JPH052135B2 - - Google Patents

Description

[Detailed description of the invention]

B. Industrial Application Field The present invention relates to a silver halide photographic material. B. Prior art Conventionally, silver halide color photographic materials,
In particular, silver halide photosensitive materials for photography are required to have high sensitivity and excellent image quality. In particular, in recent years in this industry, with the spread of conveniently portable compact cameras, there has been a desire for image quality on small screens to be equivalent to that of enlarged images from large screens. That is, there is a strong demand for the development of a silver halide color photographic material whose resolution and sharpness are not impaired even when the magnification is increased. One known technique for improving image quality is to reduce the particle size of silver halide grains to reduce the size of the coloring dye cloud. According to this technique,
It has the disadvantage of being accompanied by significant desensitization. Further, it is described in JP-A-57-82837, etc. that the graininess is improved by diffusion of the dye.
This may be because the RMS granularity is improved by using a non-diffusive coupler (dye-diffusing coupler) that generates a diffusive dye that causes the dye to bleed moderately, but the RMS value representing the granularity has improved. Visually, large mottles (density unevenness) are noticeable at medium density areas and above, giving the impression that the graininess is getting worse. Furthermore, it was proposed in Japanese Patent Application Laid-Open No. 59/1987 to use such a system with a coupler (fast reaction coupler) that has a high coupling rate and does not cause the generated dye to diffuse.
-Described in Publication No. 131938. When using a dye-diffusing coupler and a fast-reaction coupler together, some improvement in graininess can be expected, but it is still insufficient.
Moreover, side effects such as deterioration of sharpness and increase of fog occur. Fast-reaction type couplers can reduce the film thickness even if the amount of silver is reduced, so deterioration of sharpness can be prevented to some extent, but the deterioration of sharpness caused by dye-diffusing couplers is greater than expected, and This cancels out the slight improvements made by reactive couplers. Furthermore, if the amount of silver is reduced to make the film thinner, the number of points that can be colored will decrease and the graininess will deteriorate. In addition, it is possible to incorporate a compound that releases a fogging agent or a development accelerator into Imagewise.
−157638, JP-A-59-170840, JP-A-59-
It is described in each publication of No. 172640. However, with these known techniques, it is difficult to control diffusion, causing problems such as color mixing and fogging. In order to improve sharpness, it is necessary to significantly reduce light scattering in the emulsion layer. It is known that sharpness can be improved by increasing the grain size of silver halide emulsion grains to a region where light scattering is small. It has the disadvantage of deterioration of graininess. It is also known to use dyes to reduce light scattering in the emulsion layer, and to improve visual sharpness with its antihalation effect. However, this technique has the disadvantages of reduced sensitivity, disrupted color balance, and increased fog. Further, although techniques for significantly reducing the amount of coated silver are known, it is clear that significantly reducing the amount of coated silver leads to deterioration of graininess due to a decrease in active sites. C. Object of the Invention An object of the present invention is to provide a silver halide photographic material that has good graininess, excellent sharpness, and high sensitivity. D. Structure of the invention and its effects In other words, the present invention provides the silver density d of the silver halide emulsion layer as follows: d=N/V [However, N is the amount of silver in the silver halide emulsion layer (converted to metallic silver). (unit: g), V
is the volume of the silver halide emulsion layer (unit: cm ³ )], the silver density d of the blue-sensitive silver halide emulsion layer is 4.0 × 10 ^-1 g/cm ³ or more, and The dry film thickness of the blue-sensitive silver halide emulsion layer is 4.0 μm or less, the silver density d of the green-sensitive silver halide emulsion layer is 5.0 × 10 ^-1 g/cm ³ or more, and The dry film thickness of the silver halide emulsion layer is 4.5 μm or less, and the silver halide emulsion layer has the above-mentioned silver density in the blue-sensitive silver halide emulsion layer and/or the green-sensitive silver halide emulsion layer. , or a non-emulsion layer adjacent to at least one of these emulsion layers has a relative reaction rate of 1.6 or more,
The present invention relates to a silver halide photographic light-sensitive material characterized in that it contains a fast-reactive developing agent oxidized product scavenger having a molecular weight of 15.0 or less. In the present invention, the volume of the emulsion layer is expressed as the product of the coating area and the dry film thickness. When there are two or more emulsion layers in the present invention, the silver amount and film thickness are calculated based on the total amount of each value in each emulsion layer. The silver density of the blue-sensitive emulsion layer in the present invention is:
In order to achieve the purpose of the present invention, it should be 4×10 ⁻¹ g/cm ³ or more. However, if the silver density is too high, side effects such as deterioration of graininess and increase in fog tend to occur, so the silver density is preferably 2.0 g/cm ³ or less, more preferably 5.0 × 10 ^-1 g/cm ³ or more, 1.2
g/cm ³ or less. Furthermore, in the green-sensitive emulsion layer, it should be 5.0×10 ^-1 g/cm ³ or more within the above range, and for the same reason as above, it should be 2.5 g/cm ³
The following is good, and 7.0×10 ⁻¹ to 2.0 g/cm ³ is even better. By adjusting the silver density within the above-mentioned range of the present invention, not only graininess but also sharpness can be improved, and interimage effects, desilvering properties, and sensitivity can be greatly improved. Further, the dry film thickness of the present invention is 4.0 μm or less for each of the blue-sensitive and green-sensitive layers, respectively.
Although it is 4.5 μm or less, if the dry film thickness is made too thin, side effects such as deterioration of coating properties, pressure characteristics, and emulsion stability, and a decrease in color density will occur. Therefore, the dry film thickness is preferably 0.8 μm or more in the blue-sensitive layer, even better 1.0 to 3.8 μm, and the dry film thickness is even better in the blue-sensitive layer.
The thickness is preferably 0.8 μm or more, and even more preferably 1.0 to 4.0 μm. Note that each of the blue photosensitive layer and the green photosensitive layer may be composed of one layer or two or more layers. In the present invention, the method for measuring the amount of silver for determining the silver density is based on atomic absorption spectrometry. Also,
The film thickness, which determines the volume of the emulsion layer, is determined by taking an enlarged photograph of the cross section of the dried sample using a scanning electron microscope and measuring the film thickness of each layer. The fast-reactive oxidized developing agent scavenger (AS agent) used in the present invention has a relative reaction rate of 1.6 or more and 15.0 or less, and is used in the blue-sensitive emulsion layer and/or in the green-sensitive emulsion layer. By containing it in the layer or in the adjacent layer (non-emulsion layer), the graininess is further improved due to the synergistic effect of the combination with the above silver density range. Moreover, when the above-mentioned fast-reaction type coupler is used as the coupler, it is remarkable that sharpness is improved, graininess is improved, and sensitivity is also improved. The relative reaction rate of this oxidized developing agent scavenger should be greater than or equal to 1.6 and less than or equal to 15.0 in order to achieve the objectives of the present invention. That is, if it is too large, the sensitivity will decrease, so the upper limit is set to 15.0. Moreover, this relative reaction rate is more preferably 1.6 to 10.0. Here, the relative reaction rate can be determined as a relative value by measuring the amount of dye in a color image obtained by mixing the above coupler with a silver halide emulsion and performing color development. . The ratio (R) of the reaction activity of the oxidized developing agent scavenger and coupler N, that is, the relative reaction rate, is defined by the following equation. R=DM/DM' where DM is the color density of coupler N when the oxidized developing agent scavenger is not included DM'; the color development of coupler N when 1/10 mol of the oxidized developing agent scavenger is added to coupler N concentration If the above R is determined for various oxidized developing agent scavengers using coupler N, the relative value of the color-forming oxidized developing agent reaction rate of the oxidized developing agent scavenger can be determined. The oxidized developing agent scavenger of the present invention has an R of 15 or less from the viewpoint of preventing a decrease in sensitivity. The amount of the fast-reactive developing agent oxidized product scavenger added is not limited, but is preferably from 1.times.10.sup. ^-4 to 5.times.10.sup. ^- 1 mol per mol of coupler. Next, the general formula of the oxidized developing agent scavenger is shown. The developing agent oxidized product scavenger of the present invention is disclosed in Japanese Patent Publication No. 43-4133, Japanese Patent Application Publication No. 58-24141, Japanese Patent Application Publication No. 58-58.
-45701 and JP-A-59-5427. Specific examples of fast-reactive developing agent oxidized product scavengers are listed below, but are not limited to these. The R value is shown in parentheses. These may be used alone or in combination of two or more. Further, a method for adding the oxidized developing agent scavenger of the present invention to an emulsion layer will be described below. Either method is fine. In order to incorporate the fast-reactive developing agent oxidized product scavenger of the present invention into a silver halide emulsion,
When the developing agent oxidized product scavenger is alkali-soluble, it may be added as an alkaline solution, and when it is oil-soluble, it can be added, for example, in U.S. Pat.
According to the method described in the specifications of 2272191 and 2304940, the oxidized developing agent scavenger is dissolved in a high boiling point solvent and, if necessary, a low boiling point solvent, and dispersed in the form of fine particles. It is preferable to add it to the silver halide emulsion. At this time, other ultraviolet absorbers, browning inhibitors, etc. may be used in combination as necessary. It is also possible to use a mixture of two or more types of oxidized developing agent scavengers. Further, in detail, the preferred method of adding the oxidized developing agent scavenger in the present invention is as follows.
One or more of the oxidized developing agent scavengers may be used together with other oxidized developing agent scavengers, couplers, anti-browning agents, ultraviolet absorbers, etc., as required, such as organic acid amides, carbamates, esters, etc. Ketones, urea derivatives, ethers, hydrocarbons, etc., especially di-n-butyl phthalate, tri-thresyl phosphate, triphenyl phosphate, di-isooctyl azelate, di-n-
Butyl sebacate, tri-n-hexyl phosphate, N,N-di-ethyl-caprylamidobutyl, N,N-diethyl laurylamide, n-pentadecyl phenyl ether, di-octyl phthalate, n-nonylphenol, 3- High boiling point solvents such as pentadecyl phenyl ethyl ether, 2,5-di-sec-amyl phenyl butyl ether, monophenyl-di-o-chlorophenyl phosphate or fluorine paraffin, and/or methyl acetate, ethyl acetate, acetic acid Propyl, butyl acetate, butyl propionate, cyclohexanol,
Dissolved in low boiling point solvents such as diethylene glycol monoacetate, nitromethane, carbon tetrachloride, chloroform, cyclohexane tetrahydrofuran, methyl alcohol, acetonitrile, dimethyl formamide, dioxane, methyl ethyl ketone, and anionic surfactants such as alkylbenzenesulfonic acids and alkylnaphthalenesulfonic acids. and/or mixed with an aqueous solution containing a nonionic surfactant such as sorbitan sesquioleate and sorbitan monolaurate and/or a hydrophilic binder such as gelatin, and mixed with a high-speed rotary mixer, colloid mill, ultrasonic dispersion device, etc. It is emulsified and dispersed and added to the silver halide emulsion. In addition, the oxidized developing agent scavenger may be dispersed using a latex dispersion method. The latex dispersion method and its effects were published in Japanese Patent Application Laid-Open No.
Publications No. 74538, No. 51-59943, No. 54-32552 and Research Disclosure August 1976, No.
14850, pp. 77-79. Suitable latexes include, for example, styrene, acrylate, n-butyl acrylate, n-butyl methacrylate, 2-acetoacetoxyethyl methacrylate, 2-(methacryloyloxy)ethyltrimethylammonium methosulfate, 3
-(methacryloyloxy)propane-1-sulfonic acid sodium salt, N-isopropylacrylamide, N-[2-(2-methyl-4-oxopentyl)]acrylamide, 2-acrylamide-
Homopolymers, copolymers and terpolymers of monomers such as 2-methylpropanesulfonic acid and the like. The oxidized developing agent scavenger may be dissolved in the low boiling point solvent and added to the silver halide emulsion. Any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used as silver halide in the photographic emulsion layer of the photographic light-sensitive material according to the present invention. A preferred silver halide is silver iodobromide containing up to 15 mole percent silver iodide. Particularly preferred is silver iodobromide containing from 2 mol % to 12 mol % silver iodide. The average grain size of the silver halide grains in the photographic emulsion (the grain size is the grain diameter in the case of spherical or approximately spherical grains, the ridge length in the case of cubic grains,
(expressed as an average based on the projected area) is not particularly limited, but is preferably 3 μm or less. The particle size distribution may be narrow or wide. The silver halide grains in this emulsion may have regular crystal shapes such as cubes or octahedrons, or may have irregular crystal shapes such as spherical or plate shapes, or may have irregular crystal shapes such as spherical or plate shapes. It may also have a complex shape. It may also consist of a mixture of particles of various crystalline forms. The silver halide grains may have different phases inside and on the surface, or may consist of a uniform phase.
Further, the particles may be particles in which the latent image is mainly formed on the surface, or may be particles in which the latent image is mainly formed inside the particles. The photographic emulsion used in the present invention can be prepared using known methods. i.e. acid method,
Any method such as a neutral method or an ammonia method may be used, and any method such as a one-sided mixing method, a simultaneous mixing method, or a combination thereof may be used for reacting a soluble silver salt with a soluble halogen salt. It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method).
As one type of simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called controlled double jet method can also be used. According to this method, a silver halide emulsion with a regular crystal shape and a nearly uniform grain size can be obtained. Two or more types of silver halide emulsions formed separately may be mixed and used. In the process of forming or physically ripening silver halide grains, a cadmium salt, a zinc salt, a lead salt, a thallium salt, a pyridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present. In order to remove soluble salts from the emulsion after precipitation or physical ripening, a Nudel water washing method in which gelatin is gelatinized may be used, and inorganic salts, anionic surfactants, anionic polymers (e.g. A precipitation method (flocculation) using gelatin derivatives (eg, acylated gelatin, carbamoylated gelatin, etc.) may also be used. The silver halide grains used in the present invention can be optically sensitized to a desired wavelength range. The optical sensitization method is not particularly limited, and for example, optical sensitizers such as cyanine dyes such as zeromethine dyes, monomethine dyes, dimethine dyes, trimethine dyes, or merocyanine dyes may be used alone or in combination to optically sensitize. be able to. Combinations of sensitizing dyes are often used, especially for the purpose of supersensitization. Along with the sensitizing dye, the emulsion may contain a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light and exhibits supersensitization. These techniques are described in U.S. Patent No. 2,688,545;
Same No. 2912329, No. 3397060, No. 36615635, Same No.
3628964, British Patent No. 1195302, British Patent No. 1242588,
1293862, West German Patent (OLS) No. 2030326,
No. 2121780, Special Publication No. 43-4936, No. 44-14030,
Research Disclosure
Disclosure) Volume 176 17643 (Published December 1978) No. 23
It is also described in section J etc. on page 1. The selection can be arbitrarily determined depending on the wavelength range to be sensitized, sensitivity, etc., and the purpose and use of the photosensitive material. Silver halide crystals can be subjected to various chemical sensitization methods that are applied to general emulsions. For chemical sensitization, Herr Freezer (H.
Frieser) edited by Die Grundlagen der.
Photo Craftsman Protease Mitsutto
Die Grundlagen der
Photographische Prozesse mit
Silberhalogeniden (Akademischen)
Verlagsgesellschaft), 1968) pages 675-734 can be used. That is, a sulfur sensitization method using a compound containing sulfur that can react with silver ions or active gelatin, a reduction sensitization method using a reducing substance, a noble metal sensitization method using gold or other noble metal compounds, etc. are used alone or in combination. be able to. As the sulfur sensitizer, thiosulfates, thioureas, thiazoles, rhodanines, and other compounds can be used, and specific examples thereof include U.S. Pat.
No. 3656955, No. 4032928, and No. 4067740. As the reduction sensitizer, stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds, etc. can be used.
Specific examples thereof are U.S. Patent No. 2487850, 2419974
No. 2518698, 2983609, 2983610, 2694637
No. 3930867 and No. 4054458. For noble metal sensitization, in addition to gold complex salts, complex salts of metals in the periodic table group such as platinum, iridium, and palladium can be used.
It is described in No. 2399083, No. 2448060, British Patent No. 618061, etc. The silver salt particles of the present invention can be produced using a combination of two or more of these chemical sensitization methods. Additionally, photosensitive layers containing the particles may be present on both sides of the support. Various dopants can be doped during the formation of each shell of the core/shell type emulsion that can be used in the present invention. Examples of the internal dopants include silver, sulfur, iridium, gold, platinum, osmium, rhodium, tellurium, selenium, cadmium, zinc, lead, thallium, iron, antimony, bismuth, arsenic, and the like. In order to dope with these dopants, each water-soluble salt or complex salt can be made to coexist when forming each shell. As the binder for the silver halide grains used in the present invention or the dispersion medium used in their production, hydrophilic colloids commonly used in silver halide emulsions are used. As a hydrophilic colloid,
Not only gelatin (either lime-treated or acid-treated), but also gelatin derivatives, such as gelatin and aromatic sulfonyl chlorides, acid chlorides, acid anhydrides, as described in U.S. Pat. No. 2,614,928;
Gelatin derivatives made by reaction with isocyanates, 1,4-diketones, US Pat. No. 3,118,766
Gelatin derivatives produced by the reaction of gelatin and trimellitic anhydride as described in Japanese Patent Publication No. 1972-5514, gelatin derivatives produced by the reaction of gelatin with an organic acid containing an active halogen as described in Japanese Patent Publication No. 1972-5514; Gelatin derivatives obtained by reacting aromatic glycidyl ether with gelatin as described in No. 26845, gelatin derivatives obtained by reacting gelatin with maleimide, maleamic acid, unsaturated aliphatic diamide, etc. described in U.S. Pat. No. 3,186,846, and British Patent No. 1033189. Polyoxyalkylene derivatives of gelatin as described in U.S. Pat. Gelatin grafted with esters, amide, acrylic (or methacrylic) nitrile, styrene and other vinyl monomers alone or in combination; synthetic hydrophilic polymeric substances;
For example, vinyl alcohol, N-vinylpyrrolidone, hydroxyalkyl (meth)acrylate,
Homopolymers containing monomers such as (meth)acrylamide and N-substituted (meth)acrylamide, or copolymers of these and (meth)
Copolymers with acrylic acid esters, vinyl acetate, styrene, etc.; copolymers with any of the above with maleic anhydride, maleamic acid, etc.; natural hydrophilic polymers other than gelatin, such as casein, agar, alginic acid, etc. Saccharides and the like can also be used alone or in combination. The silver halide photographic emulsion containing silver halide grains used in the present invention can contain various commonly used additives depending on the purpose. These additives include, for example, azoles or imidazoles, such as benchazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzthiazoles, mercaptobenz Imidazoles, mercaptothiadiazoles; triazoles, such as aminotriazoles, benzotriazoles, nitrobenzotriazoles; tetrazoles, such as mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole)
mercaptopyrimidines; mercaptriazines, e.g. thioketo compounds such as oxazolinthione; azaindenes, e.g. triazaindenes, tetraazaindenes (especially 4-
Hydroxy-substituted (1,3,3a,7)tetraazaindenes), pentaazaindenes, etc.; benzenethiosulfonic acid, benzenesulfinic acid,
It can contain stabilizers and antifoggants such as benzenesulfonic acid amide, imidazolium salts, tetrazolium salts, and polyhydroxy compounds. The photographic light-sensitive material of the present invention may contain an inorganic or organic hardener in the photographic emulsion phase or other hydrophilic colloid layer. For example, chromium salts (chromium alum,
chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylol urea,
methyloldimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), active vinyl compounds (1,3,5-triacryloyl-hexahydro-S-triazine, 1,
3-vinylsulfonyl-2-propanol, etc.),
Active halogen compounds (2,4-dichloro-6-hydroxy-S-triazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxychloroic acid, etc.), and the like can be used alone or in combination. The photographic sensitizer of the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer in the photographic emulsion layer or other hydrophilic colloid layer for the purpose of improving dimensional stability. For example alkyl(meth)acrylate, alkoxyalkyl(meth)
Acrylate, glycidyl (meth)acrylate, (meth)acrylamide, vinyl ester (e.g. vinyl acetate), acrylonitrile, olefin, styrene, etc. alone or in combination, or together with acrylic acid, methacrylic acid, α,
β-unsaturated dicarboxylic acid, hydroxyalkyl (meth)acrylate, sulfoalkyl (meth)
A polymer containing a combination of acrylate, styrene sulfonic acid, etc. as a monomer component can be used. The silver halide photographic light-sensitive material according to the present invention may contain, if necessary, a development accelerator such as benzyl alcohol or a polyoxyethylene compound; an image stabilizer such as a chroman type, a claman type, a bisphenol type, or a phosphite ester type; ; It may contain lubricants such as waxes, glycerides of higher fatty acids, and higher alcohol esters of higher fatty acids, development regulators, developing agents, plasticizers, and bleaching agents. Surfactants that may be included include anionic, cationic, and nonionic coating aids, permeability improvers for processing solutions, antifoaming agents, and materials for controlling various physical properties of photosensitive materials. A variety of types or bisexual types can be used. As the antistatic agent, diacetyl cellulose, styrene perfluoroalkyl sodium maleate copolymer, alkali salt of a reaction product of styrene-maleic anhydride copolymer and p-aminobenzenesulfonic acid, etc. are effective. Examples of matting agents include polymethyl methacrylate, polystyrene, and alkali-soluble polymers. It is also possible to use colloidal silicon oxide. Further, examples of the latex added to improve the physical properties of the film include copolymers of alkali acid esters, vinyl esters, etc., and other monomers having ethylene groups. Examples of gelatin plasticizers include glycerin and glycol compounds, and examples of thickeners include styrene-sodium maleate copolymers, alkyl vinyl ether-maleic acid copolymers, and the like. The silver halide emulsion of the present invention can have a rich latitude by mixing at least two types of emulsions with different average grain sizes and different sensitivities, or by coating in multiple layers. The silver halide emulsion according to the present invention is applicable to black and white general use, X-ray use, color use, infrared use, micro use,
It can be effectively applied to photographic materials for various uses such as silver dye bleaching, reversal, diffusion transfer, high contrast, photothermography, and heat-developable materials. Suitable for color sensitive materials. In order to apply the silver halide emulsion according to the present invention to a color photographic light-sensitive material, cyan, magenta and yellow couplers are combined with an emulsion containing the above crystals of the present invention adjusted to have red sensitivity, green sensitivity and blue sensitivity. The methods and materials used for color photosensitive materials may be used, such as incorporating the same. For example, magenta couplers include 5-pyrazolone couplers, pyrazolobenzimidazole couplers,
There are pyrazolotriazole couplers, cyanoacetylcoumarone couplers, open-chain acylacetonitrile couplers, etc., yellow couplers include acylacetamide couplers (e.g. benzoylacetanilides, pivaloylacetanilides), etc., and cyan couplers include naphthol couplers, and There are phenol couplers, etc. These couplers are preferably non-diffusive and have a hydrophobic group called a ballast group in the molecule. The coupler may be either 4-equivalent or 2-equivalent to silver ions. It may also be a colored coupler that has a color correction effect, or a coupler that releases a development inhibitor (colorless DIR coupler) in accordance with the current situation. In addition to the DIR coupler, the coupling reaction product may contain a colorless DIR coupling compound that is colorless and releases a development inhibitor. In carrying out the present invention, the following known anti-fading agents may be used in combination, and color image stabilizers may be used alone or in combination of two or more. Known antifading agents include hydroquinone derivatives, gallic acid derivatives, p-alkoxyphenols, p-oxyphenol derivatives, and bisphenols. The photosensitive material of the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, benzotriazole compounds substituted with aryl groups, 4-thiazolidone compounds, benzophenone compounds, cinnamic acid ester compounds, butadiene compounds, benzoxazole compounds, and ultraviolet absorbing polymers can be used. These ultraviolet absorbers may be fixed in the hydrophilic colloid layer. The photosensitive material of the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes.
Among them, oxonol dyes, hekioxonol dyes and merocyanine dyes are useful. The light-sensitive material of the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, etc. as a color antifoggant. The invention is also applicable to multilayer, multicolor photographic materials having at least two different spectral sensitivities on the support. Multilayer natural color photographic materials usually have at least one each of a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer on a support. The order of these layers can be arbitrarily selected as necessary. Usually, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, but different combinations may be used depending on the case. In the photographic material of the present invention, the photographic emulsion layer and other hydrophilic colloid layers can be coated on the support or on other layers by various known coating methods. For coating, a tape coating method, a roller coating method, a curtain coating method, an extrusion coating method, etc. can be used. U.S. Patent No. 2681294, U.S. Patent No. 2761791, U.S. Pat.
The method described in No. 3526528 is an advantageous method. Supports for photographic materials include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass, cellulose acetate, cellulose nitrate, polyvinyl acetal, polypropylene, polyester films such as polyethylene terephthalate, and polystyrene. The material can be selected as appropriate depending on the intended use of each photographic material. These supports are subjected to undercoat processing if necessary. After exposure, the photographic light-sensitive material containing the silver halide emulsion according to the present invention can be developed by a commonly used known method. The black and white developer is an alkaline solution containing developing agents such as hydroxybenzenes, aminophenols, and aminobenzenes, and may also contain other alkali metal salts such as sulfites, carbonates, bisulfites, bromides, and iodides. I can do it. Further, when the photographic light-sensitive material is for color use, color development can be carried out by a commonly used color development method. In the reversal process, the film is first developed with a black-and-white negative developer and then exposed to white light or treated with a bath containing a fogging agent.
Further, color development is performed using an alkaline developer containing a generated developing agent. There are no particular restrictions on the processing method;
All kinds of processing methods can be applied, but typical ones include a method in which bleaching and fixing are performed after color development, followed by washing and stabilizing treatment if necessary, or a method in which bleaching and fixing are separated after color development. If necessary, a method of further performing washing with water and stabilization treatment can be applied. Color developing solutions generally consist of an alkaline aqueous solution containing a color developing agent. The color developing agent is a known primary aromatic amine developer, such as phenylenediamines (e.g., 4-amino-N,N-diethylaniline, 3-amino-N,N-diethylaniline,
Methyl-4-amino-N,N-diethylaniline, 4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N
-ethyl-N-β-hydroxyethylaniline,
3-Methyl-4-amino-N-ethyl-N-β-
methanesulfamide ethylaniline, 4-amino-3-methyl-N-ethyl-N-β-methoxyethylaniline, etc.) can be used. In addition, LFA Masson (LFA
Photographic Processing Chemistry (Mason)
Chemistry), (Focal Press
Press, 1966), pages 226-229, U.S. Patent
Those described in No. 2193015, No. 2592364, JP-A-48-64933, etc. may be used. The color developing solution can also contain a PH buffer, a development inhibitor or an antifoggant. In addition, water softeners, preservatives, organic solvents,
development accelerators, dye-forming couplers, competitive couplers,
It may also contain a fogging agent, an auxiliary developer, a viscosity imparting agent, a polycarboxylic acid chelating agent, an antioxidant, and the like. After color development, the photographic emulsion layer is usually bleached. The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. Bleach agents include iron (), cobalt (), chromium (), and copper ().
Compounds of polyvalent metals such as, peracids, quinones, nitroso compounds, etc. are used. Bleach or bleach-fix solution has US Patent 3042520
No. 3241966, Special Publication No. 1977-8506, Special Publication No. 1973
Bleach-fixing agent described in -8836 etc., JP-A-5-
In addition to the thiol compound described in No. 65732, various additives can also be added. The photosensitive material according to the present invention can be used not only for photographic film but also for printing paper. E. Examples Specific examples of the present invention will be described below. In all of the following examples, the amount added to the silver halide color photographic material is shown per 1 m ² . In addition, silver halide and colloidal silver are shown in terms of silver. Example 1 Support coated with an antihalation layer (BS)
RL-1, RH-1, shown below in order upward from
IL, GL-1, GH-1, YF, BL-1, BH-
1. Laminated Pro. Layer-1: 0.4g black colloidal silver and 3.0g gelatin
Antihalation layer-2 containing: Low-sensitivity layer (RL-1) of red-sensitive silver halide emulsion layer A monodispersed emulsion (emulsion) consisting of AgBRI containing 6 mol% of AgI was color-image-sensitized to red-sensitivity. thing 1.8
g and 0.2 g of 1-hydroxy-4-(isopropylcarbamoylmethoxy)-N-[δ-(2,
4-di-t-amylphenoxy)butyl]-2
- naphthamide (referred to as C-1), 0.07 g of 1
-Hydroxy-4-[4-(1-hydroxy-8
-acetamido-3,6-disulfo-2-naphthylazo)phenoxy]-N-[δ-(2,4-
di-t-amylphenoxy)butyl]-2-naphthamide disodium (referred to as CC-1),
0.8 g of 1-hydroxy-2-[δ-(2,4-
A dispersion in which di-t-amylphenoxy)-n-butyl]naphthamide (referred to as C-2) was dissolved in 0.5 g of tricresyl phosphate (referred to as TCP) and emulsified and dispersed in an aqueous solution containing 1.85 g of gelatin. A low-speed layer of a red-sensitive silver halide emulsion layer containing . Layer-3: High-sensitivity layer (RH-1) of red-sensitive silver halide emulsion layer A monodisperse emulsion (emulsion) consisting of AgBrI containing 6 mol% of AgI is color-sensitized to red sensitivity 2.0
g, 0.20g of cyan coupler (C-1),
0.03g colored cyan coupler (CC-1)
A high-sensitivity layer of a red-sensitive silver halide emulsion layer containing a dispersion that is dissolved in 0.23 g of TCP and emulsified and dispersed in an aqueous solution containing 1.2 g of gelatin. Layer-4: 0.04g of Q-1 dissolved in 0.07g of Q-1
n-Butyl phthalate (hereinafter referred to as DBP)
Intermediate layer containing 1.2g gelatin. Layer-5: Low-sensitivity layer of green-sensitive silver halide emulsion layer (GL-1) 1.5 g of a green-sensitized emulsion,
0.65 g of 1-(2,4,6-trichlorophenyl)-3-[3-(p-dodecyloxybenzenesulfonamido)benzamide]-5-pyrazolone (referred to as M-1), 0.15 g of 1-( 2, 4,
0.68 g of TCP in which 6-trichlorophenyl)-4-(1-naphthylazo)-3-(2-chloro-5-octadecenylsuccinimidoanilino)-5-pyrazolone (referred to as CM-1) was dissolved was added.
A low-speed layer of a green-sensitive silver halide emulsion layer containing a dispersion emulsified in an aqueous solution containing 1.4 g of gelatin. Layer-6: High-sensitivity layer of green-sensitive silver halide emulsion layer (GH-1) 2.2 g of emulsion color-sensitized to green sensitivity,
0.22g magenta coupler (M-1) and
0.045g colored magenta coupler (CM-
A high-sensitivity layer of a green-sensitive silver halide emulsion layer containing a dispersion in which 0.27 g of TCP dissolved in 1) was emulsified and dispersed in an aqueous solution containing gelatin. Layer-7: Yellow filter layer containing 0.2 g of yellow colloidal silver and 2.1 g of gelatin Layer-8: Low-speed layer of blue-sensitive silver halide emulsion layer (BL-1) Color sensitization of the emulsion to blue sensitivity 0.8g of
1.2 g of α-pivaloyl-α-(1-benzyl-
2-phenyl-3,5-dioxysoimidazolidin-4-yl)-2-chloro-5-[α-dodecyloxycarbonyl)ethoxycarbonyl]
Acetanilide (referred to as Y-1), 0.01 g
0.68g TCP in which DIR compound (D-1) was dissolved
A low-sensitivity layer of a blue-sensitive silver halide emulsion layer containing a dispersion emulsified and dispersed in an aqueous solution containing gelatin. Layer-9: High sensitivity of blue-sensitive silver halide emulsion layer (BH-1) 0.7 g of an emulsion made of AgBrI containing 8 mol% of AgI and color sensitized to blue sensitivity, and a yellow coupler (Y-1) ) A high-sensitivity layer of a blue-sensitive silver halide emulsion layer containing a dispersion in which 0.35 g of TCP dissolved in TCP is emulsified and dispersed in an aqueous solution containing gelatin. Layer-10: Protective layer (Pro) 2.3g gelatin protective layer. Regarding the samples prepared as described above, a low-sensitivity blue-sensitive layer (BL-1) and a high-sensitivity blue-sensitivity layer (BH-
1) Table of the amounts of AS agent and gelatin contained in it.
Changed it like 1. In the same table, "amount" is in g, and "film thickness" is in μm.

[Color developer]

4-amino-3-methyl-N-ethyl-N-(β
-Hydroxyethyl)-Aniline sulfate 4.75g Anhydrous sodium sulfite 4.25g Hydroxyamine 1/2 sulfate 2.0g Anhydrous potassium carbonate 37.5g Sodium bromide 1.3g Nitrilotriacetic acid trisodium salt (monohydrate)
2.5g Potassium hydroxide 1.0g Add water to make 1. [Bleach solution] Ethylenediaminetetraacetic acid iron ammonium salt
100.0g Ethylenediaminetetraacetic acid diammonium salt 10.0g Ammonium bromide 15.0g Glacial acetic acid 10.0ml Add water to make 1, and use acetic acid water to adjust pH to 6.0
Adjust to. [Fixer] Ammonium thiosulfate 175.0g Anhydrous sodium sulfite 8.5g Sodium metasulfite 2.3g Add water to make 1, and adjust the pH using aqueous ammonia.
= 6.0. [Stabilizer] Formalin (37% aqueous solution) 1.5ml Konidax (manufactured by Konishiroku Photo Industry Co., Ltd.) 7.5ml Add water to make 1. For each sample obtained, blue light (B),
Relative sensitivity (S) and
MTF and RMS were measured. The results are shown in Table 3. Note that the relative sensitivity (S) is the relative value of the reciprocal of the exposure amount that gives the fog density +0.1;
The sensitivity of G and R is expressed as a value of 100. The RMS value is expressed as 100 times the standard deviation of the variation in density values that occurs when scanning the three minimum concentrations of +0.5, +1.0, and +1.5 using a microdecitometer with a circular scanning aperture of 25 μm. . The results are shown in Table-2.

[Table] From the results in Table 2, it can be seen that the oxidized developing agent scavenger of the present invention can be used especially in a high exposure range.
It can be seen that the RMS value is reduced and the performance is greatly improved by the silver density and emulsion layer thickness of the present invention. Example 2 In Example 1, the emulsion layer to which the present invention is applied was a green-sensitive layer, and the amounts of the AS agent and gelatin were varied as shown in Table 3. When processed in the same way, the table -
Results like 4 were obtained.

【table】

【table】

[Table] Example 3 A sample was prepared in the same manner as in Example 1 except that the layer structure was reversed as shown below (Table -
5). From the bottom layer: BS → RL-1 → IL → GL-1 →
IL→BL−1→IL→RH−1→IL→GH−1→IL→
BH-1→Pro. The results are shown in Table 6, and all the examples based on the present invention have good results.

【table】

【table】

【table】

[Table] Example 4 In Example 2, a sample was prepared with the same layer structure as in Example 3 (see Table 7). The results are shown in Table 8, and all the examples based on the present invention had good results.

【table】

【table】

【table】

【table】

Claims (1)

[Claims] 1. The silver density d of the silver halide emulsion layer is d=N/V [However, N is the total amount of silver (converted to metallic silver) in the silver halide emulsion layer (unit: g), V
is the volume of the silver halide emulsion layer (unit: cm ³ )], the silver density d of the blue-sensitive silver halide emulsion layer is 4.0 × 10 ^-1 g/cm ³ or more, and The dry film thickness of the blue-sensitive silver halide emulsion layer is 4.0 μm or less, the silver density d of the green-sensitive silver halide emulsion layer is 5.0 × 10 ^-1 g/cm ³ or more, and The dry film thickness of the silver halide emulsion layer is 4.5 μm or less, and the silver halide emulsion layer has the above-mentioned silver density in the blue-sensitive silver halide emulsion layer and/or the green-sensitive silver halide emulsion layer. , or a non-emulsion layer adjacent to at least one of these emulsion layers has a relative reaction rate of 1.6 or more,
15. A silver halide photographic light-sensitive material, characterized in that it contains a fast-reactive developing agent oxidized product scavenger having a molecular weight of 15.0 or less.