JPS61249054A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance storage stability before use and to obtain a photosensitive material freed of yellowing even after long storage by incorporating a combination of a specified magenta coupler, a specified s-triazole type hardener and a specified vinylsulfone type hardener in a silver halide emulsion layer. CONSTITUTION:The silver halide emulsion layer capable of forming an image superior in color reproducibility, etc., contains a combination of the magenta coupler represented by formula I (in which Z is a nonmetallic atomic group necessary to form an N-contg. hetero ring; X is H or a group to be released by the coupling reaction with the oxidation product of a color developing agent; and R is H, CH3, or a substituent), one of the hardeners represented by formula II and III (in which R21 is Cl, OH, OM, or the like; M is a monovalent metal, -NR'R'', or the like; R', R'' are each H, alkyl, or the like; R22 is same as R21 except for Cl; R23, R24 are each Cl, OH, OM, or the like; Q, Q' are each -O-, -S-, -NH-; L is alkylene or arylene; and l, m are each 0 or 1), and the vinylsulfone type hardener.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide photographic light-sensitive material, and more specifically, to a silver halide color photographic light-sensitive material for printing with good color reproducibility and dye image storage stability, In particular, it relates to a silver halide color photographic light-sensitive material for printing using a reflective support.

[Background of the Invention] Traditionally, silver halide color photographic light-sensitive materials for printing have been subjected to imagewise exposure and color development, whereby an oxidized form of an aromatic primary amine developing agent and a color forming agent undergo a coupling reaction. For example, dyes such as indophenol, indoaniline, indamine, azomethine, phenoxazine, and phenazine are produced, and a dye image is formed.

In such photographic systems, a subtractive color reproduction method is usually adopted, and the blue-sensitive, green-sensitive, and red-sensitive light-sensitive silver halide emulsion layers contain couplers that develop yellow, magenta, and cyan colors, respectively. A silver halide color photographic light-sensitive material is used.

Examples of couplers used to form the above-mentioned yellow dye image include acylacetanilide couplers, and examples of couplers used to form magenta dye images include pyrazolone, pyrazolobenzimidazole, pyrazolotriazole, and indasilone. For example, phenol or naphthol couplers are commonly used as cyan dye image forming couplers.

It is desired that the dye image for printing obtained in this manner has little fading or discoloration even when exposed to light or stored in a dark place for a long time. Further, it is desired that the uncolored portion for printing (hereinafter referred to as white background) does not undergo yellowing (hereinafter referred to as Y-stain) or other discoloration even when exposed to light or stored in a dark place for a long time.

In particular, this Y-stin has a great influence on print image quality, and has been regarded as important, as well as discoloration and fading of dye images. In order to reduce this Y-stin, research has been conducted on antioxidants and magenta couplers, but it has become clear that further research on magenta couplers is particularly necessary to prevent the occurrence of Y-stin. It's coming.

Conventionally, pyrazolone magenta couplers, especially 3-
It is known that anilino-1,2-pyrazolo-5-one magenta coupler has good coloring properties, has desirable spectral absorption of the coloring dye, and has little adverse effect on silver halide such as fog. , No. 703,
It is described in British Patent No. 1,059,994.

However, this magenta coupler has the drawback that Y-stin on the white background is large when stored in a dark place for a long time.

As a result of research on various magenta couplers to date, magenta couplers having a pyrazolotriazole bone core described in British Patent No. 1,047,612, in particular, U.S. Patent No. 3,725,067 and British Patent No. 1,25
The 1H-pyrazolo-[3,2-CF-s-triazole coupler described in No. 2,418 and No. 1,334,515 has a white Y-
The generation of stain is extremely small, and the formed coloring dye has little sub-absorption around 430 rv, which is preferable in terms of color reproduction.

However, this pyrazolotriazole-based magenta coupler had the disadvantage that the gradation changed and the amount of capri increased during the storage period from the time the color photographic light-sensitive material was manufactured to the time it was used. (referred to as raw sample storage gradation change and fog increase).

In recent years, the number of small-volume production labs called mini-labs that perform color printing has been increasing.

However, these minilabs do not have sufficient refrigeration equipment for color photographic materials, and they are used for long periods of time for small-scale production. It is unsuitable for storage. In particular, the shelf life of raw samples is an important characteristic for stably obtaining good image quality, and there is a need to ensure a constant shelf life of raw samples in minilabs.

For this purpose, chemical sensitization methods, anti-fogging agents, and stabilizers have been investigated, but in all cases, sufficient effects cannot be obtained or there are drawbacks such as extensive desensitization. It was unsatisfactory to stably obtain good image quality.

On the other hand, in the photographic layer of silver halide color photographic light-sensitive materials,
A hydrophilic colloid such as gelatin is used as a binder, but it is resistant to recent rapid processing and is generally hardened based on demands from the productivity standpoint.

As a hardening agent used for this hardening treatment, for example, US Pat. No. 3,325,287, US Pat.
43 and JP-A-57-40244, etc., U.S. Patent No. 3,490,911 and West German Patent (OLS) No. 2,749,260J+
D description (7) l:' 2/L/Sulfone type hardeners, other hardeners such as aldehyde type, epoxy type, etc. can be mentioned.

Among them, chlorotriazine-based hardeners have excellent rapid hardening properties, film gloss, and film scratch strength, and are also good for occupational safety and health.
It has been researched as a hardening agent that is preferable in terms of environmental pollution.
No. 0, No. 51-78788, No. 52-128130, No. 52-130326, and No. 56-1043.

However, this chlorotriazine-based hardening agent has the disadvantage that it desensitizes during the storage period from the time the color photosensitive material is manufactured until it is used, causing problems such as fluctuations in sensitivity during use. Ta.

Vinyl sulfone hardeners have been studied and put to practical use as hardeners that have excellent rapid hardening properties and film scratch strength, and do not cause extensive desensitization.

However, vinyl sulfone hardeners have drawbacks such as increased fog when storing raw samples and poor gloss after processing, and these drawbacks have become even more pronounced in recent years, especially in high-temperature rapid processing. It had some problems.

[Object of the Invention] An object of the present invention is to provide a silver halide color photographic light-sensitive material that exhibits less gradation change during storage of raw samples and less increase in fog.

Yet another purpose is to maintain the white Y-
An object of the present invention is to provide a silver halide color photographic material with less staining and excellent brown color reproducibility.

[Structure of the Invention] As a result of intensive studies, the present inventors have found that the object of the present invention is to harden a silver halide photographic light-sensitive material containing a specific magenta coupler with at least two specific types of hardening agents. achieved.

That is, the above object of the present invention is to provide a silver halide photosensitive material having at least one silver halide emulsion layer on a support, in which at least one of the silver halide emulsion layers comprises a magenta coupler represented by the following general formula [I]. This is achieved by a silver halide photographic light-sensitive material containing the following: and further hardened using a combination of at least one of the hardeners represented by the general formulas [XII] and [XII] and a vinyl sulfone hardener. Ru.

General Formula [I] [In the formula, Z represents a nonmetallic atomic group necessary to form a nitrogen-containing heterocycle, and the ring formed by 2 may have a substituent. X represents a hydrogen atom or a substituent that can be separated by reaction with an oxidized product of a color developing agent. R represents a hydrogen atom or a substituent. ] Below is the blank general formula [X[I] [wherein R2 is a chlorine atom, a hydroxy group, an alkyl group, an alkoxy group, an alkylthio group, a -0M group (M represents a monovalent metal atom) or -NR'R", -NHC
OR"'(R',R" and R"' each represent a hydrogen atom, an alkyl group or an aryl group), and R2□ has the same meaning as R2No except for the chlorine atom.

] General formula [■] [In the formula, R23 and R24 are a chlorine atom, a hydroxy group, an alkyl group, an alkoxy group, or 10M! ! □ (M represents a monovalent metal atom).

Q and Q' represent a linking group representing -〇-1-S-1-NH-, and 〇 represents an alkylene group or an arylene group. p and ■ represent 0 or 1, respectively. ] [Specific Structure of the Invention] The magenta coupler represented by the general formula [I] used in at least one of the silver halide emulsion layers of the silver halide color photographic light-sensitive material of the present invention is generally a green-sensitive halogen. Used in combination with silver oxide emulsion.

For these magenta couplers, a solid dispersion method, a latex dispersion method, an oil-in-water emulsion dispersion method, etc. can be used. Conventionally known methods can be applied to the oil-in-water emulsion dispersion method,
It is usually dissolved in a high boiling point organic solvent of 150°C or higher, with a low boiling point solvent if necessary, and is placed in a hydrophilic binder such as an aqueous gelatin solution using a surfactant, using a stirrer, homogenizer, ultrasonic dispersion machine, etc. emulsify and disperse.

In the magenta coupler represented by general formula (I) according to the present invention, Z represents a nonmetallic atomic group necessary to form a nitrogen-containing heterocycle, and the ring formed by Z represents may have a substituent.

X represents a hydrogen atom or a substituent that can be separated by reaction with an oxidized product of a color developing agent.

Moreover, R represents a hydrogen atom or a substituent.

Examples of the substituent represented by R include a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a heterocyclic group,
Acyl group, sulfonyl group, sulfinyl group, phosphonyl group, carbamoyl group, sulfamoyl group, cyano group, spiro compound residue S, aromatic hydrocarbon compound residue, alkoxy group, aryloxy group, heterocyclic oxy group, siloxy group, Acyloxy group, carbamoyloxy group, ami7 group, acyl7mi7 group, sulfonamido group, imide group, ureido group, sul7amoylamino group, alkoxycarbonylamide 7 group, aryloxycarbonylamide 7 group, alkoxycarbonyl group, aryl Examples include oxycarbonyl group, alkylthio group, arylthio group, and heterocyclic thio group.

Examples of the halogen atom include a chlorine atom and a bromine atom, with a chlorine atom being particularly preferred.

The furkyl group represented by R has 1 to 32 carbon atoms, and the alkenyl group and alkynyl group have 2 to 3 carbon atoms.
2, cycloalkyl groups and cycloalkenyl groups preferably have 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms, and the alkyl groups, alkenyl groups and alkynyl groups may be linear or branched.

In addition, these alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, and cycloalkenyl groups are substituents [e.g., aryl, cyano, halogen atoms, heterocycles, cycloalkyl, cycloalkyl, spiro compound residues, and hydrocarbon compounds] In addition to residues, those substituted through a carbonyl group such as acyl, carboxy, carbamoyl, alkoxycarbonyl, and aryloxycarbonyl, and those substituted through a heteroatom (specifically, hydroxy, alkoxy, and aryloxy , heterocyclic oxy, siloxy, acyloxy, carbamoyloxy, etc. substituted via an oxygen atom, 2F''s ami/(including noalkyl 7mi/, etc.), sulfuryl 1moylaminooctaalkoxycarbonyl 7mino, 7lyloxy Those substituted via a nitrogen atom such as carponylamino, acylamino, sulfonamide, imide, ureido, etc.; those substituted via a sulfur atom such as alkylthio, arylthio, heterocyclic thio, sulfonyl, sulfinyl, sulfonyl, phosphonyl, etc. phosphorus atom, etc.)].

Specifically, for example, methyl group, ethyl group, isopropyl group, t-butyl group, pentadecyl group, heptadecyl group, 1
-hexylnonyl group, 1.1'-dipentylnonyl group,
2-chloro-butyl group, tri7fluoromethyl group, 1
-Ethoxytridecyl group, 1-7 toxyisobrobyl group, methanesulfonylethyl group, 2.4-sheet t-7 milphenoxymethyl group, anilino group, 1-phenylisopropyl group, 3-11 butanesulfonaminophenoxy Brobyl group, 3-4'-1a-(4''(p-hydroxybenzenesulfonyl)phenoxy)dodecanoylamine/
1 phenylpyl group, 3-(4'-(α-(2”, 4
"-t-amylphenoxy)butanamido]phenyl)-propyl group, 4-[Q-(.

-Chlorphenoxy)tetradecanamidophenoxy]
Examples include propyl group, allyl group, cyclopentyl group, and cyclohexyl group.

The aryl group represented by R is preferably a phenyl group, which may have a substituent (for example, an alkyl group, an alkoxy group, an acylamide group, etc.).

Specifically, phenyl group, 4-t-butyl 7-enyl group 1
2g4-not-7 milphenyl group, 4-tetradecane 7midophenyl group, hexadecyloxyphenyl group, 4
'-(a-(4″-t-butylphenoxy)tetradecanamide) phenyl group, and the like.

The heterocyclic group represented by R''Ch is preferably a 5- to 7-shell heterocyclic group, which may be substituted or fused.Specifically, a 2-7lyl group, a 2-chenyl group, Examples include 2-pyrimidinyl group and 2-pentthiazolyl group.

Examples of the acyl group represented by R include an acetyl group, a phenylacetyl group, a dodecanoyl group, a fulkylcarbonyl group such as an α-2,4-sheet-t-7-milphenoxyptanoyl group, a benzoyl group, and a 3-pentayl group. 7-arylcarbonyl groups such as denyloxybenzoyl group and p-arylbenzoyl group are preferred.

The sulfonyl group represented by R includes an alkylsulfonyl group such as a methylsulfonyl group and a dodecylsulfonyl group,
Examples include arylsulfonyl groups such as benzenesulfonyl, p-)luenesulfonyl, and the like.

Examples of the sulfinyl group represented by R include ethylsulfinyl group, octylsulfinyl group, alkylsulfinyl group such as 3-7eth/xybutylsulfinyl group, phenylsulfinyl-M, and m-pentadecylphenylsulfinyl group. Examples include arylsulfinyl groups such as.

Examples of the phosphonyl group to be R''1'! include an alkylphosphonyl group such as a butyloctylphosphonyl group, an alkoxyphosphonyl group such as an octyloxyphosphonyl group, an aryloxyphosphonyl group such as a phenoxyphosphonyl group, and a phenylphosphonyl group. and arylphosphonyl groups.

The carbamoyl group represented by R may be substituted with a furkyl group, an aryl group (preferably a phenyl group), etc.
For example, N-methylcarbamoyl group, N,N-dibutylcarbamoyl group, N-(2-pentadecyloctylethyl)carbamoyl group, N-ethyl-N-dodecylcarbamoyl group, N-(3-(2,4-di- t-7milphenoxy)propyl)carbamoyl group and the like.

The sulfamoyl group represented by the margin R below may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc.
For example, N-propylsulfamoyl group, N,N-noethylsulfamoyl group, N-(2-pentadecyloxyethyl)sulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, N-phenylsulfamoyl group etc.

Examples of spiro compound residues represented by R include spiro[
3,3]hebutan-1-yl and the like.

Examples of the bridged carbonized compound residue represented by R include bicyclo[2,2,1]hebutan-1-yl, tricyclo[3
゜3.1.13'? ] Decane-1-yl, 7,7-tumethyl-bicyclo[2,2,1]hebutan-1-yl, and the like.

The alkoxy group represented by R may be further substituted with the substituents listed above for the alkyl group, such as a methoxy group, a propoxy group, a 2-ethoxyethoxy group,
Examples include pentadecyloxy group, 2-dodecyloxyethoxy group, and 7enethyloxyethoxy group.

The aryloxy group represented by R is preferably 7-enyloxy, and the aryl nucleus may be further substituted with any of the substituents or atoms listed above for the aryl group,
Examples include phenoxy group, p-butylphenoxy group, and bell-bentadecylphenoxy group.

The heterocyclic oxy group represented by R preferably has 5 to 7 heterocycles, and the heterocycle may further have a substituent, for example, 3゜4.5.6-tetrahydro. Examples include pyranyl-2-oxy group and 1-phenyltetrazole-5-oxy group.

The siloxy group represented by R may be further substituted with an alkyl group, and examples thereof include a trimethylsiloxy group, a triethylsiloxy group, and a trimethylbutylsiloxy group.

The acyloxy group represented by R includes, for example, an alkylcarbonyloxy group, an arylcarbonyloxy group, etc., and may further have a substituent, and specifically, an acetyloxy group, an α-chloroacetyloxy group, etc. group, benzoyloxy group, and the like.

The carbamoyloxy group represented by R may be substituted with an alkyl group, an aryl group, etc., such as an N-ethylcarbamoyloxy group, an N,N-diethylcarbamoyloxy group, an N-phenylcarbamoyloxy group, etc. It will be done.

The ami7 group represented by R may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as an ethylamino group, anilino group, a so-chloroanily7 group,
Examples include 3-pentadecyloxycarbonylanilino group, 2-chloro-5-hexadecaneamide anilino group, and the like.

Examples of the acylamine 7 groups represented by R include alkylcarbonylamino 7 groups, arylcarbonylamino 7 groups (preferably phenylcarbonylamino groups), and may further have a substituent, specifically an acetamido group. , a-ethylpropanamide group, N-phenylacetamide group,
Examples include a dodecanamide group, a 2,4-di-t-amylphenoxyacetamide group, and a (Z-3-t-butyl 4-hydroxyphenoxybutanamide group).

Examples of the sulfonamide group represented by R include an alkylsulfonylamino group and an arylsulfonylamino group, which may further have a substituent.

Specific examples include 7 methylsulfonylamide groups, 7 pentadecylsulfonylamide groups, a benzenesulfonamide group, a p-toluenesulfonamide group, and a 2-methoxy-5-t-7 milbenzenesulfonamide group.

The imide group represented by R may be N-chain or cyclic, and may have a substituent, for example, a succinimide group, a 3-heptadecylsuccinimide group, a 7-talimide group. , glutarimide group, and the like.

The ureido group represented by R is an alkyl group, an aryl group (
Preferred examples include N-ethylureido group, N-methyl-N-decylureido group, N-7yonylureido group, and N-p-)lylureido group.

The sul 7 amoylami 7 group represented by R is an alkyl group,
It may be substituted with an aryl group (preferably a phenyl group) or the like, and examples thereof include N,N-diptylsul7amoylamy7 groups, N-methylsul7amoylamy7 groups, N-phenylsul7amoylamy7 groups, and the like.

As the alkoxycarbonyl 7 group represented by R,
It may further have a substituent, for example, 7 methoxycarbonylamide groups, 7 methoxyethoxycarbonylamide groups,
Examples include 7 octadecyloxycarbonylamide groups.

The aryloxycarbonylamide 7 groups represented by R may have a substituent, and examples thereof include 7enoxycarbonylamide 7 groups and 4-methylphenoxycarbonylamide 7 groups.

The alkoxycarbonyl group represented by R may further have a substituent, for example, a methoxycarbonyl group, a butyloxycarbonyl group, a dodecyloxycarbonyl group, an octadecyloxycarbonyl group, an ethoxymethoxycarbonyloxy group, a benzyloxycarbonyl group. etc.

The aryloxycarbonyl group represented by R may further have a substituent, such as a phenoxycarbonyl group,
Examples include p-chlorophenoxycarbonyl group and pentadecyloxyphenoxycarbonyl group.

The alkylthio group represented by R may further have a substituent, and examples thereof include an ethylthio group, a dodecylthio group, an octadecylthio group, a 7enethylthio group, and a 3-phenoxypropylthio group.

The 7-arylthio group represented by R is preferably a phenylthio group and may further have a substituent, for example, a phenylthio group,
Examples include p-nodoxyphenylthio group, 2-t-octylphenylthio group, 3-octadecylphenylthio group, 2-carboxyphenylthio group, and p-acetaminophenylthio group.

The heterocyclic thio group represented by R is preferably a 5- to 7-shell heterocyclic thio group, which may further have a condensed ring or a substituent. Examples include 2-pyridylthio group, 2-benzothiazolylthio group, and 2,4-diphenoxy-1,3,5-)lyazole-6-thio group.

Examples of substituents that can be removed by reaction with the oxidized product of the color developing agent represented by Examples include groups substituted via.

Examples of the group substituted via a carbon atom include carboxyl groups and, for example, those of the general formula % (R3' has the same meaning as R, Z' has the same meaning as Z, R2' and R1' are hydrogen atoms, , a group represented by ) representing an aryl group, an alkyl group or a heterocyclic group, a hydroxymethyl group, and a triphenylmethyl group.

Examples of groups substituted via an oxygen atom include alkoxy groups, aryloxy groups, heterocyclic oxy groups, acyloxy groups, sulfonyloxy groups, alkoxycarbonyloxy groups, aryloxycarbonyloxy groups, alkyloxalyloxy groups, and alkoxyoxalyloxy groups. can be mentioned.

The alkoxy group may further have a substituent, for example,
Examples include nidoxy group, 2-phenoxyethoxy group, 2-cyanoethoxy group, 7enethyloxy group, p-chloropencyloxy group and the like.

The aryloxy group is preferably a phenoxy group, and the aryl group may further have a substituent, specifically a 7eth/oxy group, a 3-methylphenoxy group, a 3-
Dodecyl 7eth/oxy group, 4-methanesulfonamidophenoxy group, 4-(a-(3'-pentadecylphenoxy)butanamido]phenoxy group, hexydecylcarbamoylmethoxy group, 4-cyanophenoxy group, 4-methanesulfonyl 7enoxy group, 1-su7tyloxy group, p-
Examples include nodoxyphenoxy group.

The heterocyclic oxy group is preferably a 5- to 7-shell heterocyclic oxy group, which may be a condensed ring or may have a substituent, specifically, 1-phenyltetrazoli and 2-benzothiazolyloxy group.

The acyloxy group includes, for example, an acetoxy group, a fulkylcarbonyloxy group such as a butazuroxy group, an alkenylcarbonyloxy group such as a cinnamoyloxy group,
Examples include arylcarbonyloxy groups such as benzoyloxy groups.

Examples of the sulfonyloxy group include a butanesulfonyloxy group and a methanesulfonyloxy group.

Examples of the alkoxy group include an ethoxycarbonyloxy group and a benzyloxycarbonyloxy group.

Examples of the 7-aryloxycarbonyl group include a phenoxycarbonyloxy group.

Examples of the alkyloxalyloxy group include a methyloxalyloxy group.

Examples of the alkoxyoxalyloxy group include an ethoxyoxalyloxy group.

Examples of the group substituting via the sulfur atom include an alkylthio group, an allinylthio group, a heterocyclic thio group, and an alkyloxythiocarbonylthio group.

Examples of the alkylthio group include a butylthio group, a 2-cyanoethylthio group, a 7enethylthio group, a pencylthio group, and the like.

The arylthio group includes phenylthio group, 4-methanesulfonamidophenylthio group, 4-dodecyl7enethylthio group, 4-7sufluorobencunamido7enethylthio group, 4-carboxyphenylthio group, 2-ethoxy-5-t -butylphenylthio group and the like.

Examples of the heterocyclic thio group include 1-722-1.
2.3.4-tetrazolyl-5-thio group, 2-benzothiazolylthio group, and the like.

Examples of the alkyloxythiocarbonylthio group include a dodecyloxythiocarbonylthio group.

Examples of the group substituted via the nitrogen atom include those represented by the general formula -N, such as aryl group, heterocyclic group, sulfonyl group, carbamoyl group, acyl group, sulfonyl group, and aryloxy group. Carbonyl group, alco. Represents a oxycarbonyl group, R4' and R3'
may be combined to form a heterocycle. However, R1' and R
Neither 5' is a hydrogen atom.

The alkyl group may be linear or branched, and preferably has 1 to 22 carbon atoms. Further, the alkyl group may have a substituent, and examples of the substituent include an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylami7 group, and an arylamino7 group.
group, acylamino group, sulfonamide group, imino group, acyl group, alkylsulfonyl group, arylsulfonyl group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkyloxycarbonylamide 7 group, aryloxycarbonylamide 7 group group, hydroxyl group, carboxyl group, cyano group, and halogen atom.

Specific examples of the alkyl group include ethyl group, oxytyl group, 2-ethylhexyl group, and 2-chloroethyl group.

The aryl group represented by R4' or R5' preferably has 6 to 32 carbon atoms, particularly a phenyl group or a naphthyl group,
The aryl group may have a substituent, and examples of the substituent include those listed above as the substituent for the alkyl group represented by R4' or R5' and an alkyl group. Specific examples of the aryl group include a phenyl group, a 1-su7tyl group, and a 4-methylsulfonylphenyl group.

The heterocyclic group represented by R4' or R5' is 5-6
Preferred examples include 2-furyl group, 2-quinolyl group, 2-pyrimidyl group, 2-benzothiazolyl group, and 2-benzothiazolyl group. Examples include pyridyl group.

The sulfamoyl group represented by R4' or R%' includes N-furkylsulfamoyl group, N,N-dialkylsulfamoyl group, N-7lylsulfamoyl group, N-furkylsulfamoyl group, N-7lylsulfamoyl group,
, N-diarylsul77 moyl group, etc., and these alkyl groups and aryl groups may have the substituents listed for the alkyl groups and aryl groups. Specific examples of the sulfamoyl group include N, N-diethylsulfamoyl group, N-methylsulfamoyl group, N
-dodecylsulfamoyl group, N-p-)lylsul7-ammoyl group.

The carbamoyl group represented by R4' or Rs' is
N-furkylcarbamoyl group, N,N-dialkylcarbamoyl group, N-7lylcarpamoyl group, N,N-diarylcarbamoyl group, etc., and these alkyl groups and aryl groups are the same as those mentioned above for the alkyl group and aryl group. Specific examples of the carbamoyl group which may have a substituent include, for example, N,N-diethylcarbamoyl group, N-methylcarbamoyl group, N-dodecylcarbamoyl M, N-p-cyanophenylcarbamoyl group,
N-p-)lylcarpamoyl group is mentioned.

Examples of the acyl group represented by R4' or Ri' include an alkylcarbonyl group, an arylcarbonyl group, and a heterocyclic carbonyl group, and the alkyl group, aryl group, and heterocyclic group have a substituent. It's okay. Specific examples of the acyl group include hexafluorobuta/yl group, 2°3.4.5.6-pentafluorobenzoyl group, acetyl group, benzoyl group, naphthonyl group, 2-7lyl carbonyl group, etc. Can be mentioned.

Examples of the sulfonyl group represented by R4' or Rs' include an alkylsulfonyl group, an arylsulfonyl group, and a heterocyclic sulfonyl group, which may have a substituent, and specific examples include an ethanesulfonyl group, Examples include benzenesulfonyl group, octanesulfonyl group, naphthalenesulfonyl M, and p-90 rubenzenesulfonyl group.

The aryloxycarbonyl group represented by R4' or R5' may have any of the substituents listed above for the aryl group, and specific examples thereof include phenoxycarbonyl group and the like.

The alkoxycarbonyl group represented by R4' or R5' may have a substituent listed next to the alkyl group, and specific examples include a methoxycarbonyl group, a dodecyloxycarbonyl group, a benzyloxycarbonyl group, etc. can be accelerated.

The heterocycle formed by combining R4' and Rs' is preferably one with 5 to 6 shells, and may be saturated or unsaturated, and may or may not have aromaticity, or,
Examples of the heterocycle, which may be a condensed ring, include an N-7 talimide group, an N-coI) phosphoric acid imide group, a 4-N-urazolyl group, a 1-N-hydantoynyl group, and a 3-N-2,4-di Oxooxazolidinyl group, 2-N-1,1-nooxo3-(2H)-oxo-1,2-benzthiazolyl group, 1-virolyl group, 1-pyrrolidinyl group, 1-pyrazolyl$-1-pyrazolidinyl group , 1-piperidinyl group, 1
'-pyrrolinyl group, 1-imidazolyl group, 1-imidazolinyl group, 1-indolyl group, 1-isoindolinyl group, 2-isoindolyl group, 2-isoindolinyl group, 1
-benzotri7zolyl group, 1-benzimidazolyl group,
1-(1,2,4-)+77zo1lyl) group, 1-(1,
2,3-)riazolyl) group, 1-(1,2,3,4-tetrazolyl) group, N-morpholinyl group, 1,2,3.4
-tetrahydroquinolyl group, 2-oxo-1-pyrrolidinyl group, 2-IH-pyridone group, 7-talanone group, 2-
Examples include oxo-1-piperidinyl groups, and these heterocyclic groups include alkyl groups, aryl groups, alkyloxy groups,
Aryloxy group, acyl group, sulfonyl group, alkylamino group, 7 arylamino groups, acylamino group, 7 sulfonami groups, carbamoyl group, sulfamoyl group, alkylthio group, arylthio group, ureido group, alkoxycarbonyl group, aryloxycarbonyl group, It may be substituted with an imide group, a nitro group, a cyano group, a carboxyl group, a halogen atom, or the like.

Examples of the nitrogen-containing bicyclic ring formed by Z or Z' include a pyrazole ring, imidazole ring, triazole ring, or tetrazole ring, and the substituents that the ring may have include those described for R above. can be mentioned.

In addition, in general formula (1) and general formulas (II) to [■] described later, the substituents on the heterocycle (for example, R1R1 to Re) are moieties (herein, R'', X and Z II are general formula (synonymous with R,

Further, the ring formed by z, z', z'' and 21 described below may be further fused with another ring (for example, a cycloalkene with 5 to 7 rings).For example, in the general formula (V), R5 and R6 are R7 and R in general formula (VI)
, and may be bonded to each other to form a ring (for example, a 5- to 7-shell cycloalkene, benzene).

What is represented by the general formula (I) below is more specifically represented by, for example, the following general formulas (n) to [■].

General formula (If) General formula (II [) General formula (IV) N -N -NH General formula (V) General formula, [■] General formula [■] In the above general formulas (n) to [■] R, -R, and X have the same meanings as R and X above.

Also, among the general formula (1), the following general formula [
■].

, General formula [■] In the formula, R, , X and Zl are R9X in the general formula [■]
It is synonymous with VZ.

Among the magenta couplers represented by the general formulas (If) to [■], the magenta couplers represented by the general formula (If) are particularly preferred.

Regarding the substituents on the heterocycle in general formulas (I) to [■], R in general formula (1) and R1 in general formulas [■] to [■] satisfy the following condition 1. It is preferable that the following conditions 1 and 2 are satisfied, and more preferable that the following conditions 1 and 2 are satisfied.
and 3 are satisfied.

Condition 1: The root atom directly connected to the heterocycle is a carbon atom.

Condition 2: Only one hydrogen atom or no hydrogen atom is bonded to the carbon atom.

Condition 3 All open bonds between the carbon atom and adjacent atoms are single bonds.

The most preferred substituents R and R on the heterocycle are those represented by the following general formula (IX).

General formula (IX) R1 Hibiki R8゜-〇- ■ R8 In the formula, R', , R, 0 and R11 are each a hydrogen atom, /
10 denene atoms, alkyl groups, cycloalkyl groups, alkenyl groups, cycloalkenyl groups, alkynyl groups, aryl groups, heterocyclic groups, acyl groups, sulfonyl groups, sulfinyl groups, phosphonyl groups, carbamoyl groups, sulfamoyl groups, cyano groups, spiro Compound residue, bridged hydrocarbon compound residue, alkoxy group 1, aryloxy group, heterocyclic oxy group, siloxy group, acyloxy group, carbamoyloxy group, amine 7 group, acylamino group, sulfonamide group, imide group, ureido group, sul 7 amoylami 7 group,'
R represents seven alkoxycarbonylamide groups, seven aryloxycarbonylamide groups, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylthio group, an arylthio group, and a heterocyclic thio group.

At least two of R1° and RlI are not hydrogen atoms.
ll.

Furthermore, two of the above R, R, and R1, for example R1 and R5, may be combined to form a saturated or unsaturated ring (e.g. cycloalkane, cycloalkene, heterocycle), and further RlI may be bonded to the ring to constitute an organic hydrocarbon compound residue.

The group represented by R9-R1 may have a substituent,
Specific examples of the groups represented by R9 to RI+ and substituents that the groups may have include specific examples of the groups and substituents represented by R in the aforementioned general formula CI).

Also, for example, a ring formed by combining R1 and R1゜ and R1
-Specific examples of organic hydrocarbon compound residues formed by R1 and 1. Examples of the substituents that R1 may have include cycloalkyl, cycloalkenyl, heterocyclic groups, and bridged groups represented by R in the aforementioned general formula (I). Specific examples of hydrocarbon compound residues and their substituents are listed.

Among the general formula CI, (i) when two of R11-RlI are alkyl groups,
(ii) When one of Rs to R1+, for example R11, is a hydrogen atom, and the other two R1 and R1° combine to form a cycloalkyl together with the root carbon atom, the following is true.

Further preferred among (i) is the case where two of R8 to R1+ are alkyl groups and the other one is a hydrogen atom or an alkyl group.

Here, the alkyl and cycloalkyl may further have a substituent, and specific examples of the alkyl, the cycloalkyl, and the substituent thereof include the alkyl, cycloalkyl, and its substitution represented by R in the general formula [1] above. Specific examples of the group are listed below.

The following blanks also describe the substituents that the ring formed by Z in general formula [1] and the ring formed by Z in general formula [■] may have, and the substituents in general formulas (II) to (VI). As R2-R8, those represented by the following general formula [X] are preferable.

General formula (X) -R'-8O2-R2 In the formula, R1 represents alkylene, and R2 represents alkyl, cycloalkyl or aryl.

The fullkylene represented by R1 preferably has 2 or more carbon atoms in the straight chain portion, more preferably 3 to 6 carbon atoms, and has 9 straight chain carbon atoms.
Regardless of branching, this alkylene may have a substituent.

Examples of the substituent include R in the general formula (I) described above.
When is a furkyl group, the substituents that the alkyl group may have include those shown below.

Preferred substituents include phenyl.

Preferred specific examples of alkylene represented by R1 are shown below.

The alkyl group represented by R2 has 9 straight chain branches and 1%
.

Specific examples include methyl, ethyl, propyl, 1so-propyl, butyl, 2-ethylhexyl, octyl, dodecyl, tetradecyl, hexadecyl, octadacil, and 2-hexyldecyl.

The cycloalkyl group represented by R2 is preferably a cycloalkyl group with 5 to 6 chains, such as cyclohexyl.

The alkyl and cycloalkyl represented by R2 may have a substituent, and examples thereof include those exemplified as the substituent for R1 above.

Specific examples of the aryl represented by R2 include phenyl and naphthyl. The aryl group may have a substituent. Examples of the substituent include linear or branched alkyl, as well as those exemplified as the substituent for R1 described above.

In addition, if there are two or more lf substituents, those substituents are
They may be the same or different.

Among the compounds represented by the general formula (1), particularly preferred are those represented by the following general formula (n).

General formula (XI) In the formula, R and X have the same meanings as R and X in general formula [1], and Rl and R2 are R1゜R2 in general formula (X)
is synonymous with

Below margin proof C.I.

C8゜ CH3 CH.

■ CH:1 C2H.

Below margin CM, CH3 C41 (9 Below margin H3 C.I.

■ H3 C.H.

5Ht Js C.I.

CHl r+■,.

Below margin ■ C.I.

6th aHIs shi2t15 Below margin CR2 Shi12N25 l5H13 Below margin H3 H3 oc, n, J CH3 CH.

stl+y(t) C.I.

C1(.

CH3 CH3CsH+7(t) C.I.

CH1 ■ Mi*Hts 13th HaCCHi Below margin N-N-N N-N-N N-N-NH rN C2H.

■ 7B In the margin below, the synthesis of the above-mentioned representative couplers is described in the Journal of the Chemical Society, Birkinje (Journal of the Chemical Society).
al Of the Chemical S
oc+ety.

Perkin I) (1977), 2047
-2052, U.S. Pat. No. 3,725,067, and JP-A Nos. 59-99437 and 58-42045, etc., for synthesis.

The couplers of the invention are typically 1x1 per mole of silver halide.
It can be used in an amount of 0-3 mol to 1 mol, preferably 1 x 10 mol to 8 x 10-1 mol.

The couplers of the present invention can also be used in combination with other types of magenta couplers.

The vinyl sulfone hardener used in the present invention is, for example, an aromatic compound as described in German Pat.
Alkyl compounds bonded with hetero atoms as described in Japanese Patent Publication No. 5373, sulfonamides and ester compounds as described in Japanese Patent Publication No. 47-8736, Japanese Patent Publication No. 47-8736,
1,3,5-tris[β-(vinylsulfonyl)-propionyl]-hexahydro-3-triazine as described in No. 9-24435 or JP-A-51-44
It includes alkyl compounds such as those described in No. 164.

Usually, these hardeners are dissolved in water or an organic solvent and used in an amount of 0.1 to 10% by weight based on gelatin, and are added to the photographic layer by a batch method or an in-line addition method.

The layer to which these hardeners are added to the photographic layer is not particularly limited; for example, the object of the present invention can be achieved even if they are added to the top layer, the bottom layer, or all the layers.

The vinyl sulfone hardener preferably used in the present invention is represented by the following general formula [IV].

General formula [IV] 8-H-A)l+D)J! 801 CH-CH2
[r1] In the above general formula [IV], B is a simple bond or an organic group, such as an alkane residue, an alkene residue,
Represents a heterocyclic residue such as an aryl residue or S-triazine.

A Ha, -CO-1-NHCO-1-〇〇NH-1-N
Represents a linking group such as H5O2-1-8OINH-.

D represents an alkylene group, an arylene group or an alkenylene group.

n is 2 to 6, - is 0 or 1, and - is 0 or 1.

Next, typical examples of the vinyl sulfone hardener represented by the above general formula [IV] are shown below, but the invention is not limited thereto.

Below margin-I H-2 H-7C2HsC(Cf(*5OxCH=CHz) 3
H-8CaH+tC(CH*SO*CH=CH2)sH
10(CHx=CH8O*CH*)sccHtBr(C
H,=CH3OICHI)ICHCH(CH,5O2S
OICH=CH,)ZH-12C(CHtSOxCH=
CHt)4H-” 'C0CH,CH
, SO, cH=CH1 and N) CH=CH8O, CH=CH2CO-N N-ωC
H*CHtso2CH"'CHtH-15CHt+C0
NHCH,5OICH=C) (2) 2H-170 rod C0
CHZCHSOzCH=CH .

H200(CH2CHtSO2CH=CHx)zH21
NH(CH2CHxSOzCH=C)f2)tH-22
CH,C(CH20CH,SO,CH=CH2)3H2
3C(CH20CHzSOzCH=CHz)4H-24
N(CHtCHiOCHtSOaCH=CHz)i(C
H,=CH8O,CHJICCH,0CHzc(CH2
SO2CH=CHJ3(CHt=CH802CH2)3
CCH, SO, CH, CHICI Below margin The vinyl sulfone hardener in the present invention includes, in addition to the above-mentioned exemplified compounds, a compound having at least three vinylsulfone groups in its molecular structure, such as exemplified compound [H-3]
These include reaction products obtained by reacting compounds having a group that reacts with a vinyl sulfone group and a water-soluble group, such as jetanolamine, thioglycolic acid, sarcosine sodium salt, and taurine sodium salt.

The alkyl group represented by R and R2m in the general formula [XII] of the present invention is, for example, a methyl group, ethyl group, butyl group, etc., and the alkoxy group represented by them is a methoxy group, ethoxy group, butoxy group, etc. -NHCH3,-
NHO2Hs, etc., a specific example of -NHCOR"' is -NHCOCH3, and M in the 10M group is, for example, a sodium atom, a potassium atom, etc.

Next, R in the general formula [XIII], alkyl 32 represented by R
The q group is, for example, a methyl group, an ethyl group, a butyl group, etc., the alkoxy group is a methoxy group, an ethoxy group, a butoxy group, etc., and M in the -0M group is, for example, a sodium atom, a potassium atom, etc.

Further, the alkylene group represented by L is, for example, -CH2-1-
(-CH, -machine-1→CH, 1 group, etc., and the arylene group is, for example, P-10- or --phenylene group, etc.).

Regarding the chlorotriazine hardeners represented by general formulas [XII] and [■ in the present invention, Japanese Patent Publication No. 47-6
No. 151, JP-A-48-19920, JP-A No. 51-787
No. 88, No. 52-128130, No. 52-13032
No. 6, and No. 56-1043.

Generally, these hardeners are dissolved in water or an organic solvent, used in an amount of 0.1 to 10% by weight based on gelatin, and added to the photographic layer by a batch method or an in-line addition method.

The layer to be added to the photographic layer is not particularly limited, and the object of the present invention can be achieved, for example, by adding it to the topmost layer, the bottommost layer, or all the layers.

Further, the object of the present invention can be achieved in the same way whether it is added to the same layer as the vinyl sulfone hardener or to a separate layer.

The ratio of the vinyl sulfone hardener to the chlorotriazine hardener is not particularly limited, but preferably the vinyl sulfone hardener accounts for 20% to 80% by weight.

Next, typical examples of hardeners represented by the general formulas [XI[] and [X[[I]] will be listed, but the present invention is not limited thereto.

Compounds shown below with general additions in the margin: (X[-1)' (XI-2)CI, ni-3in ('Xl
-4) (Xn-5) (X'L-6)
OCHs OC*Hs (E-7)
0 constant-8) (%J[-9)
(XI[-10) (l-11)
(XI[-12) (X-13) Compound represented by general formula (to) below]: (XOI-2) (XI[-3) CL CL (XIL-4) ←C-5) (X [[-6) (Item 1 7) (Top 8) (Item 1 9) (XIL-10) The following margins The silver halide photographic light-sensitive material of the present invention can be used, for example, in color negative and positive films, and color photographic paper. However, the effects of the method of the present invention are particularly effective when using color photographic paper intended for direct viewing.

The silver halide photographic material of the present invention, including this color photographic paper, may be one for monochrome use or one for multicolor use. In the case of multicolor silver halide color photographic light-sensitive materials, in order to perform subtractive color reproduction, a silver halide emulsion layer containing magenta, yellow, and cyan couplers as photographic couplers; Although it has a structure in which non-photosensitive layers are laminated on a support in an appropriate total number and layer order, the number and layer order may be changed as appropriate depending on the important performance and the purpose of use.

In the silver halide emulsion used in the silver halide color photographic light-sensitive material of the present invention, monodisperse silver halide is preferably used as silver halide.

"Monodisperse silver halide J," which is preferably used in this specification, means that when the emulsion is observed using an electron microscope, the shape of each silver halide grain appears uniform, the grain size is uniform, and , the ratio S/r of the standard deviation S of particle size distribution and the average particle diameter f is 0.22 or less, more preferably 0.15 or less.Standard deviation S of particle size distribution
is obtained according to the following formula.

In addition, the average grain size V here refers to the diameter of spherical silver halide grains, or the diameter when the projected image is converted to a circular image of the same area in the case of grains with shapes other than cubic or spherical. is the average value of the diameter of each grain, where the individual grain diameter is ri and the number of grains is ni, r is defined by the following formula.

The above particle size can be measured by various methods commonly used in the technical field for the above purpose. A typical method is Loveland's "Particle Size Analysis Method JA."

S, T, M, Symposium on Light Microscopy, 1955, pp. 94-122 or chapter 2 of ``Theory of the Photographic Process'' by Mies and James, 3rd edition, Macmillan Publishing Co., Ltd. (1966). Are listed. The particle size can be measured using the particle's projected area or diameter approximation. If the particles are of substantially uniform shape, the particle size distribution can be described fairly accurately as diameter or projected area.

The relationship between grain size distribution is described in "Empirical Relationship between Sensitometric Distribution and Particle Size Distribution in Photographic Emulsions," The Photographic Journal, Vol. LXXIX, (1949) 33.
This can be determined by the method described in the article by Trivelli and Smith, pages 0-338.

The average particle diameter of the monodisperse particles preferably used in the present invention is not particularly limited, but it is preferably 0.1 to 2.0 μl, more preferably 0.1 to 2.0 μl when measured according to the above method. It ranges from 0.35 to 055μ.

In the present invention, the (1oo) plane and (1
11) The ratio of planes is determined by using Cu-Ka rays as X-rays in X41 diffraction analysis. When the intensities of the diffraction lines attributed to (the diffraction angles (2θ) are approximately 30.9° and ss, o'', respectively) are measured, and their ratio K is determined according to the following formula, the value is is preferably in the range of 3≦≦600, more preferably in the range of 10≦≦400, particularly preferably in the range of 20≦≦200.

The preferred surface definition of silver halide grains in the present invention is described in, for example, "Bulletin of the Society of Scientific Photography of Japan", page 13, page 5. This is based on a diffraction pattern obtained by powder X-ray diffraction analysis of an emulsion containing oriented silver halide grains coated on a substrate.

The composition of the silver halide grains used in the present invention is:
For example, silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide,
Any of silver chloroiodobromide and the like can be used, but silver chlorobromide is preferable from the viewpoint of high sensitivity, developability and desilvering property, and the silver halide used in combination with the magenta coupler of the present invention is , silver chlorobromide containing 80 mol% or less of silver bromide is preferred. Further, the crystal structure of these silver halide grains may be uniform from the inside to the outside, or may have a layered structure in which the inside and outside are different.

The silver halide grains used in the present invention are r)A
It can be prepared by controlling Q, 111 degrees, addition rate, etc. or by selecting various particle generation conditions, and can be prepared by a normal single jet method or double jet method. Any known method such as an acidic method, a neutral method, an ammonia method, or a conversion method may be used for these, and a back mixing method may also be used. Further, the silver halide grains used in the present invention may be so-called core/shell type silver halide grains.

Further, these silver halide grains may be of a type in which a latent image is mainly formed on the surface or of a type in which a latent image is formed inside the grain.

By using a silver halide solvent as necessary during the production of the silver halide emulsion of the present invention, the grain size, grain shape, grain size distribution, and grain growth rate of silver halide grains can be controlled.

The silver halide grains used in the silver halide emulsion of the present invention are prepared in the process of forming and/or growing the grains such as cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or complex salt, rhodium salt or complex salt. , iron salts, complex salts, etc. can be used to incorporate metal ions inside the particles and/or on the particle surfaces, and by placing them in an appropriate reducing atmosphere, metal ions can be added inside the particles and/or on the particle surfaces. It is possible to add reduction-sensitized nuclei to.

In the silver halide emulsion of the present invention, unnecessary soluble salts may be removed after the growth of silver halide grains is completed, or they may be left contained. In the case of removing the salts, it can be carried out based on the method described in Research Disclosure No. 17643.

The silver halide grains used in the silver halide emulsion of the present invention may consist of a uniform layer inside and on the surface, or
It may consist of different layers.

The silver halide emulsion of the present invention may be a mixture of two or more separately formed silver halide emulsions.

The silver halide emulsion of the present invention is chemically sensitized by a conventional method. That is, compounds containing sulfur that can react with silver ions,
A sulfur sensitization method using activated gelatin, a selenium sensitization method using a selenium compound, a reduction sensitization method using a reducing substance, a noble metal sensitization method using gold or other noble metal compounds, etc. can be used alone or in combination.

The silver halide emulsion of the present invention can be optically sensitized to a desired wavelength range using dyes known as sensitizing dyes in the photographic industry. The sensitizing dyes may be used alone or in combination of two or more. Along with the sensitizing dye, the emulsion contains a dye that itself does not have a spectral sensitizing effect, or a supersensitizer, which is a compound that does not substantially absorb visible light and enhances the sensitizing effect of the sensitizing dye. Also good.

The silver halide emulsion of the present invention includes steps for producing light-sensitive materials,
For the purpose of preventing fog during storage or photographic processing and/or keeping photographic performance stable, silver halide emulsions are used during and/or at the end of chemical ripening, and/or after the end of chemical ripening. Compounds known in the photographic industry as antifoggants or stabilizers can be added prior to coating.

Gelatin is advantageously used as a binder (or protective colloid) for the silver halide emulsion of the present invention, but
In addition, hydrophilic colloids such as gelatin derivatives, graft polymers of gelatin and other polymers, proteins, sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymer substances such as single or copolymers can also be used.

A plasticizer can be added for the purpose of increasing the flexibility of the silver halide emulsion layer and/or other hydrophilic colloid layer of a light-sensitive material using the silver halide emulsion of the present invention.

The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material using the silver halide emulsion of the present invention contain a dispersion (latex) of a water-insoluble or poorly soluble synthetic polymer for the purpose of improving dimensional stability. I can do things.

The emulsion layer of the silver halide photographic light-sensitive material of the present invention undergoes a coupling reaction with an oxidized form of an aromatic primary amine developer (for example, a p-phenylenediamine derivative or an aminephenol derivative) during color development processing. A dye-forming coupler is used that forms a dye. The dye-forming couplers are typically selected to form a dye for each emulsion layer that absorbs light in the emulsion layer's sensitive spectrum, with a yellow dye-forming dye forming for the blue light sensitive emulsion layer. The couplers used are at least one magenta dye-forming coupler of the invention in the green light-sensitive emulsion layer and a cyan dye-forming coupler in the red light-sensitive emulsion layer. However, depending on the purpose, silver halide photographic materials may be produced using different combinations from the above.

Examples of yellow dye-forming couplers include acylacetamide couplers (e.g., benzoylacetanilides, pivaloylacetanilides); examples of magenta dye-forming couplers include, in addition to the magenta coupler of the present invention, 5-pyrazolone couplers, pyrazolobenzimidazole couplers, and pyrazolone couplers. Examples include zolotriazole, open-chain acylacetonitrile couplers, and cyan dye-forming couplers include naphthol couplers and phenol couplers.

These dye-forming couplers preferably have a group called a ballast group in the molecule, which makes the coupler non-diffusive and has 8 or more carbon atoms. Furthermore, even if these dye-forming couplers are 4-equivalent, in which 4 silver ions need to be reduced in order to form one molecule of dye, only 2 silver ions need to be reduced. Either 2-equivalent coupler may be used, but a 2-equivalent coupler is particularly preferred.

Hydrophobic compounds such as dye-forming couplers that do not need to be adsorbed onto the silver halide crystal surface can be treated with various methods such as solid dispersion, latex dispersion, and oil-in-water emulsion dispersion. can be appropriately selected depending on the chemical structure of the hydrophobic compound, etc. The oil-in-water emulsion dispersion method can be applied by dispersing a hydrophobic compound such as a coupler, and is usually mixed with a high-boiling organic solvent with a boiling point of about 150°C or higher, and if necessary with a low-boiling point and/or water-soluble organic solvent. After emulsifying and dispersing in a hydrophilic binder such as an aqueous gelatin solution using a surfactant and a dispersion means such as a stirrer, homogenizer, colloid mill, flow jet mixer, or ultrasonic device, It may be added to the hydrophilic colloid layer. A step of removing the low boiling point organic solvent may be included simultaneously with the dispersion or dispersion.

The high boiling point organic solvent preferably used in the present invention is
The compound has a dielectric constant of less than 6.0, and although the lower limit is not particularly limited, it is preferably 1.9 or more. Examples include esters such as phthalic esters and phosphoric esters, organic acid amides, ketones, and hydrocarbon compounds having a dielectric constant of less than 6.0.

Further, in the present invention, preferably a high boiling point organic solvent having a vapor pressure of 0.51 IHg or less at 100°C is used. Even more preferred are heptatarates or phosphoric acid esters in the high-boiling organic solvent. Note that the organic solvent may be a mixture of two or more types, and in this case, the dielectric constant of the mixture may be less than 6.0. Note that the dielectric constant indicates the dielectric constant at 30°C.

Examples of phthalic acid esters advantageously used in the present invention include those represented by the following general formula [Vl].

General formula [Vl In the formula, R and Rλ6 each represent an alkyl group, an alkenyl group, or an aryl group. However, the total number of carbon atoms in the groups represented by R2y and R26 is 9 to 3.
It is 2. More preferably, the total number of carbon atoms is 1
6 to 24.

In the present invention, R3 and R26 of the general formula [V]
The alkyl group represented by is linear or branched, such as butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, These include a pentadecyl group, hexadecyl group, heptadecyl group, and octadecyl group. The aryl group represented by R25- and 82g is a phenyl group, naphthyl group, etc., and the alkenyl group is a hexenyl group, heptenyl group, octadecenyl group, etc. These alkyl groups, alkenyl groups, and aryl groups may have single or multiple substituents, and examples of substituents for alkyl groups and alkenyl groups include halogen atoms, alkoxy groups, aryl groups, and aryloxy groups. , an alkenyl group, an alkoxycarbonyl group, etc., and examples of substituents for the aryl group include a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an alkenyl group, and an alkoxycarbonyl group. Two or more of these substituents may be introduced into the alkyl group, alkenyl group or aryl group.

Phosphate esters advantageously used in the present invention include those represented by the following general formula [W].

General formula [W] R,,0-P-OR2°OR2m In the formula, R2, R, and R79 each represent an alkyl group, an alkenyl group, or an aryl group. however,
R211, R5 and R2? The total number of carbon atoms represented by is 24 to 54.

R211' R2t of general formula [W]? The alkyl group represented by and R2q is, for example, a butyl group, a pentyl group,
Examples include hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group.

These alkyl groups, alkenyl groups and aryl groups may have a single substituent or a plurality of substituents. Preferably R2'7, R2r and R2? is an alkyl group, for example, 2-ethylhexyl group, n-octyl group,
3.5.5-trimethylhexyl group, n-nonyl group, n
-decyl group, 5ec-decyl group, 5ec-dodecyl group,
Examples include t-octyl group.

Specific examples of organic solvents preferably used in the present invention are shown below.

The following are examples of organic solvents in the margins: 2Cx Hs 0-CsH+5(i) 0-01゜H□(n) ■ 1oM** (nJ) for υ-, using a hydrophobic compound as a solvent alone with a low-boiling point solvent or in combination with a high-boiling point solvent Anionic surfactants as dispersion aids when dissolving and dispersing in water mechanically or using ultrasound;
Nonionic surfactants and cationic surfactants can be used.

Between the emulsion layers of the present invention (between the same color-sensitive layers and/or between different color-sensitive layers), the oxidized product of the developing agent or the electron transfer agent may migrate, causing color turbidity, deterioration of sharpness, Color anti-capri agents are used to prevent graininess from becoming noticeable.

The color antifoggant may be used in the emulsion layer itself, or may be used in an intermediate layer provided between adjacent emulsion layers.

An image stabilizer that prevents deterioration of dye images can be used in color light-sensitive materials using the silver halide emulsion of the present invention.

Image stabilizers preferably used in the present invention include those represented by the following general formulas [A] to [H], [J], and [K].

General formula [AI In the formula, R5 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group, and R2, R1, R5, R
6 each represents a hydrogen atom, a lodene atom, a hydroxy group, an alkyl group, an alkenyl group, an aryl group, an alkoxy group, or an acylamino group, and R1 represents an alkyl group, a hydroxy group, an aryl group, or an alkyl group: lJI! Represents a rainbow group.

-Also, R8 and R2 may be ring-closed with each other to form a 5- or 6-membered ring, in which case R1 represents a hydroxy group or an alkoxy group. In addition, R1 and R1 may be ring-closed to form a five-shell hydrocarbon ring, and R1 of the mackerel may be an alkyl group, an aryl group, or a heterocyclic group, provided that R
Except when 1 is a hydrogen atom and R1 is a hydroxy group.

In the general formula [AI, R represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group. Among these, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an -octyl group, tert
- Straight chain or branched alkyl groups such as octyl group and hexadecyl group can be mentioned. Examples of the alkenyl group represented by R1 include allyl, hexenyl, and octenyl groups. Furthermore, examples of the aryl group for R3 include phenyl and naphthyl groups. Further, specific examples of the heterocyclic group represented by R2 include a tetrahydropyranyl group and a pyrimidyl group. Each of these groups can have a substituent, for example, an alkyl group having a substituent is a pencil group, a nidoxymethyl group, and an aryl group having a substituent is a methoxy7enyl group, a chlorophenyl group, a 4-hydroxy Examples include -3,5-dibutylphenyl group.

In the general formula [AI, R2, R5, R1 and R8 are hydrogen atoms, halogen atoms, hydroxy groups, alkyl groups,
It includes an alkenyl group, an aryl group, an alkoxy group, or an acylamide group. Among these, the alkyl group, alkenyl group, and aryl group are the same as the alkyl group, alkenyl group, and aryl group mentioned above for R3. . Examples of the halogen atoms include fluorine, chlorine, and bromine. Further, specific examples of the alkoxy group include a methoxy group and an ethoxy group. Further, the acylamino group is represented by R'CONH-, where R'
is an alkyl group (e.g. methyl, ethyl, n-propyl,
n-butyl, 1-octyl, tert-octyl, benzyl, etc.), alkenyl groups (e.g. allyl, octenyl, oleyl, etc.), aryl groups (e.g. phenyl, methoxyphenyl, naphthyl, etc.) , or a heterocyclic group (e.g. pyridyl, pyrimidyl groups)
can be mentioned.

In the general formula [AI, R1 is an alkyl group, a hydroxy group, an aryl group, or an alkoxy group, and examples of the alkyl group, hydroxy group, aryl group, or alkoxy include the same alkyl group and aryl group as shown in R1 above. As for the alkenyl group of R4, the same alkoxy groups mentioned above for R2, R1, R1 and R6 can be mentioned.

Examples of the ring formed by R1 and R2 together with a benzene ring by closing each other include chroman, coumaran, and methylenedioxybenzene.

Further, examples of the ring formed by R1 and R1 together with a benzene ring include indane. These rings may have substituents (eg alkyl, alkoxy, aryl).

In addition, a spiro compound may be formed by using the spiro atom as an atom in the ring formed by R3 and R2, or R7 and R1, or a bis compound may be formed by using R2, R1, etc. as a linking group. good.

Among the phenolic compounds or phenyl ether compounds represented by the general formula [AI], preferred are R
〇-group (R is an alkyl group, alkeni Jl-je"PII
-Jl-je*--N・74/-4 beakt-Mis Yutaka*2
It is a biindane compound having four auto=;+), and can be particularly preferably represented by the following general formula [A-1].

General formula [A-1] In the formula, R is an alkyl group (e.g. methyl, ethyl, propyl, n-octyl, tert-octyl, benzyl, hexadecyl), an alkenyl group (e.g. allyl, octenyl, oleyl), an aryl group (e.g. , 7enyl, naphthyl) or a heterocyclic group (e.g., te)rahydropyranyl, pyrimidyl), R9 and Rlo are each a hydrogen atom, a halogen atom, (e.g., fluorine, chlorine, bromine), Alkyl groups (e.g. methyl, ethyl, n-butyl, benol), alkoxy groups (e.g. allyl, hexenyl, octenyl), * or alkoxy groups (
For example, methoxy, ethoxy, benzyloxy),
Rz is a hydrogen atom, an alkyl group (e.g. methyl, ethyl,
n-butyl, benzyl), alkenyl groups (e.g. 2-
propenyl, hexenyl, octenyl) or aryl groups (eg phenyl, methoxyphenyl, chlorphenyl, naphthyl).

The compound represented by the general formula [A] is disclosed in U.S. Patent No. 3,
No. 935,016, No. 3,982,944, No. 4
．． No. 254,216, JP-A No. 55-21004, No. 5
No. 4-145530, British Patent Publication No. 2,077.455
No. 2,062, No. 888, U.S. Patent No. 3,764
, 337, tJ43.432300, tJ43.432300, 3,57
No. 4,627, No. 3,573,050, Japanese Unexamined Patent Publication No. 1973
-152225, 53-20327, 53-1
No. 7729, No. 55-6321, British Patent No. 1,34
No. 7,556, Publication No. 2.066.975, Special Publication No. 5
It also includes compounds described in US Pat. No. 4-12337, US Pat. No. 4-12337, US Pat.

The amount of the compound represented by the general formula [A] used is preferably 5 to 300 mol%, more preferably 10 to 200 mol%, based on the magenta coupler.

Typical specific examples of the compound represented by the general formula [A] are shown below.

Type (1) RI Type (2) Type (3) Type (4) Type (5) Type (6) Type (7) Type (4) Type (5) Type (6) Below margin A -7 The following margin is general formula [B] (in the formula, R+ and R4 are each a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkenyloxy group, a hydroxy group, a 71-nol group, an aryloxy group, an acyl group, acylamide group, acyloxy group, sulfonamide group, cycloalkyl or alkoxycarbonyl group, R2 is a hydrogen atom, alkyl group, alkenyl group, aryl group, acyl group, cycloalkyl group or heterocyclic group, R3 is a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, a 7-aryl group,
Aryloxy group, acyl group, acyloxy group, sulfonamide group, dichlorofurkyl group or alkoxycarbonyl group.

Each of the groups listed above may be substituted with other substituents. For example, alkyl groups, alkenyl groups, alkoxy groups,
Examples include an aryl group, an aryloxy group, a hydroxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acylamine 7 group, an acyloxy group, a carbamoyl group, a sulfonamide group, and a sulfonyl group.

Further, R2 and R1 may be ring-closed with each other to form a 5-shell or 6-shell ring. Examples of the ring formed by R2 and R1 together with a benzene ring include a chroman ring and a methylenedioxybenzene ring.

Y represents the atomic group necessary to form a chroman or coumaran ring.

Chroman or coumaran ring is a halogen atom, furkyl group, cycloalkyl group, alkoxy group, alkenyl group,
May be substituted with an alkenyloxy group, hydroxy group, aryl group, aryloxy group, or heterocycle,
Furthermore, a spiro ring may be formed.

Among the compounds represented by general formula [B], compounds particularly useful in the present invention are general formulas [B-1], [B-2], [B
-3], [B-4], and [B-5].

General formula [B-11 h+ General formula [B-21 to 1 General formula [B-3] General formula [B-4] General formula [B-5] K' General formula [B-11, [B-21, [B-31, [
R1, R2, R in [B-4] and [B-5]
3 and R1 have the same meanings as in the general formula [B], and R6, R6, R1, R8, R9 and Ro.

is a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a hydroxy group, an alkenyl group, an alkenyloxy group,
Aryl group, aryloxy group or heterocyclic group.

Furthermore, R6 and R6, R6 and R7, R1 and R6, RIl and R1, and R9 and R2° may be cyclized with each other to form a carbocycle, and furthermore, the carbocycle may be substituted with an alkyl group.

The general formula [B-1], [, B-2], [B-3]
, [B-4] and [B-5], R3 and R1 are hydrogen atoms, alkyl groups, alkoxy groups, hydroxy groups or cycloalkyl groups, R51R@, R,, R3
, R1 and R1° are hydrogen atoms, alkyl groups, or cycloalkyl groups, which are particularly useful.

The compound represented by the general formula [B] is tetrahedron (Te
trahedron), 1970. vo126,474
3-4751 pages, Journal of the Chemical Society of Japan 1.1972. No10
, pp. 0987-1990, Chemical (chew, Le
tt, )* Represents and includes the compounds described in 1972 (4) pp. 315-316, JP-A-55-139383, and can be synthesized according to the methods described therein.

The amount of the compound represented by the general formula [B] used is 5 to 300% relative to the magenta coupler of the emulsion of the present invention.
Mol% preferably, more preferably 10 to 200 mol%
It is.

Typical specific examples of these compounds are shown below.

The following is a blank general formula [C] R1 to 2 General formula [1)] In the formula, R3 and R2 are a hydrogen atom, a halogen atom, a furkyl group, an alkenyl group, an alkoxy group, an alkenyloxy group, a hydroxy group, an aryl group, an aryloxy group , acyl group, acylamino group, acyloxy group, sulfonamide group or alkoxycarbonyl group.

Each of the groups listed above may be substituted with other substituents. For example, halogen atoms, furkyl groups, alkenyl groups,
Examples include an alkoxy group, an aryloxy group, a hydroxy group, an alkoxycarbonyl group, an aryloxygalbonyl group, an acylamino group, a carlenoid group, a sulfonamide group, and a sulfamoyl group.

Y represents the atomic group necessary to form a dichroman or dicoumaran ring together with the benzene ring.

The chroman or coumaran ring is a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkenyl group,
May be substituted with an alkenyloxy group, hydroxy group, aryl group, 7-aryloxy group or heterocyclic group,
Furthermore, a spiro ring may be formed.

Among the compounds represented by the general formulas EC] and [DI, the compounds particularly useful in the present invention are the compounds represented by the general formulas [C-11, [C-2
], [D-1] and [D-2].

General formula [C-1] General formula [C-21' General formula [D-11 General formula [D-21 General formula [C-11, [C-2], [D-1] and [D
-2], R3 and R2 have the same meanings as in the general formulas [CI and [Dl], and R1, R, .
R5JR6, R, and R8 represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a hydroxy group, an alkenyl group, an alkenyloxy group, an aryl group, an aryloxy group, or a heterocyclic group. Furthermore, Ra and R, R1 and R6, R5 and R6, R6 and R2, and R7 and R8
may be cyclized with each other to form a carbocycle, and the carbocycle may be further substituted with an alkyl group.

In the general formulas [C-1], [C-2], [D-11 and [D-2], Ro and R2 are hydrogen atoms, alkyl groups, alkoxy groups, hydroxy groups or dichlorofurkyl groups, R2, Particularly useful are compounds in which R1, R9, R6, R1 and R6 are hydrogen atoms, alkyl groups, or cycloalkyl groups.

Compounds represented by the general formula [CI, [Dl] are shown in the Journal of the Chemical Society of Japan (J, Chew, Soc, part C) 196
8. (14), pp. 1937-18, Journal of the Society of Organic Synthetic Chemistry 19f 0.28 (1), pp. 60-65, Tetrahedron Letters 19
73, (29), pp. 2707-2710, and can be synthesized according to the methods described therein.

The amount of the compound represented by the general formula [01, [Dl] is 5 to 30% relative to the magenta coupler according to the present invention.
It is preferably 0 mol%, more preferably 10 to 200 mol%.

Specific representative examples of these compounds are shown below.

Below are blanks below: Margins below are blanks General formula [E] In the formula, R1 represents a hydrogen atom, an alkyl group, an alkenyl group, a 7-aryl group, an acyl group, a dichlorofurkyl group, or a heterocyclic group, and R2 represents a hydrogen atom, a halogen atom, or an alkyl group. , alkenyl group, aryl group, aryloxy group, acyl group, acylamide 7 group, acyloxy group, sulfone 7
Represents a mido group, a cycloalkyl group, or an alkoxycarbonyl group.

R2 and R4 represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, an acyl group, an acylamino group, a sulfonamide group, a cycloalkyl group, or an alkoxycarbonyl group.

Each of the groups listed above may be substituted with other substituents. For example, an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a hydroxy group, an alkoxycarbonyl group, an aryloxycarbonyl group,
Acylamino group, carbamoyl group, sulfonamide group,
Examples include sulfamoyl group.

Further, R1 and R2 may be ring-closed with each other to form a 5- or 6-membered ring.

At that time, R and R4 are hydrogen atoms, halogen atoms, alkyl groups, alkenyl groups, alkoxy groups, alkenyloxy groups, hydroxy groups, aryl groups, aryloxy groups,
It represents an acyl group, an acylamide group, an acyloxy group, a sulfonamide group, or an alkoxycarbonyl group.

Y represents an atomic group necessary to form a chroman or coumaran ring.

The chroman or coumaran ring is a halogen atom, an alkyl group, a dichlorofurkyl group, an alkoxy group, an alkenyl group,
It may be substituted with an alkenyloxy group, a hydroxy group, an aryl group, an aryloxy group or a heterocyclic group, and may further form a spiro ring.

Among the compounds represented by the general formula (E), the compound particularly useful in the present invention is the general formula (E-1).

(E-2: +, t: E-3), (E-4) and (E
-5) is included in the compound shown.

General formula (E-1) R1 General formula (E-23 General formula (E-3) General formula (E-4) General formula (E-53 General formula (E-1) to [R1, R2 in E-53 ,R
3 and R4 have the same meaning as in the general formula (El), and RstR'tR'tR@tR" and R" are hydrogen atoms, halogen atoms, alkyl groups, alkoxy groups, hydroxy groups, alkenyl groups, alkenyloxy groups. , represents an aryl group, an aryloxy group or a heterocyclic group, and further R5 and R-R6 and R1, R1 and R・, RI and R
I, (/R. and RI6 may be cyclized with each other to form a carbocycle, and the carbocycle may be further substituted with an alkyl group.

In the general formulas (E-1) to (E-5), R1, R
2,)j3 and R4 are hydrogen atoms, alkyl groups, or cycloalkyl groups, and in the general formula (E-5), (1)
R'' R4 is a hydrogen atom, an alkyl group, an alkoxy group, a hydroxy group or a cycloalkyl group, and the odor of the general formulas (E-1) to (E-5) is RS, R@, R
? , RS, RI Oyo(/RIO) are particularly useful. Compounds are hydrogen atoms, alkyl groups, or cycloalkyl groups.

The compound represented by the general formula [E] is tetrahedron (
Tetrahedron Letters) 1965
．． (8) *Pages 457-460 Journal of the Chemical Society of Japan (J, C
hew, Soc, part C) 1966° (22
), pp. 2013-2016, (Zh, Org
, Khim) 19 fo, (e).

Compounds described on pages 1230 to 1237,
and can be synthesized according to the methods described therein.

The amount of the compound represented by the general formula [E-1] used is preferably 5 to 300 mol%, more preferably 10 to 200 mol%, based on the magenta coupler according to the present invention.

Specific representative examples of these compounds are shown below.

The following is a blank general formula CF) In the formula, R1 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an acyl group, a cycloalkyl group, or a heterocyclic group, and R2 represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group. group, aryloxy group, acyl group, acylamide group, acyloxy group, sulfonamide group, cycloalkyl group, or alkoxycarbonyl group.

R1 represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, a 7-syl group, an acylamino group, a sulfonamide group, a cycloalkyl group, or an alkoxycarbonyl group.

R1 is a hydrogen atom, a halogen atom, a furkyl group, an alkenyl group, an alkoxy group, an alkenyloxy group, a hydroxy group, an aryl group, an aryloxy group, an acyl group, an acylamino group, an acyloxy group, a sulfone 7-mido group, or an alphyl group. Hail pheasant carbonyl group.

Each of the groups listed above may be substituted with other substituents. For example, alkyl groups, alkenyl groups, alkoxy groups,
Examples include an aryl group, a 71-noloxy group, a hydroxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acylamide group, a carbamoyl group, a sulfonamide group, and a sulfamoyl group.

Further, R1 and R2 may be ring-closed with each other to form a 5-shell or 6-shell ring. At that time, R1 and R1 are a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkenyloxy group, a hydroxy group, an aryl group, an aryloxy group, an acyl group, an acylamide group, an acyloxy group, a sulfonamide group, or an alkoxy Hail carbonyl group.

Y represents the atomic group necessary to form a chroman or coumaran ring.

The chroman or coumaran ring may be substituted with a /X lodene atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkenyl group, an alkenyloxy group, a hydroxy group, an aryl group, an aryloxy group or a heterocyclic group, It may form a ring.

Among the compounds represented by the general formula IF, compounds particularly useful in the present invention are those represented by the general formula [F-11, [F-2], IF-
3], [F-4] and [F-5].

Below are blank spaces General formula (F-1) General formula CF-2) General formula CF-3) General formula (F-4) General formula (F-5) R3 in general formulas [F-1] and [F-5] ,
R2, R3 and R1 have the same meaning as in the above general formula [F], R5, R6, R2, R3, R5 and Rlo are hydrogen atoms, halogen atoms, alkyl groups, alkoxy groups, hydroxy groups, alkenyl groups, Alkenyloxy group, aryl group, aryloxy group or heterocyclic group.

Furthermore, R6 and R6, R6 and R2, R2 and R,, R, and R
3 or R5 and RIG may be cyclized with each other to form a carbocycle, and the carbocycle may be further substituted with an alkyl group.

Also, two R, -R, in [F-3], [F-4] and [F-5]. may be the same or different.

The general formula [F-1], [F-2], [F-3],
In [F-4] and [F-51, R1, R2,
and R1 is a hydrogen atom, an alkyl group, a cycloalkyl group, R1 is a hydrogen atom, an alkyl group, an alkoxy group, a hydroxy group, or a cycloalkyl group, and R6, R6, R
2, R6, R, and RIG are hydrogen atoms, alkyl groups,
or cycloalkyl groups are particularly useful.

The compound represented by the general formula [F] is tetrahedron (
Tetrahedron Letters) 1970
y Vol 2L pages 4743-4751, Journal of the Chemical Society of Japan 1972. No. 10t 1987-1990, Synthesis 1975. , V
ol 6゜392-393, (Bul Soc, C
him, Be1g) 1975* Vol84 (7
), 747-759, and can be synthesized according to the methods described therein.

The amount of the compound represented by the general formula [F] used is 5 to 300 mol% based on the magenta coupler according to the present invention.
is preferable, and more preferably 10 to 200 mol%.

Specific representative examples of the compound represented by the general formula [F] are shown below.

The following is a blank general formula CG) R' R In the formula, R1 and R3 are a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, a hydroxy group, an aryl group, an aryloxy group, an acyl group, an acylamine 7 group, Represents an acyloxy group, a sulfonamide group, a cycloalkyl group, or an alkoxycarbonyl group.

R2 represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, a hydroxy group, an aryl group, an acyl group, an acylamino group, an acyloxy group, a sulfonamide group, a cycloalkyl group, or an alkoxycarbonyl group.

The groups listed above may each be substituted with other substituents, such as alkyl groups, alkenyl groups,
Alkoxy groups, aryl groups, aryloxy groups, hydroxy groups, alkoxycarbo and R) and R6, R6 and R7, R7 and R11, and R8 and R9 may be closed to each other to form a hydrocarbon ring. Optionally, the hydrocarbon ring may also be substituted with an alkyl group.

In the general formulas ('G-1) to (G-3), R1 and R3 are a hydrogen atom, an alkyl group, an alkoxy group, a hydroxy group, or a cycloalkyl group, and R2 is a hydrogen atom, an alkyl group, a hydroxy group, or a cycloalkyl group. Rukyl group, R4
, R', R', R, SR" and (tr-R") are hydrogen atoms, alkyl groups or cycloalkyl groups, which are particularly useful.

The amount of the compound represented by the general formula [G] is preferably 5 to 300 mol% relative to the magenta coupler,
More preferably, it is 10 to 200 mol%.

Typical specific examples of the compound represented by the general formula [G] are shown below.

In the following margins General formula (G-1) General formula (G-2) General formula (G-3) General formula (G-1) to (R', R2 and R3 in G-33 are those in general formula (G) is synonymous with R4,
RS, R@, R', Rl and R" represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkenyl group, a hydroxy group, an aryl group, an aryloxy group, or a heterocyclic group. Examples include R4nyl group, aryloxycarbonyl group, acylamino group, carbamoyl group, sulfonamide group, and sulfamoyl group.

Further, R2 and R3 may be ring-closed with each other to form a pentashell or pentahydrocarbon ring. This 5-membered or 6-shell hydrocarbon ring is a halogen atom, an alkyl group, a cycloalkyl group,
It may be substituted with an alkoxy group, an alkenyl group, a hydroxy group, an aryl group, an aryloxy group, a heterocyclic group, or the like.

Y represents an atomic group necessary to form a bean ring. The indane ring is a halogen atom, an alkyl group, an alkenyl group,
It may be substituted with an alkoxy group, a dichlorofurkyl group, a hydroxy group, an aryl group, an aryloxy group, a heterocyclic group, or the like, and may further form a spiro ring.

Among the compounds represented by the general formula CG), compounds particularly useful in the present invention are included in the compounds represented by the general formulas (G-1) to [:G-3).

The following is a blank general formula (H) R3 where R1 and R2 are a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, a 7-syl group,
Acylamino group, acyloxy group, sulfone 7 mido group,
Represents a cycloalkyl group or an alkoxycarbonyl group.

R3 represents a hydrogen atom, a halogen atom, a furkyl group, an alkenyl group, an alkoxy group, a hydroxy group, an aryl group, an aryloxy group, an acyl group, an acylamino group, an acyloxy group, a sulfone 7mide group, a cycloalkyl group, or an alkoxycarbonyl group .

The groups listed above may each be substituted with other substituents, such as alkyl groups, alkenyl groups, alkoxy groups,
Examples thereof include an aryl group, a 71-noloxy group, a hydroxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl 7-moyl group, a carbamoyl group, a sulfone 7-mido group, and a sulfon-77 moyl group.

Further, R1 and R2 and R2 and R3 may be ring-closed with each other to form a 5- or 6-ring hydrocarbon ring (the hydrocarbon ring may be a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkenyl group, hydroxy group, aryl group,
It may be substituted with an aryloxy group, a heterocyclic group, etc.

Y represents an atomic group necessary to form an indane ring, and the indane ring may be substituted with a substituent capable of substituting the above hydrocarbon ring (or may further form a spiro ring).

Among the compounds represented by the general formula (H), compounds particularly useful in the present invention are included in the compounds represented by the general formulas (H-1) to (H-2).

General formula (H-1) General formula (H-2) General formula 1 (H-3) R l, R2 and R in general formulas (H-1) to (H-3) are synonymous with R4
, R5, RI, RftRI and R1 each represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a hydroxy group, an alkenyl group, a heptaryl group, an aryloxy group, or a heterocyclic group, and R'R',R' and R'
, RI and R'', Rf and RI, and R8 and R9 may be ring-closed with each other to form a hydrocarbon ring, and the hydrocarbon ring may be further substituted with an alkyl group.

In the general formulas (H-1) to (H-3), R' and R2 are each a hydrogen atom, an alkyl group or a cycloalkyl group, R3 is a hydrogen atom, an alkyl group, an alkoxy group,
Hydroxy group or cycloalkyl group, R', R', R
', R? , R" and f/R", each of which is a hydrogen atom, an alkyl group, or a cycloalkyl group, are particularly useful.

A method for synthesizing the compound represented by the general formula [H] is known, and is described in US Pat. No. 3,057,929, Chem.

Ber, 1972.95(5), 1673~
1674 pages, Chemist-ry Letter
s* 1980, 739-742.

It is preferably 5 to 300 mol%, more preferably 1% to the magenta coupler compound represented by the general formula [H].
It is 0 to 200 mol%.

Specific representative examples represented by the general formula [H] are shown below.

The following is a blank general formula (J) I'~\R1-N Y [In the formula, R1 represents an aliphatic group, a cycloalkyl group, or an aliphatic group, and Y represents a bicyclic ring having 5 to 7 shell rings together with a nitrogen atom. Represents a group of nonmetallic atoms necessary to form . However, when there are two or more heteroatoms among the nonmetallic atoms containing nitrogen atoms forming the heterocycle, at least two heteroatoms are not adjacent to each other. ] Examples of the aliphatic group represented by R' include a saturated alkyl group which may have a substituent and an unsaturated alkyl group which may have a substituent. Examples of saturated alkyl groups include methyl group, ethyl group, butyl group, octyl group, dodecyl group, tetradecyl group, hexadecyl group, etc., and examples of unsaturated alkyl groups include ethynyl group, propenyl group, etc. It will be done.

The cycloalkyl group represented by R1 is a 5- to 7-shell cycloalkyl group that may have a substituent, such as a cyclopentyl group, a cyclohexyl group, and the like.

The aryl group represented by R1 represents a phenyl group, na, or 7-tyl group, each of which may have a substituent.

Substituents for the aliphatic group, cycloalkyl group, and aryl group represented by R1 include alkyl groups, aryl groups, alkoxy groups, carbonyl groups, carbamoyl groups, acylamino groups, sulfamoyl groups, sulfonamide groups, carbonyloxy groups, Examples include an alkylsulfonyl group, an arylsulfonyl group, a hydroxy group, a heterocyclic group, an alkylthio group, an arylthio group, and these substituents may further have a substituent.

In the general formula (J), Y together with the nitrogen atom is 5 to 7
represents a group of nonmetallic atoms necessary to form a transcyclic heterocycle; at least two of the group of nonmetallic atoms containing nitrogen atoms forming the bicyclic ring must be heteroatoms, and
In this heterocyclic ring of the compound represented by formula (J), if all the heteroatoms are adjacent to each other, the magenta dye image stabilizer This is not desirable because it cannot perform its functions.

The 5- to 7-shell heterocycle of the compound represented by the general formula (J) may have a substituent, and examples of the substituent include an alkyl group, an aryl group, an acyl group, a carbamoyl group, and an alkoxycarbonyl group. group, sulfonyl group, sulfamoyl group, etc., and may further have a substituent. In addition, 5 to 7
Although the heterocycle of the shell ring may be saturated, a saturated heterocycle is preferred. Further, a benzene ring or the like may be condensed to the bicyclic ring, or a spiro ring may be formed.

The amount of the compound represented by the general formula (J) of the present invention to be used is preferably 5 to 300 mol%, more preferably 10 to 300 mol%, based on the magenta coupler represented by the general formula (1) of the present invention. It is 200 mol%.

Typical specific examples represented by general formula (J) are shown below.

Margin below J-63 J-64 J-6FJ -FO ■ ■ 12H2S Among the compounds represented by the general formula (J), piperazine compounds and homopiperazine compounds are particularly preferred;
More preferably, the following general formula (J-1) or (J-
This is a compound represented by 2).

General Formula (J-1) General Formula (J-23 In the formula, R2 and R3 each represent a hydrogen atom, an alkyl group, or a 7-aryl group. However, R2 and R3 do not become hydrogen at the same time. R4- R13 each represents a hydrogen atom, an alkyl group or an aryl group.

In the general formulas (J-1) and (J-2), R2 and R3 each represent a hydrogen atom, an alkyl group, or an aryl group, and examples of the alkyl group represented by R2 or R3 include, for example, a methyl group, Ethyl group, butyl group, octyl group, dodecyl group, tetradecyl group, hexadecyl group,
Examples include octadecyl group. Examples of the aryl group represented by R2 or R3 include a phenyl group.

The alkyl group and aryl group represented by R2 or R3 may have a substituent, and examples of the substituent include a halogen atom,
Examples include an alkyl group, an aryl group, an alkoxy group, a 7-aryloxy group, and a heterocyclic group.

The total number of carbon atoms in R1 and R3 (including substituents) is 6 to
40 is preferred.

In the general formula (J-1) or (J-2), R4
-R15 each represent a hydrogen atom, an alkyl group, or an aryl group, and examples of the alkyl group represented by R4 to R12 include a methyl group and an ethyl group.

Examples of the aryl group represented by R4 to RI3 include a phenyl group.

Specific examples of the compound represented by the general formula (J-1) or [:J-2] include the above-mentioned examples and the perazine compound (J-2).
-1) to (J-30) and exemplified homopiperazine compounds (J-51) to (J-62).

Next, a synthesis example of a typical magenta dye image stabilizer of the present invention represented by the general formula (J) will be shown.

Synthesis Example 1 (Synthesis of Compound J-2) 158 tons of anhydrous potassium carbonate was added to 77 tons of 100TIIQ in which 9.0 g of piperazine and 55 degrees of myristyl bromide were dissolved, and the mixture was boiled and refluxed for 10 hours to react.

After the reaction, add 500Wl of reaction solution! After pouring into 1 water, add 500 mi of ethyl acetate! Extracted with. After drying the ethyl acetate layer over magnesium sulfate, the ethyl acetate was distilled off to obtain the desired product as white crystals. Recrystallization with 300% acetone gave 34 g (yield: 0%) of white scaly crystals.

Melting point: 55-58°C Synthesis Example-2 (Synthesis of Compound J-34) 18 g of 4-morpholinoaniline was dissolved in 100 m of ethyl acetate.
(After dissolving in 1, 12.Q of acetic anhydride was added little by little while stirring and keeping the reaction solution at 20°C. After adding acetic anhydride, it was cooled on ice, and the precipitated crystals were collected by filtration, and then ethyl acetate was added. Recrystallization was performed to obtain 16.5 g of white powdery crystals (yield: 5%).

Melting point: 207-210°C General formula [K] In the formula, R1 represents an aliphatic group, a cycloalkyl group, or an aryl group, and Y is a simple bond necessary to form a 5- to 7-shell heterocycle with the nitrogen atom. Represents a hand or a divalent hydrocarbon group. R", R3, R4゜R5, R', and R' each represent a hydrogen atom, an aliphatic group, a cycloalkyl group, or an aryl group. However, R2 and R4 and R3 and R6 are bonded to each other to form a mere bond. may form an unsaturated 5- to 7-ring heterocycle together with the nitrogen atom and Y.Also, when Y is a simple bond, R5 and R7 bond to each other to form a simple bond. may be formed to form an unsaturated five-shell bicyclic ring together with the nitrogen atom and Y.Also, when Y is not a simple bond, Rg and Y, R' and Y, or Y itself may form an unsaturated bond. to form a nitrogen atom, unsaturated 6 with Y
Forming a bilobed ring of shells or seven shells is also more ζ.

Examples of the aliphatic group represented by R1 include a saturated alkyl group which may have a substituent, and an unsaturated furkyl group which may have a substituent. Examples of saturated alkyl groups include methyl group, ethyl group, butyl group, octyl group, dodecyl group, tetradecyl group, hexadecyl group, etc., and examples of unsaturated alkyl groups include ethynyl group, propenyl group, etc. It will be done.

The cycloalkyl group represented by R1 is a 5- to 7-shell cycloalkyl group which may have a substituent, such as a schifpentyl group and a cyclohexyl group.

The aryl group represented by R1 represents a phenyl group or a naphthyl group which may have a substituent.

Substituents for the aliphatic group, cycloalkyl group, and aryl group represented by R' include an alkyl group, an aryl group, an alkoxy group, a carbonyl group, a carbamoyl group, an acylamino group, a sulfonyl group, a sulfonamido group, and a carbonyl group. Examples include an oxy group, an alkylsulfonyl group, an arylsulfonyl group, a hydroxy group, a heterocyclic group, an alkylthio group, an arylthio group, and these substituents may further have a substituent.

In the general formula (K), Y together with the nitrogen atom is 5 to 7
It represents a simple bond or a divalent hydrocarbon group necessary to form the heterocycle of the shell ring, but when Y is a simple bond, R5 and R7 further combine with each other to form a simple bond. (If Y is a divalent monovalent hydrogen group, i.e., a methylene group, R5 and Y or R7 and Y may form an unsaturated 5-shell heterocycle. In the case of an ethylene group, R5 and Y, R' and Y, or Y itself may form an unsaturated bond to form an unsaturated six-ring heterocycle. Furthermore, the divalent hydrocarbon group represented by Y may have a substituent, and this substituent includes an alkyl group, a carbamoyl group, an alkyloxy Examples include a carbonyl group, an acylamide group, and a sulfone ring group.

In the general formula (K), R", R3, R4, R51
R6 and R7 each represent a hydrogen atom, an aliphatic group, a cycloalkyl group, or an aryl group, and the aliphatic group represented by R2-R7 includes a saturated alkyl group that may have a substituent and a substituent. Examples include unsaturated alkyl groups which may have . Examples of saturated alkyl groups include methyl group, ethyl group, butyl group, octyl group, dodecyl group, ζtetradecyl group, hexadecyl group, etc., and examples of unsaturated alkyl groups include ethynyl group, propenyl group, etc. It will be done.

The cycloalkyl group represented by R2-R7 is a 5- to 7-membered cycloalkyl group which may have a substituent, and examples thereof include a cyclopentyl group and a cyclohexyl group.

Examples of the aryl group represented by R2-R7 include a phenyl group and a naphthyl group which may have a substituent.

Substituents for the aliphatic groups, cycloalkyl groups, and aryl groups represented by R2 to R7 above include alkyl groups, aryl groups, alkoxy groups, carbonyl groups, carbamoyl groups, acylamide 7 groups, sulf 7 moyl groups, and sulfonamides. basis,
Examples include carbonyloxy group, alkylsulfonyl group, arylsulfonyl group, hydroxy group, heterocyclic group, and alkylthio group.

It is preferable that the compound represented by the general formula (K) has a 5- to 7-ring saturated heterocycle rather than an unsaturated one.

The amount of the compound represented by the general formula [K) below is as follows:
It is preferably 5 to 300 mol%, more preferably 10 to 200 mol%, based on the magenta coupler represented by the general formula [1] of the present invention.

Representative specific examples of the compound represented by the general formula (K) are shown below.

In the margins below, -34 -35 -36 -37 -38 -39 -40 -41 Next, typical synthesis examples of the compound represented by the general formula (K) are shown.

Synthesis Example 1 (Synthesis of Compound -14) 6.0 g of anhydrous potassium carbonate was added to 77 tons of 6011IQ in which 9.0 g of piperazine and 28 g of myristyl bromide were dissolved, and the mixture was reacted by boiling and refluxing for 20 hours.

After the reaction, the reaction solution was poured into 300 ml of water and extracted with 300 ml of ethyl acetate (1 ml). After drying the ethyl acetate layer with magnesium sulfate, the ethyl acetate was distilled off to obtain the desired product as white crystals. 100 ml of acetone
12g of white flaky crystals (yield 43%)
I got it.

Melting point: 175-180°C Hydrophilic colloid layers such as the protective layer and intermediate layer of the present invention contain ultraviolet absorption to prevent fogging due to discharge caused by charging of the photosensitive material due to friction, etc., and to prevent image deterioration due to UV light. It may also contain an agent.

A color light-sensitive material using the silver halide emulsion of the present invention can be provided with auxiliary layers such as a filter layer, an antihalation layer and/or an antiirradiation layer. These layers and/or the emulsion layer may contain dyes that are washed out of the color photographic paper or bleached during the development process.

In the silver halide emulsion layer and/or other hydrophilic colloid layer of the silver halide photosensitive material using the silver halide emulsion of the present invention, the gloss of the photosensitive material is reduced and the addability is increased.
A matting agent can be added for the purpose of preventing the sensitive materials from sticking to each other.

A preparation can be added to reduce the sliding friction of a light-sensitive material using the silver halide emulsion of the present invention.

An antistatic agent for the purpose of preventing static electricity can be added to a photographic material using the silver halide emulsion of the present invention.

Antistatic agents are sometimes used in the antistatic layer on the side of the support on which the emulsion is not laminated, or they are used to protect the emulsion layer and/or the side on which the emulsion layer is laminated to the support other than the emulsion layer. It may also be used in a colloid layer.

The photographic emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material using the silver halide emulsion of the present invention may include improved coatability,
Various surfactants are used for the purposes of preventing static electricity, improving slipperiness, dispersing emulsions, preventing adhesion, and improving photographic properties (such as accelerating development, increasing contrast, and sensitization).

The light-sensitive material using the silver halide emulsion of the present invention has a photographic emulsion layer, and other layers include a flexible reflective support such as baryta paper, paper laminated with α-olephne polymer, synthetic paper, cellulose acetate, nitric acid, etc. cellulose, polystyrene,
It can be applied to films made of semi-synthetic or synthetic polymers such as polyvinyl chloride, polyethylene terephthalate, polycarbonate, and polyamide, as well as rigid bodies such as glass, metal, and ceramics.

In the present invention, a reflective support, for example a support prepared by adding a white pigment such as titanium oxide to a polymer such as polyethylene and laminating paper thereon, is particularly preferably used.

The silver halide color photographic light-sensitive material of the present invention can be produced by subjecting the support surface to corona discharge, ultraviolet irradiation, flame treatment, etc., if necessary, and then directly or (adhesiveness, antistatic property, dimension (to improve stability, wear resistance, hardness, antihalation, friction properties and/or other properties)
It may be applied through one or more subbing layers.

During emulsion coating of the color photographic light-sensitive material of the present invention, a thickener may be used to improve coating properties. Particularly useful coating methods are ex-dulsion coating and curtain coating, which allow two or more layers to be applied simultaneously.

The color photographic light-sensitive material of the present invention can be exposed using electromagnetic waves in a spectral region to which the emulsion layer constituting the light-sensitive material of the present invention is sensitive. As a light source, natural light (sunlight)
Excited by , tungsten electric lamp, fluorescent lamp, mercury lamp, xenon arc lamp, carbon arc lamp, xenon flash lamp, cathode ray tube flying spot, various laser beams, light emitting diode light, electron beam, X-ray, γ-ray, α-ray, etc. Any known light source can be used, such as light emitted from a phosphor.

The exposure time is of course 1 millisecond to 1 second, which is normally used with a camera, but it is also possible to use an exposure shorter than 1 microsecond, for example, an exposure of 100 microseconds to 1 microsecond using a cathode ray tube or xenon arc lamp. Exposures longer than 1 second are also possible. The exposure may be performed continuously or intermittently.

The silver halide color photographic light-sensitive material of the present invention can form an image by color development.

The aromatic primary amine color developing agent used in the color developing solution in the present invention includes known ones that are widely used in various color photographic processes.

These developers include aminophenol and p-phenylenediamine derivatives. These compounds are generally used in the form of salts, such as hydrochlorides or sulfates, since they are more stable than in the free state. Further, these compounds are generally used in a concentration of about 0.1 g to about 30 g per 1 Jl of color developer, preferably about 1 g to about 15 g per 1 p of color developer.
Use at a concentration of g.

Examples of aminophenol-based developers include 〇-aminophenol, p-aminophenol, and 5-amino-2-
Oxytoluene, 2-amino-3-oxytoluene, 2
-oxy-3-amino-1°4-dimethylbenzene and the like.

Particularly useful primary aromatic amine color developers are N, N'
-Dialkyl-p-phenylenediamine compound, and the alkyl group and phenyl group may be substituted with any substituent. Among them, examples of particularly useful compounds include N,N'-diethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, N,N'-diethyl-p-phenylenediamine hydrochloride,
'-Dimethyl-p-phenylenediamine hydrochloride, 2-amino-5-(N-ethyl-N-dodecylamino)-toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-amino Aniline sulfate, N-ethyl-N-β-hydroxyethylaminoaniline, 4-amino-3-methyl-N.

N'-diethylaniline, 4-amino-N-(2-methoxyethyl)-N-ethyl-3-methylaniline-p-
Examples include toluene sulfonate.

In addition to the above-mentioned aromatic primary amine color developer, the color developer used in the process of the present invention further contains various components normally added to color developers, such as sodium hydroxide and sodium carbonate. , an alkali agent such as potassium carbonate, an alkali metal sulfite, an alkali metal bisulfite, an alkali metal thiocyanate, an alkali metal halide, benzyl alcohol, a water softener and a thickening agent. The pH value of this color developer is usually 7 or higher, most commonly about 10 to
It is about 13.

In the present invention, after color development processing, processing is performed with a processing liquid having a fixing ability, but if the processing liquid having a fixing ability is a fixing liquid, a bleaching treatment is performed before that. A metal complex salt of an organic acid is used as a bleaching agent in the bleaching process, and the metal complex salt has the effect of oxidizing the metallic silver produced during development and converting it into silver halide, and at the same time coloring the uncolored areas of the coloring agent. It has a structure in which metal ions such as iron, cobalt, and copper are coordinated with aminopolycarboxylic acid or organic acids such as oxalic acid and citric acid. The most preferred organic acids used to form such metal complexes of organic acids include polycarboxylic acids or aminopolycarboxylic acids. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts.

Specific representative examples of these include the following.

[1] Ethylenediaminetetraacetic acid [2] Nitrilotriacetic acid [3] Iminodiacetic acid [4] Ethylenediaminetetraacetic acid disodium salt [5] Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt [6] Ethylenediaminetetraacetic acid tetrasodium salt [7] Nitrilotriacetic acid The bleaching agent used in the sodium acetate salt contains a metal complex salt of an organic acid as described above as a bleaching agent, and may also contain various additives. As additives, it is particularly desirable to include rehalogenating agents, metal salts, and chelating agents such as alkali halides or ammonium halides, such as potassium bromide, sodium bromide, sodium chloride, and ammonium bromide.

Also, the pH of borates, oxalates, acetates, carbonates, phosphates, etc.
Those known to be added to ordinary bleaching solutions, such as l1 buffer agents, alkylamines, and polyethylene oxides, can be added as appropriate.

Furthermore, the fixer and bleach-fixer contain ammonium sulfite,
Sulfites such as potassium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, sodium metabisulfite, boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, 1) H1 buffer consisting of various salts such as potassium carbonate, sodium bisulfite, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide may be contained alone or in combination.

When carrying out the process of the present invention while replenishing the bleach-fix solution (bath) with a bleach-fix replenisher, the bleach-fix solution (bath) may contain thiosulfate, thiocyanate, sulfite, etc. These salts may be added to the bleach-fixing replenisher to replenish the processing bath. .

In the present invention, in order to increase the activity of the bleach-fix solution, air or oxygen may be blown into the bleach-fix bath and the bleach-fix replenisher storage tank, if desired, or an appropriate oxidizing agent may be added. For example, hydrogen peroxide, bromate, persulfate, etc. may be added as appropriate.

[Specific effects of the present invention] According to the present invention, when stored in a dark place for a long period of time, the Y-
Very little staining, excellent color reproduction, and less lI adjustment ratio and capri increase when storing raw samples.
A silver halide color photographic material that can stably maintain overall excellent image quality for a long period of time can be obtained.

In addition, the poor gloss, which is a drawback of vinyl sulfone-based hardeners, is improved, and a silver halide photographic material with excellent overall film properties such as rapid hardening, film gloss, and film scratch strength can be obtained. It will be done.

Furthermore, a secondary effect was surprisingly found in that the desensitization associated with preservation of raw samples, which is a drawback of the hardening agents represented by the general formulas [XII] and [XI[], is improved. done.

The present inventors conducted various experiments to confirm the effects of the present invention. Typical examples are shown below.

[Specific Examples of the Invention] Example 1 A total of 18 types of samples were prepared by coating the following 1.2 layers on a reflective support made of polyethylene-coated paper containing titanium oxide.

First layer: A layer consisting of a green-sensitive silver chlorobromide emulsion shown in Table 1, an emulsified dispersion prepared by dissolving magenta coupler and 2.5-t-octylhydroquinone in dioctyl phthalate, and a hardener ( Gelatin coating amount: 30cm per 100cm plate 9) Second layer: Protective layer consisting of the hardening agent and gelatin shown in Table 1 (20a+a per 100cm gelatin coating amount) Below margin A-1 COCH=CH.

A total of 18 types of samples prepared in this way (sample numbers 1 to 1
8) was evaluated by the method shown below, and the results are summarized in Table 2.

(1) Raw sample storage gradation change A sample stored for 3 months at 25°C and 60% relative humidity (A> and a comparative sample (B) that was not stored) was subjected to the following treatment after exposure to light, and the obtained Transfer the image to Sakura color densitometer PD
Measure the green density with A-60, and each density is 0.
．． The slope of the characteristic curve from 8 to 1.8 (γ: gamma) γ
A1γB was determined.

The gradation change during storage of the raw sample was determined by Δγ-γ8-γA.

Below is the margin [Standard processing process (processing temperature and processing time)] [11 Color development 38℃ 3 minutes 30 seconds [2] Bleach person 3
3℃ 1 minute 30 seconds [3] Water washing treatment 25-30℃ 3
Minutes [4] Drying 75-80°C Approximately 2 minutes In the treatment process, the composition of the treatment liquid used is as follows.

[Color development tank liquid] Benzyl alcohol 15ml, & ethylene glycol 15ml Potassium sulfite 2.0g Potassium bromide
0.7g sodium chloride
0.2 (1 potassium carbonate
30. OQ Hydroxylamine Sulfate
3.0g polyphosphoric acid (TPPS)
2,503-Methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl)-aniline sulfate 5.5g Optical brightener (4,4'-diaminostilbenzsulfonic acid derivative) 1. 0 (Potassium monohydroxide 2.0g Add water to bring the total amount to 11, and adjust the pH to 10.20.

[Bleach-fix solution] Ethylenediaminetetraacetic acid ferric ammonium dihydrate 609 Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% solution) 100m Ammonium thiosulfite (40% solution)
% solution > 27.5 all Adjust to pl-17.1 with potassium carbonate or glacial acetic acid, add water and bring the total volume to 1J1
Set it to 2.

Below are the margins (2) Raw sample preservation desensitization (1) Raw sample preservation gradation change (3) Raw sample preservation fog (1) Raw sample preservation Ra gradation change Samples prepared in the same way as unexposed Process as is and remove fog with Sakura color densitometer PDA
The green density was measured using a -60 model.

Raw sample storage fog - Storage sample fog - Comparison sample fog (4) The unexposed Y-stin sample was processed as described above, and the prepared sample was transferred to the Sakura Color Density Light PDA-60 model (manufactured by Konishiroku Photo Industry Co., Ltd.). After measuring the blue concentration (DB), the sample was heated to 77°C.
20 days Y-stin D-B1 under no humidification condition
It can be found from 0.

If the margin raw sample preservation gradation change below β is 0.3 or more, the image quality of Color Punto will change greatly and the print yield will be significantly reduced.

In addition, if the raw sample storage fog is 0.03 or less, good image quality can be obtained at a high yield.

The raw sample storage desensitization is preferably 5% or less. If the Y-stin is o or io or higher, the image quality will be significantly impaired after being stored in a dark place for a long period of time.

From the results shown in Table 2, the sample of the present invention (sample number 1
9 and 15.16) and the sample using the comparative magenta coupler (sample number 17.18), it can be seen that good results were obtained. Of course, compared to the sample of the present invention, the sample using the comparative magenta coupler produced more Y-stin on the white background when stored in the dark for a long period of time, indicating that only the sample of the present invention was superior overall. understood.

Example 2 A total of 20 types of samples were prepared by coating the following 1st to 7th layers on a reflective support made of polyethylene-coated paper containing titanium oxide.

First layer: blue-sensitive silver chlorobromide emulsion layer A silver chlorobromide emulsion containing 5 mol% of silver chloride, yellow coupler (Y-1) and 2,5-di-t-octylhydroquinone. Coating was performed using an emulsified dispersion prepared by dissolving in dioctyl phthalate.

Second layer: First intermediate layer was coated using an emulsified dispersion prepared by dissolving 2.5-di-t-octylhydroquinone in dioctyl phthalate.

Third layer... Green-sensitive silver chlorobromide emulsion layer The silver chlorobromide emulsion shown in Table 4, the magenta coupler shown in Table 4 and 2,5-di[-octylhydroquinone shown in Table 4] Coating was carried out using an emulsified dispersion prepared by dissolving in a high boiling point solvent.

4th layer... Second intermediate layer UV absorber (tJV-1) and an emulsified dispersion prepared by dissolving 2.5-di-t-octylhydroquinone in dioctyl phthalate are used, and are shown in Table 4. It was coated using a hardening agent.

5th layer...Red-sensitive chlorobromide emulsion layer Silver chlorobromide emulsion containing 30 mol% of silver chloride, cyan coupler (C-1) and 2,5-di-t-octylhydroquinone as dioctyl phthalate The coating was applied using an emulsified dispersion prepared by dissolving the liquid.

Sixth layer...Third intermediate layer An emulsified dispersion prepared by dissolving an ultraviolet absorber (UV-1) and 2,5-di-t-octylhydroquinone in dioctyl phthalate was used to coat the layer.

7th layer...Protective layer 1 using mainly gelatin and the hardening agent shown in Table 4.
Established.

Table shows the amount of ingredients in each layer (mg amount per 100cn+)
Shown in 3.

Margin below (Y-1) C1 A total of 20 types of samples prepared in this way (sample number 19
-38) were evaluated in the same manner as in Example 1.

In addition, the glossiness was evaluated as follows.

(5) Glossiness An unexposed sample was subjected to the treatment shown in Example 1, and the glossiness of the sample surface was measured using a crossmeter manufactured by Tokyo Denshoku Co., Ltd.

The results are summarized in Table-5.

If the margin glossiness is not 90% or more, there will be visual problems and the image quality will be greatly impaired.

From the results shown in the table, samples of the present invention (sample numbers 19 to 33)
and a sample using a comparative magenta coupler (Sample No. 3
7.38) obtained good results.

However, of course, the sample using the comparative magenta coupler had a large occurrence of Y-stin on the white background when stored in the dark for a long period of time, confirming that the sample of the present invention was overall superior.

Patent applicant: Konishi Roku Photo Industry Co., Ltd. Procedural amendment (self-imposed December 6, 1985, 1985 Patent Review No. 91586 2, Name of invention: Silver halide photographic light-sensitive material 3, Person making the amendment Relationship with the case) Patent applicant address: 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name (1)
27) Roku Konishi Photo Industry Co., Ltd. Representative Director Keio Ide 4, Agent 102 Address Kudan-Rosaka Building, 4-1-1 Kudankita, Chiyoda-ku, Tokyo Telephone 263-9524 (1) Specification No. 239] Compound The structural formula of M-2 is corrected as follows.

(2) On page 243 of the specification, 4th hit: ``Amendment for Procedures Over Raw Sample Storage Area'' (Own Ship July 19, 1985 Patent N No. 91586, 1985 2゜ Silver Rodenide Photographic Sensitivity to Title of Invention) Material 3, Relationship with the person making the amendment Patent applicant address 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name (1
27) Konishiroku Photo Industry Co., Ltd. Representative Director Keio Benko 4, Agent 102 Address Kudan-Rosaka Building, 4-1-1 Kudankita, Chiyoda-ku, Tokyo Telephone 263-9524 Name (7614) Patent Attorney Miyao Ichinose ( 1
) "The vinyl sulfone hardener is 20% to 80% by weight" on page 105 of the specification #IJ line 10 is changed to "The vinyl sulfone hardener is 20% to 80% by weight of the total hardener" to correct.

that's all

Claims (1)

[Scope of Claims] In a silver halide photographic material having at least one silver halide emulsion layer on a support, at least one of the silver halide emulsion layers contains a magenta coupler represented by the following general formula [I]. , further hardened using a combination of at least one of the hardeners represented by the general formulas [XII] and [XIII] and a vinyl sulfone hardener. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. You may. X represents a hydrogen atom or a substituent that can be separated by reaction with an oxidized product of a color developing agent. R represents a hydrogen atom or a substituent. ] General formula [XII] ▲ Numerical formulas, chemical formulas, tables, etc. ) or -NR'R'', -NHCOR'''(R',R'' and R
``' represents a hydrogen atom, an alkyl group, or an aryl group, respectively), and R_2_2 has the same meaning as R_2_1 excluding a chlorine atom.] General formula [XIII] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [ In the formula, R_2_3 and R_2_4 are a chlorine atom, a hydroxy group, an alkyl group, an alkoxy group, or an -OM group (
M represents a monovalent metal atom). Q and Q' represent a linking group representing -O-, -S-, -NH-, and L represents an alkylene group or an arylene group. l and m each represent 0 or 1. ]