JPH04335348A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance color reproduction performance and sensitivity and processing stability and to enable rapid and correct processing by forming an emulsion layer containing silver halide grains composed of the ones high in silver chloride content sensitized by a selenium compound and a specified yellow coupler in the same emulsion layer in the photosensitive material. CONSTITUTION:At least one of the emulsion layers contains the silver halide grains sensitized by the selenium compound and containing silver chloride in an amount of >=90mol%, and the yellow coupler represented by formula I in which R1 is aryl tertiary alkyl; R2 is F, alkyl, aryl, or the like; R3 is a group substitutable on the benzene ring; X is H or a group to be released by coupling with the oxidation product of an aromatic primary amine developing agent: and r is an integer of 0-4. The selenium sensitization us carried out generally by adding a instable or selenium compound and/or a stable selenium compound to the silver halide emulsion and stirring the emulsion at a high temperature of >=40 deg.C for a prescribed time.

Description

[0001] The present invention relates to a silver halide color photographic light-sensitive material, and more specifically, a silver halide color material having excellent processing stability and improved color reproducibility. It relates to photographic materials. BACKGROUND OF THE INVENTION With the spread of color photographic materials, there is a demand for faster color development processing, and at the same time, there is a demand for the provision of high-quality images. [0003] In response to these demands, research on speeding up processing and improving image quality, especially improving color reproducibility, is being conducted more vigorously than ever before with respect to color print photosensitive materials. . In order to speed up processing, for example, as described in International Publication No. WO 87/04534 and JP-A No. 64-26837, silver halide emulsions with a high silver chloride content, so-called It is known that it is preferable to use high silver chloride emulsions. [0005] In addition, much research has been conducted on improving color reproduction, and in particular, in color print photosensitive materials, there have been many attempts to improve the absorption spectra of cyan, magenta, and yellow coloring pigments, which are the constituent elements of color. It is being done. For example, as for magenta couplers, pyrazoloazole magenta couplers can be mentioned. Compared to conventional 5-pyrazolone magenta couplers, pyrazoloazole magenta couplers have a subabsorption spectrum on the short wavelength side of the coloring dye produced by the coupling reaction with the oxidation product of the developing agent. It has been found that as a result, magenta, red, and blue colors become more vivid. Regarding these, U.S. Patent No. 4,500,630, U.S. Pat.
540,654, JP 61-65245, JP 61-65246, JP 61-147254, European Patent (Publication) No. 266,849, European Patent (Publication)
No. 294,785, etc. in detail. On the other hand, in conventional yellow couplers, the hue of the color forming dye formed is generally located on the long wavelength side with respect to the spectral absorption characteristics favorable for color reproduction, and
It has the disadvantage that the absorption in the long wavelength region exceeding m is too tapered. To address these drawbacks, attempts have been made to improve color reproduction by examining the structure of the yellow coupler and reducing unnecessary absorption of longer wavelengths on the magenta side than in the past. Regarding these, please refer to JP-A-63-123
It is described in detail in No. 047 and Japanese Patent Application Laid-Open No. 63-241547. [Problems to be Solved by the Invention] However, when these yellow couplers are used, the visual sensitivity of the human eye is low, so the density is relatively increased compared to when using conventional yellow couplers. It was necessary to use this, and a darker gradation was required. However, when these yellow couplers were used in silver halide color photographic materials for rapid processing using high silver chloride, sufficient gradations and color density could not always be obtained. In particular, it has been found that when continuous development processing is carried out, the sensitivity becomes lower and the tone becomes softer depending on the processing amount, which becomes a serious problem in practical use. [0010] Therefore, the object of the present invention is to provide excellent color reproducibility;
Another object of the present invention is to provide a silver halide color photographic material, particularly a color print photographic material, which is highly sensitive and has excellent suitability for rapid processing. Means for Solving the Problems As a result of extensive research, the present inventors have discovered that the above object is to provide a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support. wherein at least one of the silver halide emulsion layers consists of silver halide grains having a silver chloride content of 90 mol % or more and is chemically sensitized using a selenium compound, and is represented by the following general formula [I]. It has been found that this can be effectively achieved by a silver halide color photographic material containing at least one type of coupler. [0012] General formula [I] [0013] [0014] In the formula, R1 is an aryl group or a tertiary alkyl group, and R2 is a fluorine atom, an alkyl group, an aryl group, an alkoxyl group, an aryloxy group, A dialkylamino group, an alkylthio group, or an arylthio group, R
3 represents a group that can be substituted on a benzene ring, X represents a group that can be separated by a coupling reaction with a hydrogen atom or an oxidized product of an aromatic primary amine developer, and γ represents an integer from 0 to 4. . However, when γ is an integer, multiple R3's may be the same or different. [0015] Furthermore, the present invention is more effectively achieved by a silver halide color photographic light-sensitive material characterized in that at least one of the layers constituting the light-sensitive material contains at least one compound represented by the following general formula [IV]. I found out that it can be done. [0016] General formula [IV] [Chemical formula 4] In the formula, Q forms a 5- or 6-membered heterocycle or a 5- or 6-membered heterocycle fused with benzene rings. It represents a necessary atomic group, and M represents a hydrogen atom or a cation. As the selenium sensitizer used in the present invention, selenium compounds disclosed in conventionally known patents can be used. Selenium sensitization is usually carried out by adding an unstable selenium compound and/or a non-unstable selenium compound to a silver halide emulsion and stirring the emulsion at a high temperature, preferably 40° C. or higher, for a certain period of time. As the unstable selenium compound, it is preferable to use the compounds described in Japanese Patent Publication No. 15748/1980, Japanese Patent Publication No. 13489/1983, Japanese Patent Application No. 130976/1996, Japanese Patent Application No. 229300/1999, and the like. Specific unstable selenium sensitizers include isoselenocyanates (for example, aliphatic isoselenocyanates such as allyl isoselenocyanate),
Selenoureas, selenoketones, selenoamides, selenocarboxylic acids (e.g., 2-selenopropionic acid, 2-selenopropionic acid,
-selenobutyric acid), selenoesters, diacylselenides (eg, bis(3-chloro-2,6-dimethoxybenzoyl)selenide), selenophosphates, phosphine selenides, colloidal metal selenium, and the like. Although preferred types of unstable selenium compounds have been described above, these are not intended to be limiting. Those skilled in the art understand that when it comes to unstable selenium compounds used as sensitizers in photographic emulsions, the structure of the compound is not particularly important as long as selenium is unstable; It is generally understood that the moiety has no role other than to support the selenium and allow it to exist in an unstable form in the emulsion. In the present invention, unstable selenium compounds having such a broad concept are advantageously used. Examples of non-unstable selenium compounds used in the present invention include Japanese Patent Publication No. 46-4553 and Japanese Patent Publication No. 52-34.
The compounds described in No. 492 and Japanese Patent Publication No. 52-34491 are used. Non-labile selenium compounds include, for example, selenite, potassium selenocyanide, selenazole compounds, quaternary salts of selenazole compounds, diaryl selenide, diaryl diselenide, dialkyl selenide, dialkyl diselenide, 2-selenazolidinedione, Examples include 2-selenoxazolidinethione and derivatives thereof. Among these selenium compounds, the following general formulas (I) and (II) are preferred. General formula (A) ##STR5## In the formula, Z1 and Z2 may each be the same or different and represent an alkyl group (for example, methyl, ethyl, t-butyl, adamantyl, t-octyl)
, alkenyl groups (e.g. vinyl, propenyl), aralkyl groups (e.g. benzyl, phenethyl), aryl groups (e.g. phenyl, pentafluorophenyl, 4-
chlorophenyl, 3-nitrophenyl, 4-octylsulfamoylphenyl, α-naphthyl), heterocyclic groups (e.g. pyridyl, thienyl, furyl, imidazolyl),
Represents NR4 (R5), -OR6 or -SR7. R1, R2, R3 and R4 may each be the same or different and represent an alkyl group, an aralkyl group, an aryl group or a heterocyclic group. As an alkyl group, aralkyl group, aryl group or heterocyclic group, Z
An example similar to 1 can be given. However, R1 and R
2 is a hydrogen atom or an acyl group (e.g., acetyl, propanoyl, benzoyl, heptafluorobutanoyl,
difluoroacetyl, 4-nitrobenzoyl, α-naphthoyl, 4-trifluoromethylbenzoyl). In the general formula (A), preferably Z1 represents an alkyl group, an aryl group or -NR1 (R2), and Z2 represents -NR5 (R6). R1, R2
, R5 and R6 may each be the same or different and represent a hydrogen atom, an alkyl group, an aryl group, or an acyl group. In general formula (A), more preferably N, N-
Dialkylselenourea, N,N,N'-trialkyl-
N'-acylselenourea, tetraalkylselenourea,
Represents N,N-dialkyl-arylselenoamide, N-alkyl-N-aryl-arylselenoamide. General formula (B) ##STR6## In the formula, Z3, Z4 and Z5 may be the same or different, and represent an aliphatic group, an aromatic group, a heterocyclic group, -OR7 , -NR8 (R9), -S
Represents R10, -SeR11, -X or a hydrogen atom. R7, R10 and R11 are aliphatic groups,
Represents an aromatic group, a heterocyclic group, a hydrogen atom or a cation,
R8 and R9 represent an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom, and X represents a halogen atom. In the general formula (B), Z3, Z4,
Z5, R7, R8, R9, R10 and R11
The aliphatic group represented by is a straight chain, branched or cyclic alkyl group, alkenyl group, alkynyl group, aralkyl group (for example, methyl, ethyl, n-propyl, isopropyl, t
-butyl, n-butyl, n-octyl, n-decyl, n
-hexadecyl, cyclopentyl, cyclohexyl, allyl, 2-butenyl, 3-pentenyl, propargyl,
3-pentynyl, benzyl, phenethyl). In the general formula (B), Z3, Z4,
Z5, Z7, R8, R9, R10 and R11
The aliphatic group represented by represents a monocyclic or condensed aryl group (eg, phenyl, pentafluorophenyl, 4-chlorophenyl, 3-sulfophenyl, α-naphthyl, 4-methylphenyl). In the general formula (B), Z3, Z4,
Z5, Z7, R8, R9, R10 and R11
The heterocyclic group represented by is a 3- to 10-membered saturated or unsaturated heterocyclic group containing at least one of a nitrogen atom, an oxygen atom, or a sulfur atom (e.g., pyridyl, thienyl,
(furyl, thiazolyl, imidazolyl, benzimidazolyl). In the general formula (B), the cations represented by R7, R10 and R11 represent alkali metal atoms or ammonium, and the halogen atom represented by X is
For example, it represents a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. In general formula (B), preferably Z3, Z4
or Z5 is an aliphatic group, aromatic group or -OR7
and R7 represents an aliphatic group or an aromatic group. In general formula (B), more preferably it represents trialkylphosphine selenide, triarylphosphine selenide, trialkylselenophosphate or triarylselenophosphate. Specific examples of compounds represented by formulas (A) and (B) are shown below, but the present invention is not limited thereto. [Formula 7] [Formula 7] [Formula 8] [Formula 8] [Formula 9] [Formula 10] [Formula 10] [Formula 11] [Formula 11] [Formula 11] [Formula 13] The amount of selenium sensitizer used depends on the selenium compound used, the silver halide grains (the type and content of halogen,
Although it varies depending on grain size, crystal shape, etc.), chemical ripening conditions, etc., it is generally 10-8 to 10-4 per mole of silver halide.
The amount used is preferably about 10-7 to 10-5 moles. Conditions for chemical sensitization in the present invention are as follows:
Although there is no particular limitation, the pAg is generally 5 to 10, preferably 5.8 to 8, more preferably 6 to 7.5,
The temperature is generally 30-80°C, preferably 40-70°C.
It is 0°C. The pH is generally 4-10, preferably 5-8. As the silver halide emulsion used in the present invention, it is preferable to use one made of silver chlorobromide or silver chloride, which has a silver chloride content of 90 mol % or more and does not substantially contain silver iodide. can. Here, "substantially free of silver iodide" means that the silver iodide content is 1 mol% or less, preferably 0.2 mol% or less. The halogen composition of the emulsion may be different or the same among the grains, but if an emulsion having the same halogen composition among the grains is used, it is easy to make the properties of each grain uniform. In addition, regarding the halogen composition distribution inside silver halide emulsion grains, there are grains with a so-called uniform structure in which the composition is the same in every part of the silver halide grain, and grains with a core inside the silver halide grain and a shell surrounding it. (Shell) [Single layer or multiple layers] Particles with a so-called layered structure with different halogen compositions, or structures with non-layered portions with different halogen compositions inside or on the particle surface (if on the particle surface, the edge of the particle,
structure in which parts of different compositions are joined on a corner or surface)
Particles such as these can be appropriately selected and used. In order to obtain high sensitivity, it is more advantageous to use one of the latter than particles with a uniform structure, and it is also preferable from the viewpoint of pressure resistance. When silver halide grains have the above-mentioned structure, even if the boundaries between parts with different halogen compositions are clear boundaries, the boundaries may be unclear due to the formation of mixed crystals due to compositional differences. It is also possible to have continuous structural changes. In the present invention, the silver chloride content of all silver halide emulsion layers is preferably 90 mol % or more, more preferably 95 mol % or more. Such a high silver chloride emulsion preferably has a structure in which the silver bromide localized phase is present inside and/or on the surface of the silver halide grains in a layered or non-layered manner as described above. The halogen composition of the localized phase is at least 10 mol% in terms of silver bromide content.
It is preferred that the content exceeds 20 mol%, and more preferred that it exceeds 20 mol%. These localized phases can be located inside the grain or on the edges, corners, or surfaces of the grain surface, but one preferred example is one epitaxially grown at the corner of the grain. On the other hand, in order to minimize the decrease in sensitivity when a photosensitive material is subjected to pressure, even in a high silver chloride emulsion with a silver chloride content of 90 mol% or more, a uniform structure with a small distribution of halogen composition within the grains is used. It is also preferred to use particles of It is also effective to further increase the silver chloride content of the silver halide emulsion for the purpose of reducing the amount of replenishment of the processing solution. In such cases, the silver chloride content is 98%.
Emulsions of substantially pure silver chloride, such as from mol % to 100 mol %, are also preferably used. The average grain size of the silver halide grains contained in the silver halide emulsion used in the present invention (grain size is defined as the diameter of a circle equivalent to the projected area of the grain, and the number average thereof is taken) is 0. 1μ to 2μ is preferable. The particle size distribution thereof is preferably so-called monodisperse, with a coefficient of variation (standard deviation of particle size distribution divided by average particle size) of 20% or less, preferably 15% or less. At this time, in order to obtain a wide latitude, it is preferable to blend the above-mentioned monodispersed emulsions in the same layer or to apply multilayer coating. The shape of the silver halide grains contained in the photographic emulsion may be a regular crystal shape such as a cube, a tetradecahedron or an octahedron, or an irregular crystal shape such as a spherical shape or a plate shape. It is possible to use those having irregular crystal forms, or those having a composite form thereof. Moreover, it may be made of a mixture of crystals having various crystal forms. In the present invention, among these particles, 50 particles having the above-mentioned regular crystal shape are used.
% or more, preferably 70% or more, more preferably 90%
It is better to contain more than that. [0054] In addition to these, the average aspect ratio (
An emulsion in which tabular grains having a diameter (diameter in terms of circle equivalent to thickness) of 5 or more, preferably 8 or more in terms of projected area exceeds 50% of the total grains can also be preferably used. The silver chlorobromide emulsion used in the present invention is P. Gl
``Chemistry and Physics of Photography'' by afkides (Chi
mie et phisique photog
Raphique), (Paul Montel, 1967), G. F. "Photographic Emulsion Chemistry" by Duffin
Chemistry), (Focal Pres.
s, 1966), V. L. Zelikman
“Manufacture and Coating of Photographic Emulsions” by Makin et al.
g andCoating Photography
ic Emulsion), (Focal Pre
It can be adjusted using the method described in, for example, published by S.S. Co., Ltd., 1964). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and methods for reacting soluble silver salts with soluble halogen salts include one-sided mixing method,
Any method such as a simultaneous mixing method or a combination thereof may be used. A method in which particles are formed in an atmosphere containing excess silver ions (so-called back mixing method) can also be used. 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 having a regular crystal shape and a nearly uniform grain size can be obtained. Various polyvalent metal ion impurities can be introduced into the silver halide emulsion used in the present invention during the process of emulsion grain formation or physical ripening. Examples of the compounds used include salts of cadmium, zinc, lead, copper, thallium, etc., or salts or complex salts of Group VIII elements such as iron, ruthenium, rhodium, palladium, osmium, iridium, platinum, etc. can. In particular, the Group VIII elements mentioned above can be preferably used. The amount of these compounds added varies over a wide range depending on the purpose, but is preferably from 10@-9 to 10@-2 mol relative to silver halide. All of the silver halide emulsions used in the present invention are conventionally subjected to chemical and spectral sensitization. Regarding chemical sensitization methods, in addition to selenium sensitization alone using the selenium compound of the present invention, sulfur sensitization represented by the addition of unstable sulfur compounds, noble metal sensitization represented by gold sensitization, or reduction sensitization, etc. Can be used in combination. As for the compounds used for chemical sensitization, those described in the lower right column on page 18 to the upper right column on page 22 of JP-A-62-215272 are preferably used. Spectral sensitization is carried out for the purpose of imparting spectral sensitivity in a desired light wavelength range to the emulsion of each layer in the light-sensitive material of the present invention. In the present invention, it is preferable to add a dye-spectral sensitizing dye that absorbs light in a wavelength range corresponding to the desired spectral sensitivity. Spectral sensitizing dyes used at this time include, for example, F. M. Harmer
"Heterocyclic Compounds - Cyanine Dyes and Related Compounds" (He
terocyclic compounds-Cyani
ne dies and related c
(John Wiley &
Sons [New York, London], 1964). Examples of specific compounds and spectral sensitization methods are:
Those described in the above-mentioned JP-A-62-215272, page 22, upper right column to page 38 are preferably used. The silver halide emulsion used in the present invention contains various compounds or their precursors for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of light-sensitive materials, or for stabilizing photographic performance. body can be added. Specific examples of these compounds are given in the above-mentioned JP-A-62-2.
Those described on pages 39 to 72 of the specification of Japanese Patent No. 15272 are preferably used. The emulsion used in the present invention is a so-called surface latent image type emulsion in which latent images are mainly formed on the grain surfaces. Next, the compound of general formula [I] used in the present invention will be explained in more detail. In general formula [I], R1 is preferably an aryl group having 6 to 24 carbon atoms (e.g., phenyl, p-tolyl, o-tolyl, 4-
methoxyphenyl, 2-methoxyphenyl, 4-butoxyphenyl, 4-octyloxyphenyl, 4-hexadecyloxyphenyl, 1-naphthyl) or trivalent alkyl groups having 4 to 24 carbon atoms (e.g. t-butyl, t-
Pentyl, t-hexyl, 1,1,3,3-tetramethylbutyl, 1-adamantyl, 1,1-dimethyl-2-
chloroethyl, 2-phenoxy-2-propyl, bicyclo[2,2,2]octan-1-yl). In the general formula [I], R2 is preferably a fluorine atom or an alkyl group having 1 to 24 carbon atoms (for example, methyl, ethyl, isopropyl, t-butyl, cyclopentyl, n-octyl, n-hexadecyl, benzyl). , an aryl group having 6 to 24 carbon atoms (e.g. phenyl, p-tolyl, o-tolyl, 4-methoxyphenyl),
Alkoxy groups having 1 to 24 carbon atoms (e.g. methoxy,
ethoxy, butoxy, n-octyloxy, n-tetradecyloxy, benzyloxy, methoxyethoxy),
Aryloxy groups having 6 to 24 carbon atoms (e.g. phenoxy, p-tolyloxy, o-tolyloxy, p-methoxyphenoxy, p-dimethylaminophenoxy, m-
pentadecylphenoxy), dialkylamino groups having 2 to 24 carbon atoms (including amino groups in which these alkyl groups are linked together to form a ring, such as dimethylamino,
diethylamino, pyrrolidino, piperidino, morpholino), alkylthio groups having 1 to 24 carbon atoms (e.g. methylthio, butylthio, n-octylthio, n-hexadecylthio) or arylthio groups having 6 to 24 carbon atoms (e.g. phenylthio, 4-methoxyphenyl) Thio, 4
-t-butylphenylthio, 4-dodecylphenylthio). In the general formula [I], R3 is preferably a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), an alkyl group having 1 to 24 carbon atoms (for example, methyl, t-butyl, n-dodecyl ), number of carbon atoms 6-2
4 aryl groups (e.g. phenyl, p-tolyl, p-dodecyloxyphenyl), alkoxy groups having 1 to 24 carbon atoms (e.g. methoxy, n-butoxy, n-octyloxy, n-tetradecyloxy, benzyloxy, methoxyethoxy), aryloxy groups having 6 to 24 carbon atoms (e.g. phenoxy, pt-butylphenoxy,
4-butoxyphenoxy), alkoxycarbonyl groups having 2 to 24 carbon atoms [e.g. ethoxycarbonyl, dodecyloxycarbonyl, 1-(dodecyloxycarbonyl)ethoxycarbonyl], aryloxycarbonyl groups having 7 to 24 carbon atoms [e.g. phenoxy carbonyl, 4-t-octylphenoxycarbonyl, 2,4-di-t-pentylphenoxycarbonyl), number of carbon atoms: 1
~24 carbonamide groups [e.g. acetamido, pivaloylamino, benzamide, 2-ethylhexanamide, tetradecanamide, 1-(2,4-di-t-pentylphenoxy)butanamide, 3-(2,4-di-t
-pentylphenoxy)butanamide, 3-dodecylsulfonyl-2-methylpropanamide], number of carbon atoms: 1
-24 sulfonamide groups (e.g. methanesulfonamide, p-toluenesulfonamide, hexadecanesulfonamide), carbamoyl groups having 1 to 24 carbon atoms (e.g. N-methylcarbamoyl, N-tetradecylcarbamoyl, N,N-dihexyl) carbamoyl, N-octadecyl-N-methylcarbamoyl, N-phenylcarbamoyl), alkylsulfonyl groups having 1 to 24 carbon atoms (e.g. methylsulfonyl, benzylsulfonyl, hexadecylsulfonyl), arylsulfonyl groups having 6 to 24 carbon atoms (e.g. phenylsulfonyl, p-tolylsulfonyl, p-dodecylphenylsulfonyl, p-methoxyphenylsulfonyl), ureido groups having 1 to 24 carbon atoms (e.g. 3-methylureido, 3-phenylureido, 3,3-dimethylureido) , 3-tetradecylureido), a sulfamoylamino group having 0 to 24 carbon atoms (e.g. N,N-dimethylsulfamoylamino)
, alkoxycarbonylamino groups having 2 to 24 carbon atoms (e.g. methoxycarbonylamino, isobutoxycarbonylamino, dodecyloxycarbonylamino), nitro groups, heterocyclic groups having 1 to 24 carbon atoms (e.g. 4-pyridyl, 2- thienyl, phthalimide, octadecylsuccinimide), cyano group, acyl group having 1 to 24 carbon atoms (e.g. acetyl, benzoyl, dodecanoyl),
Acyloxy group having 1 to 24 carbon atoms (e.g. acetoxy, benzoyloxy, dodecanoyloxy), alkylsulfonyloxy group having 1 to 24 carbon atoms (e.g. methylsulfonyloxy, heisadecylsulfonyloxy) or 6 to 24 carbon atoms 24 arylsulfonyloxy groups (eg, p-toluenesulfonyloxy, p-dodecylphenylsulfonyloxy). In general formula [I], r is preferably 1
or an integer of 2. In general formula [I], , bromine, iodine), a heterocyclic group bonded to the coupling active position with a nitrogen atom having 1 to 24 carbon atoms, an aryloxy group having 6 to 24 carbon atoms, an arylthio group having 6 to 24 carbon atoms (e.g., phenylthio , p-t-butylphenylthio, p-chlorophenylthio, p-carboxyphenylthio), acyloxy groups having 1 to 24 carbon atoms (e.g. acetoxy, benzoyloxy, dodecanoyloxy), alkyl having 1 to 24 carbon atoms a sulfonyloxy group (e.g. methylsulfonyloxy, butylsulfonyloxy, dodecylsulfonyloxy), a C6-C24 arylsulfonyloxy group (e.g. benzenesulfonyloxy, p-chlorophenylsulfonyloxy) or a C1-C24 hetero Ring oxy groups (e.g. 3-pyridyloxy, 1-phenyl-1,2,3,4-tetrazole-
(5-yloxy), more preferably a heterocyclic group or aryloxy group bonded to the coupling active position through a nitrogen atom. When X is a nitrogen atom and represents a nitrogen ring group bonded to the coupling active position, X includes, in addition to the nitrogen atom, a heteroatom selected from oxygen, sulfur, nitrogen, phosphorus, selenium, and tellurium. A 5- to 7-membered optionally substituted monocyclic or fused heterocyclic ring, examples of which include succinimide, maleimide, phthalimide, diglycolimide, pyrrole, pyrazole, imidazole, 1, 2,4-triazole, tetrazole, indole, benzopyrazole, benzimidazole, benzotriazole, imidazolidine-2,4-dione, oxazolidine-2,4-dione, thiazolidine-
2,4-dione, imidazolidin-2-one, oxazolin-2-one, thiazolin-2-one, benzimidazolin-2-one, benzoxazolin-2-one, benzothiazolin-2-one, 2-pyrroline- 5-on,
2-imidazolin-5-one, indoline-2,3-dione, 2,6-dioxypurine, parabanic acid, 1,2,
4-triazolidine-3,5-dione, 2-pyridone,
4-pyridone, 2-pyrimidone, 6-pyridazone, 2-
Examples include pyrazone, and these heterocyclic groups may be substituted. Examples of substituents include hydroxy group, carboxyl group, sulfo group, amino group (such as amino, N-
In addition to (methylamino, N,N-dimethylamino, N,N-diethylamino, anilino, pyrrolidino, piperidino, morpholino), there are substituents listed as examples of R3 above. When X represents an aryloxy group, it is preferable that X has 6 to 24 carbon atoms, and the aryl group may be substituted. Examples of substituents include carboxyl group, sulfo group, cyano group, nitro group, alkoxycarbonyl group, halogen atom, carbonamide group, sulfonamide group, carbamoyl group, sulfamoyl group, alkyl group, alkylsulfonyl group, arylsulfonyl group, or acyl group. Groups are preferred. Next, the above-mentioned substituents R1, R2, R
Examples of substituents particularly preferably used in the present invention will be described for each of 3 and X. General formula [I]
, R1 is particularly preferably a 2- or 4-alkoxyaryl group (e.g. 4-methoxyphenyl, 4-
butoxyphenyl, 2-methoxyphenyl) or t-
Butyl group, most preferably t-butyl group. In the general formula [I], R2 is particularly preferably a methyl group, ethyl group, alkoxy group, aryloxy group or dialkylamino group, and is preferably a methyl group, ethyl group, alkoxy group, aryloxy group or dimethylamino group. is most preferred. In the general formula [I], R3 is particularly preferably an alkoxy group, a carbonamide group or a sulfonamide group. In the general formula [I], X is particularly preferably a heterocyclic group or an aryloxy group bonded to the coupling active position through a nitrogen atom. When X represents the above-mentioned heterocyclic group, X is preferably represented by the following general formula [II]. General formula [II] [Chemical formula 14] [0073] In the general formula [II], Z is -O-CR4
(R5)-, -S-CR4 (R5)-, -N(
R6)-C(R4)R5-, -N(R6)-N
(R7)-, -N(R6)-CO-, -CR4 (
R5 )-CR8 (R9)-, or -C(R10
)=C(R11)-. Here, R4, R5, R8 and R9
represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, or an amino group, and R6 and R7 represent a hydrogen atom, an alkyl group, an aryl group, an alkyl It represents a sulfonyl group, an arylsulfonyl group, or an alkoxycarbonyl group, and R10 and R11 represent a hydrogen atom, an alkyl group, or an aryl group. R10 and R11 may be combined with each other to form a benzene ring. R4 and R5, R5 and R6, R6 and R
7 or R4 and R8 may be bonded to each other to form a ring (eg, cyclobutane, cyclohexane, cycloheptane, cyclohexene, pyrrolidine, piperidine). Among the heterocyclic groups represented by the general formula [III], particularly preferred ones are Z in the general formula [III]
is -O-CR4 (R5)-, -N(R6)-CR
4 (R5)- or -N(R6)-N(R7)
- is a heterocyclic group. The total number of carbon atoms in the heterocyclic group represented by the general formula [III] is 2 to 24, preferably 4 to 20, more preferably 5 to 16. Examples of the heterocyclic group represented by the general formula [III] include a succinimide group, a maleimide group, a phthalimide group, a 1-methylimidazolidine-2,4-dione-3-yl group, and a 1-benzylimidazolidine-2,4 -dione-3-yl group, 5,5-dimethyloxazolidine-2,4-dione-3-yl group, 5-
Methyl-5-propyloxazolidine-2,4-dione-3-yl group, 5,5-dimethylthiazolidine-2,4
-dione-3-yl group, 5,5-dimethylimidazolidine-2,4-dione-3-yl group, 3-methylimidazolidinetrion-1-yl group, 1,2,4-triazolidine-3,5 -dione-4-yl group, 1-methyl-2-
Phenyl-1,2,4-triazolidine-3,5-dione-4-yl group, 1-benzyl-2-phenyl-1,2
, 4-triazolidine-3,5-dione-4-yl group,
5-hexyloxy-1-methylimidazolidine-2,
4-dione-3-yl group, 1-benzyl-5-ethoxyimidazolidine-2,4-dione-3-yl group, 1-benzyl-5-dodecyloxyimidazolidine-2,4-
There is a diion-3-yl group. Among the above heterocyclic groups, imidazolidine-2
,4-dione-3-yl group (e.g. 1-benzyl-imidazolidine-2,4-dione-3-yl group) is the most preferred group. When X represents an aryloxy group, 4-
Orboxyphenoxy group, 4-methylsulfonylphenoxy group, 4-(4-benzyloxyphenylsulfonyl)phenoxy group, 4-(4-hydroxyphenylsulfonyl)phenoxy group, 2-chloro-4-(3-chloro-
4-hydroxyphenylsulfonyl) phenoxy group, 4
-methoxycarbonylphenoxy group, 2-chloro-4-
Methoxycarbonylphenoxy group, 2-acetamido-
4-methoxycarbonylphenoxy group, 4-isopropoxycarbonylphenoxy group, 4-cyanophenoxy group, 2-[N-(2-hydroxyethyl)carbamoyl]
Phenoxy group, 4-nitrophenoxy group, 2,5-dichlorophenoxy group, 2,3,5-trichlorophenoxy group, 4-methoxycarbonyl-2-methoxyphenoxy group, 4-(3-carboxypropanamide) phenoxy group This is the most preferred example. The coupler represented by the general formula [I] has 2 in the substituent R1, X or the group represented by the following formula 15.
valence or ##STR15## A dimer or a multimer of more than two molecules may be formed which are bonded to each other via a group having a valence of two or more. This place,
The number of carbon atoms in each of the above substituents may be outside the specified range. When the coupler represented by the general formula [I] forms a multimer, it is typically an addition polymer containing an ethylenically unsaturated compound (yellow coloring monomer) or a copolymer having a yellow dye-forming coupler residue. This is an example. In this case, the multimer contains repeating units of the general formula [III], and one or more types of yellow-coloring repeating units represented by the general formula [III] may be contained in the multimer, and non-containing as a copolymerization component. It may also be a copolymer containing one or more color-forming ethylene type monomers. General formula [III] [Chemical formula 16] In the formula, R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a chlorine atom, and A represents -CONH-, -C
OO- or a substituted or unsubstituted phenylene group, B represents a substituted or unsubstituted alkylene group, phenylene group or aralkylene group, L represents -CONH-, -
NHCONH-, -NHCOO-, -NHCO-, -O
CONH-, -NH-, -COO-, -OCO-, -C
O-, -O-, -S-, -SO2 -, -NHSO2
- or -SO2NH-. a, b, and c represent 0 or 1. Q is R1 of the compound represented by general formula [I]
, X or a group represented by the following chemical formula 17, if a hydrogen atom is [
##STR17## Showing the detached yellow coupler residue. As the multimer, a copolymer of a yellow color-forming monomer represented by a coupler unit of general formula [III] and the following non-color-forming ethylene-like monomer is preferred. Examples of non-color-forming ethylene monomers that do not couple with the oxidation products of aromatic primary amine developers include acrylic acid, α-
Chloroacrylic acid, α-alkylacrylic acid (e.g. methacrylic acid, etc.) Amides or esters derived from these acrylic acids (e.g. acrylamide, methacrylamide, n-butylacrylamide, t-butylacrylamide, diacetone acrylamide, methyl acrylate) , ethyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl acrylate, iso-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and β- hydroxy methacrylate), vinyl esters (e.g. vinyl acetate, vinyl propionate and vinyl laurate), acrylonitrile, methacrylonitrile, aromatic vinyl compounds (e.g. styrene and its derivatives, e.g. vinyltoluene, divinylbenzene, vinylacetophenone and sulfostyrene) ), itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ethers (e.g. vinyl ethyl ether), maleic acid esters, N-vinyl-2-pyrrolidone, N-vinylpyridine and 2- and -4-vinylpyridine, etc. There is. Particularly preferred are acrylic esters, methacrylic esters, and maleic esters. Two or more types of the non-color-forming ethylene monomers used here can also be used together. For example, methyl acrylate and butyl acrylate, butyl acrylate and styrene, butyl methacrylate and methacrylic acid, methyl acrylate and diacetone acrylamide, etc. can be used. As is well known in the field of polymer couplers, the ethylenically unsaturated monomer to be copolymerized with the vinyl monomer corresponding to the above general formula [III] depends on the physical properties and/or properties of the copolymer to be formed. Alternatively, the chemical properties, such as solubility, compatibility with binders such as gelatin of the photographic colloid composition, its flexibility, thermal stability, etc., can be selected to be favorably influenced. The yellow polymer coupler used in the present invention is obtained by dissolving a lipophilic polymer coupler obtained by polymerizing a vinyl monomer to give a coupler unit represented by the above general formula [III] in an organic solvent, and adding gelatin to the coupler. It may also be made by emulsifying and dispersing it in the form of latex in an aqueous solution.
Alternatively, it may be produced by a direct emulsion polymerization method. A method of emulsifying and dispersing a lipophilic polymer coupler in the form of latex in an aqueous gelatin solution is described in US Pat. No. 3,451,820, and emulsion polymerization is described in US Pat. No. 4,080,211 and US Pat. ,370,95
The method described in No. 2 can be used. Specific examples of the yellow dye-forming couplers R3 and X represented by the general formula [I] are shown below, but the present invention is not limited thereto. A specific example of X is shown below. [0094] [Chemical 18] [Chemical 19] [Chemical 19] [Chemical 20] [Chemical 21] [Chemical 21] [0098] Next, specific examples of R3 are shown below. embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded    22 22 20 25 35 35 45 45 45 55 65 85 80 80 80 80 80 80 80 80 80 80 80 80 90 90 90 80 80 80 100 100 100 100 100 100 100 100 100 20 20 20 20 20 20 30 30 30 30 30 30 40 45 50 45 50 65 6 Specific examples of the yellow dye-forming coupler represented by the general formula [I] used in the present invention are as follows. Shown in the table. [Table 1] [Table 2] [Table 3] [0106] In the table, the numbers in parentheses represent the numbers assigned to the specific examples of X and R3, and the numbers in parentheses The numbers represent the substitution positions on the anilide group. The couplers of the present invention may be used alone, or may be used in combination of two or several kinds, or may be used in combination with known yellow dye-forming couplers. The couplers of the present invention can be used in any layer of the light-sensitive material, but are preferably used in the light-sensitive silver halide emulsion layer or a layer adjacent thereto, most preferably in the light-sensitive silver halide emulsion layer. [0108] The coupler of the present invention can be synthesized by conventionally known synthesis methods.
There is a synthesis method described in the A2 specification. The amount of the coupler of the present invention used in the photosensitive material is 1 x 10-5 mol to 10-2 mol, preferably 1 x 10-4 mol to 5 x 10-3 mol, per m2.
More preferably, it is 2×10 −4 mol to 10 −3 mol. The yellow coupler represented by the general formula [I] used in the present invention reacts with the oxidation product of a color developing agent consisting of an aromatic primary amine to produce a yellow dye. is characterized by less absorption of long wavelengths than those conventionally used for color photographic paper. Specifically, in a color print made of a dye produced by reaction with N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline, the absorption peak of the yellow dye wavelength concentration is 1
．． It is preferable that the wavelength at which the reflection density reaches 40% of the peak on the long wavelength side of the absorption peak wavelength of the spectral reflection spectrum in the 0 portion is at a wavelength shorter than 508 nm. More preferably, the wavelength is shorter than 505 nm. Particularly preferably, the wavelength is shorter than 502 nm and longer than 490 nm. The general formula [I] used in the present invention will be explained below.
The compound represented by V] will be explained in detail. In the general formula [IV], Q represents an atomic group necessary to form a 5- or 6-membered heterocycle or a 5- or 6-membered heterocycle fused with benzene rings; Examples of the ring include an imidazole ring, a tetrazole ring, a thiazole ring, an oxazole ring, a selenazole ring, a benzimidazole ring, a naphthoimidazole ring, a benzothiazole ring, a naphthothiazole ring, a benzoselenazole ring,
Examples include naphthoselenazole ring and benzoxazole ring. Examples of the cation represented by M include alkali metals (eg, sodium, potassium, etc.), ammonium groups, and the like. The mercapto compound represented by the general formula [IV] can be further synthesized by the following [IV-1] and [IV-
2], [IV-3] and [IV-4] are preferred. [0114] General formula [IV-1] [Chemical formula 25] [0116] In the formula, RA is a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, a halogen atom, a carboxyl group or a salt thereof, a sulfo group or a salt thereof. represents a salt or an amino group, Z represents -NH-, -O-, or -S-, and M has the same meaning as M in general formula [IV]. [0117] General formula [IV-2] [Chemical formula 26] [0119] In the formula, Ar represents a group represented by the following formula 26; Alkyl group, alkoxy group, carboxyl group or its salt, sulfo group or its salt, hydroxyl group, amino group, acylamino group,
Represents a carbamoyl group or a sulfonamide group. n is 0
Represents an integer between ~2. M has the same meaning as M in general formula [IV]. [0122] In general formulas [IV-1] and [IV-2], examples of the alkyl group represented by RA and RB include methyl group, ethyl group, butyl group, etc., and examples of the alkoxy group include methoxy group, ethoxy group, etc. Examples of the salts of carboxyl or sulfo groups include sodium salts and ammonium salts. In the general formula [IV-1], examples of the aryl group represented by RA include a phenyl group and a naphthyl group, and examples of the halogen atom include a chlorine atom and a bromine atom. In the general formula [IV-2], examples of the acylamino group represented by RB include methylcarbonylamino group, benzoylamino group, etc., and examples of the carbamoyl group include ethylcarbamoyl group, phenylcarbamoyl group, etc. Examples of the sulfonamide group include a methylsulfonamide group and a phenylsulfonamide group. The above-mentioned alkyl groups, alkoxy groups, aryl groups, amino groups, acylamino groups, carbamoyl groups, sulfonamide groups, etc. include those having further substituents. General formula [IV-3] ##STR28## In the formula, Z represents -NRA1-, an oxygen atom or a sulfur atom. RA is a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a cycloalkyl group, -SRA1
, -NRA2(RA3)-, -NHCORA4, -NH
SO2 RA5 or a heterocyclic group, RA1 is a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group,
It represents an aryl group, -CORA4, or -SO2 RA5, RA2 and RA3 represent a hydrogen atom, an alkyl group, or an aryl group, and RA4 and RA5 represent an alkyl group or an aryl group. M has the same meaning as M in general formula [IV]. RA, RA in general formula [IV-3]
Examples of the alkyl group represented by 1, RA2, RA3, RA4 and RA5 include methyl group, benzyl group, ethyl group, propyl group, etc., and examples of the aryl group include phenyl group, naphthyl group, etc. Examples of the alkenyl group represented by RA and RA1 include a propenyl group, and examples of the cycloalkyl group include a cyclohexyl group. Examples of the heterocyclic group represented by RA include furyl group and pyridinyl group. [0130] The above RA, RA1, RA2, RA3, R
The alkyl group and aryl group represented by A4 and RA5, the alkenyl group and cycloalkyl group represented by RA and RA1, and the heterocyclic group represented by RA further include those having a substituent. [0131] General formula [IV-4] [0132] [0133] In the formula, RA and M each represent the general formula [
IV-3] represents a group having the same meaning as RA and M in [IV-3]. Further, RB1 and RB2 are each represented by the general formula [IV-3
] represents the same group as RA1 and RA2. Specific examples of the compound represented by the general formula [IV] are shown below, but the present invention is not limited thereto. [Formula 30] [Formula 30] [Formula 31] [Formula 32] [Formula 32] [Table 4] [Table 5] [Table 6] [Table 7] [Table 8] [Table 9] [Table 9] The amount of the compound represented by the general formula [IV] added is 1 x 10-5 to 5 x 10 per mole of silver halide.
-2 mol is preferred, more preferably 1 x 10-4 to 1 x 10-
2 mol is preferred. Further, there is no particular restriction on the place where it is added, and it may be either in the photosensitive layer or in the non-photosensitive layer. Further, there is no particular restriction on the method of addition, and it may be added during the formation of silver halide grains, during physical ripening, during chemical ripening, or during preparation of the coating solution. [0145] In the photosensitive material according to the present invention, for the purpose of improving image sharpness, etc., a hydrophilic colloid layer which can be decolorized by the treatment described on pages 27 to 76 of European Patent EP 0,337,490A2 is added. Dyes (especially oxonol dyes) are added to the sensitive material so that the optical reflection density at 680 nm is 0.70 or more, and di- to tetrahydric alcohols (among others) are added to the water-resistant resin layer of the support. For example, titanium oxide surface-treated with trimethylolethane)
The content is preferably 2% by weight or more (more preferably 14% by weight or more). Photographic additives such as cyan, magenta and yellow couplers that can be used in the present invention can be dissolved in a high boiling point organic solvent and emulsified and dispersed in an aqueous hydrophilic colloid solution. Such high boiling point organic solvents have a melting point of 100°C.
The following are compounds that are immiscible with water and have a boiling point of 140°C or higher,
Any good solvent for the coupler can be used. The melting point of the high-boiling organic solvent is preferably 80°C or lower. The boiling point of the high boiling point organic solvent is preferably 160°C or higher, more preferably 170°C or higher. Details of these high boiling point organic solvents are described in the lower right column on page 137 to the upper right column on page 144 of the specification of JP-A-62-215272. Cyan, magenta or yellow couplers can also be used in loadable latex polymers (e.g., U.S. Pat. No. 4,203,716) in the presence or absence of the high-boiling organic solvents described above.
It can be emulsified and dispersed in an aqueous hydrophilic colloid solution by impregnating it with a hydrophilic colloid or by dissolving it in an organic solvent together with a water-insoluble but organic solvent-soluble polymer. Preferably US Pat. No. 4,857,449
No. 12 of International Publication No. WO88/00723
Homopolymers or copolymers described on pages 30 to 30 are used, and methacrylate or acrylamide polymers, particularly acrylamide polymers, are preferably used from the viewpoint of color image stabilization. [0149] Further, in the light-sensitive material according to the present invention, it is preferable to use a color image preservability improving compound as described in European Patent EP 0,277,589A2 together with the coupler. Particularly preferred is the combination with a pyrazoloazole coupler. That is, the compound (F) and/or which chemically bonds with the aromatic amine developing agent remaining after color development processing to produce a chemically inert and substantially colorless compound.
Alternatively, a compound (G) that chemically bonds with the oxidized aromatic amine color developing agent remaining after color development processing to produce a chemically inert and substantially colorless compound is used simultaneously or singly. However, this is preferable in order to prevent the generation of stains and other side effects due to the reaction of the coupler with the color developing agent or its oxidized product remaining in the film during storage after processing. [0151] The photosensitive material of the present invention is also coated with anti-mildew agents as described in JP-A No. 63-271247 in order to prevent various types of mold and bacteria that grow in the hydrophilic colloid layer and degrade images. It is preferable to add an agent. [0152] The support used in the light-sensitive material according to the present invention may be a white polyester support for display purposes or a support on the side having a silver halide emulsion layer on which a layer containing a white pigment is provided. A support may also be used. In order to further improve sharpness, it is preferable to coat an antihalation layer on the side on which the silver halide emulsion layer is coated or on the back side of the support. In particular, the transmission density of the support was set to 0.3 so that the display can be viewed with both reflected and transmitted light.
It is preferable to set it in the range of 5 to 0.8. The photosensitive material according to the present invention may be exposed to visible light or infrared light. The exposure method may be low-intensity exposure or high-intensity short-time exposure, and particularly in the latter case, a laser scanning exposure method in which the exposure time per pixel is shorter than 10 -4 seconds is preferred. [0154] Also, upon exposure, US Patent No. 4,88
Preferably, a band stop filter as described in US Pat. No. 0,726 is used. This removes light color mixing,
Color reproducibility is significantly improved. [0155] The exposed photosensitive material can be subjected to expensive color development processing, but for the purpose of rapid processing, it is preferable to carry out bleach-fixing processing after color development. In particular, the pH of the bleach-fix solution is preferably about 6.5 or less for the purpose of promoting desilvering.
More preferably, it is about 6 or less. [0156] Silver halide emulsions and other materials (additives, etc.) and photographic constituent layers (layer arrangement, etc.) applied to the light-sensitive material of the present invention, and processing methods applied to process this light-sensitive material. As processing additives, the following patent publications, especially European Patent EP 0,355,660A2 (
Those described in JP-A-2-139544) are preferably used. [Table 10] [Table 11] [Table 11] [Table 159] [Table 12] [Table 13] [Table 14] [Table 14]
In addition to the diphenylimidazole cyan coupler described in No. 33144, European Patent EP 0,333,185A2
3-hydroxypyridine cyan coupler (
Among them, 4 of couplers (42) listed as specific examples
Particularly preferred are equivalent couplers with a chlorine leaving group to make them di-equivalent, couplers (6) and (9), and cyclic active methylene cyan couplers described in JP-A No. 64-32260 (especially preferred). Particular preference is given to the couplers examples 3, 8, 34 listed by way of example). [0163] Processing methods for silver halide color light-sensitive materials using high silver chloride emulsions with a silver chloride content of 90 mol% or more are described in JP-A-2-207250, page 27, upper left column to page 34, upper right column. The method described in the column is preferably applied. [Examples] The present invention will be specifically explained below with reference to Examples, but the present invention is not limited thereto. (Preparation of emulsion A) Add 25 g of lime-treated gelatin to 80 g of distilled water.
18.8 cc of sulfuric acid (1N) and 4.5 g of sodium chloride were added. 3 cc of N,N'-dimethylimidazoline-2-thione (1% aqueous solution) was added to this solvent, and 140 cc of an aqueous solution containing 5.0 g of silver nitrate and 1.7 g of sodium chloride were dissolved while keeping the temperature at 60°C and stirring vigorously. 140 cc of the aqueous solution was added and mixed using a double jet method over 10 minutes. After 10 minutes, add 120 g of silver nitrate to this solution.
320cc of aqueous solution and 38.8ml of sodium chloride
g, potassium bromide 0.44 g, iron(II) hexacyano
Silver halide particles were prepared by adding and mixing 320 cc of an aqueous solution in which 0.4 mg of potassium acid trihydrate and 3.6 x 10 -2 mg of potassium hexachloroiridate (IV) were dissolved using a double jet method over 25 minutes. Continuing, 4
After desalting and washing with water at 0°C, 90 g of lime-treated gelatin was added, and the pAg was adjusted to 7.4 and the pH to 6.4 with sodium chloride and sodium hydroxide. Subsequently, triethylthiourea was added at 1×10 −
5 mol was added and sulfur sensitization was optimally performed at 58°C. The silver chlorobromide emulsion thus obtained was designated as Emulsion A. (Preparation of Emulsion B) The chemical sensitization process of Emulsion A was changed, and instead of sulfur sensitization, 1 x 10-5 mol of dimethylselenourea was added per 1 mol of silver, and selenium was optimally sensitized at 58°C. Sensitized. The silver chlorobromide emulsion thus obtained was designated as Emulsion B. (Preparation of Emulsion C) The chemical sensitization process of Emulsion A was changed to add 0.8 dimethylselenourea per mole of silver.
x 10-5 mol and 2 x 10-6 mol of chloroauric acid were added,
Gold selenium sensitization was optimally performed at 58°C. The silver chlorobromide emulsion thus obtained was designated as Emulsion C. The grain shape, grain size and grain size distribution of the emulsion thus prepared were determined using an electron microscope. The particle size was expressed as the average value of the diameter of a circle equivalent to the projected area of the particles, and the particle size distribution was calculated using the value obtained by dividing the standard deviation of the particle diameter by the average particle size (coefficient of variation). These emulsions all have a grain size of 0.80μ
m, the coefficient of variation of the particle size distribution consisted of cubic particles with a value of 0.08. Example 1 A multilayer color print material having the layer structure shown below was prepared on a paper support laminated on both sides with polyethylene. (Sample No. 1) The coating solution was prepared as follows. First layer coating solution preparation Yellow coupler (ExY) 19.1g, color image stabilizer (Cod-1) 4.4g and color image stabilizer (Cpd-1)
7) Add 27.2 cc of ethyl acetate and solvent (S
Add and dissolve 8.2g of olv-1), and dilute this solution to 10%
1 containing 8 cc of sodium dodecylbenzenesulfonate
It was emulsified and dispersed in 185 cc of 0% gelatin aqueous solution. Separately, a silver chlorobromide emulsion (emulsion B) was prepared by adding the following blue-sensitive sensitizing dyes at 2.0 x 10 -4 mol per mol of silver. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a first layer coating solution having the composition shown below. Coating solutions for layers other than those described above were also prepared in the same manner as the first layer coating solution. As the gelatin hardening agent for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. The following spectral sensitizing dyes were used in each layer. For blue-sensitive emulsion layer [0170] [0171] (2.0× each per mol of silver halide)
10-4 mol) for the green-sensitive emulsion layer [Image Omitted] (per mol of silver halide, 4.0 x 10-4 mol for large size emulsions, for small size emulsions is 5.6 x 10-4 mol) and [Image Omitted] (per mol of silver halide, 7.0 x 10-5 mol for large-sized emulsions, and 7.0 x 10-5 mol for small-sized emulsions) (1.0 x 10-5 mol for red-sensitive emulsion layer) [0176] [0177] (0.9 x 10-4 for large size emulsion per 1 mol of silver halide) (or 1.1 x 10-4 mol for small size emulsions)) For the red-sensitive emulsion layer, the following compounds were added at a concentration of 2.6 mol per mol of silver halide.
x10-3 mol was added. ##STR37## The following dyes were added to the emulsion layer to prevent irradiation. [Image Omitted] [Image Omitted] [Image Omitted] [Image Omitted] [Image Omitted] [Image Omitted] In addition, 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer. per mole of silver halide, respectively,
1 x 10-4 mol and 2 x 10-4 mol were added. Also,
The following compound was used as a preservative. (Numbers are coating amounts) ##STR40## (Layer structure) The composition of each layer is shown below. The numbers represent the coating amount (g/m2). The silver halide emulsion represents the coated amount in terms of silver. First layer (blue-sensitive layer) Silver chlorobromide emulsion A
0.30
gelatin
1
．． 22 Yellow coupler (ExY)
0.82
Color image stabilizer (Cpd-1)
0.19 Solvent (S
olv-1)
0.35 Color image stabilizer (
Cpd-7)
0.06 0186 Second layer (color mixing prevention layer) Gelatin

0.64 Color mixing prevention agent (Cpd-5)
0.10
Solvent (Solv-1)
0.16
Solvent (Solv-4)
0.08 018
7] Third layer (green-sensitive layer) Silver chlorobromide emulsion (cubic, average grain size 0.55μ
A 1:3 mixture (Ag molar ratio) of 0.39μ and 0.39μ. The coefficient of variation of particle size distribution is 0.10
and 0.08, each emulsion contains 0.8 mol% AgBr.
localized on a part of the particle surface)

0.12 Gelatin

1.28 Magenta coupler (ExM)
0.20 Color image stabilizer (C
pd-2)
0.03 Color image stabilizer (Cpd-3
)
0.15 Color image stabilizer (Cpd-4)

0.02 Color image stabilizer (Cpd-9)
0.02
Solvent (Solv-2)
0.40 0
188] Fourth layer (ultraviolet absorption layer) Gelatin

1.41 Ultraviolet absorber (UV-1)
0.47
Color mixing inhibitor (Cpd-5)
0.05 Solvent (Solv-5)
0.24 Fifth layer (red sensitive layer) Silver chlorobromide emulsion (cubic, average grain size 0.60μ
A 1:4 mixture (Ag molar ratio) of 0.45μ and 0.45μ. The coefficient of variation of particle size distribution is 0.09
and 0.11, and 0.6 mol% of AgBr in each emulsion.
localized on a part of the particle surface)

0.22 Gelatin

1.04 Cyan coupler (ExC)
0.32 Color image stabilizer (
Cpd-6)
0.17 Color image stabilizer (Cpd-
7)
0.40 Color image stabilizer (Cpd-8)

0.04 Solvent (Solv-6)
0
．． 15 0190 Sixth layer (ultraviolet absorption layer) Gelatin

0.48 Ultraviolet absorber (UV-1)
0.16
Color mixing inhibitor (Cpd-5)
0.02 Solvent (Solv-5)
0.08 0191 Seventh layer (protective layer) Gelatin

1.10 Acrylic modified copolymer of polyvinyl alcohol 0.17 (degree of modification 17%)

liquid paraffin

0.03 The compounds used in the above photosensitive material are as follows. [Formula 41] [Formula 42] [Formula 42] [Formula 43] [Formula 44] [Formula 44] ##STR48## As described above, sample No. I made 1. Next, sample No. 1 was prepared in the same manner as above except that the emulsion and yellow coupler in the first layer (blue-sensitive layer) were changed as shown in the table below. 2
~No. I made 9. [0202] Sample No. Emulsion yellow coupler
1. A Ex-
Y Comparative example 2.
AY-1
〃 3.
AY-5
〃 4. B
Ex-Y
〃 5. B
Y-1 Present invention
6. B
Y-5 〃
7. C Ex
-Y Comparative example 8.
CY-1
Present invention 9.
CY-5
〃
The amounts of coupler and emulsion added were all equimolar to Sample 1. [0203] In order to investigate the photographic properties of these samples, the following experiment was conducted. First, apply 30% of the amount of silver coated to each sample.
Exposure was given such that 0% was developed. The exposed sample was subjected to continuous processing (running test) using a paper processing machine until twice the color development tank capacity was replenished in the next processing step. Sensitometry was performed on each sample using the liquid at the start of continuous processing and the running liquid thus obtained. Each sample was subjected to gradation exposure for sensitometry through blue, green, and red filters using a sensitometer (Model FWH manufactured by Fuji Photo Film Co., Ltd., color temperature of light source 3200°K). Gave. The exposure at this time is 1/
The exposure time was 10 seconds and the exposure amount was 250 CMS. Processing process Temperature Time Replenisher* Tank capacity Color development 35°C 45 seconds 161ml 17 liters Bleach-fixing 30-35°C 45 seconds
215ml 17 liter rinse■
30~35℃ 20 seconds ───
10 liter rinse■ 30~3
5℃ 20 seconds ───
10 liter rinse■ 30-35℃
20 seconds 350ml 10 liters drying 70-80℃ 60
seconds * Replenishment amount is per 1m2 of photosensitive material
(A 3-tank countercurrent system was used for rinsing ■ → ■.) The composition of each treatment liquid is as follows. Color developer
tank liquid
replenisher water
800m
l 800ml ethylenediamine-N,
N, N, N-
Tetramethylenephosphonic acid 1
．． 5g 2.0g Potassium bromide

0.015g --- Triethanolamine
8.0g 12.0g Sodium chloride
1.4g --- Potassium carbonate
25g 2
5g N-ethyl-N-(β-methasulfone

(amidoethyl)-3-methyl-
4-
Aminoaniline sulfate 5.0
g 7.0g N,N-bis(carboxymethyl)hydrogen
Drazin
5.5g 7.0g
Fluorescent brightener (WHITEX 4B,

(manufactured by Sumitomo Chemical) 1.0g
Add 2.0g water
1
000ml 1000ml pH (25℃)

10.05 10.45 0206 Bleach-fix solution (tank solution and replenisher solution are the same) Water


400ml ammonium thiosulfate (700g/
liter) 100m
l Sodium sulfite

17g Iron ethylenediaminetetraacetate (I
II) Ammonium
55g Disodium ethylenediaminetetraacetate

5g ammonium bromide

Add 40g water

1000ml p
H (25℃)

6.0 [0207] Rinse solution (tank solution and replenishment solution are the same) [0208] Ion-exchanged water (calcium and magnesium are each 3 ppm or less) Measure the color density of each sample after treatment and find the sensitivity and gradation. Ta. The sensitivity was defined as the reciprocal of the exposure amount that gives a color density 1.0 higher than the fogging density, and was expressed as a relative value when the sensitivity of each sample in a fresh developer was taken as 100. In addition, the gradation is the logarithm of the exposure amount that gives a color density of 0.5,
The difference from the logarithm of the exposure amount that gives a color density of 2.0 was defined as an absolute value, and the gradation change was expressed as the difference in the value of processing with the running liquid based on the value of the fresh developer. The larger this value is, the more the gradation is softened by the running liquid. [0209] These results are summarized in the following table. Sample No. sensitivity
gradation change
1. 88 0.
05 Comparative example 2.
80 0.18
〃 3. 7
9 0.17 〃
4. 93
0.10 〃
5. 94 0.06
Present invention 6.
93 0.05 〃
7. 97
0.10 Comparative example
8. 96 0.06
Present invention 9.
98 0.05 〃
As is clear from the above table, general formula [I
] The decrease in sensitivity and softening of the tone caused by the yellow coupler after running treatment can be significantly improved by combining the emulsion of the present invention. In addition, sample 2 using a yellow coupler represented by general formula [I],
Samples 3, 5, 6, 8, and 9 had a yellow color with high purity and less reddish than Samples 1, 3, and 6 using conventional couplers. Example 2 A coating solution was prepared in the same manner as in Example 1, the emulsion in the blue-sensitive emulsion layer and the yellow coupler were changed as shown in Table 3, and the compound represented by the general formula [IV] was added to the blue-sensitive emulsion layer. sensitive emulsion layer,
8.5 x 10-5 mol and 7.7 x 10-4 mol per mol of silver for the green-sensitive emulsion layer and the red-sensitive emulsion layer, respectively.
Samples 11 to 19 were prepared by adding 2.5×10 −4 mol. Sample No. of blue-sensitive emulsion layer.
Emulsion yellow coupler
Compound of general formula [IV] 11. A
Y-1
None 12. A
Y-1
IV-2-6 13.
B Ex-Y
None 14. B
Ex-Y
IV-2-6 15. B
Y-1
None 16. B
Y-1
IV-2-6 17.
B Y-1
IV-2-2 18.
CY-1
IV-2-6 19.
CY-1
IV-2-2 The same test as in Example 1 was conducted on these samples. The results obtained are shown in the table below. [0213] Sample No. sensitivity
gradation change
11. 80 0.1
8 Comparative example 12.
83 0.18 〃
13. 93
0.10 〃
14. 95 0.11
〃 15.
94 0.06 Present invention 16. 97
0.02 〃
17. 96 0.03
〃 18.
98 0.02 〃
19. 97
0.03 〃 021
4] As is clear from the table above, the decrease in sensitivity and softening in the solution after running treatment using the yellow coupler represented by the general formula [I] can be prevented by adding the compound represented by the general formula [IV] Further improvement can be achieved by doing so. According to the present invention, it is possible to obtain a silver halide photographic material which has excellent color reproducibility and which is prevented from decreasing sensitivity and softening when a processing solution after running is used.

Claims (2)

[Claims] 1. A silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, in which at least one of the silver halide emulsion layers is a chloride compound chemically sensitized using a selenium compound. Silver content is 90
1. A silver halide color photographic material comprising at least mol % of silver halide grains and containing at least one coupler represented by the following general formula [I]. General formula [1] [Formula 1] In the formula, R1 represents an aryl group or a tertiary alkyl group,
3 is a fluorine atom, an alkyl group, an aryl group, an alkoxyl group, an aryloxy group, a dialkylamino group, an alkylthio group, or an arylthio group, R3 is a group that can be substituted on a benzene ring, and X is a hydrogen atom or an aromatic group. γ represents an integer of 0 to 4, and γ represents a group that can be separated by a coupling reaction with an oxidized product of a primary amine developer. However, when γ is an integer, multiple R3's may be the same or different. 2. The silver halide color photographic light-sensitive material according to claim 1, wherein at least one of the layers constituting the light-sensitive material contains at least one kind of compound represented by the following general formula [IV]. . General formula [IV] [Chemical formula 2] In the formula, Q represents an atomic group necessary to form a 5- or 6-membered multiple ring or a 5- or 6-membered multiple ring condensed with benzene rings, and M is Represents a hydrogen atom or a cation.