula­tion-precipitation method; or the like methods.
• the light-sensitive silver halide emulsions applicable to the invention can be optically sensitized to a desired wavelength region.
• optical sensitization methods There is no special limitation to the optical sensitization methods.
• Such an optical sensitization can be made by using, independently or in combination, optical sensitizers including, for example, cyanine dyes such as zeromethine dye, monomethine dye, dimethine dye, trimethine dye and so forth, merocyanine dyes, or the like.
• cyanine dyes such as zeromethine dye, monomethine dye, dimethine dye, trimethine dye and so forth, merocyanine dyes, or the like.
• the combinations of the sensitizing dyes are often used especially with the purpose of making a supersensitization.
• An emulsion is also allowed to contain, together with the sensitizing dyes, a dye not having any spectral sensitizing function in itself or a substance substantially not capable of absorbing visible rays of light, but capable of providing a supersensitization.
• the techniques of the above are described in, for example, U.S. Patent Nos. 2,688,545, 2,912,329, 3,397,060, 3,615,635 and 3,628,964; British Patent Nos. 1,195,302, 1,242,588 and 1,293,862; West German Patent (OLS) Nos. 2,030,326 and 2,121,780; Japanese Patent Examined Publication Nos. 43-4936/1968 and 44-14030/1969; Research Disclosure, Vol.
• the light-sensitive silver halide emulsions applicable to the invention may be treated in any of a variety of chemical sensitization methods which may also be applied to ordinary type emulsions.
• a sulfur sensitization method utilizing a compound containing sulfur capable of reacting with silver ions or an active gelatin, a selenium sensitization method, a reduction-sensitization method utilizing a reducing substance, a noble-metal sensitization method utilizing gold or other noble-metal compounds, and so forth.
• the above-mentioned sulfur sensitizers applicable to the invention include those publicly known, such as thiosulfate, allylthiocarbamidothiourea, allylisothiacyanate, cystine, p-toluenethiosulfonate, rhodanine and so forth. Besides the above, it is also allowed to use the sulfur sensitizers described in, for example, U.S. Patent Nos. 1,574,944, 2,410,689, 2,278,947, 2,728,668, 3,501,313 and 3,656,955; German Patent No. 1,422,869; Japanese Patent Examined Publication No. 56-24937/1981; Japanese Patent O.P.I. Publication No.
• the sulfur sensitizer as given above may be added in such an amount as is enough to effectively make the sensitivity of an emulsion higher.
• the amounts thereof to be added are varied to a considerably wide extent according to various conditions such as the variations of pH values, concentrations, silver halide grain sizes and so forth.
• As for the rough standard it is preferable to add them in an amount of the order of from about 10 ⁇ 7 mol to about 10 ⁇ 1 mol per mol of silver halides used therein.
• a selenium sensitization may be made either in place of or in combination with the sulfur sensitization.
• the selenium sensitizers include, for example, aliphatic isoselenocyanates such as allyliso­selenocyanate; selenoureas; selenoketones; selenoamides; selenocarboxylic acids and the esters thereof; seleno­ phosphates; selenides such as diethyl selenide and diethyl diselenide; and so forth.
• aliphatic isoselenocyanates such as allyliso­selenocyanate
• selenoureas selenoketones
• selenoamides selenoamides
• selenocarboxylic acids and the esters thereof seleno­ phosphates
• selenides such as diethyl selenide and diethyl diselenide; and so forth.
• the amounts thereof to be added are varied to the considerably wide extent similar to the case of the above-mentioned sulfur sensitizers.
• they are preferably added in an amount in the order of from about 10 ⁇ 7 mol to 10 ⁇ 3 mol per mol of silver halides used.
• gold sensitizers applicable to the invention a variety of gold compounds including those each having either a +1 valent gold-oxidation number or a +3 valent gold-oxidation number.
• the typical examples thereof include chloroauric acid, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodoaurate, tetra­cyanoauric acid, ammonium aurothiocyanate, pyridyl tri­chlorogold, and so forth.
• the amounts of the gold sensitizers to be added are varied to meet various conditions. However, they are preferably added, as a rough standard, in an amount within the range of from about 10 ⁇ 9 mol to 10 ⁇ 1 mol per mol of silver halides used.
• the sensitization methods for light-sensitive silver halides emulsions may be combined with other sensitization methods utilizing such a metal compound as a compound of platinum, palladium, iridium or rhodium.
• reduction-­sensitization method in combination.
• the reduction-­sensitizers applicable thereto shall not specially be limitative, but they include, for example, stannous chloride, thiourea dioxide, hydrazine derivatives and silane compounds.
• Such reduction-sensitization is preferably carried out in the course of growing light-sensitive silver halide grains or after completing a sulfur sensitization and/or a gold sensitization.
• a remarkably high sensitization can be achieved with a light-sensitive silver halide emulsion, when a chemical sensitization is applied to the emulsion in the presence of a silver halide solvent.
• the silver halide solvents applicable to the invention include, for example, (a) organic thioethers such as those described in U.S. Patent Nos. 3,271,157, 3,531,289 and 3,574,628, Japanese Patent O.P.I. Publication Nos. 54-1019/1979 and 54-158917/1979, and so forth; (b) thiourea derivatives such as those described in Japanese Patent O.P.I. Publication Nos. 53-82408/1978, 55-77737/1980 and 55-2982/1980, and so forth; (c) silver halide solvents each having a thiocarbonyl group sandwiched between an oxygen or sulfur atom and a nitrogen atom, such as those described in Japanese Patent O.P.I. Publication No.
• the light-sensitive silver halide emulsions applicable to the invention may be doped with a variety of dopants when the grains thereof are formed.
• the internal dopants include, for example, silver, sulfur, iridium, gold, platinum, osmium, rhodium, tellurium, selenium, cadmium, zinc, lead, thallium, iron, antimony, bismuth, arsenic and so forth.
• the water-­soluble salts thereof or the complex salts thereof may be made coexistingly when each shell is formed.
• the binders applicable to the silver halide emulsions used in the invention or the dispersion media applicable to the preparation of the emulsions include, for example, hydrophilic colloids applicable to ordinary type silver halide emulsions.
• hydrophilic colloids include, for example, not only gelatin, lime-treated or acid-treated, but also those exemplified as follows.
• Gelatin derivatives such as described in U.S. Patent No. 2,614,928, those prepared through the reaction of gelatin with aromatic sulfonyl chloride, acid chloride, acid anhydride, isocyanate or 1,4-diketones; Gelatin derivatives such as described in U.S. Patent No. 3,118,766, those prepared through the reaction of gelatin with trimelitic acid anhydride; Gelatin derivatives such as described in Japanese Patent Examined Publication No. 39-5514/1964, those prepared through the reaction of gelatin with an organic acid having an active halogen; Gelatin derivatives such as described in Japanese Patent Examined Publication No.
• Macromolecular graft-gelatin compounds including, for example, Acrylic acid and methacrylic acid, and their esters or amides or monovalent or polyvalent alcohol, and the compounds prepared by grafting together gelatin and acryl or methacryl nitrile, styrene or other vinyl monomers independently or in combination;
• Synthetic hydrophilic macromolecular substances including, Homopolymers comprising monomers as the component thereof, such as vinyl alcohol, N-vinyl pyrolidone, hydroxyalkyl (metha)acrylate, (metha)acryl amide, N-sub­stituted (metha)acryl amide or the like, or the copolymers of the above-given monomers; Copolymers of the above-given monomers and (metha)­acrylate, vinyl acetate, styrene or the like; Copolymers of either one of the above-given monomers and maleic anhydride, maleamic acid or the like; and
• hydrophilic colloids may be used independently or in the a thereof.
• the light-sensitive silver halide emulsions applicable to the invention are allowed to contain a variety of popular stabilizers and antifoggants to meet the purposes of using the emulsions.
• Those stabilizers and antifoggants include, for example, Azoles or imidazoles such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzthia­azoles, mercaptobenzimidazoles and mercaptothiadiazoles; Triazoles such as aminotriazoles, benzotriazoles and nitrobenzotriazoles; Tetrazoles such as mercaptotetrazoles including particularly 1-phenyl-5-mercaptotetrazole, and so forth; Mercaptopyrimidines; Mercaptotriazines including thioketo compounds such as oxazolinthione; Azain
• the photographic emulsion layers and other hydrophilic colloidal layers thereof are allowed to contain organic or inorganic hardeners including, for example, chromium salts such as chrome alum, chromium acetate and so forth, aldehydes such as formaldehyde, glyoxal, glutar aldehyde and so forth; N-methylol compounds such as dimethylol urea, methyloldimethyl hydantoine and so forth; dioxane derivatives such as 2,3-dihydroxydioxane and so forth; active vinyl compounds such as 1,3,5-triacryloyl-­hexahydro-S-triazine, 1,3-vinylsulfonyl-2-propanol and so forth; active halogen compounds such as 2,4-dichloro-6-­hydroxy-S-triazine and so forth; and mucohalogen acids such as mucochloric acid, mu
• the photographic emulsion layers and other hydrophilic colloidal layers thereof are also allowed to contain water-insoluble or slightly-water-soluble synthetic polymer dispersions, with the purposes of improving the dimensional stability of the light-sensitive materials and so forth.
• Such synthetic polymers include, for example, those each comprising a monomer component which is a single or a combination of alkyl (metha)acrylate, alkoxyalkyl (metha)acrylate, glycidyl (metha)acrylate, (metha)acrylamide, vinyl esters including vinyl acetate and so forth, acrylo­nitrile, oleffin, styrene, and so forth, or a monomer component which is a further combination of the above-given monomer and acrylic acid, methaacrylic acid, ⁇ , ⁇ -unsaturated dicarboxylic acid, hydroxyalkyl (metha)acrylate, sulfoalkyl (metha)acrylate, styrenesulfonic acid and so forth.
• a monomer component which is a single or a combination of alkyl (metha)acrylate, alkoxyalkyl (metha)acrylate, glycidyl (metha)acrylate, (metha)acrylamide
• the silver halide light-sensitive photographic material relating to the invention is also allowed to contain a development accelerator such as benzyl alcohol, polyoxyethylene type compounds and so forth; an image stabilizer such as those of the chroman, coumaran, bisphenol or phosphite type; a lubricant such as wax, glyceride of higher fatty acid, higher alcohol ester of higher fatty acid and so forth; a development controller; a developing agent; a plasticizer; and a bleaching agent.
• a development accelerator such as benzyl alcohol, polyoxyethylene type compounds and so forth
• an image stabilizer such as those of the chroman, coumaran, bisphenol or phosphite type
• a lubricant such as wax, glyceride of higher fatty acid, higher alcohol ester of higher fatty acid and so forth
• a development controller a developing agent
• plasticizer a plasticizer
• a variety of surfactants such as those of anionic, cationic, nonionic or amphoteric type may also be used in the photographic material to serve as a coating aid, permeation improver to a processing solution or the like, defoaming agent or a raw material for controlling the various physical properties of a light-sensitive material.
• the effective antistatic agents include, for example, diacetyl cellulose, styrene-parfluoroalkyl sodium maleate copolymer, the alkali salts of the reacted products of styrene-maleic anhydride copolymer with p-aminobenzene sulfinic acid, and so forth.
• Matting agents include, for example, polymethacrylic acid methyl, polystyrene, alkali-soluble polymers and so forth, and, further, colloidal silica oxide may also be used.
• the latexes which are to be added for improving the physical properties of layers include, for example, a copolymer of a monomer such as an acryl ester or a vinyl ester or the like and another monomer having an ethylene group.
• the gelatin plasticizers include, for example, glycerol and glycol type compounds.
• Thickeners include, for example, a sodium styrene-maleate copolymer, an alkylvinylether-maleic acid copolymer, and so forth.
• the silver halide light-sensitive photographic materials of the invention can be provided with an ample latitude when they contain a mixture of at least 2 kinds of the emulsions different from each other in grain sizes and sensitivities or they are coated with such emulsions onto a plurality of the layers thereof.
• the silver halide light-sensitive photographic materials of the invention can effectively be utilized for a variety of applications such as those of black-and-white photography, X-ray photography, color photography, infra-red photography, microphotography, silver-dye bleaching process, reversal photography, diffusion-transfer process, high-contrast photography, photothermography, heat-developable light-­sensitive materials and so forth.
• the invention may be applied to a color photographic light-sensitive material by applying the method and materials usually applied to ordinary type color light-sensitive materials.
• cyan, magenta and yellow couplers are contained coordinately into the light-sensitive emulsions so prepared as to be sensitive to red, green and blue rays of light, respectively.
• magenta couplers include those of 5-pyrazolone, pyrazolobenzimido­azole, pyrazolotriazole, cyanoacetylcumarone, open-chained acylacetonitrile, and so forth.
• the yellow couplers include, those of acylacetoamide such as benzoylacetoanilides and pivaloylacetoanilides, and so forth.
• the cyan couplers include those of naphthol, phenol, ureido and so forth. It is usual that a red-sensitive emulsion layer contains a cyan-dye forming coupler, a green-sensitive emulsion layer contains a magenta-dye forming coupler and a blue-sensitive emulsion layer contains a yellow-dye forming coupler. If should the necessity arise, it is also allowed to have different combinations than the above. It is preferable that the above-mentioned couplers should be those of the non-diffusible type each having a hydrophobilc group, that is the so-called ballast group, in the molecules of the couplers.
• Such couplers may be of either 4-equivalent type or 2-equivalent type with respect to silver, and they may also be either a colored coupler capable of displaying a color correction effect or a coupler capable of releasing a development inhibitor while a development is being carried out, that is the so-called DIR coupler. Besides the DIR couplers, it is allowed to contian a non-dye forming DIR coupling compound which is capable of rendering a colorless coupling reaction product from which a development inhibitor is discharged.
• the publicly known antifading agents such as a hydroquinone derivative, a gallic acid derivative, a p-alkoxyphenol, a bisphenol and so forth.
• the silver halide photographic light-sensitive materials of the invention are allowed to contain a UV absorbent in the hydrophilic colloidal layers thereof.
• a UV absorbent applicable thereto include, for example, a benzotriazole compound substituted with an aryl group, a 4-thiazolidone compound, a benzophenone compound, a cinnamate compound, a butadiene compound, a benzoxazole compound, a UV-absorbable polymer, and so forth.
• the above-given UV absorbents may also be fixed to the inside of the above-mentioned hydro­philic colloidal layers.
• the light-sensitive emulsion layers of the color light-sensitive photographic material may be constituted either in the so-called normal layer arrangement or in the so-called inverted layer arrangement.
• the silver halide light-sensitive photographic materials of the invention are also allowed to contain a water-soluble dyestuff in the hydrophilic colloidal layers thereof, so as to serve as a filter dye or with the various purposes of, for example, preventing irradiation and so forth.
• a water-soluble dyestuff in the hydrophilic colloidal layers thereof, so as to serve as a filter dye or with the various purposes of, for example, preventing irradiation and so forth.
• Such dyestuffs include, for example, the dyes of oxonol, hemioxonol, styryl, merocyanine, cyanine, and azo.
• the oxonol, hemioxonol and merocyanine dyes are useful.
• the silver halide light-sensitive photographic materials of the invention are also allowed to contain anticolor-­foggants including, for example, a hydroquinone derivative, an aminophenol derivative, a a gallic acid derivative, an ascorbic acid derivative and so forth.
• the photographic emulsion layers and other hydrophilic colloidal layers thereof may be coated over a support or other layers in any publicly known method.
• coating methods include, for example, a dip-coating method, a roller-coating method, a curtain-coating method, an extrusion-coating method and so forth.
• the methods described in, for example, U.S. Patent Nos. 2,681,294, 2,761,791 and 3,526,528 are advantageous.
• the supports for the light-sensitive photographic materials include, for example, baryta paper sheet, polyethylene-coated paper sheet, polypropylene synthetic paper sheet, glass plate, cellulose acetate film, cellulose nitrate film, polyvinyl acetal film, polypropylene film, polyester films such as polyethyleneterephthalate film, polystyrene film and so forth, each of which are usually used.
• the above-given supports may be selectively used to meet the various applications.
• a silver halide light-sensitive photo­graphic material of the invention Upon exposing a silver halide light-sensitive photo­graphic material of the invention to light, it may be developed in any publicly known process which is used, commonly.
• a black-and-white developer is an alkaline solution containing such a developing agent as a hydroxybenzene, an aminophenol, an aminobenzene or the like.
• a developing agent as a hydroxybenzene, an aminophenol, an aminobenzene or the like.
• developers may also contain the sulfites, carbonates, bisulfites, bromides, iodides or the like of an alkali-metal.
• such light-sensitive photographic material is for color photographic use, it may be color-developed in any color-­developing process which is usually used.
• a color-development is carried out in such a manner that, after a light-sensitive material is developed with a black-and-white negative developer first, it is exposed to white light or treated in a bath containing a fogging agent and is then color-developed with an alkaline developer containing a color developing agent.
• the processing methods shall not be limitative, but may be freely selected.
• the typical methods include, for example, a method in which, after color-development is completed, a bleach-fixation is carried out and, if required, a washing and stabilizing step is further carried out, or another method in which, after a color-development is completed, a bleaching step and a fixing step are carried out separately and, if required, a washing and stabilizing step is further carried out.
• Such color-developer is generally comprised of an aqueous alkaline solution containing a color developing agent.
• color developing agents it is allowed to use publicly known primary aromatic amine type developing agents including, for example, phenylenediamines such as 4-amino-N,N-diethylaniline, 3-methyl-4-amino-N,N-­diethylaniline, 4-amino-N- ⁇ -hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -hydroxyethylaniline, 3-methyl-­4-amino-N-ethyl-N- ⁇ -methanesulfonamidoethylaniline, 4-amino-3-methyl-N-ethyl-N- ⁇ -methoxyethylaniline, and so forth.
• phenylenediamines such as 4-amino-N,N-diethylaniline, 3-methyl-4-amino-N,N-­diethylaniline, 4-amino-N- ⁇ -hydroxyethylaniline, 3-methyl-4-amin
• the color developer is also allowed to contain the color developing agents described in, for example, L.F.A. Mason, Photographic Processing Chemistry, Focal Press, 1966, pp. 226-229; U.S. Patent Nos. 2,193,015 and 2,592,364; Japanese Patent O.P.I. Publication No. 48-64933/1973; and so forth.
• color developers are also allowe dto contain a pH buffer, a development inhibitor, an antifoggant and so forth and, if required, a hard-water softener, a preservative, an organic solvent, a development accelerator, a dye-forming coupler, a competing coupler, a foggant, an auxiliary developing agent, a thickener, a polycarboxylic chelating agent, an antioxidizer and so forth.
• a photographic emulsion layer is usually bleached after it is color-developed. Such a bleaching step may be carried out either at the same time a fixing step is carried out or separately.
• the bleaching agents applicable thereto include, for example, polyvalent metal compounds such as iron (III), cobalt (IV), chromium (VI), copper (II) and so forth, a peroxy acid, a quinone, a nitroso compound and so forth.
• Such bleaching agents or bleach-fixers are allowed to contain a variety of additives, as well as the bleaching accelerators such as those described in, for example, U.S. Patent Nos. 3,042,520 and 3,241,966, Japanese Patent Examined Publication Nos. 45-8506/1970 and 45-8836/1970, and so forth; and the thiol compounds described in, Japanese Patent O.P.I. Publication No. 53-657332/1978.
• Sample I was prepared by coating the following light-sensitive emulsion layers and non-light-sensitive layers in order over a subbed cellulose triacetate film base.
• the amounts of the materials added into each light-sensitive material will be expressed in a an amount per sq. meter of the light sensitive material prepared, and the amounts of silver halides and colloidal silver will be expressed in terms of the silver contents, respectively.
• Layer 1 A non-light-sensitive layer containing 0.8 g of gelatin
• Layer 2 A green-light-sensitive emulsion layer, which was prepared in the following manner.
• a 1.0 ⁇ m average grain sized polydisperse type silver iodobromide emulsion A having a grain size variation coefficient of 24% and an average iodide content of 4 mol% was chemically sensitized, in an ordinary method, with both sodium thiosulfate and potassium chloroaurate and was then color-sensitized to be green-sensitive by adding the following green-sensitive sensitizing dye (a) in an amount of 12.0x10 ⁇ 5 mol per mol of silver halides used and a similar dye (b) in an amount of 11.0x10 ⁇ 5 mol per the same, respectively.
• the resulting emulsion was added with 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene in an amount of 7x10 ⁇ 3 mol per mol of silver halides used for the purposes of stabilizing the emulsion and preventing fog production.
• the above-mentioned color-sensitized and chemically sensitized polydisperse type silver iodobromide emulsion in an amount of 1.8g was added with a solution consisting of 0.5g of di-tertiary nonylphenol DNP dispersion in which 0.20g of magenta coupler M-1 and 0.05g of colored magenta coupler CM-1 were dissolved, and 1.9g of gelatin.
• the resulting coating solution was coated over Layer 1, so that the green light-sensitive emulsion layer was formed.
• Layer 3 A non-light-sensitive layer containing 0.04g of n-dibutyl phthalate DBP dispersion in which 0.07g of 2,5-dioctyl hydroquinone were dissolved, and 0.8g of gelatin.
• a gelatin hardener and a surfactant were also added, besides the above-described compositions.
• Sample 2 was prepared in the same manner as in Sample 1, except that the polydisperse type silver iodobromide emulsion A of Sample 1 was replaced by a 1.0 ⁇ m grain-sized mono­disperse type silver iodobromide emulsion B having a grain-size variation coefficient of 11% and an average iodide content of 4 mol%.
• non-light-sensitive silver halide fine grains, a to g may be prepared in an ordinary method and those for a monodisperse type emulsion having a grain-size variation coefficient of not more than 20% as shown in Table-1.
• Samples 1 through 11 each prepared by the above-­mentioned sample preparation method were coated and dried. Then, they were cut into an appropriate sample size and were treated through a series of the steps of exposure - processing - measurement. Thus, the resulting samples were subjected to the sensitometric evaluation.
• the samples were exposed to green light through a wedge in an ordinary method.
• Processing step Processing time Color developing 3min. 15sec. Bleaching 6min. 30sec. Washing 3min. 15sec. Fixing 6min. 30sec. Washing 3min. 15sec. Stabilizing 1min. 30sec. Drying
• compositions of the processing solutions used in the above-given processing steps were as follows.
• the sensitivity of each sample is expressed by a reciprocal number of an exposure capable of giving a total optical density of a minimum optical density that is a fog level on the characteristic curve obtained through the sensitometric measurement of the subject sample and +0. 1 of the fog level, and each sensitivity is also expressed in terms of a relative value to the sensitivity of Sample-1 that is regarded as a value of 100.
• Sample 12 was prepared by coating the following light-sensitive emulsion layers and the non-light-sensitive layers in order over a subbed cellulose triacetate film base.
• Layer 1 A non-light-sensitive layer containing 0.8g of gelatin.
• Layer 2 A green light-sensitive emulsion layer, which was prepared in the following manner.
• a 0.38 ⁇ m grain-sized monodisperse type silver iodo­bromide emulsion C having a grain-size variation coefficient of 17% and an average iodide content of 6 mol% was chemically sensitized, in an ordinary method, with both sodium thiosulfate and potassium chloroaurate and was then color-sensitized to be green-sensitive by adding the following green-sensitive sensitizing dye (c) in an amount of 2.5x10 ⁇ 5 mol per mol of silver halides used and a similar dye (d) in an amount of 1.2x10 ⁇ 5 mol per the same, respectively.
• the resulting emulsion was added with 4-hydroxy-6-­methyl-1,3,3a,7-tetrazaindene in an amount of 7x10 ⁇ 3 mol per mol of silver halides used for the purposes of stabilizing the emulsion and preventing fog production.
• Layer 3 A non-light-sensitive layer containing 0.3g of dioctyl phthalate DOP dispersion in which 0.1g of 2,5-di-t- octyl hydroquinone were dissolved, 0.08g of yellow colloidal silver and 0.6g of gelatin.
• a gelatin hardener and a surfactant were also added, besides the above-described compositions.
• Samples 13 through 19 were prepared in the same manner as in Sample 12, except that the substantially not light-­sensitive silver halide fine grains shown in Table-1 were added into Layer 1 of Sample 12 as shown in Table-3 and the exemplified compound C-5 in an amount shown in Table-3 was added into Layer 2 of Sample 12.
• Sample No. 14 that is other than the samples of the invention is least sensitized in comparison with Sample No. 12 and, in contrast with the above, Sample No. 16 of the invention displays remarkable sensitizing effects.
• the results of the comparison are due to the fact that, in Example-1, the non-light-sensitive layer containing AgBrI 0.27 ⁇ m-grain-sized substantially non-light-sensitive emulsion 'a' displayed the effects of an optically scattering layer and, in Sample No. 14, the same non-light-sensitive layer did not play the same role.
• Sample No. 1 the non-light-sensitive layer containing AgBrI 0.27 ⁇ m-grain-sized substantially non-light-sensitive emulsion 'a' displayed the effects of an optically scattering layer and, in Sample No. 14, the same non-light-sensitive layer did not play the same role.
• Sample No. 17 can display a remarkable sensitization effect because the non-light- sensitive layer of Sample No. 17 contains 0.12 ⁇ m-grain-sized substantially non-light-sensitive chloride emulsion 'g' which doesn't have on effective scattering function to green rays of light.
• a multilayer-coated sample was prepared. With respect to the sample, the effects of the invention were examined especially on sensitivity-to-fog characteristics, graininess and processing stability.
• Sample No. 20 comprising 13 layers including blue, green and red light-sensitive layers, was prepared.
• Layer 1 An antihalation layer containing 0.4 g of black colloidal silver and 3.0 g of gelatin
• Layer 2 A low-speed red light-sensitive emulsion layer containing 1.4 g of a red light-sensitized low speed red-sensitive silver iodobromide emulsion having a silver iodide content of 7 mol%, 1.2 g of gelatin, and 0.65 g of tricresyl phosphate, TCP, dissolved therein 0.8 g of 1-hydroxy-4-( ⁇ -methoxyethylaminocarbonylmethoxy)-N-­[ ⁇ -(2,4-di-t-amylphenoxy)butyl]-2-naphthamide (hereinafter called C-1), 0.075 g of disodium 1-hydroxy-4-[4-(1-­hydroxy- ⁇ -acetamido-3,6-disulfo-2-naphthylazo)phenoxy]-­ -N-[ ⁇ -(2,4-di-t-amylphenoxy) butyl-2-naphth
• Layer 3 An interlayer containing 0.04 g of n-dibutyl phthalate, DBP, dissolved therein 0.07 g of 2,5-di-t-octyl hydroquinone (hereinafter called antistaining agent HQ-1), and 0.8 g of gelatin
• Layer 4 A low-speed green light-sensitive emulsion layer containing 0.80 g of a green-sensitized low-speed silver iodobromide emulsion having a silver iodide content of 6 mol%, 2.2 g of gelatin, and 0.95 g of TCP dissolved therein 0.8 g of 1-(2,4,6-trichlorophenyl)-3-[3-(2,4-di-t-amyl-­phenoxyacetamido)benzamido]-5-pyrazolone (hereinafter called magenta coupler M-1), 0.15 g of 1-(2,4,6-trichlorophenyl)-4-­(1-naphthylazo)-3-(2-chloro-5-octadecenylsuccinimidoanilino)­-5-pyrazolone (hereinafter called colored magenta coupler CM-1) and 0.016 g of DIR compound D-1
• Layer 5 The same layer as Layer 3
• Layer 6 A low-speed blue light-sensitive emulsion layer containing 0.2 g of a blue-sensitized low-speed silver iodobromide emulsion having a silver iodide content of 4 mol%, 1.9 g of gelatin, and 0.6 g of TCP dissolved therein 1.5 g of ⁇ -pivaloyl- ⁇ -(1-benzyl-2-phenyl-3,5-dioxo-­ imidazolidine-4-yl)-2′-chloro-5′-( ⁇ -dodecyloxycarbonyl)-­ethoxycarbonyl]acetoanilide (hereinafter called Y-1)
• Layer 7 The same layer as Layer 3
• Layer 8 A high-speed red light-sensitive emulsion layer containing 1.3 g of a high-speed red light-sensitive silver iodobromide emulsion, 1.2 g of gelatin, and 0.23 g of TCP dissolved therein 0.21 g of cyan coupler C-1 and 0.02 g of colored cyan coupler CC-1
• Layer 9 The same layer as Layer 3
• Layer 10 A high-speed green light-sensitive emulsion layer containing 1.8 g of a green-sensitized high-speed green sensitive silver iodobromide emulsion, 1.9 g of gelatin, and 0.25 g of TCP dissolved therein 0.20 g of magenta coupler M-1 and 0.049 g of colored magenta coupler CM-1
• a monodisperse type silver iodobromide emulsion D having a grain-size of 1.6 ⁇ m was prepared to be of a multilayered core/shell type structure, by following the procedures described in Japanese Patent O.P.I. Publication No. 60-86659/1985. so as to have a grain-size variation coefficient of 11%, an average iodide content of 5.6%.
• Such a core/shell type structure was comprised of a nucleus and three shells, namely, the 1st shell to the 3rd shell from the inside of each grain, and the iodide contents and the volumetric occupancy of each shell were as follows; 15 mol% and 22% for the 1st shell, 5 mol% and 39% for the 2nd shell and 0.3 mol% and 27% for the 3rd shell, respectively.
• emulsion D was chemically sensitized in an ordinary method, with sodium thiosulfate and potassium aurochloride, and the foregoing sensitizing dyes (a) and (b) were added in the amounts of 7.5x10 ⁇ 5 and 7.0x10 ⁇ 5 mol each per mol of silver halide used, and the resulted emulsion was color-­sensitized to green-light, respectively.
• 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene was added in an amount of 7x10 ⁇ 3 mol per mol of the silver halide used.
• Layer 11 The same layer as the 3rd layer
• Layer 12 A high-speed blue-sensitive emulsion layer containing 1.0 g of a high-speed silver iodobromide emulsion color-sensitized to blue-light, 1.5 g of gelatin, and 0.65 g of TCP into which 1.30 g of yellow coupler Y-1 were dissolved
• Layer 13 A protective layer containing 2.3 g of gelatin.
• Sample No. 21 through Sample No. 36 each were prepared in the same manner as in Sample No. 20, except that Layer 9 through Layer 11 of Sample No. 20 were each added with the substantially non-light-sensitive silver halide fine grains shown in Table-4 and the following Exemplified compounds B-1 and D-5.
• Granularity RMS was measured through green-light, and the graininess of each sample was obtained by scanning the magenta dye-image of each sample already subjected to the sensitometric evaluations, by making use of a microdensito­meter having a circular scanning aperture of 25 ⁇ m, when the density was in a total of fog plus 0.8, so as to find the density variations. Then, the graininess of each sample was expressed in values obtained by multiplying the resulting standard deviation of the density variations by 1000 and made relative to the value of the control sample which was regarded as a value of 100. The greater these relative graininess values are, the more the graininess is undesirably coarse.
• Processing stability was measured in the same manner as in ordinary sensitometry, except that the sodium bromide concentration was changed in the color developer used. In the case that a sodium bromide concentration of a color developer is changed, the less the sensitometry is changed, the better the processing stability.
• Table-5 Sample No. Sodium bromide 1.3g/liter of developer(control) Sodium bromide 1.17g/liter of developer Sodium bromide 1.43g/liter of developer Fog Speed RMS Fog Speed Fog Speed 20 0.40 100 32 0.43 119 0.38 77 21 0.37 97 25 0.40 125 0.36 72 22 0.38 92 25 0.40 115 0.35 66 23 0.42 116 37 0.44 124 0.39 94 24 0.43 124 35 0.46 139 0.40 103 25 0.41 135 33 0.43 147 0.39 121 26 0.41 126 32 0.42 144 0.38 102 27 0.38 145 24 0.39 160 0.36 129 28 0.40 140 27 0.42 158 0.38 134 29 0.42 138 35 0.45 150 0.40 126 30 0.39 160 26 0.41 169 0.37 143 31 0.39 152 28 0.41 163 0.38 133 32 0.43 143 36 0.47 150 0.40 130 33 0.42 109 40 0.46 131 0.39 86 34
• the system of the invention containing silver halide fine grains having a high chloride content is proved to be able to provide a light-sensitive material having little sensitometric change and an excellent processing stability, as compared with a system not containing any silver halide fine grains or another system containing silver iodobromide fine grains which do not contain any chloride.

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• 1988
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