JPH0575096B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a silver halide photographic material,
In particular, the present invention relates to a silver halide photographic material using an emulsion comprising silver halide grains having a novel structure. (Prior Art) The basic properties required of silver halide emulsions for photography are high sensitivity, low fog, fine grain size, and high development activity. Silver halides include silver fluoride, silver chloride, silver bromide, and silver iodide, but because silver fluoride is highly water-soluble, it is not normally used in photographic emulsions, and the remaining three types of silver halides are Efforts have been made to improve the basic performance of emulsions by combining them. Regarding light absorption, silver chloride, silver bromide, and silver iodide become stronger in that order, but development activity decreases in that order, making it difficult to achieve both light absorption and development activity. Klein and Moisal proposed mixed silver halide emulsions (specifically, silver bromide , a first layer made of silver iodobromide containing 1 mol % of silver iodide, and an outer layer made of silver bromide), it was disclosed that photosensitivity can be enhanced without impairing development activity. (Japanese Patent Publication No. 43-13162) Koitabashi et al. found that when a thin shell with a thickness of 0.01 to 0.1 μm was attached to a core grain with a relatively low silver iodide content, favorable photographic properties such as improved covering power were obtained. disclosed what can be obtained. (Unexamined Japanese Patent Publication 1987)
-154232 publication) These inventions have a low silver iodide content in the core part,
Therefore, it is useful when the total silver iodide content is low. However, in order to achieve even higher sensitivity and higher image quality, it was essential to increase the iodine content of the emulsion. High sensitivity and high image quality by increasing the iodine content of the core part are disclosed in Japanese Patent Application Laid-open Nos. 138538-1982 and 1983-1989.
Publication No. 88253, Japanese Patent Application Publication No. 177535/1986, Japanese Patent Application Publication No. 177535
It is disclosed in JP-A No. 61-112142, Japanese Unexamined Patent Publication No. 143331-1980, and the like. The common technical idea of these series of patents is to achieve both development activity and photosensitivity by increasing the iodine content of the core part as much as possible and lowering the iodine content of the shell part. However, dual-structure particles based on this technical concept still have problems such as large inherent desensitization caused by the sensitizing dye and the sensitizing dye being easily desorbed when the sensitive material is stored under high humidity conditions. Ta. (Problems to be Solved by the Invention) Therefore, the first object of the present invention is to provide a silver halide photographic material that has excellent color sensitization and therefore has an improved sensitivity/granularity ratio. . The second object is to provide a silver halide photographic material that exhibits less deterioration in performance when stored under high humidity conditions. (Means for Solving the Problems) As a result of intensive research, the present inventors have found that the object of the present invention is to have a silver iodobromide phase with a silver iodide mole fraction of 10 to 40 mol% inside the grains. However, this silver iodobromide phase is coated with silver halide containing lower silver iodide, and the surface of the grain, that is, XPS (X-ray
It has been found that this can be achieved when the silver iodide content in a portion with a depth of about 50 Å analyzed by a surface analysis method (photoelectron spectroscopy) is 5 mol % or more. The mechanism by which the object of the present invention is achieved by controlling the distribution of iodide ions in silver halide grains is not clear. Regarding the principle of the XPS method used to analyze the iodine content near the surface of silver halide grains, refer to Junichi Aihara et al.'s "Electron Spectroscopy" (Kyoritsu Library 16, published by Kyoritsu Publishing, 1978). can do. The standard XPS measurement method uses Mg as the excitation X-ray.
-Kα is used to observe the intensity of photoelectrons of iodine and silver (usually I-3d _5/2 , Ag-3d _5/2 ) emitted from silver halide grains in an appropriate sample form. be. To determine the iodine content, several types of standard samples with known iodine contents are used to measure iodine I and silver.
Intensity ratio of photoelectrons of Ag (Intensity (I)/Intensity (Ag))
A calibration curve can be created and the calculation can be made from this calibration curve. In the case of silver halide emulsions, XPS measurements must be performed after the gelatin adsorbed on the silver halide grain surfaces is decomposed and removed using a protease or the like. The silver iodide content in the core and shell portions can be measured by X-ray diffraction. An example of applying the X-ray diffraction method to silver halide grains is given in H. Hirsch's Journal of Photographic Science, Vol. 10 (1962), pages 129 onwards. When the lattice constant is determined by the halogen composition, a diffraction peak occurs at a diffraction angle that satisfies Bragg's condition (2dsinθ=nλ). For information on X-ray diffraction measurement methods, please refer to the Basic Analytical Chemistry Course
24 “X-ray analysis” (Kyoritsu Shuppan) and “X-ray diffraction guide”
(Rigaku Denki Co., Ltd.) and others. The standard measurement method is to use Cu as a target and obtain the diffraction curve of the (220) plane of silver halide using Cu's Kβ rays as a radiation source (tube voltage 40 KV, tube current 60 mA). In order to increase the resolution of the measuring device, the width of the slit (diverging slit, receiving slit, etc.), the time constant of the device, the scanning speed of the goniometer, and the recording speed are selected appropriately and the measurement accuracy is confirmed using a standard sample such as silicon. There is a need to. (220) of silver halide using Cu Kβ radiation
10 ~ when obtaining the curve of diffraction intensity versus diffraction angle of the surface
In some cases, the diffraction peak corresponding to a high iodine layer containing 45 mol% silver iodide and the diffraction peak corresponding to a low iodine layer are clearly separated, and in other cases, two distinct peaks are detected when they overlap each other. The peaks may not be separated. The method of decomposing a diffraction curve made up of two diffraction components is well known, and is explained in, for example, Experimental Physics Course 11 Lattice Defects (Kyoritsu Publishing). It is also useful to assume that the curve is a function such as a Gaussian function or a Lorentzian function and to analyze it using a Du Pont curve analyzer or the like. The silver halide grains used in the present invention may or may not have a clear separation between the low iodine layer and the high iodine layer. Even in the case of an emulsion in which two types of grains having different halogen compositions coexist and do not have a clear layered structure, two peaks appear in the X-ray diffraction. Such emulsions cannot exhibit the excellent photographic performance obtained with the present invention. In order to judge whether a silver halide emulsion is an emulsion according to the present invention or an emulsion in which two types of silver halide grains coexist as described above, in addition to the X-ray diffraction method, the EPMA method (Electron −Probe Micro
This is possible by using the Analyzer method). In this method, a well-dispersed sample is prepared so that the emulsion grains do not come into contact with each other, and then an electron beam is irradiated. Elemental analysis of extremely small parts can be performed by X-ray analysis using electron beam excitation. By this method, the halogen composition of each particle can be determined by determining the characteristic X-ray intensities of silver and iodine emitted from each particle. By confirming the halogen composition of at least 50 grains by the EPMA method, it can be determined whether the emulsion is an emulsion according to the present invention. In the emulsion of the present invention, it is preferable that the iodine content among grains is more uniform. When the distribution of iodine content among particles was measured using the EPMA method, the relative standard deviation was 50% or less, and
It is preferably 35% or less, particularly 20% or less. Preferred halogen compositions of the silver halide grains of the present invention are as follows. The core part is high iodine silver halide, and the average iodine content ranges from 10 mol% to 40 mol%, which is the solid solution limit.
It's between. Preferably, it is 15 to 40 mol%,
More preferably, it is 20 to 40 mol%. Depending on the method of preparing the core particles, the optimum value of the core iodine content may exist between 20 and 40 mol%, and in other cases between 30 and 40 mol%. Silver halide other than silver iodide in the core portion is preferably silver bromide. The average iodide content of the shell portion is lower than that of the core portion, preferably silver halide containing 10 mol% or less of silver iodide, more preferably 5
It is a silver halide containing less than mol% of silver iodide.
The distribution of silver iodide in the shell portion may be uniform or non-uniform. The grains of the present invention have an average silver iodide content on the grain surface measured by the XPS method of 5 mol% or more, preferably 7 mol% or more and 15 mol% or less, and higher than the average silver iodide content of the shell portion. It is. The distribution of silver iodide near the grain surface may be uniform or non-uniform. The silver halide other than silver iodide on the surface may be silver chloride, silver chlorobromide or silver bromide, but it is preferable that the proportion of silver bromide is high. Regarding the total halogen composition, the effect of the present invention is remarkable when the silver iodide content is 7 mol % or more. More preferably, the total silver iodide content is 9 mol% or more, particularly preferably 12 mol% or more, and 18
It is less than mol%. The size of the silver halide grains of the present invention is not particularly limited, but is preferably 0.4 μm or more, more preferably 0.6 μm.
It is preferable that it is 2.5 micrometers. The silver halide grains of the present invention may have regular crystal shapes (normal crystal grains) such as hexahedrons, octahedrons, dodecahedrons, and dodecahedrons, or may have spherical, diagonal, or cylindrical shapes. It may have an irregular crystal shape such as a shape or a plate shape. In the case of normal crystal grains, grains having 50% or more (111) planes are particularly preferred. Even in the case of irregular crystal shapes, particles having 50% or more (111) planes are particularly preferred.
The surface ratio of the (111) plane can be determined by the Kubelka-Munk dye adsorption method. This preferentially adsorbs to either the (111) or (100) plane, and the (111)
Select a dye in which the association state of the dye on the plane and the association state of the dye on the (100) plane differ spectrally. The surface ratio of the (111) plane can be determined by adding such a dye to an emulsion and examining the spectra in detail with respect to the amount of dye added. In the case of twin grains, tabular grains are preferred.
It is particularly preferred that grains with a thickness of 0.5 μm or less, a diameter of 0.6 μm or more, and an average aspect ratio of 2 or more, preferably 3 to 10, occupy at least 50% of the total projected area of the silver halide grains present in the same layer. . For the definition and measurement method of average aspect ratio, see
Publication No. 113926, Japanese Patent Publication No. 113930, Japanese Patent Publication No. 1983-113930, Japanese Patent Publication No. 113926
It is specifically described in Publication No. 58-113934. Although the emulsions of the present invention can have a wide grain size distribution, emulsions with a narrow grain size distribution are preferred. In particular, in the case of normal crystal grains, the total weight or number of silver halide grains in each emulsion
The particle size that accounts for 90% is ± of the average particle size.
A monodispersed emulsion having a dispersion within 40%, more preferably within ±30%, is preferable. The silver halide grains of the present invention can be prepared by selecting and combining various methods. First, the core particles can be prepared using methods such as acid method, neutral method, ammonia method, etc., and one-sided mixing method, which involves reacting soluble silver salt and soluble halide salt.
You can choose from simultaneous mixing methods, their combinations, etc. As one type of simultaneous mixing method, a method of keeping the pAg in the liquid phase in which silver halide is produced constant, ie, a controlled double jet method, can also be used. As another type of simultaneous mixing method, a triple-jet method in which soluble halogen salts of different compositions are added independently (for example, soluble silver salt, soluble bromine salt, and soluble iodine salt) can also be used. Silver halide solvents such as ammonia, rhodan salts, thioureas, thioethers, and amines may be selected and used during core preparation. It is desirable that the emulsion has a narrow grain size distribution of core grains. In particular, the above-mentioned monodisperse core emulsion is preferred. Whether the halogen composition of each particle is uniform at the core stage can be determined by the aforementioned X-ray diffraction method and EPMA method. When the halogen composition of the core particles is more uniform, the diffraction width of X-ray diffraction becomes narrower and sharper peaks are obtained. Japanese Patent Publication No. 49-21657 discloses a method for preparing core particles having a uniform halogen composition among the particles. One method is to make a solution of 5 g of inert gelatin and 0.2 g of potassium bromide in 700 ml of distilled water using the double jet method, stir this at 50°C, and mix 52.7 g of potassium bromide and 24.5 g of potassium bromide. Add 1 aqueous solution containing 1 g of potassium iodide and 1 aqueous solution containing 100 g of silver nitrate to the previously stirring solution at the same constant speed over a period of about 80 minutes, and add distilled water to bring the total volume to 3. Silver iodobromide with a silver iodide content of 25 mol% was obtained. It has been determined by X-ray diffraction that the silver iodobromide grains have a relatively sharp iodine distribution. Another method is the lattice adhesion method, which uses 33g of inert bone gelatin and potassium bromide.
An aqueous solution of 5.4 g of potassium iodide and 4.9 g of potassium iodide dissolved in 500 ml of distilled water was stirred at 70°C, and 125 ml of an aqueous solution of 12.5 g of silver nitrate was instantly added thereto to reduce the silver iodide content to 40 mol. %, relatively uniform silver iodobromide grains were obtained. JP-A No. 56-16124 discloses that a silver iodobromide emulsion containing silver iodide with a halogen composition of 15 to 40 mol% is used to maintain the pAg of a solution containing a protective colloid in the range of 1 to 8, thereby producing a uniform iodine odor. It is disclosed that silver oxide can be obtained. After preparing silver iodobromide seed crystals containing a high concentration of silver iodide, the addition rate is accelerated over time as disclosed by Irie and Suzuki in Japanese Patent Publication No. 48-36890, or by Saito in US Pat. 4242445
Uniform silver iodobromide can also be obtained by the method of growing silver iodobromide grains by increasing the additive concentration over time, as disclosed in the above publication. These methods give particularly favorable results. The method of Irie et al.
In a method for producing poorly soluble inorganic crystals for photography by a double decomposition reaction in which two or more inorganic salt aqueous solutions are simultaneously added in approximately equal amounts in the presence of a protective colloid, the inorganic salt aqueous solutions to be reacted are added at a constant addition rate. above, and at an addition rate Q that is less than or equal to the addition rate that is proportional to the total surface area of the growing poorly soluble inorganic salt crystal, that is, Q = γ or more and Q = αt ²
It is added at a value below +βt+γ. On the other hand, Saito's method is a silver halide crystal production method in which two or more inorganic salt aqueous solutions are simultaneously added in the presence of a protective colloid, and the concentration of the inorganic salt aqueous solution to be reacted is adjusted so that almost no new crystal nuclei are produced during the crystal growth period. This is to increase the amount to such an extent that it does not occur. In addition, JP-A-60-138538, JP-A-61-
Publication No. 88253, Japanese Patent Application Publication No. 177535/1986, Japanese Patent Application Publication No. 177535
It can be prepared by applying the emulsion preparation method described in JP-A-61-112142, JP-A-60-143331, and the like. There are many methods for introducing silver iodide into the shell portion of the silver halide grains of the present invention. When an aqueous solution of a water-soluble bromide salt and an aqueous solution of a water-soluble silver salt are added by a double jet method, the silver iodide in the core portion may ooze out into the shell portion. In this case, the amount and distribution of silver iodide in the shell portion can be controlled by adjusting pAg during addition and using a silver halide solvent. Furthermore, an aqueous solution containing a mixture of water-soluble bromide and water-soluble iodide and a water-soluble silver salt aqueous solution can be added by the double-jet method, or a water-soluble aqueous bromide solution, a water-soluble iodide aqueous solution, and a water-soluble silver salt can be added by the triple-jet method. It can also be added. To introduce silver iodide onto the grain surface or at a position 50 to 100 Å from the grain surface,
After grain formation, an aqueous solution containing water-soluble iodide may be added, or fine silver iodide grains of 0.1 μm or less or fine silver halide grains with a high silver iodide content may be added. In preparing the silver halide grains of the present invention,
Although shelling may be carried out directly after the formation of core grains, it is preferable to wash the core emulsion with water for desalination before carrying out shelling. Shelling can also be prepared by various methods known in the field of silver halide photographic materials, but a simultaneous mixing method is preferred. The aforementioned methods of Irie et al. and Saito's method are preferred as methods for producing emulsions having a clear layered structure. The required shell thickness varies depending on the particle size, but is 0.1μ for large particles of 1.0μ or more.
0.05μm for small particles of 1.0μm or more and 1.0μm or less
It is desirable that the shell be covered with a shell thickness greater than or equal to the thickness of the shell. It is preferable that the silver content ratio between the core part and the shell part is in the range of 1/5 to 5, more preferably 1/5.
-3, and a range of 1/5 to 2 is particularly preferable. In the present invention, in the process of silver halide grain formation or physical ripening, cadmium salt, zinc salt, lead salt,
A thallium salt, an iridium 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 coexisting. The silver halide emulsions of the present invention are chemically sensitized.
For chemical sensitization, see, for example, Die H.Frieser.
Grundlagen der Photographischen Prozesse
mit Silberhalogeniden (Akademische
Verlagsgesellschaft, 1968) pages 675-734 can be used. Namely, sulfur sensitization using sulfur-containing compounds that can react with active gelatin and silver (e.g., thiosulfates, thioureas, mercapto compounds, rhodanines); reducing substances (e.g., stannous salts, reduction sensitization using noble metal compounds (e.g., gold complex salts,
Complex salts of periodic table group metals such as Pt, Ir, and Pd)
A noble metal sensitization method using a sensitizer can be used alone or in combination. Specific examples of these include U.S. Patent Nos. 1574944, 2410689, and 2278947 for sulfur sensitization methods;
U.S. Patent Nos. 2728668 and 3656955, etc., and U.S. Patent Nos. 2983609 and 2419974 for reduction sensitization methods,
4054458, U.S. Patent No. 2399083, U.S. Patent No. 2448060, British Patent No.
It is described in each specification such as No. 618061. Gelatin is advantageously used as a protective colloid and as a binder for other hydrophilic colloid layers used in the preparation of emulsions comprising silver halide grains according to the invention, but other hydrophilic colloids may also be used. can. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol , polyvinyl alcohol partial acetal,
Poly-N-vinylpyrrolidone, polyacrylic acid,
A wide variety of synthetic hydrophilic polymeric materials can be used, such as single or copolymers of polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, and the like. In addition to lime-processed gelatin, acid-processed gelatin and Bull.Soc.Sci.Phot.Japan, No. 16,
Enzyme-treated gelatin as described in P30 (1966) may be used, and gelatin hydrolysates and enzymatically decomposed products may also be used. The photographic emulsions used in the present invention may be spectrally sensitized with methine dyes and others. The pigments used include cyanine pigments, merocyanine pigments,
Included are complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and these A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus of Nucleus, quinoline nucleus, etc. can be applied.
These nuclei may be substituted on carbon atoms. The merocyanine dye or composite merocyanine dye includes a nucleus having a ketomethylene structure such as a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thioxazolidine-2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanine nucleus, A 5- to 6-membered heteroartic ring nucleus such as a thiobarbituric acid nucleus can be applied. These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization.
Typical examples are U.S. Patent No. 2688545, U.S. Patent No. 2977229,
3397060, 3522052, 3527641, 3527641, 3522052, 3527641,
No. 3617293, No. 3628964, No. 3666480, No.
No. 3672898, No. 3679428, No. 3703377, No. 3672898, No. 3679428, No. 3703377, No.
No. 3769301, No. 3814609, No. 3837862, No. 3837862, No. 3814609, No. 3837862, No.
4026707, British Patent No. 1344281, British Patent No. 1507803,
Special Publication No. 43-4936, No. 53-12375, Japanese Patent Publication No. 52-
It is described in No. 110618, No. 52-109925, etc. 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. The silver halide grains used in the present invention are preferably spectrally sensitized with a sensitizing dye of the following general formula [] or []. These sensitizing dyes may be used alone or in combination. General formula []

embedded image In the formula, Z ₁ and Z ₂ represent a group of atoms forming a 5- or 6-membered nitrogen-containing heterocycle, which may be different or the same. For example, thiazoline, thiazole, benzothiazole, naphthothiazole, selenazoline, selenazole, benzoselenazole, naphthoselenazole, oxazole, benzoxazole, naphthoxazole, benzimidazole, naphthoimidazole, pyridine, quinoline, indolenine,
Examples include heterocycles such as imidazo[4,5-b]quinoxaline, and these heterocycle nuclei may be substituted. Examples of substituents include lower alkyl groups (preferably having 6 or less carbon atoms, which may be further substituted with a hydroxy group, a halogen atom, a phenyl group, a substituted phenyl group, a carboxy group, an alkoxycarbonyl group, an alkoxy group, etc.) ),
lower alkoxy group (preferably carbon number 6 or less),
Examples thereof include an acylamino group (preferably having 8 or less carbon atoms), a monocyclic aryl group, a carboxy group, a lower alkoxycarbonyl group (preferably having 6 or less carbon atoms), a hydroxy group, a cyano group, and a halogen atom. Q ₁ represents a 5-, 6-membered nitrogen-containing ketomethylene ring-forming atom group, such as thiazolidin-4-one, selenazolidin-4-one, oxazolidin-4-
ion, imidazolidin-4-one, and the like. R ₁ , R ₂ , R ₃ and R ₄ represent a hydrogen atom, a lower alkyl group (preferably having 4 or less carbon atoms), an optionally substituted phenyl group, an aralkyl group, and l ₁
represents 2 or 3, and n represents 2 or 3
When representing different R ₁ and R ₁ , R ₂ and R ₂ , R ₃ and R ₃
Alternatively, R ₄ and R ₄ can be linked to form a 5- or 6-membered ring that may contain an oxygen atom, a sulfur atom, a nitrogen atom, or the like. R ₅ , R ₆ and R ₇ are carbon numbers that may contain oxygen atoms, sulfur atoms or nitrogen atoms in the carbon chain.
Represents an optionally substituted alkyl group or alkenyl group of 10 or less. Examples of substituents include:
Examples include a sulfo group, a carboxy group, a hydroxy group, a halogen atom, an alkoxycarbonyl group, a carbamoyl group, a phenyl group, and a substituted phenyl group. In addition, when the heterocycle represented by Z ₁ and Z ₂ contains another substitutable nitrogen atom such as benzimidazole, naphthoimidazole, imidazo[4,5-b]quinoxaline, the other heterocycle of those heterocycles The nitrogen atom may be substituted with an alkyl group, an alkenyl group, etc., which may be further substituted with, for example, a hydroxy group having 6 or less oxygen atoms, an alkoxy group, a halogen atom, a phenyl group, or an alkoxycarbonyl group. l ₁ and n ₁ are 0 or positive integers less than or equal to 3, and l ₁ +
When n ₁ represents 3 or less and l ₁ is 1, 2 or 3, R ₅ and R ₁ may be linked to form a 5- or 6-membered ring. j ₁ , k ₁ and m ₁ represent 0 or 1. X ₁ ^- represents an acid anion, and n represents 0 or 1. More preferably, at least one of R ₅ , R ₆ and R ₇ is a group containing a sulfo group or a carboxy group. Among the sensitizing dyes included in the general formula [], preferred ones are as follows.

【formula】

【formula】

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【formula】

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[ka] General formula []

embedded image In the formula, Z ₁₁ represents a nitrogen-containing 5-, 6-membered heterocyclic ring-forming atom group. For example, thiazoline, thiazole,
Benzothiazole, naphthothiazole, selenazoline, selenazole, benzoselenazole, naphthoselenazole, oxazole, benzoxazole, naphthoxazole, benzimidazole, naphthimidazole, pyridine, quinoline,
Pyrrolidine, indolenine, imidazo [4,5-
b] Heterocyclic nuclei commonly used for cyanine formation, such as quinoxalinetetrazole, may be mentioned, and these heterocyclic nuclei may be substituted. Examples of substituents include lower alkyl groups (preferably
10 or less, which may be further substituted with a hydroxy group, a halogen atom, a phenyl group, a substituted phenyl group, a carboxy group, an alkoxycarbonyl group, an alkoxy group, etc.), a lower alkoxy group (preferably having 7 or less carbon atoms), an acylamino group (preferably carbon number 8 or less), monocyclic aryl group, monocyclic aryloxy group, carboxy group, lower alkoxycarbonyl group (preferably carbon number 7 or less), hydroxy group,
Examples include a cyano group and a halogen atom. Q ₁₁ represents a nitrogen-containing 5-, 6-membered ketomethylene ring-forming atom group. For example, thiazolidin-4-one, selenazolidin-4-one, oxazolidin-4-one
Examples include atomic groups forming one, imidazolidin-4-one, and the like. Q ₁₂ represents a nitrogen-containing 5-, 6-membered ketomethylene ring-forming atom group. For example, rhodanine, 2-thiohydantoin, 2-selenathiohydantoin, 2-thioxazolidine-2,4-dione, 2-selenaoxazolidine-2,4-dione, 2-thioselenazolidine-2,4-dione, 2-selenathiazolidine-2,4-dione, 2-selenazolidine-
Examples include atomic groups that form heterocyclic nuclei such as 2,4-dione that can normally form merocyanine dyes. In the heterocycle represented by Z ₁₁ , Q ₁₁ and Q ₁₂ above, when the heterocycle atoms contain two or more nitrogen atoms, such as benzimidazole or thiohydantoin, R ₁₃ , R ₁₅ , R The nitrogen atom to which ₁₄ is not connected may be substituted, and as a substituent, the carbon atom in the alkyl chain may be substituted with an oxygen atom, sulfur atom or nitrogen atom,
Further examples include an alkyl group having 8 or less carbon atoms which may have a substituent, an alkenyl group, or a monocyclic aryl group which may be substituted. R ₁₁ represents a hydrogen atom or an alkyl group having 4 or less carbon atoms, and R ₁₂ represents a hydrogen atom, an optionally substituted phenyl group (examples of substituents include alkyl having 4 or less carbon atoms, an alkoxy group, or a halogen atom, (carboxy group, hydroxy group, etc.), or an alkyl group which may be substituted with a hydroxy group, a carboxy group, an alkoxy group, a halogen atom, etc. When m ₂₁ represents 2 or 3, different R ₁₂ and R ₁₂ are connected to form an oxygen atom,
5,6 which may contain a sulfur atom or a nitrogen atom
It may form a membered ring. R ₁₃ represents an optionally substituted alkyl group or alkenyl group having 10 or less carbon atoms which may contain an oxygen atom, sulfur atom or nitrogen atom in the carbon chain. Examples of the substituent include a sulfo group, a carboxy group, a hydroxy group, a halogen atom, an alkoxycarbonyl group, a carbamoyl group, a phenyl group, a substituted phenyl group, or a monocyclic saturated heterocyclic group. R ₁₄ and R ₁₅ have the same meaning as R ₁₃ , and also have a hydrogen atom or an optionally substituted monocyclic aryl group (examples of substituents include sulfo group, carboxy group, hydroxy group, halogen atom, carbon number It also represents an alkyl group of 5 or less, an acylamino group, an alkoxy group, etc.). m ₂₁ represents 0 or a positive integer less than or equal to 3, and j ₂₁
represents 0 or 1, and n ₂₁ represents 0 or 1. When m ₂₁ is a positive integer less than or equal to 3, R ₁₁ and
It may be linked with R ₁₃ to form a 5- or 6-membered ring. More preferably, at least one of R ₁₃ , R ₁₄ and R ₁₅ is a group containing a sulfo group or a carboxy group. Among the sensitizing dyes included in the general formula [], the following compounds are particularly preferred.

【formula】

【formula】

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【formula】

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【formula】

【formula】

[Formula] In the present invention, it is particularly preferable to carry out supersensitization using a compound represented by the following general formula [] described in JP-A-62-89952. General formula []

[Formula] (wherein, R represents an aliphatic group, aromatic group, or heterocyclic group substituted with at least one -COOM or -SO ₃ M, and M represents a hydrogen atom, an alkali metal atom, a quaternary represents ammonium or quaternary phosphonium.) Preferred specific examples of the compound represented by the general formula [] used in the present invention are listed below. (however,
It is not limited only to these. )

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embedded image It is preferable that the silver halide grains used in the present invention contain a sulfur-containing silver halide solvent. The sulfur-containing silver halide solvent used in the present invention may be added at any step from grain formation to coating. The amount of the sulfur-containing silver halide solvent used in the present invention is 5.0 per mole of silver for silver halide grains with a grain size of 0.5μ.
×10 ^-4 mol to 5.0×10 ^-2 mol, silver halide grains with a grain size of 1.0 μm, silver halide grains with a grain size of 2.0 μm, 2.5×10 ⁻⁴ mol to 2.5×10 ⁻² mol per silver mole Then, 1.25×10 ^-4 mole per mole of silver
1.25×10 ⁻³ mol is preferred. The sulfur-containing silver halide solvent in the present invention is
It is a silver halide solvent that can coordinate silver ions with sulfur atoms. Here, the silver halide solvent is more specifically a silver halide solvent present in water or a water/organic solvent mixed solvent (for example, water/methanol = 1/1) at a concentration of 0.02 molar. It is capable of dissolving more than twice the weight of silver chloride that can be dissolved at 60°C. Specifically, thiocyanates (such as rhodanpotash and rhodan ammonium), organic thioether compounds (for example, U.S. Pat. No. 3,574,628, U.S. Pat. No. 3,021,215,
Same No. 3057724, Same No. 3038805, Same No. 4276374,
No. 4297439, No. 3704130, JP-A-57-
Compounds described in No. 104926, etc. ), thione compounds (for example, tetrasubstituted thiourea described in JP-A-53-82408, JP-A-55-77737, and U.S. Pat. No. 4,221,863, and compounds described in JP-A-53-144319), and Examples include mercapto compounds that can promote the growth of silver halide grains as described in Japanese Patent Publication No. 57-202531, and thiocyanates and organic thioether compounds are particularly preferred. More specifically, as an organic thioether,
A compound represented by the general formula () is preferred. R ₁₆ (-S-R ₁₈ ) _n -S-R ₁₇ () In the formula, m represents 0 or an integer from 1 to 4. R ₁₆ and R ₁₇ may be the same or different,
It represents a lower alkyl group (1 to 5 carbon atoms) or a substituted alkyl group (1 to 30 carbon atoms in total). Here, examples of substituents include -OH, -
COOM, _-SO3M (M represents a hydrogen atom or a cation [e.g. _, alkali metal ion, ammonium ion]), _-NHR19 , _-NR19R19 (However, _R19
may be the same or different), −OR ₁₉ , −
Examples include CONHR ₁₉ , -COOR ₁₉ , heterocycle, and the like. R ₁₉ may be a hydrogen atom, a lower alkyl group, or a substituted alkyl group further substituted with the above substituent. Moreover, two or more substituents may be substituted, and they may be the same or different. R ₁₈ is an alkylene group (preferably 1 to 1 carbon atoms)
12). However, when m is 2 or more, m R _18s may be the same or different. In addition, one or more -O in the middle of the alkylene chain
It may contain groups such as -, -CONH-, _-SO2NH- , or it may be substituted with the substituents described for _R16 and _R17 . Furthermore, R ₁₆ and R ₁₇ may be combined to form a cyclic thioether. As the thione compound, a compound represented by the general formula () is preferable.

[ka] In the formula, Z is

[Formula] represents -OR ₂₄ or -SR ₂₅ . R ₂₀ , R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ and R ₂₅ may each be the same or different and represent an alkyl group, an alkenyl group, an aralkyl group, an aryl group or a heterocyclic residue; It may be substituted (preferably each having a total number of carbon atoms of 30 or less). Also, R ₂₀ and R ₂₁ , R ₂₂ and R ₂₃ , or R ₂₀ and
R ₂₂ , R ₂₀ and R ₂₄ , and R ₂₀ and R ₂₅ may be combined to form a 5- to 6-membered heterocycle, which may have a substituent. As the mercapto compound, a compound represented by the general formula () is preferable.

[Chemical formula] In the formula, A represents an alkylene group, and R ₂₆ is -NH ₂ , -NHR ₂₇ ,

【formula】

[Formula] −CONHR ₃₀ , −OR ₃₀ , −COOM, −COOR ₂₇ , −SO ₂ NHR ₃₀ , −NHCOR ₂₇ or −
Represents SO ₃ M (preferably total carbon number 30 or less), L is R ₂₆

[Formula] represents -S, and other times represents -SM. Here, R ₂₇ , R ₂₈ and R ₂₉ each represent an alkyl group, R ₃₀ represents a hydrogen atom or an alkyl group, and M represents a hydrogen atom or a cation (for example, an alkali metal ion or an ammonium ion). etc.). These compounds can be synthesized by the methods described in the above-mentioned patent specifications or cited documents. Moreover, some compounds are commercially available. Examples of compounds of the sulfur-containing silver halide solvent used in the present invention are listed below. SSS−(1) KSCN SSS−(2) NH ₄ SCN SSS−(3) HO(CH ₂ ) ₂ S(CH ₂ ) ₂ OH SSS−(4) HO(−CH ₂ ) ₆ S(CH ₂ ) ₅ S(CH ₂ ) ₆ OH SSS−(5) HO(−CH ₂ ) ₂ −S−(CH ₂ ) ₂ −S−(CH ₂ ) ₂ −
OH SSS−(6) HO−(CH ₂ ) ₃ −S−(CH ₂ ) ₂ −S−(CH ₂ ) ₃ −
OH SSS−(7) HO(−CH ₂ ) ₆ −S−(CH ₂ ) ₂ −S−(CH ₂ ) ₆ −
OH SSS−(8) HO(CH ₂ ) ₂ S(CH ₂ ) ₂ S(CH ₂ ) ₂ S(CH ₂ ) ₂ OH SSS−(9) HO(CH ₂ ) ₂ S(CH ₂ ) ₂ O( CH ₂ ) ₂ O(CH ₂ ) ₂ S
(CH ₂ ) ₂ OH SSS−(10) HOOCCH ₂ S(CH ₂ ) ₂ SCH ₂ COOH SSS−(11) H ₂ NCO(CH ₂ ) ₂ S(CH ₂ ) ₂ S(CH ₂ ) ₂ CONH ₂ SSS −(12) NaO ₃ S(CH ₂ ) ₃ S(CH ₂ ) ₂ S(CH ₂ ) ₃ SO ₃ Na SSS−(13) HO(CH ₂ ) ₂ S(CH ₂ ) ₂ CONHCH ₂ NHCO
( _CH2 ) _2S ( _CH2 ) _2OH SSS−(14)

[ka] SSS−(15)

[ka] SSS−(16)

[ka] SSS−(17)

[ka] SSS−(18)

[ka] SSS−(19)

[ka] SSS−(20)

【formula】 SSS−(21)

[Formula] SSS−(22) C ₂ H ₅ S(CH ₂ ) ₂ S(CH ₂ ) ₂ NHCO(CH ₂ ) ₂
COOH SSS−(23)

【formula】 SSS−(24)

【formula】 SSS−(25)

【formula】 SSS−(26)

【formula】 SSS−(27)

[ka] SSS−(28)

[ka] SSS−(29)

【formula】 SSS−(30)

[ka] SSS−(31)

【formula】 SSS−(32)

【formula】 SSS−(33)

【formula】 SSS−(34)

【formula】 SSS−(35)

[ka] SSS−(36)

【formula】 SSS−(37)

【formula】 SSS−(38)

【formula】 SSS−(39)

【formula】 SSS−(40)

【formula】 SSS−(41)

[ka] SSS−(42)

【formula】 SSS−(43)

【formula】 SSS−(44)

【formula】 SSS−(45)

【formula】 SSS−(46)

【formula】 SSS−(47)

[Formula] The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. . Namely, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. such as benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole); mercaptopyrimidines; mercaptotriazines; Zaindenes, tetraazaindenes (especially 4-hydroxy substituted (1,3,
3a, 7) tetraazaindenes), pentaazaindenes, etc.; many compounds known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfonic acid, benzenesulfonic acid amide, etc. can be added. For example, U.S. Patent No. 3954474, U.S. Patent No. 3982947,
-28660 can be used. The photographic emulsion layer of the photographic light-sensitive material of the present invention contains, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholinic acid, and quaternary ammonium salts for the purpose of increasing sensitivity, increasing contrast, or accelerating development. compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidones, and the like. For example, US Patent No. 2400532,
Same No. 2423549, No. 2716062, No. 3617280, Same No.
Those described in No. 3772021, No. 3808003, and British Patent No. 1488991 can be used. The photosensitive material produced using 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
Included are oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful. In the photographic material produced using the present invention, the photographic emulsion layer and other hydrophilic colloid layers may contain a stilbene-based, triazine-based, oxazole-based, or coumarin-based brightener. These brighteners may be water-soluble, or water-insoluble brighteners may be used in the form of a dispersion. In carrying out the present invention, the following known anti-fading agents may be used in combination, and the color image stabilizers used in the present invention may be used alone or in combination of two or more. Known anti-fading agents include, for example, U.S. Pat.
No. 2675314, No. 2701197, No. 2704713, No.
No. 2728659, No. 2732300, No. 2735765, No. 2735765, No. 2732300, No. 2735765, No.
Hydroquinone derivatives described in No. 2710801, No. 2816028, British Patent No. 1363921, etc., US patent
Gallic acid derivatives described in US Pat. No. 3457079 and US Pat. No. 3069262, etc.;
Alkoxyphenols, US Pat. No. 3,432,300,
3573050, 3574627, 3764337, JP 52-35633, 52-147434, 52-152225
p-oxyphenol derivatives described in US Pat. No. 3,700,455, and bisphenols described in US Pat. No. 3,700,455. The light-sensitive material produced using 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 photographic material of the present invention includes a black and white light-sensitive material,
Any of the multilayer multicolor photosensitive materials can be mentioned.
It is particularly preferably used as a color photosensitive material for high-sensitivity photography. A multilayer natural color photographic material usually has 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 required. 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. As the yellow coloring coupler, a known open-chain ketomethylene coupler can be used. Among these, benzoylacetanilide and pivaloylacetanilide compounds are advantageous. A specific example of a yellow coupler that can be used is a US patent.
No. 2875057, No. 3265506, No. 3408194, No.
No. 3551155, No. 3582322, No. 3725072, No.
No. 3891445, West German Patent No. 1547868, West German Application Publication
No. 2219917, No. 2261361, No. 2414006, British Patent No. 1425020, Japanese Patent Publication No. 10783, No. 1978, Japanese Patent Publication No. 1977-
No. 26133, No. 48-73147, No. 51-102636, No. 50
-6341, 50-123342, 50-130442, 50-123342, 50-130442,
No. 51-21827, No. 50-87650, No. 52-82424,
This is described in No. 52-115219. As the magenta coloring coupler, pyrazolone compounds, indazolone compounds, cyanoacetyl compounds, etc. can be used, and pyrazolone compounds are particularly advantageous. Specific examples of magenta coloring couplers that can be used include U.S. Pat. No. 2,600,788;
No. 2983608, No. 3062653, No. 3127269, No. 3127269, No.
No. 3311476, No. 3419391, No. 3519429, No.
No. 3558319, No. 3582322, No. 3615506, No.
No. 3834908, No. 3891445, West German Patent No. 1810464,
West German patent application (OLS) No. 2408665, OLS No. 2417945,
No. 2418959, No. 2424467, Special Publication No. 40-6031,
JP-A No. 51-20826, No. 52-58922, No. 49-
No. 129538, No. 49-74027, No. 50-159336, No.
No. 52-42121, No. 49-74028, No. 50-60233,
This is described in No. 51-26541, No. 53-55122, etc. As the cyan coloring coupler, phenol compounds, naphthol compounds, etc. can be used. Specific examples include U.S. Patent No. 2369929 and
No. 2434272, No. 2474293, No. 2521908, No.
No. 2895826, No. 3034892, No. 3311476, No. 3311476, No.
No. 3458315, No. 3476563, No. 3583971, No.
3591383, 3767411, 4004929, West German patent application (OLS) 2414830, 2454329, JP 48-59838, 51-26034, 48-5055,
These are those described in No. 51-146828, No. 52-69624, and No. 52-90932. As a cyan coupler, JP-A No. 57-204545,
Couplers having a ureido group described in JP 56-65134, JP 58-33252, JP 58-33249, etc. can be preferably used. The coupler is 4-equivalent or 2-equivalent to silver ion.
Either equivalence coupler may be used, but in order to reduce the silver content in the light-sensitive material, it is preferable to use a two-equivalence coupler, which has higher silver utilization efficiency. Particularly in a silver halide emulsion having an average silver iodide content of 7 mol % or more, it is advantageous in terms of photographic performance to use a two-equivalent coupler to more effectively utilize the oxidized form of the developing agent. Two-equivalent couplers that can be used in the present invention are represented by the following general formulas (Cp-1) to (Cp-9). General formula (Cp-1)

【formula】 General formula (Cp-2)

[ka] General formula (Cp-3)

【formula】 General formula (Cp-4)

【formula】 General formula (Cp-5)

【formula】 General formula (Cp-6)

【formula】 General formula (Cp-7)

【formula】 General formula (Cp-8)

【formula】 General formula (Cp-9)

[Cp-9] Next, R ₅₁ of the general formulas (Cp-1) to (Cp-9)
~R ₅₉ , l, m and p will be explained. In the formula, R ₅₁ represents an aliphatic group, an aromatic group, an alkoxy group, or a heterocyclic group, and R ₅₂ and R ₅₃ each represent an aromatic group or a heterocyclic group. In the formula, the aliphatic group represented by R ₅₁ preferably has 1 to 22 carbon atoms, and may be substituted or unsubstituted, chain or cyclic. Preferred substituents for the alkyl group include an alkoxy group, an aryloxy group, an amino group, an acylamino group, and a halogen atom, which may themselves have further substituents. Specific examples of aliphatic groups useful as _R51 are:
Such as: isopropyl, isobutyl, tert-butyl, isoamyl, tert-
amyl group, 1,1-dimethylbutyl group, 1,1-
Dimethylhexyl group, 1,1-diethylhexyl group, dodecyl group, hexadecyl group, octadecyl group, cyclohexyl group, 2-methoxyisopropyl group, 2-phenoxyisopropyl group, 2-p-
tert-butylphenoxyisopropyl group, α-aminoisopropyl group, α-(diethylamino)isopropyl group, α-(succinimide)isopropyl group, α-(phthalimido)isopropyl group,
α-(benzenesulfonamido)isopropyl group, etc. When R ₅₁ , R ₅₂ or R ₅₃ represents an aromatic group (particularly a phenyl group), the aromatic group may be substituted. Aromatic groups such as phenyl groups include alkyl groups with 32 or fewer carbon atoms, alkenyl groups, alkoxy groups,
It may be substituted with an alkoxycarbonyl group, an alkoxycarbonylamino group, an aliphatic amide group, an alkylsulfamoyl group, an alkylsulfonamide group, an alkylureido group, an alkyl-substituted succinimide group, etc. In this case, the alkyl group is substituted with phenylene, etc. in the chain. Aromatic groups may also be present. The phenyl group may also be substituted with an aryloxy group, an aryloxycarbonyl group, an arylcarbamoyl group, an arylamido group, an arylsulfamoyl group, an arylsulfonamido group, an arylureido group, etc., and the aryl group of these substituents The moiety may be further substituted with one or more alkyl groups having a total of 1 to 22 carbon atoms. The phenyl group represented by R ₅₁ , R ₅₂ or R ₅₃ further includes an amino group, a hydroxy group, a carboxy group, a sulfo group, a nitro group, a cyano group, including those substituted with a lower alkyl group having 1 to 6 carbon atoms. , a thiocyano group or a halogen atom. Further, R ₅₁ , R ₅₂ or R ₅₃ may represent a substituent in which a phenyl group is fused with another ring, such as a naphthyl group, a quinolyl group, an isoquinolyl group, a chromanyl group, a coumaranyl group, a tetrahydronaphthyl group, and the like. These substituents may themselves have further substituents. When R ₅₁ represents an alkoxy group, the alkyl portion has 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms.
represents a straight-chain or branched-chain alkyl group, alkenyl group, cyclic alkyl group, or cyclic alkenyl group, which may be substituted with a halogen atom, an aryl group, an alkoxy group, or the like. When R ₅₁ , R ₅₂ or R ₅₃ represents a heterocyclic group, the heterocyclic group is the carbon atom of the carbonyl group of the acyl group in alpha acylacetamide or the amide group, respectively, through one of the carbon atoms forming the ring. Combines with nitrogen atoms. Such heterocycles include thiophene, furan, pyran, pyrrole,
Pyrazole, pyridine, pyrazine, pyrimidine,
Examples include pyritazine, indolizine, imidazole, thiazole, oxazole, triazine, thiadiazine, and oxazine. These may further have a substituent on the ring. In the general formula (Cp-3), R ₅₅ is a straight or branched alkyl group having 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms (e.g. methyl, isopropyl,
tert-butyl, hexyl, dodecyl group, etc.), alkenyl group (e.g. allyl group, etc.), cyclic alkyl group (e.g. cyclopentyl group, cyclohexyl group, norbornyl group, etc.), aralkyl group (e.g. benzyl, β-phenylethyl group, etc.), cyclic Represents an alkenyl group (e.g. cyclopentenyl, cyclohexenyl group, etc.), which includes a halogen atom, a nitro group, a cyano group, an aryl group, an alkoxy group, an aryloxy group, a carboxy group, an alkylthiocarbonyl group, an arylthiocarbonyl group, and an alkoxycarbonyl group. group, aryloxycarbonyl group, sulfo group, sulfamoyl group, carbamoyl group, acylamino group, diacylamino group, ureido group, urethane group, thiourethane group,
Sulfonamide group, heterocyclic group, arylsulfonyl group, alkylsulfonyl group, arylthio group,
It may be substituted with an alkylthio group, alkylamino group, dialkylamino group, anilino group, N-arylanilino group, N-alkylanilino group, N-acylanilino group, hydroxyl group, mercapto group, etc. Furthermore, R ₅₅ is an aryl group (e.g. phenyl group,
(α- or β-naphthyl group, etc.) may also be represented. The aryl group may have one or more substituents, such as an alkyl group, an alkenyl group, a cyclic alkyl group, an aralkyl group, a cyclic alkenyl group, a halogen atom, a nitro group, a cyano group, an aryl group, and an alkoxy group. group, aryloxy group, carboxyl group, alkoxycarbonyl group,
Aryloxycarbonyl group, sulfo group, sulfamoyl group, carbamoyl group, acylamino group,
diacylamino group, ureido group, urethane group, sulfonamide group, heterocyclic group, arylsulfonyl group, alkylsulfonyl group, arylthio group, alkylthio group, alkylamino group, dialkylamino group, anilino group, N-alkylanilino group,
It may have an N-arylanilino group, an N-acylanilino group, a hydroxyl group, etc. Furthermore, R ₅₅ is a heterocyclic group (for example, a 5- or 6-membered heterocyclic ring containing a nitrogen atom, an oxygen atom, or a sulfur atom as a heteroatom, a fused heterocyclic group, a pyridyl group, a quinolyl group, a furyl group, a benzothiazolyl group) , oxazolyl group, imidazolyl group, naphthoxazolyl group, etc.), a heterocyclic group substituted with the substituents listed for the above aryl group, an aliphatic or aromatic acyl group, an alkylsulfonyl group, an arylsulfonyl group, It may also represent an alkylcarbamoyl group, an arylcarbamoyl group, an alkylthiocarbamoyl group or an arylthiocarbamoyl group. In the formula, R ₅₄ is a hydrogen atom, a straight chain or branched alkyl having 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms,
alkenyl, cyclic alkyl, aralkyl, cyclic alkenyl groups (which may have the substituents listed above for R ₅₅ ), aryl groups and heterocyclic groups (which may have the substituents listed above for R ₅₅ ); ), alkoxycarbonyl groups (e.g. methoxycarbonyl group, ethoxycarbonyl group, stearyloxycarbonyl group, etc.),
Aryloxycarbonyl group (e.g. phenoxycarbonyl group, naphthoxycarbonyl group, etc.),
Aralkyloxycarbonyl groups (e.g., benzyloxycarbonyl group, etc.), alkoxy groups (e.g., methoxy, ethoxy, heptadecyloxy, etc.), aryloxy groups (e.g., phenoxy, tolyloxy, etc.), alkylthio groups (e.g., ethylthio, dodecylthio group, etc.), arylthio group (e.g., phenylthio group, α-naphthylthio group, etc.), carboxy group, acylamino group (e.g., acetylamino group, 3-[(2,4-di-
tert-amylphenoxy)acetamide]benzamide group, etc.), diacylamino group, N-alkylacylamino group (e.g., N-methylpropionamide group, etc.), N-arylacylamino group (e.g., N-phenylacetamide group, etc.), ureido group (e.g. ureido, N-arylureido, N
-alkylureido group), urethane group, thiourethane group, arylamino group (e.g. phenylamino, N-methylanilino group, diphenylamino group, N-acetylanilino group, 2-chloro-5
-tetradecanamide anilino group, etc.), alkylamino groups (e.g. n-butylamino group, methylamino group, cyclohexylamino group, etc.), cycloamino groups (e.g. piperidino group, pyrrolidino group, etc.), heterocyclic amino groups (e.g. -pyridylamino group, 2-benzoxazolylamino group, etc.),
Alkylcarbonyl group (e.g. methylcarbonyl group, etc.), arylcarbonyl group (e.g. phenylcarbonyl group, etc.), sulfonamide group (e.g. alkylsulfonamide group, arylsulfonamide group, etc.), carbamoyl group (e.g. ethylcarbamoyl group, dimethylcarbamoyl group, etc.) group, N-
methyl-phenylcarbamoyl, N-phenylcarbamoyl, etc.), sulfamoyl group (e.g. N-phenylcarbamoyl), sulfamoyl group (e.g.
-alkylsulfamoyl, N,N-dialkylsulfamoyl group, N-arylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, N,N-diarylsulfamoyl group, etc.),
Represents any one of a cyano group, a hydroxy group, and a sulfo group. In the formula, R ₅₆ is a hydrogen atom or a carbon number of 1 to 32,
It preferably represents 1 to 22 straight-chain or branched-chain alkyl groups, alkenyl groups, cyclic alkyl groups, aralkyl groups, or cyclic alkenyl groups, which may have the substituents listed for R ₅₅ above. Further, R ₅₆ may represent an aryl group or a heterocyclic group, and these may have the substituents listed for R ₅₅ above. R ₅₆ is a cyano group, an alkoxy group, an aryloxy group, a halogen atom, a carboxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, a sulfo group, a sulfamoyl group, a carbamoyl group, an acylamino group, a diacylamino group, a ureido group, urethane group, sulfonamide group, arylsulfonyl group, alkylsulfonyl group, arylthio group, alkylthio group, alkylamino group, dialkylamino group, anilino group, N-arylanilino group, N-alkylanilino group, N- It may also represent an acylanilino group or a hydroxyl group. R ₅₇ , R ₅₈ and R ₅₉ each represent a group used in a typical 4-equivalent type phenol or α-naphthol coupler. Specifically, R ₅₇ is a hydrogen atom, a halogen atom, an alkoxycarbonylamino group, an aliphatic carbonized Hydrogen residue, N-arylureido group, acylamino group, -O-R ₆₂ or -
S-R ₆₂ (where R ₆₂ is an aliphatic hydrocarbon residue), and when two or more R ₇ exist in the same molecule, even if two or more R ₅₇ are different groups, Often, aliphatic hydrocarbon residues include those bearing substituents. In addition, when these substituents contain an aryl group,
The aryl group may have the substituents listed for R ₅₅ above. R ₅₈ and R ₅₉ are aliphatic hydrocarbon residues,
Examples include groups selected from aryl groups and heterocyclic residues, one of which may be a hydrogen atom, and these groups include those having substituents. Further, R ₅₈ and R ₅₉ may jointly form a nitrogen-containing heterocyclic nucleus. The aliphatic hydrocarbon residue may be either saturated or unsaturated, and may be linear, branched, or cyclic. and preferably alkyl groups (e.g. methyl, ethyl, propyl, isopropyl, butyl,
groups such as t-butyl, isobutyl, dodecyl, octadecyl, cyclobutyl, cyclohexyl),
It is an alkenyl group (eg, allyl, octenyl, etc.). Typical aryl groups include phenyl and naphthyl groups, and representative heterocyclic residues include pyridinyl, quinolyl, thienyl, piperidyl, imidazolyl, and the like. Substituents introduced into these aliphatic hydrocarbon residues, aryl groups, and heterocyclic residues include halogen atoms, nitro, hydroxy, carboxyl, amino, substituted amino, sulfo, alkyl, alkenyl, aryl, heterocycle, alkoxy, Examples include groups such as aryloxy, arylthio, arylazo, acylamino, carbamoyl, ester, acyl, acyloxy, sulfonamide, sulfamoyl, sulfonyl, and morpholino. l is an integer from 1 to 4, m is an integer from 1 to 3, p is 1
Represents an integer between ~5. Among the above coupler residues, as the yellow coupler residue, in the general formula (Cp-1), R ₅₁
represents a t-butyl group or a substituted or unsubstituted aryl group, R ₅₂ represents a substituted or unsubstituted aryl group, and in general formula (Cp-2), R ₅₂ and R ₅₃ represent a substituted or unsubstituted aryl group. It is preferable to represent a group. Preferred magenta coupler residues include R ₅₄ in general formula (Cp-3), which is an acylamino group;
ureido group and arylamino group, when R ₅₅ represents a substituted aryl group, when R ₅₄ in general formula (Cp-4) represents an acylamino group, ureido group and arylamino group, when R ₅₆ represents a hydrogen atom, and General formula (Cp-5) and (Cp-6)
In this case, R ₅₄ and R ₅₆ represent a linear or branched alkyl group, alkenyl group, cyclic alkyl group, aralkyl group, or cyclic alkenyl group. Preferred cyan coupler residues are those in which R ₅₇ in general formula (Cp-7) represents an acylamino group or ureido group at the 2nd position, an acylamino group or an alkyl group at the 5th position, and a hydrogen atom or a chlorine atom at the 6th position. case and general formula (Cp-9)
R ₅₇ is a hydrogen atom at the 5-position, an acylamino group, a sulfonamide group, an alkoxycarbonyl group, R ₅₈ is a hydrogen atom, and R ₅₉ is a phenyl group,
This refers to an alkyl group, an alkenyl group, a cyclic alkyl group, an aralkyl group, and a cyclic alkenyl group. Z ₁ represents a halogen atom, a sulfo group, an acyloxy group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, or a heterocyclic thio group, and these groups further include an aryl group (e.g. phenyl group), Nitro group, hydroxyl group,
Cyano group, sulfo group, alkoxy group (e.g. methoxy group), aryloxy group (e.g. phenoxy group), acyloxy group (e.g. acetoxy group), acylamino group (e.g. acetylamino group), sulfonamide group (e.g. methanesulfonamide group) ,
Sulfamoyl group (e.g. methylsulfamoyl group), halogen atom (e.g. fluorine, chlorine, bromine, etc.), carboxy group, carbamoyl group (e.g. methylcarbamoyl group), alkoxycarbonyl group (e.g. methoxycarbonyl group), sulfonyl group ( For example, it may be substituted with a substituent such as a methylsulfonyl group). Z ₂ and Y represent a leaving group bonded to the coupling position with an oxygen atom, nitrogen atom or sulfur atom, and when Z ₂ and Y are bonded to the coupling position with an oxygen atom, nitrogen atom or sulfur atom, , these atoms are bonded to an alkyl group, an aryl group, an alkylsulfonyl group, an arylsulfonyl group, an alkylcarbonyl group, an arylcarbonyl group, or a heterocyclic group, and in the case of a nitrogen atom, including the nitrogen atom. It also means a group that can form a member or a 6-membered ring and serve as a leaving group (for example, an imidazolyl group, a pyrazolyl group, a triazolyl group,
tetrazolyl group, etc.). The above alkyl group, aryl group, and heterocyclic group are
It may have a substituent, specifically an alkyl group (e.g. methyl group, ethyl group, etc.), an alkoxy group (e.g. methoxy group, ethoxy group, etc.),
Aryloxy group (e.g., phenyloxy group), alkoxycarbonyl group (e.g., methoxycarbonyl group), acylamino group (e.g., acetylamino group), carbamoyl group, alkylcarbamoyl group (e.g., methylcarbamoyl group, ethylcarbamoyl group, etc.), dialkylcarbamoyl (e.g. dimethylcarbamoyl group), arylcarbamoyl group (e.g. phenylcarbamoyl group), alkylsulfonyl group (e.g. methylsulfonyl group), arylsulfonyl group (e.g. phenylsulfonyl group), alkylsulfonamide group (e.g. methanesulfonamide group) ), arylsulfonamide groups (e.g. phenylsulfonamide group), sulfamoyl groups, alkylsulfamoyl groups (e.g. ethylsulfamoyl group), dialkylsulfamoyl groups (e.g. dimethylsulfamoyl group), alkylthio groups (e.g. methylthio group), arylthio group (e.g. phenylthio group), cyano group, nitro group, halogen atom (e.g. fluorine, chlorine, bromine, etc.), and when there are two or more of these substituents, they may be the same or different. . Particularly preferred substituents include a halogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, and a cyano group. Preferred groups for Z ₂ include groups that bond to the coupling site via a nitrogen atom or sulfur atom, and preferable groups for Y include groups that bond to the coupling site via a chlorine atom, an oxygen atom, a nitrogen atom, or a sulfur atom. be. Z ₃ is a hydrogen atom or the following general formula [R-] [R-
] [R-] or [R-].

embedded image R ₆₃ represents an optionally substituted aryl group or heterocyclic group.

【formula】

[Formula] R ₆₄ and R ₆₅ are each a hydrogen atom, a halogen atom, a carboxylic acid ester group, an amino group, an alkyl group, an alkylthio group, an alkoxy group, an alkylsulfonyl group, an alkylsulfinyl group, a carboxylic acid group,
It represents a sulfonic acid group, an unsubstituted or substituted phenyl group, or a heterocycle, and these groups may be the same or different.

[Formula] W ₁ is in the formula

[Formula] represents a nonmetallic atom required to form a 4-, 5-, or 6-membered ring. In the general formula [R-], preferably [R-
] to [R-].

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【formula】

[Chemical formula] In the formula, R ₆₆ and R ₆₇ are each a hydrogen atom, an alkyl group,
R ₆₈ , R ₆₉ and R ₇₀ each represent a hydrogen atom, an alkyl group, an aryl group, an aralkyl group or an acyl group, and W ₂ represents an oxygen or sulfur atom. The coupler used in the present invention has the following general formula (C
) is derived from the coupler monomer represented by
A polymer having a repeating unit represented by the general formula (C) or one or more non-color-forming monomers containing at least one ethylene group that does not have the ability to oxidatively couple with an aromatic primary amine developer. It may also be a copolymer. Two or more types of coupler monomers may be simultaneously polymerized. General formula (C)

【formula】 General formula (C)

[Formula] In the formula, R' represents a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, or a chlorine atom, and K ₁ is -
CONR″−, −NR″CONR″−, −NR″COO−, −
COO−, −SO ₂ −, −CO−, NR″CO−, −SO ₂
NR″−, −NR″SO ₂ −, −OCO−, −OCONR″−,
-NR″-, -S- or -O-, K ₂ is -
CONR"- or -COO-, R" represents a hydrogen atom, an aliphatic group, or an aryl group, and when there are two or more R" in one molecule, they may be the same or different. K ₃ represents an unsubstituted or substituted alkylene group, an aralkylene group, or an unsubstituted or substituted arylene group having 1 to 10 carbon atoms, and the alkylene group may be linear or branched. (Examples of the alkylene group include methylene, methylmethylene, Dimethylmethylene, dimethylene, trimethylene, tetramethylene, pentamethylene,
Examples of hexamethylene, decylmethylene, and aralkylene groups include benzylidene; examples of arylene groups include phenylene and naphthylene; and examples of substituents for the alkylene, aralkylene, and arylene groups represented by _K3 include aryl groups (eg, phenyl). , nitro group, hydroxyl group, cyano group, sulfo group, alkoxy group (e.g. methoxy group), aryloxy group (e.g. phenoxy group), acyloxy group (e.g. acetoxy group), acylamino group (e.g. acetylamino group), sulfonamide group ( For example, methanesulfonamide group), sulfamoyl group (for example, methylsulfamoyl group), halogen atom (for example, fluorine,
chlorine, bromine, etc.), carboxyl group, carbamoyl group (e.g. methylcarbamoyl group), alkoxycarbonyl group (e.g. methoxycarbonyl group, etc.), sulfonyl group (e.g. methylsulfonyl group)
can be mentioned. When there are two or more of these substituents, they may be the same or different. i, j and k represent 0 or 1. Q is R ₅₁ of the above general formulas (Cp-1) to (Cp-9)
Any part of ~R ₅₉ , Z ₁ to Z ₃ and Y is bonded to general formula (C) or a part other than Q in (C). Next, examples of non-color-forming ethylene-like monomers that do not couple with the oxidation products of aromatic primary amine developing reagents include acrylic acid, α-chloroacrylic acid,
α-Alkylacrylic acids (e.g. acrylic acid, methacrylic acid) and esters or amides derived from these acrylic acids (e.g. acrylamide, methacrylamide, t-butylacrylamide, methyl acrylate, methyl methacrylate, ethyl acrylate, n- propyl acrylate, iso-propyl acrylate, n
-butyl acrylate, t-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate, n-hexyl acrylate,
n-octyl acrylate, lauryl acrylate, and methylene bisacrylamide), vinyl esters (e.g. vinyl acetate, vinyl propionate, and vinyl laurate), acrylonitrile, methacrylonitrile, aromatic vinyl compounds (e.g. styrene and its derivatives,
vinyltoluene, divinylbenzene, vinylacetophenone), vinylidene chloride, vinyl alkyl ether (e.g. vinyl ethyl ether),
Maleic esters, N-vinyl-2-pyrrolidone, N-vinylpyridine, and 2- and 4-
Examples include vinylpyridine. Particularly preferred are acrylic esters, methacrylic esters, and maleic esters. Two or more kinds of the non-color-forming ethylenically unsaturated monomers used here can also be used together. For example, n-butyl acrylate and divinylbenzene, styrene and methacrylic acid, n-butyl acrylate and methacrylic acid, etc. can be used. The polymer coupler used in the present invention may be water-soluble or water-insoluble, but polymer coupler latex is particularly preferred. Polymer coupler latex can be obtained by first taking out a hydrophilic polymer coupler made by polymerizing coupler monomers, then redissolving it in an organic solvent and dispersing it in the form of a latex, or by dispersing it in the form of a latex. A solution of the hydrophilic polymeric coupler may be directly dispersed in the form of a latex, or a polymeric coupler latex prepared by emulsion polymerization, or even a layered polymeric coupler latex, may be added directly to the gelatin silver halide emulsion. In the silver halide photographic light-sensitive material of the present invention, preferably two of these two-equivalent couplers are used.
It is an equivalent magenta coupler or a 2-equivalent cyan coupler, more preferably a 2-equivalent magenta coupler. 2 equivalent yellow coupler

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【formula】

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[ka] 2-equivalent magenta coupler

【formula】

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【formula】

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[ka] cyan coupler

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【formula】

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【formula】

【formula】

【formula】

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【formula】

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[C] Colored couplers include, for example, US patents.
No. 3476560, No. 2521908, No. 3034892, Tokko Akira
No. 44-2016, No. 38-22335, No. 42-11304, No. 42-11304, No.
No. 44-32461, JP-A No. 51-26034, No. 52-
Specification No. 42121, West German patent application (OLS) 2418959
You can use those listed in the issue. As a DIR coupler, for example, the US patent
No. 3227554, No. 3617291, No. 3701783, No. 3227554, No. 3617291, No. 3701783, No.
No. 3790384, No. 3632345, West German patent application (OLS)
No. 2414006, No. 2454301, No. 2454329, U.S. Patent No. 953454, JP-A-52-69624, No. 49-122335
Those described in Japanese Patent Publication No. 51-16141 can be used. In addition to the DIR coupler, the light-sensitive material may also contain a compound that releases a development inhibitor during development; for example, U.S. Pat.
West German Patent Application (OLS) No. 2417914, Japanese Unexamined Patent Publication No. 1983-
Those described in No. 15271 and No. 53-9116 can be used. Further, couplers which release a development accelerator or a fogging agent upon development as described in JP-A-57-150845 can be particularly preferably used. Also preferably used are non-diffusible couplers which form slightly diffusible dyes, such as those described in GB 2083640. These couplers are generally added in an amount of 2 x 10 ^-3 mol to 5 x 10 -1 mol, preferably 1 x 10 ^-2 mol to 5 x ^{10 -1 mol} , per mol of silver in the emulsion layer. The photosensitive material produced using the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, benzotriazole compounds substituted with aryl groups (such as those described in U.S. Pat. No. 3,533,794), 4-thiazolidone compounds (such as those described in U.S. Pat.
3314794 and 3352681)) benzophenone compounds (for example, those described in JP-A-46-2784), cinnamic acid ester compounds (for example, those described in U.S. Pat. Nos. 3705805 and 3707375), butadiene compounds (eg, as described in US Pat. No. 4,045,229), or benzoxazole compounds (eg, as described in US Pat. No. 3,700,455). Furthermore, those described in US Pat. No. 3,499,762 and Japanese Patent Application Laid-Open No. 54-48535 can also be used. An ultraviolet absorbing coupler (for example, an α-naphthol cyan dye-forming coupler) or an ultraviolet absorbing polymer may be used. These ultraviolet absorbers may be mordanted in specific layers. When the present invention is applied to a color light-sensitive material, there are no particular restrictions on where the emulsion of the present invention can be used, but it is preferably used in a blue-sensitive layer, particularly a high-sensitivity blue-sensitive layer. Further adjacent to the emulsion layer,
Preferably, fine-grained silver halide having a grain size of 0.2 μm or less is present. For photographic processing of the light-sensitive material of the present invention, any known method can be used, and known processing solutions can be used. Further, the treatment temperature is usually selected between 18°C and 50°C, but it may be lower than 18°C or higher than 50°C.
Depending on the purpose, either a development process for forming a silver image (black and white photographic process) or a color photographic process consisting of a development process for forming a dye image can be applied. In particular, when the photosensitive material of the present invention is subjected to so-called parallel development, typified by color development, extremely favorable results can be obtained in terms of sensitivity and graininess. Color developers generally consist of an alkaline aqueous solution containing a color developing agent. The color developing agent is a known general aromatic amine developer, such as phenylene diamines (e.g., 4-amino-N,N-diethylaniline, 3-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. 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. As a bleach,
For example, iron (), cobalt (), chromium (),
Compounds of polyvalent metals such as copper, peracids, quinones, nitroso compounds, etc. are used. for example,
Ferricyanide, dichromate, organic complex salts of iron () or cobalt (), aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, 1,3-diamino-2-propanoltetraacetic acid, or citric acid, tartaric acid, Complex salts of organic acids such as malic acid; persulfates, permanganates; nitrosophenols, etc. can be used. Of these, potassium ferricyanide, sodium ferric ethylenediaminetetraacetate, and ammonium ferric ethylenediaminetetraacetate are particularly useful. Ethylenediaminetetraacetic acid iron() complexes are useful in both stand-alone bleach solutions and single bath bleach-fix solutions. The present invention will be further explained below with reference to Examples, but the present invention is not limited thereto. (Examples) Example 1 Silver iodobromide flat plates A to G were prepared by the method described in JP-A-62-209445. An aqueous solution containing 30 g of inert gelatin, 6 g of potassium bromide, and 1 part of distilled water was stirred at 60°C, and 35 c.c. of an aqueous solution containing 5.0 g of silver nitrate, 3.2 g of potassium bromide, and 0.98 g of potassium iodide were dissolved therein. After adding 35 c.c. of each aqueous solution for 30 seconds at a flow rate of 70 c.c./min, the pAg was raised to 10 and ripened for 30 minutes to prepare a seed emulsion. Next, a predetermined amount of aqueous solution 1 in which 145 g of silver nitrate was dissolved and an aqueous solution of a mixture of potassium bromide and potassium iodide were added in equimolar amounts at a predetermined temperature, a predetermined pAg, and an addition rate close to the critical growth rate. A core emulsion was prepared. Subsequently, equimolar amounts of the remaining silver nitrate aqueous solution and an aqueous solution of a mixture of potassium bromide and potassium iodide having a composition different from that used in preparing the core emulsion were added at a rate close to the critical growth rate to coat the core. Core/shell type silver iodobromide flat plates A to G were prepared. The aspect ratios of Emulsions A to G were changed by adjusting pAg. Particle size is 0.75μ in equivalent sphere diameter for all A to G.
It was adjusted so that Particle size distribution is Emulsion A
~G, the coefficient of variation is close to 30% and is considered to be almost the same. Table 1 shows the size and cord content composition of emulsions A to G.

【table】

[Table] XPS measurements were performed using ESCA-750 manufactured by Shimadzu Corporation. Mg-Kα (acceleration voltage 8KV current 30mA) was used as the excitation X-ray, and I-3d _5/2 and
The peak area corresponding to Ag-3d _5/2 was determined, and the average silver iodide content of the surface portion of the silver halide grains was determined from the intensity ratio. Silver iodobromide tabular emulsions A to G were each chemically sensitized to exhibit optimum sensitivity at 1/100'' exposure.Table 2 shows the amount of chemical sensitizer added per mole of silver.

[Table] The 4th layer, 7th layer, and
Samples 101 to 114 were prepared by replacing the 12-layer silver iodobromide emulsion as shown in Table 3.

[Table] All coating amounts are in g/ ^m2 1st layer (antihalation layer) Black colloidal silver ...0.2 Gelatin ...1.3 ExM-9 ... UV-1 ...0.03 UV-2 ...0.06 UV- 3 ...0.06 Solv-1 ...0.15 Solv-2 ...0.15 Solv-3 ...0.05 2nd layer (intermediate layer) 3rd gelatin layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol% , uniform AgI type, equivalent sphere diameter 0.5μ, coefficient of variation of equivalent sphere diameter 20%, plate-like grains, diameter/thickness ratio 3.0) Coated silver amount...1.2 Silver iodobromide emulsion (AgI 3 mol%, uniform AgI type, Equivalent sphere diameter 0.3μ, coefficient of variation of equivalent sphere diameter 15%, spherical particles, diameter/thickness ratio 1.0) Coated silver amount...0.6 Gelatin...1.0 ExS-1...4×10 ^-4 ExS-2...5 ×10 ^-5 ExS−7 ...1×10 ^-6 ExC−1 ...0.05 ExC−2 ...0.50 ExC−3 ...0.03 ExC−4 ...0.12 ExC−5 ...0.01 4th layer (high sensitivity Red-sensitive emulsion layer) Silver iodobromide emulsion Coated silver amount ……0.7 Gelatin ……1.0 ExS−1 ……3×10 ^-4 ExS−2 ……2.3×10 ^-5 ExS−7 ……0.5×10 ^-6 ExC−6 …0.11 ExC−7 …0.05 ExC−4 …0.05 Solv−1 …0.05 Solv−3 …0.05 5th layer (middle layer) Gelatin …0.5 Cpd−1 …0.1 Solv−1 ...0.05 6th layer (low sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, surface high AgI type,
Equivalent sphere diameter 0.5μ, coefficient of variation of equivalent sphere diameter 15%, plate-like grains, diameter/thickness ratio 4.0) Coated silver amount......0.35 Silver iodobromide emulsion (AgI 3 mol%, uniform AgI type, equivalent sphere diameter 0.3μ) , coefficient of variation of equivalent sphere diameter 25%, spherical particles, diameter/thickness ratio 1.0) Amount of coated silver ……0.20 Gelatin ……1.0 ExS−3 ……5×10 ^-4 ExS−4 ……3×10 ^-4 ExS −5 ...1×10 ^-4 ExM−8 ...0.4 ExM−9 ...0.07 ExM−10 ...0.02 ExY−11 ...0.03 Solv−1 ...0.3 Solv−4 ...0.05 7th layer (high Sensitive green-sensitive emulsion layer) Silver iodobromide emulsion Coated silver amount......0.8 ExS-3...5× ^10-4 ExS-4...3× ^10-4 ExS-5...1× ^10-4 ExM-8 …0.1 ExM−9 …0.02 ExY−11 …0.03 ExC−2 …0.03 ExM−14 …0.01 Solv−1 …0.2 Solv−4 …0.01 8th layer (middle layer) Gelatin …0.5 Cpd-1 ...0.05 Solv-1 ...0.02 9th layer (donor layer for interlayer effect) Silver iodobromide emulsion (AgI 2 mol%, internal high AgI type,
Equivalent sphere diameter 1.0μ, coefficient of variation of equivalent sphere diameter 15%, plate-like grains, diameter/thickness ratio 6.0) Coated silver amount...0.35 Silver iodobromide emulsion (AgI 2 mol%, internal high AgI type,
Equivalent sphere diameter 0.4 μ, coefficient of variation of equivalent sphere diameter 20%, plate-like particles, diameter/thickness ratio 6.0) Coated silver amount …0.20 Gelatin …0.5 ExS−3 …8×10 ^-4 ExY−13 … 0.11 ExM−12 …0.03 ExM−14 …0.10 Solv− …0.20 10th layer (yellow filter layer) Yellow colloidal silver …0.05 Gelatin …0.5 Cpd−2 …0.13 Cpd−1 …0.10 11th Layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4.5 mol%, uniform AgI type, equivalent sphere diameter 0.7μ, coefficient of variation of equivalent sphere diameter 15%, plate-like grains, diameter/thickness ratio 7.0) Amount of coated silver ……0.3 Silver iodobromide emulsion (AgI 3 mol%, uniform AgI type, equivalent sphere diameter 0.3 μ, coefficient of variation of equivalent sphere diameter 25%, plate-like grains, diameter/thickness ratio 7.0) Amount of silver coated … 0.15 Gelatin …1.6 ExS−6 …2×10 ^-4 ExC−16 …0.05 ExC−2 …0.10 ExC−3 …0.02 ExY−13 …0.07 ExY−15 …0.5 Solv−1 … 0.20 12th layer (high sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion Coated silver amount ...0.5 Gelatin ...0.5 ExS−6 ...1×10 ^-4 ExY−15 ...0.20 ExY−13 ...0.01 Solv -1 ...0.10 13th layer (first protective layer) Gelatin ...0.8 UV-4 ...0.1 UV-5 ...0.15 Solv-1 ...0.01 Solv-2 ...0.01 14th layer (second protective layer) ) Fine grain silver bromide emulsion (I2 mol, s/r=0.2,
0.07μ) ...0.5 Gelatin ...0.45 Polymethyl methacrylate particles Diameter 1.5μ
...0.2 H-1 0.4 Cpd-3 ...0.5 Cpd-4 ...0.5 In addition to the above components, each layer contains an emulsion stabilizer.
Cpd-3 and surfactant Cpd-4 were added as coating aids. In addition, the following compounds Cpd5 to Cpd6 were added.

【formula】

【formula】

【formula】

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[ka] Solv-1 tricresyl phosphate Solv-2 dibutyl phthalate

【formula】

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[ka] n=50 m=25 m′=25 Molecular weight approximately 20000

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[C] These samples were subjected to conditions of 40℃ and 70% relative humidity.
After being left for 14 hours, exposure for sensitometry was applied, and the next color development process was performed. The concentration of the treated sample was measured using a red filter, a green filter, and a blue filter. Table 4 shows the photographic performance results obtained. Color development was carried out at 38°C according to the following processing steps. Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Washing with water 2 minutes 10 seconds Fixation 4 minutes 20 seconds Washing with water 3 minutes 15 seconds Stability 1 minute 05 seconds The composition of the processing solution used in each step is as follows. Ta. Color developer Diethylenetriaminepentaacetic acid 1.0g 1-hydroxyethylidene-1,1-diphosphonic acid 2.0g Sodium sulfite 4.0g Potassium carbonate 30.0g Potassium bromide 1.4g Potassium iodide 1.3mg Hydroxylamine sulfate 2.4g 4-(N- Ethyl-N-β-hydroxyethylamino)-2-methylaniline sulfate 4.5g Add water 1.0 PH 10.0 Bleach solution Ethylenediaminetetraacetic acid ferric ammonium salt
100.0g Ethylenediaminetetraacetic acid disodium salt 10.0g Ammonium bromide 150.0g Ammonium nitrate 10.0 Add water 1.0 PH 6.0 Fixer Ethylenediaminetetraacetic acid disodium salt 1.0g Sodium sulfite 4.0g Ammonium thiosulfate aqueous solution (70%) 175.0ml Sodium bisulfite 4.6g Add water 1.0 PH 6.6 Stabilizer Formalin (40%) 2.0ml Polyoxyethylene-p-monononyl phenyl ether (average degree of polymerization 10) 0.3g Add water 1.0 Red light sensitive layer, green light sensitive layer The sensitivity of each layer and blue light-sensitive layer is expressed with the sensitivity of Sample 101 being 100.

[Table] Comparative samples 108-111 have lower sensitivity than standard samples 101 and 112. Samples 102-107, 113, of the present invention
Sample 114 had a higher sensitivity than the standard samples 101 and 112, and the graininess was also at least the same. Among the samples of the present invention, samples using a sulfur-containing silver halide solvent
Samples 103, 104, 106, 107, and 114 showed particularly favorable results. In addition, if an unexposed sample that had been stored for 3 days at 45°C and 80% relative humidity was subjected to spectral resolution exposure and development at the same time as a sample that had not been exposed to these conditions, the standard Samples 101 and 112
Samples 102-107, 113, and 114 of the present invention showed excellent results in that they were hardly affected by storage conditions, whereas Samples 102-107, 113, and 114 of the present invention showed excellent results in that they were hardly affected by storage conditions.Example 2 Sample of Example 1 Samples 201-204 were prepared by replacing ExM-8 used in the seventh layer of Samples 101-104 with the following ExM-20 in an equimolar amount. ExM−20

[Chemical formula] The above sample was subjected to sensitometric exposure in the same manner as in Example 1, and the determined green-sensitive layer sensitivities are shown in Table 5. Table 5 Sample Green sensitivity layer sensitivity 101 Comparative example 100 102 Present invention 117 103 〃 130 104 〃 125 201 Comparative example 92 202 Present invention 97 203 〃 102 204 〃 100 As shown in the results of Table 5, the effects of the present invention are This is especially noticeable when combined with a two-equivalent coupler. Example 3 Octahedral monodispersed silver iodobromide core grains having a silver iodide content of 24 mol % were prepared by a controlled double jet method in the presence of ammonia. 500 c.c. of an aqueous solution containing 100 g of AgNO ₃ , 500 c.c. of an aqueous solution containing KBr and KI, and 45 c.c. of an aqueous solution containing 3% gelatin and 25% NH ₃
Added to 1000c.c. The reaction temperature was controlled at 70° C. and the silver potential was controlled at 10 mV, and the flow rate was accelerated so that the final flow rate was four times the initial flow rate. After washing the emulsion with water, shelling with pure silver bromide was carried out by a controlled double jet method until the amount of silver in the core and shell became equal. 500 c.c. of an aqueous solution containing 100 g of AgNO ₃ and 500 c.c. of an aqueous solution containing KBr were simultaneously added to the reaction vessel. The reaction temperature is 75
The silver potential was controlled at −20 mV at °C, and the flow rate was accelerated so that the final flow rate was twice the initial flow rate. The resulting particles are octahedral with an average size of 1.9 μm, and X-ray diffraction reveals approximately 22 mol% and 2 mol%.
It was confirmed that there were two peaks at the diffraction angle corresponding to the lattice constant of silver iodobromide, and the total silver iodide content was 12 mol%, forming a double structure. This emulsion is called K. Emulsions K to P shown in Table 6 were prepared in the same manner as in Emulsion K, replacing KI with equimolar KBr. Emulsions K to P were each chemically sensitized using sodium thiosulfate, potassium chloroaurate, and the sulfur-containing silver halide solvent SSS-1 to exhibit optimal sensitivity at 1/100'' exposure. Examples In place of the silver iodobromide emulsion in the 12th layer of sample 101 of 1, each of emulsions K to P was applied at 1.5 g/m ² to prepare a sample.
Created 301-306. As a comparative emulsion, emulsion Q in which the silver iodide molar fraction in the shell part was higher than that in the surface part and lower than that in the core part was prepared as follows. In the preparation of emulsion L in Example 3, the shelling operation was divided into two, and the amount of KI added in the first half of the shelling (first shell, 90% of the entire shell) was increased.
The second half of shell attachment (second shell, 10 of the whole shell)
%), Comparative Emulsion Q (average iodine content: 14 mol %) was prepared in the same manner as Emulsion L was shelled. By dividing the shell portion, it was possible to easily prepare grains having a high silver iodide mole fraction in the core portion while keeping the silver iodide mole fraction in the surface portion the same. Furthermore, by changing the iodine content of the core grains of emulsion L, emulsion R of the present invention, which has approximately the same average iodine content and surface iodine content as the above-mentioned comparative emulsion Q, can be used.
(average iodine content 14 mol%) was prepared. Emulsion Q,
The characteristics of R are also shown in Table 6. Sample 307 was prepared in the same manner as Samples 301 to 306, except that Emulsions Q and R were chemically sensitized in the same manner as Emulsions K to P of Example 3, and the silver iodobromide emulsions in the 12th layer were changed to Q and R. ，
308 was created. Table 7 shows the results of sensitometry.
Shown accordingly. Sample 308 of the present invention is different from other samples 302 and 303 of the present invention.
showed high sensitivity as well as the comparative example sample.
307 felt low. This is Emulsion Q of Comparative Example,
Although the surface iodine content and average iodine content were the same as those of Emulsion R of the present invention, the iodine content in the shell portion was higher than the surface iodine content. The above samples were subjected to sensitometric exposure in the same manner as in Example 1, and the blue-sensitive layer sensitivities determined are shown in Table 7. The sensitivity of sample 301 is expressed as 100.

【table】

[Table] Prepared by adding an aqueous potassium iodide solution at the time point.
**The X-ray diffraction peak corresponding to the second shell of Emulsion Q could not be identified.
Table 7 Sample name Blue sensitive layer sensitivity 301 Comparative example 100 302 Invention 115 303 〃 109 304 Comparative example 75 305 〃 80 306 〃 79 307 〃 85 308 Invention 117 As can be seen from the results in Table 7, the samples of the invention
Samples 302, 303, 305, and 306 were more sensitive than the standard samples 301 and 304, and their graininess was also the same or better. In particular, favorable results were obtained with 302 and 303, which have a high total iodine content.

Claims (1)

[Claims] 1 In a photographic light-sensitive material having at least one silver halide emulsion layer on a support, chemically sensitized silver halide grains contained in one emulsion in the emulsion layer contain iodide inside the grains. Silver mole fraction is 10
A core part consisting of ~40 mol% silver iodobromide, a shell part provided between the core part and the surface part and having a lower silver iodide mole fraction than the core part, and a shell part having a silver iodide mole fraction lower than that of the core part. 1. A silver halide photographic light-sensitive material containing silver halide grains, characterized in that the silver halide grains include a surface portion having a surface content of 5 mol % or more.