JPS62184458A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide emulsion layer suppressed in yellow stains due to humidity and heat during storage by incorporating a magenta coupler and a specified compound in at least one of said emulsion layers. CONSTITUTION:At least one of the silver halide emulsion layers of a silver halide photographic sensitive material formed on a support contains the magenta coupler and the compound represented by the formula I in which each of R1 and R2 is H, an aliphatic or aromatic group, or they may combine with each other to form a cyclic aliphatic group; R3 is an aliphatic or aromatic group; R4 is H, an aliphatic or aromatic group, or -(J2)n-COOR5; R5 is an aromatic group; each of J1 and J2 is a divalent bonding group; and each of m and n is 0 or 1. The magenta coupler is represented by formula II in which Z is a nonmetallic atomic group necessary to form an N-containing ring; X is H or a substituent to be released by reaction with the oxidation product of a color developing agent; and R is H or a substituent.

Description

[Detailed description of the invention] [Industrial application field].

The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material with improved yellowing caused by humidity.

[Background of the Invention] After a silver halide color photographic light-sensitive material is exposed to light,
Developed using an aromatic primary amine color developing agent,
A dye image is formed by the reaction between the oxidized form of the coloring agent and the coupler. In this method, usually yellow,
Acylacetamide or benzoylmethane yellow couplers, pyrazolone, cyanoacedel, indacylon or pyrazolotriazole magenta couplers, respectively, to form magenta and cyan dye images;
Phenol or naphthol-based cyan couplers are used.

The resulting dye image consists of an azomethine or indoaniline dye formed by the reaction of an oxidized color developing agent with a coupler.

The color photographic images obtained in this way are usually stored for a long time as records or exhibited, but the non-colored parts of the dye images, that is, the white background, are not necessarily stable against light, heat, and humidity. Exposure to light for long periods of time or storage in high temperature and humidity may cause discoloration of the white background and deterioration of image quality.

If the resulting color photographic image is exposed to light for a long time, or stored or displayed in high temperature and humidity, the white background will turn yellow (
Hereinafter referred to as Yellowstin. ) phenomenon is well known.

This phenomenon is mainly due to the decomposition of magenta coupler contained in silver halide photographic materials, and is also reported in the Journal of American Photographic Science (J.

A, P, S, ) 5,200 (1979), R, J, Tuit
e) reports that yellow stain is produced using a magenta coupler as a starting material.

As specific methods for preventing yellow stain, studies have been conducted to develop magenta couplers that are resistant to decomposition under light and high temperature and humidity, and to search for compounds that prevent yellow stain on white backgrounds.

Examples of compounds conventionally known as compounds that prevent yellow stain include antioxidants, such as 2.
Hydroquinone derivatives including 5-di-t-butylhydroquinone, 2,6-di-t-butyl-p-cresol, 4.4'-methylenebis(2,6-di-t-butylphenol), 2.2'- There are compounds such as phenol derivatives such as methylenebis(4-ethyl-6-t-butylphenol) and 4,4'-isopropylidenediphenol, and tocopherol. These compounds such as hydroquinone derivatives, phenol derivatives, and tocopherols were substantially ineffective in preventing yellow stain caused by humidity and heat during storage.

On the other hand, a metal complex is used in the magenta coupler-containing layer for the purpose of improving light resistance, but although the use of gold FAI improves light resistance, it has the disadvantage of increasing yellow stain. .

Therefore, a silver halide photographic material that does not generate yellow stain due to humidity and heat during storage has been desired.

[Object of Chewing] An object of the present invention is to provide a silver halide photographic material with improved yellow stain caused by humidity and heat during storage.

[Structure of the Invention] An object of the present invention is to provide a silver halide photographic material having at least one silver halide emulsion layer on a support, in which at least one of the silver halide emulsion layers contains a magenta coupler and the following general This was achieved using a silver halide photographic material containing the compound represented by formula (1).

In the formula, R1 and R2 each represent a hydrogen atom, an aliphatic group or an aryl group. Further, R1 and R2 may be combined to form a cycloaliphatic group.

R3 represents an aliphatic group or an aryl group. R4 is a hydrogen atom, an aliphatic group, an aryl or +J2+VCooR5
(R5 represents an aliphatic group or an aryl group), aJ+ and J2 each represent a 21iffi linking group. m and n each represent 0 or 1.

[Specific Configuration of the Invention] The magenta coupler used in the present invention will be explained.

Examples of magenta couplers used in the present invention include 5-pyrazolone type, cyanoacetophenone type, indashilon type, pyrazolinobenzimidazole type, and pyrazolotriazole type couplers.

These magenta couplers are described, for example, in U.S. Pat.
No. 600.788, No. 3,062,653, No. 3
, No. 684.514, No. 1,183,515, Belgian Patent No. 1.130,287, Special Publication No. 1973-265
No. 89, No. 45-20036, No. 45-41473
No. 49-111631, etc.

Preferable magenta couplers used in the present invention are magenta couplers represented by the following general formulas [XIl, ] and [I], and particularly preferable are the magenta couplers represented by the general formula [I]
Magenta coupler Y2 Y.

In the above general formula [X[], methoxy group, ethoxy group, etc.), aryloxy M (e.g. phenoxy group, etc.),
Represents an amide group (eg, acetylamide group, etc.), hydroxy group, amino group, or nitro group, and Yl, Y2, and Y3 are each a hydrogen atom, a halogen atom, (eg, a chlorine atom, etc.)1. Alkyl groups (e.g. methyl, ethyl, etc.), alkoxy groups (e.g. methoxy, ethoxy, etc.), carboxyl groups, alkoxycarbonyl groups (e.g. ethoxycarbonyl, etc.), dil-0 groups, aryloxy groups (e.g. phenyl) oxy group, etc.), cyano group or acylamino group (e.g. acetylamino group, etc.);
l is a hydrogen atom, a halogen atom (for example, a chlorine atom, etc.)
or 1 lilli organic group.

Z2 represents an atom or group that is separated upon coupling.

A is -NH-1-NHCO-1-CONH- or -
Represents NHCONH-.

Examples of the monovalent organic group represented by Wl include a nitro group, an alkyl group including those each having a substituent, an alkoxy group, an acylamino group, a sulfonamide group, an alkylcarbamoylurbamoyl group, an alkylsulfayl group, and an arylsulfayl group. Famoyl group, alkylsuccinimide group, alkoxycarboxamide group, alkoxycarboalkylaminoamino arylaminocarboalkylaminoaralkylaminocarboalkylamino are preferred.

Examples of magenta couplers represented by general formula [XII] are listed below.

The following margins are exemplified magenta couplers MC-4CL MC-5 MC-6 CHs t MC-8 MC-1C-8 MC-10ct The following margins are General formula [I] Y In the general formula [I], 2 is a nitrogen-containing m element Represents a group of nonmetallic atoms necessary to form a ring, and the ring formed by Z is set! ! may have a group.

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

Further, R represents a hydrogen atom or a substituent.

Examples of the substituent represented by R include a halogen atom,
Alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkynyl group, aryl group, heterocyclic group, acyl group, sulfonyl group, sulfinyl group, phosphonyl group, carbamoyl group, sulfamoyl group, cyano group,
Spiro compound residue, bridged hydrocarbon compound residue, alkoxy group, aryloxy group, heterocyclic oxy group, siloxy group, acyloxy group, carbamoyloxy group, ami7 group, 7syl7mi7 group, sulfonamide group, Examples include imide group, ureido group, sul7amoylamy7 group, flukoxylponyl7m7 group, aryloxycarbonyl7m7 group, alkoxycarbonyl group, aryloquinylcarbonyl group, furkylthio group, 7lylthio group, and heterocyclic thio group. It will be done.

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

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

In addition, these alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, and cycloalkenyl groups include monosubstituted groups (e.g., aryl, Schiff), halogen atoms, heterocycles, dichlorofurkyl, cycloalkenyl, spiro compound residues, and bridged hydrocarbons. In addition to compound residues, those substituted via a carbonyl group such as acyl, carboxy, carbamoyl, flukoxycarbonyl, and 7-aryloxycarponyl, and those substituted via a heteroatom, hydroxy, alkoxy, aryloxy, heterocyclic oxy,
Those substituted via an oxygen atom such as siloxy, acyloxy, carbamoyloxy, nitro, amino (including cyfurkyl 7mino, etc.), sul77moyl7mino, alkoxycarbonylamino, aryloxycarbonylamino, acylamino, sulfonamide, Those substituted through a nitrogen atom such as imide and ureido, alkylthio, arylthio, heterocyclic thio, sulfonyl, sulfinyl,
[1] such as those substituted via a sulfur atom such as sulf77moyl, and those substituted via a phosphorus atom such as phosphonyl.

Specifically, for example, methyl group, ethyl group, isopropyl group, L-butyl group, pentadecyl group, heptadecyl group, 1
-hexylnonyl group, 1,1'-dipendylnonyl JC
-9-/F m n-Ichiban Ichigo Honsai Ito 1J Fluoromethyl group, 1-ethoxytridecyl group, 1-methoxyinpropyl group, methanesulfonylethyl group, 2.4-not-7milphenoxy group dimethyl group, anilino group, 1-phenylisopropyl group, 3-m-butanesulfonaminophenoxyprobyl group, 3-4'-1cI (4"(p
-hydroxybenzenesulfonyl)phenoxy]dodecanoylamino)phenylpropylIt, 3-14'-(
α-(2”,4”-di-t-amylphenoxy)butanamiP)phenyl)-propyl group, 4-(α-(0-chlorophenoxy)tetradecanamidophenoxy)propyl group, allyl group, cyclopentyl group, cyclohexyl Examples include groups.

The aryl group represented by R is preferably a phenyl group, which may have a substituent (for example, a furkyl group, an alkoxy group, a 7-syl amino group, etc.).

Specifically, phenyl group, 4-t-butyl 7-enyl group,
2!4-di-t-7mylphenyl group, 4-tetradecanamidophenyl group, hexadecyloxyphenyl group, 4'
-[α-(4″-t-butyl heptanoxy)tetradecanamide] phenyl group and the like.

The heterocyclic group represented by R is preferably a 5-7 ring group, and may be substituted or fused.

Specific examples include 2-furyl group, 2-chenyl group, 2-pyrimidinyl group, and 2-benzothiazolyl group.

Examples of the acyl group represented by R include acetyl group, phenyl 7cetyl group, dodecanoyl group, α-2,4-di-
Examples thereof include a furkylcarbonyl group such as a t-amylphenoxybutanoyl group, a 7-arylcarbonyl group such as a benzoyl group, a 3-pentadecyloxybenzoyl group, and a p-chlorobenzoyl group.

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 group and p-)luenesulfonyl group.

The sulfinyl group represented by R includes alkylsulfinyl i, 7z such as ethylsulfinyl group, octylsulfinyl group, and 3-phenoxybutylsulfinyl group.
Nylsulfinyl i, l-pentadecylphenylsulfinyl group! '717-Rusulfinyl group and the like.

The phosphonyl group represented by R includes 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. Examples include arylphosphonyl groups such as.

The carbamoyl group represented by R may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc.
For example, N-methylcarbamoyl, N,N-dipylcarbamoyl, N-(2-pentadecyloctylethyl)carbamoyl, N-ethyl-N-dodecylcarbamoyl, N-+3-(2,4-not- Examples include 7-methylphenoxy)propyl)carbamoyl group.

The sulfamoyl group represented by the margin R"ch below may be substituted with an alkyl group, a 7-aryl group (t? or phenyl group), etc., such as an N-propylsulfamoyl group, N, N-
Examples thereof include a noethylsulf77moyl group, an N-(2-pentadecyloxy, ethyl)sulfamoyl group, an N-ethyl-N-dodecylsulfamoyl group, and a N-phenylsulf77moyl group.

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

Examples of the bridged carbonized compound residue represented by R include bicyclo[2,2,1]heptan-1-yl, tricyclo[3
, 3,1,1co°7]decane-1-yl, 7,7-nomethyl-bicyclo[2,2,11butan-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 and 2-ethoxy group.

The aryloxy group represented by R is preferably 7enyloxy, and the aryl nucleus may be further substituted with the substituents or atoms listed above for the aryl group,
For example, phenoxy group, p- is -butylphenoxy group, m
-pentadecylphenoxy group and the like.

The heterocyclic oxy group represented by R preferably has 5 to 7 heterocyclic rings, and the heterocyclic ring may further have a substituent (for example, 3°, 4.5.6- Examples include tetrahydropyranyl-2-oxy group and 1-phenyltetrazol-5-oxy group.

The siloxy group represented by R may be further substituted with an alkyl group, and examples thereof include a lyntylsiloxy group, a triethylsiloxy group, a dimethylbutylsiloxy group, and the like.

Examples of the acyloxy group represented by R include a furkylcarbonyloxy group, a carbonyloxy group, a carbonyloxy group, and a carbonyloxy group.
1-II tatami + 7) Pattern: Lightning by Hajime Imagure! Nine plasters may also be used, and specific examples include acetyloxy, a-chloroacetyloxy, and benzoyloxy groups.

The carbamoyloxy group represented by R″C′ may be substituted with an alkyl group, an aryl group, etc., such as N-ethylcarbamoyloxy group, N,N-noethylcarbamoyloxyi, N-phenylcarbamoyloxy Examples include groups.

The ami7 group represented by R may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as an ethyl7mino group, an anilino group, a 1-chloroanily7 group,
Examples include 7 groups of 3-pentadecyloxyluponylanily, and 7 groups of 2-chloro-5-hexadecaneamide anily.

Examples of the acylamine 7 group represented by R include alkylcarbonyl amine 7 groups, arylcarbonyl 7mino groups (preferably phenylcarbonyl 7mino groups), and may further have a substituent (specifically, is an a7doamide group, an a-ethylpropanamide group, an N-phenyl7ceto7mido group,
Dodecane 7mido i, 2,4-di[-amylphenoxyace)7mido group, α-3-t-butyl 4-hydroxy 7
Examples include eth/xybutane 7-mido group.

Examples of the sulfone 7 mido group represented by R''Ch include furkylsulfonyl amide 7 groups and arylsulfonyl amide 7 groups, and may further have a substituent group.

Specifically, 7 groups of methylsulfonylamine, 7 groups of pentadecylsulfonylamine, and 7 groups of benzenesulfone)'i, p-
) Luenesulfonamide group, 2-methoxy-5-t-7
Examples include milbenzenesulfone 7-mido group.

The imide group represented by R may be open-chain or cyclic, and may have a substituent, such as a succinimide group, a 3-heptadecylphuccinimide group, a 7-talimide group, etc. , glutarimide group, and the like.

The ureido group represented by R is a furkyl group, a 7-aryl group (
(preferably phenyl group), etc., for example, N-ethylureido group, N-methyl-N-decylureido group, N-722lureido group, N-p-)lylureido group, etc. Can be mentioned.

The sulfT moyl 7 group represented by R is a furkyl group,
It may be substituted with an aryl group (preferably a phenyl group), and examples thereof include N,N-dibutylsul7amoylami7 group, N-methylsul77moylaminoi, N-phenylsul77moyl7moyl7 group, and the like.

The alkoxycarbonylamino convex represented by R″t′ may further have a substituent, such as a methoxycarbonylamino group, a methoxyethoxycarbonyl 7-mino group, an octadecyloxycarbonyl 7-mino group, etc. .

The aryloxycarbonyl 7mino group represented by R may have a substituent, and examples thereof include phenoxycarbonyl 7mino group and 4-methyl 7e/xycarbonyl 7mino group.

The alkoxycarbonyl group represented by R may further have a substituent, such as a methoxycarboxycarbonyl group, an octadecyloxycarbonyl group, an ethoxymethoxycarbonyloxy group, a benzyloxycarbonyl group, and the like.

The aryloxycarbonyl group to be substituted by R''ch may further have a substituent, such as a 7-enoxycarbonyl group, p-chlorophenoxycarbonyl group, -1pentadecyloxy7dinoxycarbonyl group, etc. .

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 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-octylphenylthio group, 3-octadecylyarynylthio group, 2-carboxyphenylthio group, and p-a7todoaminophenylthio group.

A shellfish heterocyclic thio group is preferred, and may further have a condensed ring or a substituent. Examples include 2-pyridylthio group, 2-benzothiazolylthio group, and 2,4-nophenoxy(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.

Groups substituted via a carbon atom include, in addition to carboxyl groups, for example, the general formula (R1' is the same as the above R, Z' is the same as the above Z, R2' and R3' are hydrogen atoms, group, an alkyl group or a heterocyclic group, a group represented by ), a human miximethyl group, and a toIJ phenylmethyl group.

Examples of groups that can be replaced via an oxygen atom include an alkoxy group, an aryloxy group, a heterocyclic oxy group, a 7-syloxy group, a sulfonyloxy group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an alkyloxalyloxy group, and an alkoxyoxalyl group. An example is an oxy group.

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

The aryloxy group is preferably a phenoxy group, and the aryl group may further have a substituent, specifically, a phenoxy group, a 3-methyl 7eth/oxy group, a 3-
dodecylphenoxy group, 4-methanesulfonamidophenoxy group, 4-(α-(3'-pentadecylphenoxy)butanamido]phenoxy group, hexydecylcarbamoylmethoxy group, 4-cyanophenoxy group, 4-methanesulfonylphenoxy group, 1-s7tyloxy group, p-
Examples include nodoxyphenoxy group.

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

The acyloxy group includes, for example, an acetoxy group, a fulkylcarbonyloxy group such as a butazuroxy group, an alkenylcarbonyloxy group such as a nnnamoyloxy 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 alkoxycarbonyloxy group include an ethoxycarbonyloxy group and a benzyloxycarbonyloxy group.

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

Examples of the alkyloxalyloxy group include a notyloxalyloxy group.

Examples of the alkoxyoxalyloxy group include an ethoxyoxalyloxy group.

Examples of groups substituted via a sulfur atom include alkylthio groups, arylthio groups, heterocyclic thio groups, and flukyloxythiocarbonylthio groups.

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

The arylthio group includes phenylthio group, 4-methanesulfonamidophenylthio group, 4-dodecyl7enethylthio group, 4-7su7fluoropentane7mido7enethylthio 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 general formula -N include aryl groups, heterocyclic groups, sulfamoyl groups, carbamoyl groups, 7-syl groups, sulfonyl groups, aryloxycarbonyl groups, and alkoxycarbonyl groups, and R4' and R7' are May be combined to form a heterocycle, provided that R, 7 and R5
' cannot both be hydrogen atoms.

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 f1 substituent include a 7-aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylami 7 group, and an arylami 7 group.
group, acylamide 7 group, sulfonamide group, imino group, acyl group, alkylsulfonyl group, arylsulfonyl group, carbamoyl group, sulfonamide group, alkoxycarbonyl group, aryloxycarbonyl group, alkyloxycarbonylamide 7 group, aryloxy Examples include carbonyl amine 7 groups, hydroxyl groups, carboxyl groups, cyano groups, and halogen atoms.

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 (substituents include those listed above as substituents for the alkyl group represented by R4' or Rs' and an alkyl group.Specific examples of the aryl group include Examples include phenyl group, 1-s7tyl group, and 4-methylsulfonylphenyl group.

The heterocyclic group represented by R4' or R5' is 5 to 6
Shellfish are preferred, and may be fused rings and may have substituents. Specific examples include 2-furyl group, 2-quinolyl group, 2-pyrimidyl group, 2-benzothiazolyl group, 2- Examples include pyridyl group.

The sulfamoyl group represented by R4' or Rs/ includes N-furkylsul77moylf, N,N-noalkylsul7amoyl group, N-7lylsul7amoyl group,
Examples include N,N-diarylsul 7-amoyl group, and these furkyl groups and 7-aryl groups may have the substituents listed for the alkyl groups and aryl groups.
Specific examples of the sulfamoyl group include N,N-quethylsul7ammoyl group, N-methylsulfamoyl group, N-F7'silsulfamoyl group, and N-p-)lylsul7Tmoyl group.

The carbamoyl group represented by R4' or R,7 is,
Examples include N-furkylcarbamoyl group, N,N-dialkylcarbamoyl group, N-7arylcarbamoyl 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. It may have a substituent. Specific examples of the carbamoyl group include N,N-noethylcarbamoyl group, N-methylcarbamoyl group, N-dodecylcarbamoyl group, N-p-cyanophenylcarbamoyl group, N-
p) List the lylcarbamoyl group.

, R1'' or Rs' include, for example, a furkylcarbonyl group, a 7-arylcarbonyl group, and a heterocyclic carbonyl group, and the alkyl group, the
The heterocyclic group may have a substituent. Specific examples of the acyl group include hexafluorobutanoyl group, 2゜3.4,5.6-pentafluorobenzoyl group, acetyl group, benzoyl group, naphthonyl group, 2-furylcarbonyl group, etc. .

Examples of the sulfonyl group represented by R4' or R5' include an alkylsulfonyl group, an arylsulfonyl group, and a heterocyclic sulfonyl group, which may have a substituent, and specific examples include ethanesulfonyl. group, benzenesulfonyl group, octanesulfonyl group, naphthalenesulfonyl a, p-90 rubenzenesulfonyl group, and the like.

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 R may have the substituents listed above for the alkyl group, and specific examples include /toxycarbonyl group, dodecyloxycarbonyl group, benzyloxycarbonyl group etc.

The heterocycle formed by combining R4' and zoR5' is preferably one with 5 to 6 shells, and may be saturated or -unsaturated, and may or may not have aromaticity. Examples of the heterocycle, which may be a fused ring, include an N-7 talimide group, an N-succinimide group, a 4-N-urazolyl group, a 1-N-hyguntoynyl group, and a 3-N-2,4- Dioquinoxazolidinyl group, 2-N-1,1-dioxo-3-(2H)-oxo-1,2-benzthiazolyl group, 1-pyrrolyl group, 1-pyrrolinonyl group, 1-pyrazolyl group, 1- piperidinyl group, 1-piperinonyl group, 1-
Pyrrolinyl group, 1-imidazolyl group, 1-indolyl group, 1-indolyl group, 1-isoindolinyl group, 2-ineindolyl group, 2-isoindolinyl group, 1-benzotriazolyl group, 1-pencyimigzolyl group , 1-(1
,2,4-)riazolyl) group, 1-<1.2.3-)
+77 zolyl) group, 1-(1,2,3,4-teFrazolyl) group, N-morpholinyl group, 1,2,3.4-tetrahydroquinolyl group, 2-oxo-1-pyrrolidinyl group,
2-IH-pyridone group, 7thalathion group, 2-oxo-
1-piperidinyl groups, etc., and these heterocyclic groups include alkyl groups, aryol groups, alkyloxy groups, aryloxy groups, acyl groups, sulfonyl groups, alkylamino groups, 7 arylamino groups, and 7 acylamino groups. , sulfonamide 7
group, carbamoyl group, sulfamoyl group, alkylthio group, arylthio group, ureido group, alkoxycarbonyl group, 7lyloxycarbonyl group, imido group, nitro group, cyano group, carboxyl group, halogen atom, etc.

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

, 2, general formula (1) and general formula (II) to be described later ~ [■
) on the heterocycle (for example, R.

When R1-R1) has a moiety (here, R'', included in

Further, the ring formed by z, z', z'' and 21 described below may be further fused with another ring (for example, 5 to 7 dichloroflukenes).For example, in general formula (V), R3 and R6 are R, and R in general formula (Vl)
1 may be bonded to each other to form a ring (for example, 5 to 7 shell dichloroflukene, benzene).

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

General formula (III) General formula (II) N -N -N General formula [■] N -N -Nl (General formula (V) General formula (W) N -N -NH General formula [■] General formula (II) ) ~ [■] R1-R8 and X
has the same meaning as R and X above.

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

General formula [■] In the formula, R, , X and 2. has the same meaning as RlX and Z in general formula CI).

Among the magenta couplers represented by the general formulas (n) to [■], particularly preferred is the magenta coupler represented by the general formula (II).

Regarding the substituents on the heterocycle in general formulas (1) to [■], R in general formula (1) and RI in general formulas [■] to [■] satisfy the following condition 1. It is preferable that the following conditions 1 and 2 are satisfied, and even 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 bonds between the carbon atom and adjacent atoms are single bonds.

The most preferred substituents R and R1 on the heterocycle are those represented by the following general formula ([).

General formula (II R1 R3゜-C- RI where R,,R, and RII are each a hydrogen atom)1
0 den atom, alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkynyl group, 717-l group, heterocyclic group, acyl group, sulfonyl group, sulfinyl group, phosphonyl group, carbamoyl group, sulfamoyl group, cyano group , spiro compound residue, bridged hydrocarbon compound residue, alkoxy group, 717-loxy group, heterocyclic oxy group, siloxy group, acyloxy group, carbamoyloxy group, ami7 group, acyl 7mi7 group, sulfonamide group , represents an imido group, a ureido group, a 7-amoylamino group, an alkoxycarbonylamino group, a 7-aryloxycarbonylamino group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylthio group, an arylthio group, a heterocyclic thio group, R91R1, +1 and at least two of R1 are not hydrogen atoms. and two of R11, for example R1
and R1° may be combined to form a saturated or unsaturated ring (e.g., cycloalkane, cycloalkene, heterocycle), and R1 may be further combined with the ring to form a bridged hydrocarbon compound residue. It's okay.

The group represented by R5-R1 may have a substituent, and specific examples of the group represented by R5 to R11 and the substituent that the group may have include the above-mentioned general formula ( Specific examples of the group represented by R in 1) and substituents are listed.

Also, for example, a ring formed by combining R3 and RIo and R9
Specific examples of the bridged hydrocarbon compound residue formed by ~R11 and its optional substituents include the cycloalkyl, cycloalkenyl, and heterocyclic groups represented by R in the general formula (1) above; Specific examples of hydrocarbon compound residues and their substituents are listed.

Among the general formulas ([X], (i) R, ~
When two of RI+ are furkyl groups, (ii) R=~
One of RI +, for example R1, is a hydrogen atom,
When the other 2Rs and R10 combine to form dichlorofurkyl with the root carbon atom, the following is true.

Furthermore, it is preferable among (i) that two of Rg to R1+ are alkyl groups and one of the groups is a hydrogen atom or an alkyl group.

Here, the alkyl and the cycloalkyl may further have a substituent. Specific examples of the alkyl, the cycloalkyl, and the substituent thereof include R II in the general formula (13).
Specific examples of furkyl, cycloalkyl and their substituents represented by / are listed.

In addition, substituents that the ring formed by Z in general formula (1) and the ring formed by Zl in general formula [■] may have, and R in general formulas [U] to (Vl)
As 2-R8, those represented by the following general formula (X) are preferable.

General formula (X) -R'-5Q, -R'' In the formula, R1 represents alkylene and R'' represents alkyl, cycloalkyl or aryl.

The alkylene represented by R1 preferably has 2 or more carbon atoms in the straight chain portion, more preferably 3 to 6 carbon atoms, and the straight chain portion has 1 or more carbon atoms.
This alkylene may have any substituents.

Examples of the substituent include R in the general formula (I) described above.
When is an alkyl group, examples of the ra substituents that the furkyl 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 is 1llf frt, and the branch is 1.

Specifically, methyl, ethyl, propyl, 1so-propyl, butyl, 2-ethylhexyl, octyl, dodecyl, tetradecyl, hexatenyl, oftagyl, 2-
Examples include hexyldecyl.

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

The alkyl and dichlorofurkyl 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, and examples of the substituent include, for example, a head-shaped or branched furkyl group, as well as those exemplified as the substituent for R1 described above.

Moreover, when there are two or more substituents, those substituents may be the same or different.

Among the compounds represented by the general formula [I], particularly preferred are those represented by the following general formula (XI).

The general formula is] In the formula, R and X are synonymous with R and X in general formula (1), and R' and R2 are R'IR2 in general formula [X]
is synonymous with

Specific examples of compounds used in the present invention are shown below.

Margin below OR.

C flood ■ CI(] Margin below 4H9 CH3 CH.

C.H.

2H5 C1l.

C.I.

CH.

C.I.

CI(.

CJ+s Shil,
L;5tlt(tJCI.

CsH+3 I:- CH3 OCR, C0NHCH2C1 (20CH30CH, CH
25O2CH.

I C! Hs H3 Shi2NS 10f CH3 CH.

C2H5 11f H3 Hz UJ+t(t) Ward H3 H3 12f ■ H3 CH1 ■ C? H15 H3CCH3 4B 0(CH2)20C12H2!1 N -fi -N fiNN C,. Hz+
1゛68 N N Nl1 N 2H5 ■ Also, the above coupler is gloss-op-the-chemical.
Society (Journal of the Ch)
chemical society) * Parkin (
Perkin) I (1977), 2047~
2052, U.S. Patent No. 3,725.067, JP-A-59
-99437, 58-42045, 59-16
No. 2548, No. 59-171956, No. 60-335
No. 52, No. 8G-43659, No. 6G-172982
No. 60-190779 and the like.

The couplers of this invention are typically 7% silver lodenide at 1x per mole of silver lodenide.
10-comole 1 mol, preferably 1X10-'' mol~
It can be used in the range of 8x10-' moles.

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

In the following margin, the compound represented by the general formula (1) will be explained. In the general formula (1), R1 and R2 may be the same or different, and each represents a hydrogen atom, an aliphatic group, or an aryl group. Examples of the aliphatic groups represented by R1 and R2 include alkyl groups and alkenyl groups.

The alkyl group may be 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, pentadecyl group, Examples of the alkenyl group include hexadecyl group, heptadecyl group, and octadecenyl group. Examples of the alkenyl group include hexenyl group, heptenyl group, and octadecenyl group. Examples of the aryl group represented by R1 and R2 include phenyl group and naphthyl group. These alkyl groups,
Alkenyl groups and aryl groups each include those having substituents, and examples of substituents for alkyl groups include halogen atoms, alkenyl groups, alkoxy groups, aryl groups, aryloxy groups, alkenyl groups, alkoxycarbonyl groups, -O- Examples include P-+OR')2 (R' represents an alkyl group or an aryl group).

Examples of the substituent for the alkenyl group include the same substituents as for the alkyl group except for the alkenyl group, and an alkyl group. Examples of substituents for the aryl group include those similar to the substituents for the alkyl group described above except for the aryl group, and alkyl groups.

Furthermore, R1 and R2 may be combined to form a cycloaliphatic group (for example, a cycloalkenyl group).

Preferred R1 and R2 are each a hydrogen atom.

R3 represents an aliphatic group (for example, an alkyl group, an alkenyl group, etc.) or an aryl group. Specific examples of these alkyl groups, alkenyl groups, aryl groups, etc. include those mentioned above for R1 and R2. Further, each of these groups includes those having a substituent, and specific examples of the substituent include the same as those for R1 and R2 described above.

Preferred as R3 are aliphatic groups, particularly preferred are alkyl groups.

R4 is a hydrogen atom, an aliphatic group, an aryl group, or fJ2
rCOORs (Rs represents an aliphatic group or an aryl group), and specific examples of the aliphatic group and aryl group represented by R4 and R5 include the above-mentioned R1
and R2, and each of these groups also includes those having a substituent, and specific examples of the substituent include the same as R1 and R2 above.

Preferred as R4 is -f-J 2-b “-COOR
5, and it is particularly preferable that R5 is an aliphatic group, especially an alkyl group.

Jl and J2 each represent a divalent linking group, but 2
Preferred as the valent M group are alkylene groups (eg, methylene group, ethylene group, etc.).

In general formula (1), R3 and R4 including substituents
The total number of carbon atoms in the group represented by is preferably 8 to 30, particularly preferably 12 to 20.

Typical specific examples of the compound represented by the general formula (1) are shown below, but the invention is not limited thereto.

Margin below -I HCC00CxHsHC-
COOC-Hs M-2HC-COOC,H.

HCC00C48* M-3HC-COOCaH,.

HCC00C*H+t M-4HC-COOC,H.

H,C,00C-CH M-5HC-C00C*H+t I M-8CH2=C-C00CH2CH20-P→OC4
Hs) 2CH.

M-9CH, =CH-C00CH, CH20-P-+O
C, HI)! h4-10 CH2=C-C00CHz
CHzO-is→OC,H, ).

CH・0 M−11CH,=CH−C00CH2CH,0−P−+
Oc, H,, ) m or less margin The layer used of the compound represented by the general formula (1) has a preferable ratio of 0.25 to 2 double mother to 11 of the magenta couplers, and 0.5 to 1.5 double G The ratio of is more preferable.

In the silver halide photographic light-sensitive material of the present invention, at least one of the silver halide emulsion layers contains the magenta coupler and the compound represented by general formula (1). As a method for adding it to a photosensitive material, there is, for example, an oil-in-water emulsion dispersion method. In the oil-in-water emulsion dispersion method, a magenta coupler is dissolved in the compound represented by the general formula (1), and a surfactant is used in a hydrophilic binder such as an aqueous gelatin solution using a stirrer, a homogenizer, a colloid mill, or a flow controller. It may be emulsified and dispersed using a dispersing means such as a jet mixer or an ultrasonic device, and then added to the desired silver halide emulsion layer.

In the present invention, when dispersing the magenta coupler, other high boiling point organic solvents may be used in combination with the compound represented by the general formula (1).

In the present invention, the high boiling point organic solvent that can be used in combination with the compound represented by the general formula (1) when dispersing the magenta coupler is preferably a compound with a dielectric constant of 6.0 or less. Examples include esters such as phthalic esters and phosphoric esters having a molecular weight of 6.0 or less, organic acid amides, ketones, and hydrocarbon compounds. Preferably, it is a high-boiling organic solvent with a dielectric constant of 6.0 or lower and 1.9 or higher and a vapor pressure of 0.5 mmH (l or lower) at 100°C.More preferably, phthalate esters in the high-boiling organic solvent are Alternatively, it is a phosphoric acid ester.Furthermore, the high boiling point organic solvent may be a mixture of two or more kinds.

Note that the dielectric constant in the present invention refers to 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 [a].

The following is a general formula [al] in which R1 and R2 each represent an alkyl group, an alkenyl group, or an aryl group. However, R1 and R
The total number of carbon atoms in the group represented by 2 is 8 to 32. More preferably, the total number of carbon atoms is 16 to 24.

In the present invention, R1 and R2 of the general formula [a]
The alkyl group represented by may be straight chain 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 R1 and R2 is, for example, a phenyl group, a naphthyl group, etc., and the alkenyl group is, for example, a hexenyl group, a heptenyl group, an 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. substituents for aryl groups include, for example, halogen atoms, alkyl groups, alkoxy groups,
Examples include an aryl group, an aryloxy group, an alkenyl group, and an alkoxycarbonyl group.

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

General formula [b] In the formula, R3, R4 and R5 are each an alkyl group,
Represents an alkenyl group or an aryl group.

However, the total number of carbon atoms represented by R3, R+ and R5 is 24 to 54.

The alkyl groups represented by R3, R4 and R5 in the general formula [b] are, for example, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group. group, pentadecyl group, hexadecyl group, heptadecyl group,
Examples of the aryl group include a phenyl group and a naphthyl group, and examples of the alkenyl group include a hexenyl group, a heptenyl group, and an octadecenyl group.

These alkyl groups, alkenyl groups and aryl groups may have single or multiple substituents. Preferably R3, R4 and R5 are alkyl groups, such as 2-ethylhexyl group, n-octyl group, 3.5.
Examples include 5-trimethylhexyl group, n-nonyl group, n-decyl group, 5ec-decyl group, 5ec-dodecyl group, t-octyl group, and the like.

Typical specific examples of organic solvents used in the present invention are shown below, but the present invention is not limited thereto.

Margin below Exemplary organic solvent error C,H.

5-12 C28S■ 0 C*H+5(i) 0C1,H21(; ) 0-C+oHz+(n) 0 =P -0-C+ o H* I(n)0-C+
oH2+(n) -2O When these high boiling point organic solvents and the compound represented by the general formula (1) are used together, the high boiling point organic solvent is used. 20011
It is preferable to use it in the range of m%, and it is particularly preferable to use it in the range of 50 to 100% by weight.

Various metal complexes can be used in the magenta coupler-containing layer of the silver halide photographic material of the present invention for the purpose of improving light resistance.

The metal complex used in the present invention has the following general formula [L-1
Those represented by 1 to [1-V] are preferred.

General formula [L-I] General formula [1-III Zo ■ General formula [L-I [[] In general formula [L-II, general formula [L-III and general formula [L-I MG represents a metal atom.

x1 and x2 each represent an oxygen atom, a sulfur atom, or -NR'- (R' represents a hydrogen atom, an alkyl group, an aryl group, or a hydroxyl group). ×3 represents a hydroxyl group or a mercapto group, Y represents an oxygen atom or a sulfur atom. R3, R4, R5
and R6 each represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an aryl group, a cycloalkyl group, or a complex m M @ bonded to a carbon atom directly or via a divalent linking group. Further, at least one of the combinations of R3 and R4 and R5 and R6 may form a 5- or 6-membered ring together with the carbon atoms that are connected to each other.

Zo is M! : Represents a compound capable of coordination or its residue. ] General formula [L-IV] [In the formula, R21, R22, R23 and R2 each represent a hydrogen atom, a halogen atom, a hydroxy group, a cyano group, or directly or indirectly on the benzene ring via a divalent linking group. Represents an alkyl group, aryl group, cycloalkyl group or heterocyclic group bonded to a carbon atom. Further, R2+ and R22, R22 and R23, or R23 and R2+ may be bonded to each other to form a 6-membered ring.

R25 represents a hydrogen atom, an alkyl group or an aryl group. A represents a hydrogen atom, an alkyl group, an aryl group or a hydroxy group. M stands for gold miko. ] The above general formula [L-11, general formula [L-n] and general formula [
1-1 [[] ×1 and ×2 may be the same or different, but each represents an oxygen atom, a sulfur atom, or -
NR? -(R7 is a hydrogen atom, an alkyl group (e.g. methyl group, ethyl group, n-propyl group, i-propyl group, n-
butyl group, t-butyl group, i-butyl group, benzyl group, etc.), aryl group (eg, phenyl group, tolyl group, naphthyl group, etc.), or hydroxyl group. ),
Preferably it is an oxygen atom or a sulfur atom, and more preferably an oxygen atom.

In the general formula [L-[[], x3 represents a hydroxyl group or a mercapto group, preferably a hydroxyl group.

General formula [L-II, general formula [1-III and general formula [
Y in L-[1 represents an oxygen atom or a sulfur atom (in the general formula [L-II, two Y's may be the same or different), preferably a sulfur atom.

General formula [1-II, general formula [L-III and general formula [
R3, R4, R5 and R6 of [L-III] may be the same or different, and may be a hydrogen atom, a halogen atom (fluorine, chlorine, bromine, iodine), a siam L direct or divalent linking group [e.g. -〇-1-S-1-N R”-1
(R7' is a hydrogen atom, a hydroxyl group, an alkyl group (e.g. methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, t-butyl group, i-butyl group, etc.)
, represents a monovalent group such as an aryl group (eg, phenyl group, tolyl group, naphthyl group, etc.). ), -0CO-5-CO
-1-NHCO-1-CONH-1-COO-1-S
02 N H-1=NH8O2-1-3O2-, etc.], an alkyl group (e.g., methyl group,
These include ethyl group, propyl group, butyl group, hexyl group, octyl group, dodecyl group, hexadecyl group, etc., and these alkyl groups may be straight chain alkyl groups or branched alkyl groups. ), aryl group (for example, LfA, phenyl group, naphthyl group, etc.), cycloalkyl group (e.g. cyclopentyl group, cyclohexyl group) or heterostyl group (e.g. pyridyl group, imidazolyl group, furyl group, chenyl group, pyrrolyl group, pyrrolidinyl group, quinolyl group, morpholinyl group, etc.). Among these, examples of the group formed by an alkyl group, aryl group, cycloalkyl group, or heterocyclic group bonded to a carbon atom via a divalent linking group together with the linking group of 21i1[i include, for example, an alkoxy group (e.g. straight-chain or branched alkyloxy groups such as methoxy, ethoxy, n-butyloxy, and octyloxy groups), alkoxycarbonyl groups (e.g., methoxycarbonyl groups,
ethoxycarbonyl group, n-hexadecyloxycarbonyl group, etc.), alkylcarbonyl group (e.g., acetyl group, valeryl group, stearoyl group, etc. linear or branched alkylcarbonyl group), aryl carbonyl group (e.g. benzoyl group etc.), alkylamino group (e.g. N-n-butylamino group, N,N-di-n-butylamino group, N,N
- straight-chain or branched alkylamino groups such as di-n-octylamino), alkylcarbamoyl groups (e.g. n-
Straight chain or branched alkylcarbamoyl groups such as butylcarbamoyl rhododecylcarbamoyl group (e.g. straight chain or branched alkylsulfamoyl groups such as n-butylsulfamoyl group, n-dodecylsulfamoyl group), alkylacyl Amino groups (e.g. linear or branched alkylcarbonylamino groups such as acedylamim L palmylamino groups), aryloxy groups (e.g. phenoxy groups, naphthoxy groups, etc.), aryloxycarbonyl groups (e.g. phenoxycarbonyl groups, naphthoxycarbonyl groups) groups), arylamino groups (
For example, N-phenylamino group, N-7enyl-N-methylamine group, etc.), arylcarbamoyl group (e.g. phenylcarbamoyl group, etc.), arylsulfamoyl group (
For example, phenylsulfamoyl group, etc.), arylacylamino group (eg, benzoylamino group, etc.), and the like.

In addition, R3, R4, R5 and R6 of general formula [1-I], general formula [L-III and general formula [1-1 [[]] are
At least one of the combinations of R3 and R4 and R5 and R6 together with the carbon atoms to which they are connected and bonded to each other is 5- or 6-membered.
It may form a ring of members.

In this case, the 5-membered or 6-membered ring formed by at least one of the combinations of R3 and R4 and R5 and R6 together with the carbon atoms to which they are bonded is, for example, a cyclopentene ring, a cyclohexene ring, a benzene ring (however, This benzene ring includes a hydrocarbon ring having at least one unsaturated bond such as a fused benzene ring (including, for example, a naphthalene ring and an anthracene ring), a heterocycle (for example, a nitrogen-containing 5- or 6-membered heterocycle), etc. Can be mentioned. These 5
When the membered or 6-membered ring has a substituent, examples of the substituent include a halogen atom (fluorine, chlorine, bromine, iodine), a cyano group, an alkyl group (e.g. methyl group, ethyl group, n-propyl group, n-butyl group, n-octyl group,
1 carbon atom such as t-octyl group, n-hexadecyl group, etc.
~20 linear or branched alkyl groups), aryl groups (e.g. phenyl group, naphthyl group, etc.), alkoxy groups (
For example, straight chain or branched alkyloxy groups such as methoxy group, n-butoxy group, t-butoxy group), aryloxy group (e.g. phenoxy group, etc.), alkoxycarbonyl group (e.g. n-pentyloxycarbonyl group, t-pentyl group, etc.) Linear or branched alkyloxycarbonyl groups such as oxycarbonyl group and n-octyloxycarbonylthyloxycarbonyl group (e.g. phenoxycarbonyl group, etc.), acyl group (e.g. linear or branched alkyl group such as acetyl group, stearoyl group, etc.) carbonyl group, etc.), acylamino group (
For example, a linear or branched alkylcarbonylamino group such as an acetamido group, a 7-aryl carbonylamino group such as a benzoylamino group), an arylamino group (such as an N-phenylamino group), an alkylamino group (such as an N-n
-butylamino group, N,N-diethylamino group, etc., straight chain or branched alkylamine 1, carbamoyl group (e.g., straight chain or branched alkylcarbamoyl group, such as n-butylcarbamoyl group, etc.), sulfamoyl group (e.g., N, straight chain or branched alkylsulfamoyl groups such as N-di-n-butylsulfamoyl I, N-n-dodecylsulfamoyl group, etc.), sulfonamide groups (straight chain or branched alkylsulfamoyl groups such as methylsulfonylamino group, etc.), Branched furkylsulfonylamino groups, arylsulfonylamine groups such as phenylsulfonylamine groups), sulfonyl groups (for example, linear or branched alkylsulfonyl groups such as mesyl groups, arylsulfonyl groups such as tosyl groups), cycloalkyl groups ( For example, cyclohexyl group, etc.) can be mentioned.

General formula [L-II, general formula [L-III and general formula C]
L-1[1] preferably represents R3, R4, R5 and R
At least one of the alkyl group, aryl group, or combination of R3 and R4 and R5 and R6 represented by 6 is selected from the group consisting of a 5- or 6-membered ring with the carbon atoms connected to each other, and Preferably, R
This is the case when the combinations of 3 and R4 and R5 and R6 form a 6-membered ring, particularly preferably a benzene ring, together with the carbon atoms to which they are connected.

Further, M in general formula [L-II, general formula [LM] and general formula [1-nl] represents a metal atom, preferably a transition metal atom, more preferably a nickel atom, a copper atom, or an iron atom. atom, a cobalt atom, a palladium atom, a platinum atom, and most preferably a nickel atom.

The compound capable of coordinating with M represented by Zo in the general formula [1-III is preferably an alkylamine having a linear or branched alkyl group, and particularly preferably an alkylamine having a total number of carbon atoms of the alkyl group of 2. ~36, even 3-2
These are dialkylamines and trialkylamines, which have 4 amines, and specific examples thereof include butylamine, octylamine (e.g. [-octylamine), dodecylamine (
monoalkylamines such as n-dodecylamine), hexadecylamine, octatoolamine, dialkylamines such as diethylamine, dibutylamine, dioctylamine, didodecylamine, jetanolamine, jetanolamine, and triethylamine, tributylamine, Examples include trialkylamines such as trioctylamine, triethanolamine, tributanolamine, and trioctaturamine.

General formula [1-II, general formula [L-III and general formula [
More preferable metal complexes according to the present invention represented by 1-1 [[] are represented by the following general formula [1-Ia], general formula [L
-I[a] and a goldfish complex represented by the general formula [L-1[[a]].

Below are the blanks General formula [L-Ia] General formula [1-I[a] O ↓ General formula [L-1 [[a] General formula [L-Ia], General formula [L-I[a] and General formula [L-I[[a], M, X', X2
, ×3, Y and zo each have the same meanings as above.

In general formula [1-Ia], general formula [L-IIa] and general formula [L-1[Ia], R11, R12, R
+3 and R14 are each an alkyl group (e.g. methyl group,
Straight chain or branched alkyl groups having 1 to 20 carbon atoms such as ethyl group, n-propyl group, n-butyl group, n-octyl group, t-octyl group, n-hexadecyl group), aryl group (e.g. phenyl group, naphthyl group, etc.), alkoxy group (e.g. straight chain or branched alkyloxy group such as methoxy group, n-butoxy group, t-butoxy group), aryloxy group (e.g. phenoxy group etc.), alkoxycarbonyl group ( For example, n-pentyloxycarbonyl group, [
-pentyloxycarbonyl group, n-octyloxycarbonyl group, (linear or branched alkyloxycarbonyl group such as -octyloxycarbonyl group), aryloxycarbonyl group (e.g. phenoxycarbonyl group, etc.), acyl group (e.g. acetyl group) , linear or branched alkylcarbonyl groups such as stearoyl groups), acylamino groups (e.g. linear or branched alkylcarbonylamino groups such as acetamido groups, arylcarbonylamino groups such as benzoylamino groups), arylamino groups (e.g. N-phenylamino group, etc.), alkylamino group (e.g. linear or branched alkylamino group such as N-n-butylamino group, N,N-diethylamine group), carbamoyl group (e.g. n-butylcarbamoyl group, etc.) Straight chain or branched alkylcarbamoyl group (e.g. N.N-di-n-butylsulfamoyl group,
Straight chain or branched alkylsulfamoyl groups such as N-n-dodecylsulfamoyl groups), sulfonamide groups (
For example, straight-chain or branched alkylsulfonylamino groups such as methylsulfonylamino groups, arylsulfonylamino groups such as phenylsulfonylamino groups), sulfonyl groups (straight-chain or branched alkylsulfonyl groups such as mesyl groups, tosyl groups, etc.) arylsulfonyl group) or a cycloalkyl group (eg, cyclohexyl group, etc.). m and n each represent an integer of 0 to 4.

General formula [L-Ia], [L-IIa], [L-ma
], more preferable compounds have the general formula [L-ffal
This is a compound represented by The most preferred compound among the compounds represented by the general formula [L-I[al] is the compound represented by the general formula [L-1
1b ].

In the general formula [L-Ib] or "RIS N-Rn ↓ in the general formula [L-I[b], M% x 1, x 2, y,
RI+, R+2, m, and n are the same as above,
RIS, RIS, and R 17 are hydrogen atoms, alkyl groups (e.g., butyl group, octyl group, stearyl group, etc.) or aryl groups (e.g., phenyl group, naphthyl group, etc.)
represents. However, at least two of R15, R16, and R17 represent an alkyl group or an aryl group.

In the following margin, in the general formula [L-IV], R20Rz2y R
Examples of the halogen atom represented by 2 and R24 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The alkyl group represented by R211Rzzy R2co and R24 is preferably an alkyl group having 1 to 19 carbon atoms, and may be either a straight-chain alkyl group or a branched alkyl group, and also includes those having a substituent.

The aryl group represented by R211R2□tR2co and R24 is preferably an aryl group having 6 to 14 carbon atoms, and includes those having a substituent.

The heterocyclic group represented by R2+v R2□, R2, and R2 is preferably a five-shell ring or a six-shell ring, and includes those having a substituent.

The cycloalkyl group represented by Rz+t R2ze R2) and R24 is preferably a five-shelled ring group or a six-shelled ring group, including those having a substituent.

Examples of the 6F1 ring formed by bonding R21 and R22 include the following.

The six-shell ring formed by R22 and R2z or R23 and R24 bonding to each other is preferably a benzene ring, and this benzene ring also includes one having a substituent, and
6R2+1 R221R, which may be combined
Examples of the alkyl group represented by za and R24 include methyl group, ethyl group, propyl group, butyl group, and
Examples include butyl group, hexyl group, octyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, and octadecyl group.

Examples of the aryl group represented by R2□ R221R23 and zoR24 include a phenyl group and a naphthyl group.

R211Rzz* The heterocyclic group represented by R23 and R24 is preferably a 5- to 6-membered heterocyclic group containing at least one nitrogen atom, oxygen atom, or sulfur atom in the ring as a heteroatom, for example, Examples include a furyl group, a hydrofuryl group, a chenyl group, a pyrazolyl group, a pyrrolinol group, a pyrinol group, an imidazolyl group, a pyrazolyl group, a quinolyl group, an indolyl group, an oxacylyl group, and a thiazolyl group.

Rz+t R22t Examples of the cycloalkyl group represented by R23 and R24 include a cyclopentyl group,
Examples include a cyclohexyl group, a cyclohexenyl group, and a cyclohexagenyl group.

Examples of the six-shell ring formed by bonding R211R2□lR23 and R24 to each other include a benzene ring, a naphthalene ring, an inbenzothiophene ring, an isobenzofuran ring, and an inton ring.

Above R211R:! 21 The alkyl group, cycloalkyl group, aryl group, or heterocyclic group represented by R2s and R24 is a divalent linking group, such as an oxy group (-o
-), thio group (-s-), amine 7 group, oxycarbonyl group, carbonyl group, carbamoyl group, sulfamoyl group, carbonyl amine 7 group, sulfonyl amine 7 group, sulfonyl group or carbonyloxy group, etc. It may be bonded to a carbon atom on the ring, and some of these are preferred groups.

Examples of the alkyl groups represented by R211R2□, R2, and R24 bonded to carbon atoms on the benzene ring via the above-mentioned divalent linking group include alkoxy groups (e.g., methoxy group, ethoxy group, butoxy group). group, propoxy group, 2-ethylhexyloxy group, n-decyloxy group,
n-dodecyloxy group, n-hexadecyloxy group, etc.), alfkidicarbonyl group (e.g. methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group, n-decyloxycarbonyl group, n-hexadecyloxycarbonyl group, etc.) , acyl group (e.g., acetyl group, valeryl group, stearoyl group, benzoyl group, toluoyl group, etc.), acyloxy group (e.g., acetoxy group, hexadecylcarbonyloxy group, etc.), alkylami 7 group (e.g., n-butyl amine 7 group, N, N
-diethylamide/group or N,N-nobucylamit group), alkylcarbamoyl group (e.g. butylcarbamoyl group, N,N-diethylcarbamoyl group,
)'f-carbamoyl group, etc.), alkylsulfamoyl group (e.g., butylsulfamoyl group, N,N-noethylsulfamoyl group, or n-dodecylsulfamoyl group, etc.), sulfonylamino group (e.g., methylsulfonyl group, etc.), (7 amine groups, 7 butylsulfonyl amine groups, etc.)
, sulfonyl groups (for example, mesyl group or ethanesulfonyl group, etc.), or 7 acylamino groups (for example, 7 acetylamino groups, 7 valeryl amine groups, 7 valmitoylamino groups, 7 benzoylamino groups, or toluoyl amino groups), etc. I can do it.

Examples in which the cycloalkyl groups represented by Rz+ + R2□, R2, and R24 are bonded to a carbon atom on the ring via the above divalent linking group include a cyclohexyloxy group, a cyclohexylcarbonyl group, Examples include cyclohexyloxycarbonyl group, cyclohexylami7 group, cyclohexenylcarbonyl group, and cyclohexenyloxy group.

R211R221R2: An example in which the aryl group represented by l and R24 is bonded to a carbon atom on the ring via the above divalent linking group is an aryloxy group (e.g.
phenoxy group or 7-toxy group, etc.), aryloxycarbonyl group (e.g., 7-ethycarbonyl group or 7-toxycarbonyl group, etc.), acyl group (e.g., benzoyl group or 7-toyl group, etc.), anilino group ( For example, phenylami/group, N-methyl7nylino group or N-7
cetylanili7 groups, etc.), acyloxy groups (e.g., benzoyloxy groups or toluoyloxy groups, etc.), arylcarbamoyl! (e.g., phenylcarbamoyl group, etc.), arylsulfonyl group (e.g., phenylsulfamoyl group, etc.), arylsulfonylamino group (e.g., phenylsulfonylamine group, p-)lylsulfonylamine group, etc.), aryl Sulfonyl group (e.g., benzenesulfonyl group, tosyl group, etc.), or acylamide 7
Mention may be made of groups such as benzoylami/groups, etc.

The alkyl group, teryl group, heterocyclic group, cycloalkyl group represented by R2□R2□, R2, and R24 above, or R21 and R2□, R22 and R2 co, or R23 and R21 are bonded to each other. The 6-membered ring formed is a halogen atom (e.g. chlorine atom, bromine atom or fluorine atom*)
, cyano group, alkyl group (for example, methyl group, ethyl group, i-propyl group, butyl group, hexyl group, octyl group, decyl group, do'decyl group, tetradecyl group, hexadecyl group, heptadecyl group, octadecyl group, or methoxyethoxyethyl group, etc.), oryl group (e.g., phenyl group, tolyl group, naphthyl group, chloro7enyl group,
methoxyphenyl group or acetyl 7-enyl group), alkoxy group (e.g. methoxy group, nidoxy group, butoxy group, propoxy group or methoxyethoxy group etc.), aryloxy group (e.g. phenoxy group, triloxy group,
naphthoxy group or methoxyphenoxy group), alkoxycarbonyl group (e.g. methoxycarbonyl group, butoxycarbonyl group or phenoxymethoxycarbonyl group etc.), aryloxycarbonyl group (e.g. 7E/
oxycarbonyl group, triloxycarbonyl group, methoxyphenoxycarbonyl group, etc.), acyl group (e.g.
formyl group, acetyl group, valeryl group, stearoyl group, benzoyl group, toluoyl group, naphthoyl group or p
-nodoxybenzoyl group, etc.), acyloxy group (e.g., acetoxy group or acyloxy group, etc.), acylamide group (e.g., acetamide group, benzamide group, or methoxyacetamide group, etc.), anilino group (e.g.,
phenylami7 group, N-methylanilino group, N-phenylami/group, or N-acetylanilino group), alkylaminogroup (e.g. -butylamino group, N,N-diethylami7 group, 4-methoxy-n- butylamino group, etc.), carbamoyl group [e.g., n-butylcarbamoyl group, N,N-diethylcarbamoyl group, n-butylsulfamoyl group, N,N-noethylsulfamoyl group, n
-dodecylsulfamoyl group, or N=(4-7toxyn-butyl)sulfamoyl group], 7 sulfonylamide groups (e.g. 7 methylsulfonylamide groups, 7 phenylsulfonylamide groups, or 7 methoxymethylsulfonylamide groups) etc.), or a sulfonyl group (e.g., mesyl group, tosyl group, or methoxymethanesulfonyl group, etc.) h
4 may be substituted.

The alkyl groups represented by R25 and 1/A include those having substituents, and may be linear or branched. These alkyl groups preferably have 1 to 20 carbon atoms, excluding the carbon atoms in the substituent moiety, such as methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, etc. group, dodecyl group, tetradecyl group, hexadecyl group, heptadecyl group, or octadecyl group.

The aryl group represented by R2S and A includes those having a substituent, and is preferably a 7-aryl group having 6 to 14 carbon atoms, excluding the carbon atoms in the substituent part, for example,
Examples include phenyl group, tolyl group, and heptyl group. Furthermore, two ligands may be linked via A.

In the formula, M represents a metal atom, preferably a transition metal atom. More preferably CLl, CO+Nl+
Pd, Fe or Pt, particularly preferably Ni. A preferred group for A is a hydroxy group.

Furthermore, among the complexes represented by the above general formula (L-IV), those in which R21 is an oxy group,
a thio group, an alkyl group via a carbonyl group, a cycloalkyl group, a teryl group or a heterocyclic group, a hydroxy group or a 77 atom, and at least one of the groups represented by R22, R23 or R24 is a hydrogen atom, a hydroxy group, furkyl group or alkoxy group. More preferred among these are those in which R2S is a hydrogen atom, and R2S is a hydrogen atom.
2,.

It is a complex in which the total number of carbon atoms in the groups represented by R2□, R2, or R24 is at least 4 or more.

Specific examples of metal complexes according to the present invention are shown below, but the present invention is not limited to these compounds.

Exemplary metal complex H C8H17(t) C11H17(t)(4)
NH2C8H17 (su↓ -Ni-0 1 ↑ I H (5) NR2C8
H17(su↓ -Ni-0 (5) NH2C8H17
↓ 0- Ni-0 (73N R2, C12R2s ↓ -Ni-O C8H17(ri) C11H17(suC5Hr
) CaHtt(t)(”0)NH2C5Hty
(t) ↓ (11) NH2C8H1met)↓ (12) NH2C・Hty(t) ↓ Q-Ni-0 NH(C4H80H)2 ↓ 0- Ni -0 (14) N(C4H1lOH)3↓ -Ni- 0 ↓ 0-Ni knee 0 (17) NH (C4H9) 2 ↓ (18) NH (C, Hg) 2 ↓ 0-Ni-0 (19) N (CzHs) 3 ↓ C3H17 (ri C11H17 (t) (21 )
C2H5H-N-CsHr7 (25)NH(.5Hty)z ■ NH(Cl2H25)2 C111(17(t) C5Ht 7(suOC+
sH3koOCHzC)l(C2Hs)C,Hs tζ 1 ) (52) C2H5C4Hs
(CzHs)CHCH:OOCHzC)l(C2H
s ) C<Hs (7) (IQ3) (i i 2) H! 5) /i i 91 r19'J<127> Below is a blank space CFlx '-Fix General formula IL-V] In the formula, R6 and R8 each represent an alkyl group, a cycloalkyl group, or an aryl group.

Was.

Examples of the alkyl group represented by R6 and R8 include methyl group, ethyl group, t-butyl group, t-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, n-dodecyl group, Examples include n-heptadecyl group and n-octadecyl group. Specific examples of the cycloalkyl group represented by R6 and R8 include a cyclopentyl group and a cyclohexyl group. The aryl group represented by R6 and R8 specifically includes a phenyl group,
Examples include naphthyl group. Further, R6 and R8 may be the same or different.

The above alkyl groups, cycloalkyl groups and aryl groups each include those having substituents. Examples of substituents for the alkyl group include a halogen atom, a cyano group, a cycloalkyl group, an aryl group, and a heterocyclic group. Examples of the substituent for the cycloalkyl group include the same substituents as for the alkyl group except for the cycloalkyl group, and an alkyl group. Substituents for aryl groups include those similar to substituents for alkyl groups other than aryl groups,
and alkyl groups. Also, the above R6 and R
The alkyl group, cycloalkyl group, and aryl group represented by 8 are divalent linking groups R' [specifically 10-1-S-1-N-1 (R' is a hydrogen atom, a hydroxyl group, Alkyl groups (e.g. methyl group, ethyl group, n-propyl group, i-propyl group, Loebdell group, t-butyl group, i-butyl group, etc.), aryl groups (e.g. phenyl group, 1-lyl group, naphthyl group) etc.), -COO-1-OCO-1-CO
-1-NHCO-1-CONH-1-3O2N)I-1
-NH8O2-1-8O2- etc.], an alkyl group,
The cycloalkyl group or aryl group may be substituted.

Specifically, the halogen atom as a substituent is a fluorine atom,
Specific examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, etc., and specific examples of the cycloalkyl group include chlorine atom, bromine atom, and iodine atom. Examples include cyclohexyl group,
Specific examples of the aryl group include phenyl group, naphthyl group, etc., and specific examples of the heterocyclic group include pyridyl group, indazolyl group, furyl group, chenyl group, pyrrolyl group, pyrrolidyl group, quinolyl group, morphonyl group, etc. can be mentioned.

R7 represents an alkyl group, a cycloalkyl group, an aryl group, an alkyl group or an aryl group, or -N HC
OR++ (RH is a hydrogen atom, specific examples of an alkylulkyl group and an aryl group, and specific examples of a substituent when having a substituent include a group, 2,4-di[-amyl-anilino group, etc.), -N HCOR11 Specific examples include t-octylcarbonamide group, n-dodecylcarbonamide phenylcarbonamide carbonamide group, phenylaminocarbonamide group, etc. Here, the alkyl group and aryl group represented by R 9 , R +o and Rh are It also includes those having a substituent, and specific examples of the substituent include the above-mentioned Rs.
, Ra.

Preferred as R6 is an aryl group, and preferred as R7 and R8 are alkyl groups.

Also, Rs, R? The total number of carbon atoms including the substituents of R8 is preferably 16 or more, and more preferably 2
More preferably, it is 4 or more and 42 or less.

In the general formula [L-Vl, M represents a metal atom, preferably a transition metal atom, more preferably a Fe, Ni, Co, Cu, pd, or Pt atom, and particularly preferably a Ni atom. .

The gold Ii1 & R body represented by the general formula [L-Vl is 2
Although the two ligands are dentate ligands, the two ligands may be the same or different.

Specific examples of the metal complex represented by the general formula [L-Vl are shown below, but the present invention is not limited thereto.

Margin below 14ヰ Il 19 Margin below +1;ff 1 19? 1&’7 +l′l.

In the present invention, the general formulas [L-I], [L-■], [
Among the metal complexes represented by L-1 [[ ], [L-IV] oc[F [1-V], the quenching rate constant of -heavyt oxygen is preferably 3X 10'M'' -sec -1 or more. is a metal complex, more preferably 1×10”M−+・
It is 5ec-1 or more. In addition, in the present invention, gold 1! which is not represented by these general formulas! Even if it is a complex, a metal complex with a -heavyt oxygen quenching rate constant of 3X10'M-1·sec-1 or more can be preferably used, and 1 x 1
Range (7) mo(7) of 08M"-5ec-1 or more can be used more preferably.

The above-mentioned quenching rate constant of heavyt oxygen is given in the Journal of Physical Chemistry (Journal 0fph
(chemical chemistry) 83. 591
(1979) and others, by the method of measuring photobleaching of rubrene.

That is, a chloroform solution of rubrene and a chloroform solution containing a mixture of rubrene and the compound to be measured are irradiated with light of equal energy.

The initial concentration of rubrene at this time is [R], the concentration of the compound to be measured is [Q], the concentration of rubrene in the single solution of rubrene after the test is [R], and the concentration of rubrene and the compound to be measured after the test is The concentration of rubrene in the mixed solution is [R]:
Then, the -ffi term oxygen quenching rate constant (kq) is calculated as follows.

The metal complexes represented by the general formulas [L-I] to [L-Dll can be synthesized by the methods described in British Patent No. 858,890, German Patent Application Publication No. 2,042,652, etc. .

The metal complex represented by the general formula [L-rV] is described in E.G. Cox, F. Double Pinkard, Double Wardlow and C.C. Webster, Journal of Chemical Society (E. G, C
ox, F., W., Pinkard, W.

Wardlaw and K, C, Webste'
r, J, Chem.

Sac, , ) 1935. It can be synthesized by the method described in 459.

The metal complexes represented by the general formulas [L-I] to [L-rV] may be used in amounts of 0.1 mol to 2 mol per mol of the coupler, although it varies depending on the type of metal complex used and the type of coupler used. Preferably used in the molar range,
More preferably, it is used in a range of 0.5 mol to 1 mol.

The metal complex represented by the general formula [L-Vl is synthesized by a method similar to that described in JP-A-58-216244.

Use of the metal complex represented by the general formula [1-Vl] 1 is used in an amount of 0.01 to 1 mol, preferably 0.05 to 0.5 mol, per 1 mol of coupler.

The silver halide photographic light-sensitive material of the present invention can be, for example, a color negative film, a positive film, or a color photographic paper. The effects of the invention are effectively exhibited.

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 photographic materials, in order to perform subtractive color reproduction, a photographic coupler is usually used.
It has a structure in which a silver halide emulsion layer containing magenta, yellow, and cyan couplers and a non-light-sensitive layer are laminated on a support in an appropriate number and order of layers. The order may be changed as appropriate depending on the important performance and purpose of use.

When the silver halide photographic light-sensitive material of the present invention is a multicolor light-sensitive material, the specific layer structure includes, on the support, a yellow dye-forming layer, an intermediate layer, a magenta dye layer, and Particularly preferred is an arrangement of an image forming layer, an intermediate layer, a cyan dye image forming layer, an intermediate layer, and a protective layer.

Silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention (hereinafter referred to as the silver halide emulsion of the present invention).

) can be any silver halide used in ordinary silver halide emulsions, such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride. .

The silver halide grains used in the silver halide emulsion of the present invention may be obtained by any of the acid method, neutral method, and ammonia method. The particles may be grown all at once, or may be grown after seed particles are produced. The method of creating and growing the seed particles may be the same or different.

In the silver halide emulsion, halide ions and silver ions may be mixed simultaneously, or one may be mixed in the presence of the other. In addition, considering the critical growth rate of silver halide crystals, we added halide ions and silver ions to I
)H,I)A! They may be generated by sequentially and simultaneously adding them while controlling If. After growth, a conversion method may be used to change the halogen composition of the particles.

When producing 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 by using a silver halide solvent as necessary.

The silver octaride grains used in the silver halide emulsion of the present invention are formed by cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or complex salt, rhodium salt or Metal ions can be added to the inside of the particles and/or on the surface of the particles by using complex salts, iron salts, or complex salts. It is possible to add reduction-sensitized nuclei to.

In the silver halide emulsion of the present invention, soluble salts may be removed after the growth of silver halide grains is completed, or the salts 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 grains used in the silver halide emulsion of the present invention may be grains in which a latent image is mainly formed on the surface, or grains in which a latent image is mainly formed inside the grains.

The silver halide grains used in the silver halide emulsion of the present invention may have a regular crystal shape or may have an irregular crystal shape such as a spherical shape or a plate shape. In these particles, any ratio of the (1oo) plane to the (111) plane can be used.

Further, the particles may have a composite form of these crystal forms, or particles of various crystal forms may be mixed.

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

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 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. Sensitizing dyes may be used alone, but
You may use two or more types in combination. 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 may be used during chemical ripening for the purpose of preventing capri during the manufacturing process, storage, or photographic processing of light-sensitive materials, and/or maintaining stable photographic performance.
and/or at the end of the chemical ripening, and/or after the end of the chemical ripening and before coating the silver halide emulsion, compounds known in the photographic industry as antifoggants or stabilizers can be added.

As the binder (or protective colloid) for the silver halide photographic material of the present invention, gelatin is advantageously used, but gelatin derivatives, graft polymers of gelatin and other polymers, proteins, sugar derivatives, Hydrophilic colloids such as cellulose conductors, synthetic hydrophilic polymeric materials such as single or copolymers can also be used.

The photographic emulsion layer and other hydrophilic colloid layers of the silver halide photographic light-sensitive material of the present invention can be formed by using, alone or in combination, a hardening agent that crosslinks binder (or protective colloid) molecules and increases film strength. It is hardened. It is desirable that the hardening agent be added to the processing solution to the extent that it can harden the photosensitive material, but it is also possible to add the hardening agent to the processing solution.

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 the silver halide photographic material of the present invention.

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

The emulsion layer of the silver halide photographic light-sensitive material of the present invention is subjected to a coupling reaction with an oxidized form of an aromatic primary amine developer (for example, p-phenylenediamine derivatives, aminophenol derivatives, etc.) during color development treatment. A dye-forming coupler is used that performs this process to form a dye. The dye-forming couplers are typically selected such that for each emulsion layer a dye is formed that absorbs light in the emulsion layer's sensitive spectrum, with a yellow dye-forming coupler for the blue light-sensitive emulsion layer. However, a 7-zenta dye-forming coupler is used in the B color light-sensitive emulsion layer, and a cyan dye-forming coupler is used in the red light-sensitive emulsion layer. However, depending on the purpose, silver halide color photographic materials may be produced using different combinations than those described above.

The cyan dye-forming couplers used in the present invention include:
Phenol-based and naphthol-based 4-equim or 2-equim cyan dye-forming couplers are typical, and specific examples thereof include U.S. Pat. Nos. 2,423,730 and 2,474,2.
No. 93, No. 3,227,554 and No. 3.488
．． Specifications of No. 193 and JP-A-50-10135
No. 50-25228, No. 50-130441,
It is described in various publications such as No. 51-37647, No. 51-108841, and Japanese Patent Publication No. 45-6993.

Further, as the cyan dye-forming coupler used in the silver halide emulsion of the present invention, the following general formula [(, C-11) is preferred.

In the general formula [CG-1], R1 represents an alkyl group or an aryl group. R
2 represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group; R3 represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. Also, R3 is R1
It may be combined with to form a ring. Z represents a hydrogen atom or a group capable of eliminating t1 by reaction with an oxidized product of an aromatic primary amine color developing agent.

In the present invention, the alkyl group represented by R1 in the general formula [CG-1] is a linear or branched one, such as a methyl group, an ethyl group, an iso-propyl group, a butyl group, a pentyl group, an octyl group. , a nonyl group, a tridecyl group, etc., and the aryl group is, for example, a phenyl group, a naphthyl group, etc.

These groups represented by R1 include those having single or multiple substituents. For example, substituents introduced into the phenyl group include halogen atoms (e.g., fluorine, chlorine, bromine, etc.). each atom), alkyl M (e.g., methyl group, ethyl group, propyl group, butyl group, dodecyl group, etc.), hydroxyl group, cyam L nitro group, alkoxy group (e.g., methoxy, cy group, ethoxy group), Alkylsulfonamide groups (e.g., methylsulfonamide group, octylsulfonamide group, etc.), arylsulfonamide groups (e.g., phenylsulfonamide group, naphthylsulfonamide group, etc.), alkylsulfamoyl groups (e.g., butylsulfonamide group, etc.) groups), arylsulfamoyl groups (e.g., phenylsulfamoyl groups, etc.)
, alkyloxycarbonyl group (e.g., methyloxycarbonyl group, etc.), aryloxycarbonyl group (e.g., phenyloxycarbonyl group, etc.), aminosulfonamide group (e.g., N,N-dimethylaminosulfonamide group, etc.), acylamino group, carbamoyl group, sulfonyl group, sulfinyl group, sulfoxy group, sulfo group,
Aryloxy groups, alkoxy groups, and carboxyl groups are formed.

Two or more of these substituents may be introduced into the phenyl group.

The halogen atom represented by R3 is, for example, each atom such as fluorine, chlorine, or bromine, and the alkyl group is, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a dodecyl group, or an alkoxy group. is, for example, a methoxy group,
Y is an ethoxy group, a propyloxy group, and a butoxy group.

R3 may combine with R1 to form a ring.

In the present invention, the alkyl group represented by R2 in the general formula [CG-1] is, for example, a methyl group, an ethyl group, a butyl group, a hexyl group, a tridecyl group, a pentadecyl group, a heptadecyl group, or a so-called fluorine substituted group. These include polyfluoroalkyl groups.

The aryl group represented by R2 is, for example, a phenyl group or a naphthyl group, preferably a phenyl group. R2
The heterocyclic group represented by is, for example, a pyridyl group or a furan group. The cycloalkyl group represented by R2 is, for example, a cyclopropyl group or a cyclohexyl group. These groups represented by R2 include those having a single substituent or a plurality of substituents. For example, a typical substituent introduced into a 2-enyl group is a halogen atom (PA
For example, each atom such as fluorine, chlorine, bromine, etc.), alkyl group (for example, methyl group, ethyl group, propyl group, butyl group, dodecyl group, etc.), hydroxyl group, Siam L nitro group, alkoxy! S (for example, methoxy group, ethoxy group, etc.), alkylsulfonamide group (for example, methylsulfonamide group, octylsulfonamide group, etc.), arylsulfonamide group (for example, phenylsulfonamide group, naphthylsulfonamide group, etc.), alkyl Sulfamoyl group (
(e.g., butylsulfamoyl group, etc.), arylsulfamoyl group (e.g., phenylsulfamoyl group, etc.), alkyloxycarbonyl group (e.g., methyloxycarbonyloxycarbonyl group (e.g., phenyloxycarbonyl group, etc.), aminosulfone Amide group, acylamino group,
Examples include carbamoyl group, sulfonyl group, sulfinyl group, sulfoxy group, sulfo group, aryloxy group, alkoxy group, carboxylalkylcarbonyl group, and arylcarbonyl group. Two or more of these substituents may be introduced into the phenyl group.

Preferred groups represented by R2 include polyfluoroalkyl groups, phenyl groups or halogen atoms, alkyl groups, alkoxy groups, alkylsulfonamide groups, arylsulfonamide groups, alkylsulfamoyl groups, arylsulfamoyl groups, and alkylsulfonyl groups. arylsulfonyl group, alkylcarbonyl group, arylcarbonyl group, or cyano group as a substituent.

In the present invention, the cyan dye-forming coupler represented by the general formula [CG-11] is preferably a cyan dye-forming coupler represented by the following general formula [CC-2
] It is a compound represented by.

General Formula [CC-2] In Formula 11 [CC-21], R6 represents a phenyl group. This phenyl group includes those having single or multiple substituents, and typical substituents to be introduced include halogen atoms (e.g., fluorine, chlorine, bromine, etc. atoms), alkyl groups (e.g., methyl group), , ethyl group, propyl group, butyl group, octyl group, dodecyl group, etc.), hydroxyl group, cyano group, nitro group, alkoxy group (e.g. methoxy group, ethoxy group, etc.), alkylsulfonamide group (e.g. methylsulfonamide group, octylsulfonamide group, etc.), arylsulfonamide group (e.g. phenylsulfonamide group, naphthylsulfonamide group, etc.),
Alkylsulfamoyl groups (e.g. butylsulfamoyl groups, etc.), arylsulfamoyl groups (e.g. phenylsulfamoyl groups, etc.), alkyloxycarbonyl groups (
For example, methyloxycarbonyl group, etc.), aryloxycarbonyl group (for example, phenyloxycarbonyl group, etc.)
etc. can be mentioned. Two or more of these substituents may be substituted with a phenyl group. Preferred groups represented by R6 include a phenyl group, a halogen atom (preferably fluorine, chlorine, and bromine atoms), an alkylsulfonamide group (preferably an 0-methylsulfonamide group, and a p-octylsulfonamide group). , 0-dodecylsulfonamide group), arylsulfonamide group (preferably phenylsulfonamide group), alkylsulfamoyl group (preferably butylsulfamoyl group), arylsulfamoyl group (preferably phenylsulfamoyl group) ), an alkyl group (preferably a methyl group or a trifluoromethyl group), or an alkoxy group (preferably a methoxy group or an ethoxy group) as a substituent.

R7 is an alkyl group or an aryl group. Alkyl groups or aryl groups include those having single or multiple substituents, and typical examples of these substituents include halogen atoms (e.g., fluorine, chlorine, bromine, etc. atoms), hydroxyl groups, and carboxyl groups. , alkyl groups (e.g. methyl group, ethyl group, propyl group, butyl group, octyl group, dodecyl group, etc.), aralkyl group, cyano group, nitro group, alkoxy group (e.g. methoxy group, ethoxy group), aryloxy group, alkyl group Sulfonamide group (e.g. methylsulfonamide group, octylsulfonamide group, etc.)
, arylsulfonamide group (e.g. phenylsulfonamide group, naphthylsulfonamide group, etc.), alkylsulfamoyl group (e.g. butylsulfamoyl group, etc.),
Arylsulfamoyl group (e.g., phenylsulfamoyl group, etc.), alkyloxycarbonyl group (e.g., methyloxycarbonylcarbonyl group (e.g., phenyloxycarbonyl group, etc.)
, an aminosulfonamide group (such as a dimethylaminosulfonamide group), an alkylsulfonyl group, an arylsulfonyl group, an alkylcarbonyl group, an arylcarbonyl group, an aminocarbonylamide group, a carbamoyl group, and a sulfinyl group. Two or more types of these substituents may be introduced.

Preferred groups represented by R7 are an alkyl group when nl=O, and an aryl group when n1=1 or more. More preferable groups represented by R7 include r
When l+=0, it is an alkyl group having 1 to 22 carbon atoms (preferably a methyl group, ethyl group, propyl group, butyl group, octyl group, dodecyl group), and when n1=1 or more, it is a phenyl group, or Alkyl group (preferably t-butyl group, t-amyl group, octyl group), alkylsulfonamide group (preferably butylsulfonamide group, octylsulfonamide group, dodecylsulfonamide group), arylsulfonamide group (preferably phenyl sulfonamide group), an aminosulfonamide group (preferably a dimethylaminosulfonamide group), or an alkyloxycarbonyl M (preferably a methyloxycarbonyl group or a butyloxycarbonyl group) as a substituent. be.

R8 represents an alkylene group. It represents a straight or branched alkylene group having 1 to 20 carbon atoms, and further having 1 to 12 carbon atoms.

R9 represents a hydrogen atom or a halogen atom (fluorine, chlorine, bromine, iodine, etc.). Preferably it is a hydrogen atom.

nl is 0 or a positive integer, preferably 0 or 1
It is.

X is 10-, -CO-, -COO-, -OCO-, -SO2NR-, -NR'802NR''
-, -S-, -s o -Mataha- 302-Base 2
Represents a valence group. Here, R / and R IT represent an alkyl group, and R / and R LJ each include those having a substituent. X is preferably -〇-, -S-, -
SO-, -SO2-ES.

In the general formulas [CC-1] and [CC-2], the groups each represented by Z that can be separated by reaction with an oxidized product of an aromatic primary amine color developing agent are well-known to those skilled in the art. II!, modifying the reactivity of the coupler or converting the coupler fflB2L, which acts advantageously by performing functions such as yA image suppression, bleaching suppression, and color correction in coating layers or other layers containing couplers in silver halide color photographic light-sensitive materials. Typical examples include halogen atoms such as chlorine and fluorine, substituted and unsubstituted alkoxy groups, aryloxy groups, arylthio groups, carbamoyloxy groups, acyloxy groups, sulfonyloxy groups, sulfonamide groups, and Examples include teroylthio group and heteroyloxy group. Particularly preferred Z is a hydrogen atom or a chlorine atom.

More specifically, JP-A-50-10135, JP-A No. 50-10135;
No. 120334, No. 50-130441, No. 54-
No. 48237, No. 51-146828, No. 54-1
No. 4736, No. 47-37425, No. 50-1233
No. 41, No. 58-95346, Special Publication No. 48-3f3f
l194, U.S. Patent No. 3,476.563, U.S. Patent No. 3.7
37.316 and 3.227551.

Typical specific examples of cyan couplers represented by the general formula [CC-1,1 are shown below in the margins, but are not limited to these (n
) Ctg&s 5O2NH C4Hs(n) Cxx Above LnJ CL The yellow dye-forming coupler used in the present invention is preferably a compound represented by the following general formula [Yl.

General formula [Yl In the formula, R11 represents an alkyl group (e.g., methyl group, ethyl group, propyl group, butyl group, etc.) or an aryl group (e.g., phenyl group, p-methoxyphenyl, etc.), and R11
2 represents an aryl group, and Yl represents a hydrogen atom or a group that leaves during the color development reaction process.

Furthermore, particularly preferred yellow dye-forming couplers are compounds represented by the following general formula [Y'].

General formula [Y'] In the formula, R+3 represents a halogen atom, an alkoxy group or an aryloxy group, and RI4, R15, and R+s are
hydrogen atom, halogen atom, alkyl group, alkenyl group, alkoxy group, aryl group, aryloxy group, respectively.
It represents a carbonyl group, a sulfonyl group, a carboxylcarbamylsulfonamide group, an acylamide group, a ureido group or an amino group, and Yl has the above-mentioned meaning.

These include, for example, U.S. Patent Nos. 2,778,658, 2,875,057, 2,908,573,
Same No. 3.227155, Same No. 3,227,550,
Same No. 3, 253, 924, Same No. 3, 265,
506, 3,277, 155, 3,34
No. 1, 331, No. 3, 369, 895, No. 3
, No. 384, 657, No. 3, 408, 194,
3,415,652, 3.447, 928
No. 3, 551, 155, No. 3, 582
, No. 322, No. 3, 725, 012, 3,
894, 875, etc., German Patent Publication Tube 1
, No. 547, 868, No. 2,057,941,
2,162,899, 2,163, 81
No. 2, No. 2, 213,461, No. 2,219,9
No. 17, No. 2,261,361, No. 2,263,
No. 875, Japanese Patent Publication No. 13576/1973, Japanese Patent Publication No. 48-2
No. 9432, No. 48-66834, No. 49-1073
No. 6, No. 49-122335, No. 50-28834, and No. 50-132926.

Typical examples of yellow dye-forming couplers represented by the general formula [Yl are shown below, but the invention is not limited thereto.

The following margin is Y-3) The following margin is between the emulsion layers of the silver halide photographic light-sensitive material of the present invention.
(between color-sensitive layers and/or between different color-sensitive layers), the oxidized form of the developing agent or the electron transfer agent may migrate, causing color turbidity,
Color antifogging agents are used to prevent deterioration of sharpness and noticeable graininess.

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

In the color light-sensitive material using the silver halide emulsion of the present invention, an image stabilizer can be used to prevent deterioration of the dye image.

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

Below is the general formula [AI], where R1 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group, and R2, R1, Rs, R
= is a hydrogen atom, a halogen atom, a hydroxy group,
a furkyl group, an alkenyl group, an aryl group, an alkoxy group or an acylamide group, R1 is an alkyl group,
Represents a hydroxy group, an aryl group, or an alkoxy group.

Further, R+ and R7 may be ring-closed with each other to form a 5-shell or 6-shell ring, in which case R1 may have a hydroxy group or an alkoxy group, or R1 and R1 may be ring-closed to form a 5-shell hydrocarbon ring. may be formed, and the final R is an alkyl group, an aryl group, or a heterocyclic group, provided that R3
except when is a hydrogen atom and R1 is a hydroxy group.

In the general formula [AI, R1 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, and an n-octyl group. group, tert-
Examples include straight-chain or branched furkyl groups such as octyl and hexadecyl groups. Examples of the alkenyl group represented by R1 include allyl, hexenyl, and octenyl groups. Furthermore, 7 of R1
Examples of the lyl group include phenyl and naphthyl groups. Further, specific examples of the heterocyclic group represented by R9 include a tetrahydropyranyl group and a pyrimidyl group. Each of these groups can have a substituent, for example, a benzyl group, a nidoxymethyl group as an alkyl group having a substituent, a methoxy7enyl group, a chlorophenyl group, and a 717-l group having a substituent. 4-H)
``roxy 3,5-dibutylphenyl group, etc.

In the general formula [AI, R2, R3, R2 and R6 are hydrogen atoms, halogen atoms, hydroxy groups, alkyl groups,
It includes an alkenyl group, an aryl group, an alkoxy group, or an acylamino group. Among these, the furkyl group, alkenyl group, and aryl group include the same alkyl group, alkenyl group, and 7-aryl group mentioned above for R6. . 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 7-sylamine group is represented by R'CONH-, where R' is a fulkyl group (e.g. methyl, ethyl, n-propyl,
n-butyl, n-octyl, tert-octyl, pencil, etc.), alkenyl groups (e.g. allyl, octenyl, oleyl, etc.), aryl groups (e.g. phenyl, methoxyphenyl, naphthyl) groups such as ), or heterocyclic groups (e.g. pyridyl, pyrimidyl groups)
can be mentioned.

In addition, in the general formula [AI, R4 represents an alkyl group, a hydroxy group, an aryl group, or an alkoxy group,
Among these, for the alkyl group and aryl group, the above R1
Specific examples include the same alkyl groups and aryl groups as shown in . As for the alkenyl group of R4, the same alkoxy groups as mentioned above for R2, R3, R9 and R6 can be mentioned.

Examples of the ring that R1 and R2 form together with a benzene ring by closing each other include chroman, coumaran, and methylene oxybenzene.

Furthermore, examples of the ring formed by R3 and R1 together with a benzene ring include bean. 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 R1 and R2, or R5 and R4, or a bis compound may be formed by using R2, R4, etc. as a linking group. good.

Among the phenolic compounds or phenyl ether compounds represented by the general formula [A], preferred are R
〇-group (R is an alkyl group, an alkenyl group, an aryl group,
or representing a heterocyclic group), and is 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), A group represented by a group (e.g., phenyl, naphthyl) or a heterocyclic group (e.g., tetrahydropyranyl, pyrimidyl), R9 and R1° each represent a hydrogen atom, a halogen atom, (e.g., fluorine, chlorine, odor l), a furkyl group (e.g. methyl, ethyl, n-butyl, benzyl), an alkoxy group (e.g. allyl, hexenyl, octenyl), or an alkoxy group (e.g. allyl, hexenyl, octenyl),
e.g. methoxy, ethoxy, penciloxy),
R1 is a hydrogen atom, an alkyl group (e.g. methyl, ethyl,
n-butyl, benzyl), fluorenyl it (M, for example, 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. 2,0177.45
No. 5, No. 2,062, No. 888, U.S. Patent No. 3,76
4,337, same No. 3.432300, same vJ3,57
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
No. 4-12337, No. 48-31625, U.S. Patent f
:1IJ3,700,455 and the like.

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.

Representative types (1) of the compound represented by the general formula [A] above are shown below. RI type (2) Type (3) Type (4) Type (5) Type (6) Type (7) K1 type (2) ) Below margin type (4) Below margin type (5) Below margin type (6) Below margin A-7 Below margin general formula [B] (In the formula, R1 and R1 are each a hydrogen atom.)) Rodene atom, alkyl group, alkenyl group, alkoxy group, alkenyloxy group, hydroquine group, oryl group, 71J-
R2 is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an acyl group, a cycloalkyl group, or a heterocyclic group. group, R1 is a hydrogen atom,
Includes halogen atom, alkyl group, alkenyl group, 71-nol group, aryloxy group, acyl group, acyloxy group, sulfonamide group, cycloalkyl or alkoxycarbonyl group.

Each of the groups listed above may be substituted with other substituents. Examples include alkyl groups, alkenylalkoxy groups, 7-aryl groups, aryloxy groups/hydroxy groups, alkoxycarbonyl groups, aryoloxycarbonyl groups, acylamino groups, 7-syloxy groups, carbamoyl groups, sulfonamide groups, and sulfamoyl groups. It will be done.

Furthermore, R2 and R may be ring-closed with each other to form a 5-shell or 6-shell ring. Examples of the ring formed by R and R 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 a fulkenyloxy group, a hydroquine group, an aryl group, a 7-aryloxy group, or a heterocycle,
Furthermore, a spiro ring may be formed.

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

General formula [B-1] General formula [B-2] General formula [B-3] General formula [B-4] General formula [B-51 General formula [B-1], [B-2], [B -3], [B
-4] and [B-5], R1, R2, R3 and R4 have the same meanings as in the above general formula [B], and R5, R61, R2, R8, R1 and R3° are hydrogen atoms and halogen atoms. , an alkyl group, an alkoxy group, a hydroxy group, an alkenyl group, an alkenyloxy group, an aryl group, a 7-aryloxy group, or a heterocyclic group.

Furthermore, R5 and R, R6 and R1, R7 and R, R, and R
9, R3, and R3° may be cyclized with each other to form a carbocycle, and the carbocycle may be further substituted with an alkyl group.

The general formula [B-1], [B-2], [B-3],
[B-4] and [B-5] R3 and VR,
is a hydrogen atom, an alkyl group, an alkoxy group, a hydroxy group or a cycloalkyl group, R1, R6, R1, R-1R
Particularly useful are compounds in which 1 and R+o are hydrogen atoms, alkyl groups, or cycloalkyl groups.

The compound represented by the general formula [B] is tetrahedron (Te
trahedron), 1970. vo126,474
3-4751, Journal of the Chemical Society of Japan, 1972. No1ff
, pp. 0987-1990, Chemical (ehem, Let
t, )-1972 (4) pp. 315-316, Japanese Unexamined Patent Publication No. 1972.
5-139383, and can be synthesized according to the methods described therein.

The amount of the compound to be attenuated by the general formula [B]''t' is 5 to 3% relative to the magenta coupler of the emulsion of the present invention.
It is preferably 00 mol%, more preferably 10 to 200 mol%.

Typical specific examples of these compounds are shown below.

The following is a blank general formula [C] 8-member general formula [DI -I= In the formula, R and R3 are hydrogen atoms, hal:I atoms, alkyl groups, alkenyl groups, alkoxy groups, alkenyloxy groups, hydroxy groups, aryl group, 7-lyloxy group, 7-syl group, acylamino group, acyloxy group, sulfone 7-mido group or alkoxycarbonyl group.

Each of the groups listed above may be substituted with other substituents (e.g., halogen atom, alkyl group, alkenyl group,
Examples include an alkoxy group, an aryloxy group, a hydroxy group, an alkoxycarbonyl group, a 7-aryloxycarbonyl group, an acylamide 7 group, a carbamoyl group, a sulfone 7-mido group, and a sulfamoyl group.

Y represents an atomic group necessary to form a cycloman or nocoumaran ring together with a benzene 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 heterocyclic group,
Furthermore, a spiro ring may be formed.

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

General formula [C-1] General formula [C-2] General formula [D-1] General formula [D-2] General formula (e-B, [C-2], [D-1] Ascending [D −
R8 and R2 in [2] are the general formulas [C] and I
In FI'DI, between 1°Kai Kujyo p-R4,
R6, R, %R7 and R3 are hydrogen atoms, halogen atoms, alkyl groups, alkoxy groups, hydroxy groups, alkenyl groups, alkenyloxy groups, aryl groups, aryloxy groups or heterocyclic groups, and R1 and R1
, R1 and R6 and R6, R6 and R7 and R2 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-13, [C-2], [D-1] and [D-2], R3 and R2 are hydrogen atoms, alkyl groups, alkoxy groups, hydroxy groups or cycloalkyl groups, R1 , R4, R1, R7, and R are hydrogen atoms, alkyl groups, or cycloalkyl groups, which are particularly useful.

Compounds represented by general formulas [C] and [D] are published in the Journal of the Chemical Society of Japan (J, Chew, Soc, part C) 1
968. (14), pp. 1937-18, Japan Society of Organic Synthetic Chemistry 197G, 2B(1), pp. 60-65, Tetrahedron Letters
) 1973, (29), 2707-2710 and can be synthesized according to the methods described therein.

The amount of the compounds represented by the general formulas [C] and [D] used 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.

The following is a blank space: General formula (El) In the formula, R1 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a 7-syl group, a dichlorofurkyl group, or a heterocyclic group, and R3 represents a hydrogen atom, a halogen atom, an alkyl group, or an alkenyl group. , 7lyl group, 7lyloxy group,
It represents an acyl group, an acylamide group, an acyloxy group, a sulfonamide group, a cycloalkyl group, or an alkoxycarbonyl group.

R2 and R4 are hydrogen atom, halogen atom, alkyl group, alkenyl group, aryl group, acyl group, acylami7
group, sulfonamide group, cycloalkyl group or alkoxycarbonyl group.

Each of the groups listed above may be substituted with other substituents. For example, a furkyl group, a flutenyl group, an alkoxy group, an aryl group, a 7-aryloxy group, a hydroxy group, an alkoxycarbonyl group, an aryloxycarbonyl group,
Examples include a 7syl7mino group, a carnozumoyl group, a sulfone7mido group, and a sulf1moyl group.

Further, R' and R2 may be ring-closed with each other to form a 5-shell or 6-shell ring.

At that time, R3 and R4 are hydrogen atoms, halogen atoms, furkyl groups, alkenyl groups, alkoxy groups, alkenyloxy groups, hydroxy groups, 7-aryl groups, aryloxy groups,
It represents a 7-syl group, an acyl-7 group, a 7-syloxy group, a sulfonamide group, or an alkoxycarbonyl group.

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

Chroman or coumaran rings contain halogen atoms, furkyl groups, cycloalkyl groups, alkoxy groups, alkenyl groups,
, alkenyloxy group, hydroxy group, 7-aryl group, 7
It may be substituted with a lyloxy group or a heterocyclic group, and may further form a spiro ring.

Among the compounds represented by the general formula (E), compounds particularly useful in the present invention are those represented by the general formula (E-13° (E-2), (E-3
3, (E-4) and (E-5).

General formula (E-13 OR+ General formula (E-2) nR plate general formula [E-3) General formula (E-4) General formula (E-5) General formula (E-1) to (E-53) R', R2, R
' and R4 have the same meanings as in the above general formula (E), and R5, R', R', R', and R rising RIo are hydrogen atoms, /% rogen atoms, alkyl groups, alkoxy groups, hydroxy groups. , alkenyl group, alkenyloxy group,
Representing an aryl group, an aryloxy group or a heterocyclic group, f-etc. R5 and R6, Ra and Rf, Rf and Ra,
R8 and R1 and R9 and R1° may be cyclized with each other to form a carbocycle, and the carbocycle may be further substituted with an alkyl group.

In the general formula (E-1)-(E-5), R', R
2, R' and I/R' are a hydrogen atom, a furkyl group, or a cycloalkyl group, in the general formula (E-5), R
3 and R4 are hydrogen atoms, alkyl groups, alkoxy groups,
A hydroxy group or a cycloalkyl group, and further the general formulas (E-1) to (E-5) niote, R', Ra, R'
, R., R' and (/R'' are hydrogen atoms, alkyl groups, or cycloalkyl groups) are particularly useful.

The compound represented by the general formula [E] is tetrahedron (
Tetrahedron Letters) 1985
．． (8), pp. 457-460 Journal of the Chemical Society of Japan (J, C
hew, Soc, part C) 1966° (2
2), pp. 2013-2016, (Zh, erg, K
him) 1970=(6).

1230-1237,
and can be synthesized according to the methods described therein.

Usage amount of the compound represented by the general formula [E-1]: 5 to 3
00 mol% is preferable, and more preferably 10 to 200 mol%.

Specific representative examples of these compounds are shown below.

The following is a general formula (F) in which R0 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a 7-sil group, a cycloalkyl group, or a heterocyclic group, and R2 represents a hydrogen atom, a halogen atom, an alkyl group, or an alkenyl group. , an aryl group, a 7-aryloxy group, an acyl group, an acylami-7 group, a 7-syloxy group, a sulfonamido group, a dichlorofurkyl group, or an alkoxycarbonyl group.

R1 represents 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.

R1 is 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 acylamino group, an acyloxy group, a sulfonamide group, or an alkoxycarbonyl group. vinegar.

Each of the groups listed above may be substituted with other substituents, such as an alkyl group, an alkenyl group, an alkoxy group,
Examples include an aryl group, an aryloxy group, a hydroxyl group, a flufkidicarbonyl group, an aryloxycarbonyl group, a heptadylamide 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, in which case R3 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. group, 7-lyloxy group, 7-syl group, acyl-7 group, acyloxy group, sulfonamide group, or alkoxycarbonyl group.

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,
Alkenyloxy group, hydroxy group, aryl group, 71
It may be substituted with a 7-loxy group or a heterocyclic group, and may further form a spiro ring.

Among the compounds represented by general formula [F], compounds particularly useful in the present invention are those represented by general formula [F-11, [F-2], [F-3].
], [F-4] and [F-51].

Below are the blanks General formula (F-1) General formula CF-23 General formula CF-3) OR' General formula (F-4) General formula (F-5) In general formula [F-1] and [F-5] R3, R2
, R, and R1 have the same meanings as in the general formula [F], and R2, R2, R7, R6, R, and R1
゜ represents a hydrogen atom, a hydrogen atom, a furkyl group/alkoxy group, a hydroxy group, an alkenyl group, a flukenyloxy group, a heptaryl group, an aryloxy group, or a heterocyclic group.

Furthermore, R1 and R, R6 and R1, R2 and R8, R, and R
9, Rs, and R10 may be cyclized with each other to form a carbocycle, and the carbocycle may be further substituted with an alkyl group.

Further, in [F-3], [F-4] and [F-5], two R1-R3 degrees may be the same or different.

The general formula [F-1], [F-2], IF-31, [F
-4] and [F -5], R, , R, and R2 are hydrogen atoms, furkyl groups, dichlorofurkyl groups, R4
is a hydrogen atom, an alkyl group, an alkoxy group, a hydroxy group or a cycloalkyl group, and further R6, R1, R7, R
Particularly useful are compounds in which 1, R1, and RIG are hydrogen atoms, alkyl groups, or cycloalkyl groups.

The compound represented by the general formula [F] is tetrahedron (
Tetrahedron Letters) 1970
．． Vol 2B, pages 4743-4751, Journal of the Chemical Society of Japan 1972. No. 10.1987-1990,
Synthesis 1975v V
ol 6w pp. 392-393, (Bul 5oc.
Chins Be1g) 1975*
Vol. 184 (7), pages 747-759, and can be synthesized according to the methods described therein.

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

Representative examples of compounds represented by the general formula [F]''Ch are shown below.

The following is a blank general formula CG) R1 and R3 in the formula are a hydrogen atom, a denyl atom, an alkyl group, an alkenyl group, an alkoxy group, a hydroxy group, an aryl group, an aryloxy group, an acyl group, an acylamino group, 7 Represents a syloxy 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, a 7-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,
Examples include an alkoxy group, an aryl group, an aryloxy group, a hydroxy group, an alkoxycarbonyl group, a 7-aryloxycarbonyl group, an acylamino group, a carbamoyl group, a sulfonamide group, and a sulf-7 moyl group.

Further, R2 and R3 may be ring-closed with each other to form a 5-shell or 6-shell hydrocarbon ring, and this 5-shell 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 an indane ring, an indane ring is a halogen atom, an alkyl group, an alkenyl group,
It may be substituted with an alkoxy group, a cycloalkyl 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 (G), compounds particularly useful in the present invention are included in the compounds represented by the general formulas (G-1) to (G-3).

In the following margins General formula CG-1) h+ General formula (G-2) General formula CG-3) R', R2 and R3 in General formulas (G-1) to (G-3) are the same as those in General formula CG) are synonymous, R',
R', R', R', R'' and (/R'l!, trembling hydrogen atom, halogen atom, alkyl group, alkoxy group, alkenyl group, hydroxy group, aryl group, 7-aryloxy group or heterocyclic group represents R4 and R5, R1 and R'%
R' and R', R' and R'', and VR@ and R1 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 (G-1) to (G-3), R' and R3 are a hydrogen atom, an alkyl group, a flukoxy group, a hydroxy group, or a cycloalkyl group, and R2 is a hydrogen atom, an alkyl group, a hydroxy group, or a dichlorofurkyl group. , R', R
Particularly useful are compounds in which ', R', R' and R' are hydrogen atoms, furkyl groups or cycloalkyl groups.

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.

The following is a blank general formula (H) R″′ where R′ and R2 are each a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, an acyl group,
7syl7mino group, acyloxy group, sulfonamide group,
Represents a cycloalkyl group or an alkoxycarbonyl group.

R3 is a hydrogen atom, a halogen atom, a furkyl group, an alkenyl group, an alkoxy group, a hydroxy group, an aryl group, an aryloxy group, a 7-syl group, an acylami-7 group, a 7-syloxy group, a sulfonamide group, a dichlorofurkyl group, or an alkoxycarbonyl group. represent.

The groups listed above may each be substituted with other substituents, such as furkyl, alkenyl, alkoxy,
Examples include an aryl group, an aryloxy 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 and R2 and R3 may be ring-closed with each other to form a five-shell or six-shell hydrocarbon ring, and the hydrocarbon ring may include a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkenyl group, hydroxy group, aryl group,
It may be substituted with a 7-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, and 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-2] General formula (H-3) R', R2 and R3 in general formulas (H-1) to (H-3) have the same meanings as in general formula (H), and R',
R', R', R', R'' and (/'R'l!, which are hydrogen atoms, halogen atoms, alkyl groups, alkoxy groups, hydroxy groups, alkenyl groups, aryl groups, aryloxy groups or hetero R4 and R5, R5 and RG, R1 and R), R5 and R'', and R8 and R' may be closed to each other to form a hydrocarbon ring, and furthermore, the hydrocarbon ring may be It may be substituted with an alkyl group.

In the general formulas (H-1) to (H-3), R1 and R2 are each a hydrogen atom, an alkyl group or a dichlorofurkyl group, and R3 is a hydrogen atom, an alkyl group, an alkoxy group,
Hydroxy group or cycloalkyl group, R', R', R
', R? , R'' and R1 are each a hydrogen atom, an alkyl group or a cycloalkyl group, which are particularly useful.

A method for synthesizing compounds having the general formula [H1m' is known, and is described in US Pat. No. 3,057,929, Chem.

Ber, 1972.95(5) = 1673-1
674 pages, Chemist-ry Letters,
According to 1980, pp. 739-742! l! Can be built.

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]''C are shown below.

The following margin is R1-NY [wherein, R' represents an aliphatic compound, a cycloalkyl group, or an aryl group, and Y represents a group of nonmetallic atoms necessary to form a 5- to 7-shell heterocycle together with a nitrogen atom. However, when there are two or more heteroatoms among the nitrogen atom-containing nonmetallic atoms forming the polychoric ring, at least two heteroatoms are not adjacent to each other. ] 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 dichlorofurkyl group represented by R'''C' is a 5- to 7-shell cycloalkyl group that may have a substituent, for example,
Examples include cyclopentyl group and cyclohexyl group.

The aryl group represented by R1 includes a phenyl group and a naphthyl group, each of which may have a substituent.

Substituents for the aliphatic group, cycloalkyl group, and aryol group represented by R' include alkyl groups, aryl groups, alkoxy groups, carbonyl groups, carbamoyl groups, acylamino groups, sulfamoyl groups, and sulfone 7-mido groups. , a carbonyloxy group, an alkylsulfonyl group, an arylsulfonyl group, a hydroxy group, a heterocyclic group, a furkylthio 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
It represents a group of nonmetallic atoms necessary to form the heterocycle of the shell ring, and at least two of the group of nonmetallic atoms including nitrogen atoms forming the heterocycle must be heteroatoms, and
These at least two heteroatoms must not be adjacent to each other.If all the heteroatoms are adjacent to each other in the heterocycle of the compound represented by general formula (J), the function as a magenta dye image stabilizer It is not desirable because it does not fully demonstrate its characteristics.

The 5- to 7-R heterocyclic ring of the compound represented by the general formula (J) may have a substituent, and examples of the substituent include an alkyl group, a 7-aryl group, a 7-syl group, a carbamoyl group, and an alkoxy group. carbonyl group, sulfonyl group, sulfonyl group, etc., which may further have a substituent;
The heterocycle of the shell ring may be saturated, but a saturated heterocycle is preferable, and a benzene ring or the like may be fused to the heterocycle (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-F O ■ ■ CI2 I25 Among the compounds represented by the above general formula (J), piperanone compounds and homobiperanone-based compounds are particularly preferred,
More preferably, the following general formula (J-1) or (
J-2 This is a compound represented by 3.

General Formula (J-1) General Formula (J-2) In the formula, R2 and R3 each represent a hydrogen atom, an alkyl group, or an aryl group. However, R2 and R2 cannot be hydrogen at the same time. R4 to R I3 each represent a hydrogen atom, an alkyl group, or an aryl group.

In the general formulas (J-13 and (J-23), R2 and R3 each represent a hydrogen atom, an alkyl group, or a ryoryl group. , ethyl group, butyl group, octyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, etc. Examples of the 7-aryl group represented by R2 or R3 include phenyl group, etc. The alkyl group and aryl group may have a substituent, and examples of the substituent include a halogen atom, a furkyl group, a heptalyl group, an alkoxy group, an aryloquine group, and a polycyclic group.

The total number of carbon atoms in R2 and R3 (including the lt substituent) is 6
~40 is preferred.

In the general formula (J-1) or (J-2)i, R
4 to R'' are each a hydrogen atom, an alkyl group, or 7
The furkyl group represented by R4-R13 includes, for example, a methyl group, an ethyl group, etc., and the aryl group represented by R4 to R'' includes a phenyl group, etc. .

In the general formula (J-1) or (J-2), 2! Specific examples of compounds include the above-mentioned exemplified piperazine compounds (J
-1) - (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) 15 g of anhydrous potassium carbonate was added to 100 ml of 77 tons in which 9.0 g of piperazine and 55 g of myristyl bromide were dissolved, and the mixture was boiled and refluxed for 10 hours to react.

After the reaction, the reaction solution was poured into 500 ml of water and extracted with 500 ml of ethyl acetate. After drying the ethyl acetate layer over magnesium sulfate, the ethyl acetate was distilled off to obtain the desired product as white crystals. Recrystallization was performed using 300 ml of 7setone to obtain 34 g of white flaky crystals (yield: 70%).

Melting point: 55-58°C Synthesis Example-2 (Combination of Compound J-34*) 18 g of 4-morpholinoaniline was mixed with 100.1 g of ethyl #acid.
After dissolving in the solution, while keeping the reaction solution at 20°C under stirring,
Acetic anhydride 12- was added portionwise. After adding acetic anhydride, the mixture was cooled with water, and the precipitated crystals were filtered and recrystallized with ethyl acetate to obtain 16.5 g of white powdery crystals (yield: 4175%).

Melting point: 207-210°C General formula (K) In the formula, R1 is an aliphatic group, a cycloalkyl group, or 717
- represents a group, and Y represents a simple bond or a divalent hydrocarbon group necessary to form a 5- to 7-shell heterocycle with a nitrogen atom * R', R', R4tR5, Ri, R7
represent a hydrogen atom, an aliphatic group, a cycloalkyl group, or an aryl group, respectively. However, R2 and R4 and R3 and R6 combine with each other to form a simple bond and, together with the nitrogen atom and Y, represent an unsaturated A heterocycle with 5 to 7 shells may be formed. *When Y is a simple bond, R5 and R7 combine with each other to form a simple bond and form an unsaturated ring with the nitrogen atom and Y. May form a 5-shell heterocycle, and Y
When is not a mere bond, R1, 7% R7 and Y or Y itself may form an unsaturated bond to form an unsaturated 6- or 7-shell heterocycle together with the nitrogen atom and Y.

Examples of the aliphatic group substituted by R1 include a saturated furkyl group which may have a substituent, and an unsaturated furkyl group which may have a 1/jl substituent. As a saturated furkyl group,
For example, methyl group, ethyl group, butyl group, octyl group,
Examples of the unsaturated furkyl group include a dodecyl group, a tetradecyl group, and a hexadecyl group. Examples of the unsaturated furkyl group include an ethynyl group and a propenyl group.

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

The aryl group represented by R't% 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 alkyl groups, aryl groups, alkoxy groups, carbonyl groups, carbamoyl groups, and acyl groups.
groups, sulfamoyl groups, sulfonemide groups, carbonyloxy groups, alkylsulfonyl groups, arylsulfonyl groups, hydroxy groups, heterocyclic groups, alkylthio groups, arylthio groups, etc., and these substituents further have a substituent. It's okay.

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. When Y is a divalent monovalent hydrogen group, that is, a methylene group, R5 and Y or R7 and Y may form an unsaturated bond. (In the case of an ethylene group, R5 and Y%R7 and Y or Y itself may form an unsaturated bond, forming an unsaturated 7-shell heterocycle.) The divalent hydrocarbon group represented by Y that may form a bilobed shell ring may also have a substituent, and this substituent may include an alkyl group, a carbamoyl group, an alkyloxycarbonyl group, etc. , an acylamino group, a sulfonamide group, a sulfamoyl group, a heptalyl group, a heterocyclic group, and the like.

In the general formula (K), R2, R3, R', R5°R'' and 1/R' each represent a hydrogen atom, an aliphatic group, a cycloalkyl group or an aryl group; Examples of the aliphatic group include a saturated furkyl group that may have a substituent and an unsaturated alkyl group that may have a substituent. Examples of the saturated alkyl group include a methyl group, an ethyl group, a butyl group, and an unsaturated alkyl group that may have a substituent. group, octyl group, dodecyl group,
Examples of the unsaturated alkyl group include a tetradecyl group and a hexadecyl group, and examples of the unsaturated alkyl group include an ethynyl group and a propenyl group.

The cycloalkyl group represented by R2-R7 is a 5- to 7-shell 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 group, dichlorofurkyl group, and aryl group represented by R2 to Rt above include a furkyl group, an aryl group, an alkoxy group, a carbonyl group, a carbamoyl group, an acylamide 7 group, a sulfamoyl group, a sulfone 7 mido group,
Examples include carbonyloxy group, alkylsulfonyl group, arylsulfonyl group, hydroxy group, heterocyclic group, and furkylthio group.

It is more preferable that the compound represented by the general formula (K) has 5 to 7 saturated heterocycles than unsaturated.

The amount of the compound represented by the general formula (K) below is as follows:
The amount of "c" relative to the magenta coupler represented by the general formula (1) of the present invention is preferably from 5 to 300 mol%, more preferably from 10 to 200 mol%.

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

In the margins below, -34 to -35 to -36 to -37 to -39 to -40 to -41 Next, an example of vicarious decay synthesis of a compound decayed by the general formula (K) is shown.

Synthesis Example-1 (Synthesis of Compound @ K-14) Piperazine9.
28g of OgXV myristyl bromide folded into f#60
．． 6.0 g of anhydrous potassium carbonate was added to 77 tons of No. 11, and the mixture was refluxed for 20 hours to react.

After the reaction, the reaction solution was poured into 300ml of water and extracted with 300ml of ethyl acetate (I). After drying the ethyl acetate layer over magnesium sulfate, the ethyl acetate was distilled off to obtain the desired product as white crystals. Recrystallization was performed with 100 + J of acetone to obtain 12 g of white scaly crystals (yield: 43%).

Melting temperature, 175-180°C Prevents fogging due to discharge caused by electrostatic charging of the photosensitive material due to friction, etc. in hydrophilic colloid layers such as protective layers and intermediate layers of the silver halide photographic light-sensitive material of the present invention, and improves image U It may contain an ultraviolet absorber to prevent deterioration due to light.

The silver halide photographic material of the present invention may 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 flow out of the color light-sensitive material or are bleached during development.

The silver halide emulsion layer and/or other hydrophilic colloid layer of the silver halide photographic light-sensitive material of the present invention is matted with the aim of reducing the gloss of the light-sensitive material, increasing the ease of writing, and preventing mutual sticking of the light-sensitive materials. Agents can be added.

A lubricant can be added in order to reduce cleaning and rubbing of the silver halide photographic light-sensitive material of the present invention.

An antistatic agent for the purpose of preventing static electricity can be added to the silver halide photographic material 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 other than the emulsion layer on which the emulsion layer is laminated with respect to the support. It may also be used in a colloid layer.

The photographic emulsion layer and/or the silver halide photographic light-sensitive material of the present invention
Other hydrophilic colloid layers may contain various additives for the purpose of improving coating properties, preventing static electricity, improving slipperiness, emulsifying and dispersing, preventing adhesion, and improving photographic properties (promoting phenomena, increasing contrast, sensitizing, etc.). Surfactants are used.

The silver halide photographic light-sensitive material of the present invention includes a photographic emulsion layer, a flexible reflective support such as baryta paper or paper laminated with α-olephne polymer, synthetic paper, cellulose acetate, 1111M 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.

The silver halide photographic light-sensitive material of the present invention can be produced by subjecting the support surface to corona discharge, ultraviolet irradiation, flame treatment, etc. as necessary, and then directly or It may be applied via one or more subbing layers to improve stability, abrasion resistance, hardness, antihalation properties, frictional properties, and/or other properties.

When coating the silver halide photographic 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 silver halide 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 has sensitivity. 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.

Exposure times include not only exposure times of 1 millisecond to 1 second commonly used in cameras, but also exposure times shorter than 1 microsecond, such as exposure times of 100 microseconds to 1 microsecond using a negative ray tube or xenon flash lamp.
Microsecond exposures can be used, and exposures longer than 1 second are also possible. The exposure may be performed continuously or intermittently.

The silver halide photographic material of the present invention can be used to form an image by color development known in the art.

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 sulfur salts, since they are more stable than in the free state. Additionally, these compounds generally have a concentration of about 0.1 g to about 30 g per color developer 11, preferably about 1 g to about 15 g per color developer 111.
CI's: Used in degrees.

Examples of amine phenol developers include 0-aminophenol, p-aminophenol, and 5-amino-2-
Oxytoluene, 2-amino-3-oxytoluene, 2
-oxy-3 to amino-1,4-dimethylbenzene and the like.

Particularly useful primary aromatic amine color developers are N, N'
-Dialkyl-〇-phenylenediamine type compound, and the alkyl group and phenyl group are arbitrary Ii! W1 with substitution
may have been replaced. Among them, the particularly useful compound 'I!
7! 'A' includes N,N'-diethyl-p-phenylenediamine [1f salt, N-methyl-p-phenylenediamine hydrochloride, N,N'-dimethyl-p-phenylenediamine hydrochloride, 2-amino-5 -(N-ethyl-N-
dodecylamino)-toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfur [! 1N-ethyl-N-β-hydroxyethylaminoaniline, 4-amino-3-methyl-NN'-diethylaniline, 4-amino-N-(2-methoxyethyl)-N-ethyl-3-methylaniline-p- Examples include toluene sulfonate.

In addition to the above-mentioned primary aromatic amine color developer, the color developer used in the process of the present invention includes a series of components that are normally added to color developers, such as sodium hydroxide and sodium carbonate. , alkaline agents such as potassium carbonate, alkaline total sulfites, alkali gold B bisulfites,
Alkali metal thiocyanates, alkali metal halides, benzyl alcohol, water softeners, cJ thickening agents, and the like can also be optionally included. The pH fii of this color developer is usually 7 or higher, most commonly about 1
0 to 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 the bleaching agent in the bleaching process, and the metal complex salt has the effect of oxidizing the metallic silver generated during development and converting it into silver halide, and at the same time coloring the uncolored areas of the coloring agent. It has a composition in which a fully bent ion such as iron, cobalt, copper, etc. is coordinated with aminopolycarboxylic acid, oxalic acid, citric acid, etc. The most preferred organic acids used to form such metal complex salts of organic acids include polycarboxylic acids or amitubolicafrebonic 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 r, ri [4] Ethylenediaminetetraacetic acid disodium salt [5] Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt [6] Ethylenediaminetetraacetic acid tetrasodium salt [7] Nitrilotriacetic acid sodium salt The bleaching agent used contains the above metal complex salt of acid as a bleaching agent and may also contain various additives. As additives, it is particularly desirable to include rehalogenating agents such as alkali halides or ammonium halides, such as potassium bromide, sodium bromide, sodium chloride, and ammonium bromide, gold salts, and chelating agents.

Also, the pH of borates, M salts, acetates, carbonates, phosphates, etc.
Buffers, alkylamines, polyethylene oxides, and other substances known to be added to ordinary bleaching solutions can be added as appropriate.

Furthermore, the fixer and bleach-fixer contain ammonium sulfite,
Potassium sulfite, ammonium bisulfite, bisulfite III!
! potassium acid, sodium bisulfite, metabisulfite Lm W
Sulfites such as ammonium, potassium metabisulfite, sodium metabisulfite, boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bisulfite, sodium bicarbonate, potassium bicarbonate, acetic acid, acetic acid IIH buffers made of various salts such as thorium 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 diosulfate, thiocyanate, sulfite, etc. , the bleach-fixing replenisher may contain these salts and be replenished into the processing bath.

In the present invention, in order to increase the activity of the bleach-fix solution, air may be blown into the bleach-fix bath and the storage tank for the bleach-fix replenisher as desired, or an appropriate oxidizing agent may be added. Agents such as hydrogen peroxide, bromine M salts, persulfates, etc. may be added as appropriate.

[Effects of the Invention] By incorporating the magenta coupler of the present invention and the compound represented by the general formula (1) into the silver halide emulsion layer of a silver halide photographic light-sensitive material, humidity during storage,
It was possible to improve yellow stain caused by temperature.

[Examples] The present invention will be explained in more detail by showing specific examples below, but the embodiments of the present invention are not limited thereto.

Example 1 On a support made of polyethylene-coated paper, the exemplary magenta coupler MC-1 was 4 mQ/dm', the green-sensitive silver chlorobromide emulsion was 4 m1J/d12 in terms of silver, and dibutyl phthalate was 41110/d1128° and 16 gelatin
It was applied so that the coating material m had mq/d12.

Furthermore, gelatin was coated on the top layer so as to form a coating opening of 9 m+1/dm''.

The sample thus prepared is referred to as sample 1. Next, the above sample 1
Sample 1 except that the combination of coupler and organic solvent in the coupler-containing layer was changed as shown in Table 1.
Samples 2 to 8, which were the same as those described above, were prepared. However, the silver coating amount for Samples 7 and 8 was 2 mO/dm'. In addition, the organic solvent coating material m used in samples 3 and 4 was 411117/
d1? Closed.

These samples were subjected to green light wedge exposure using a photosensitive needle (model KS-7, manufactured by Konishiroku Photo Industry Co., Ltd.), and then subjected to the following treatments.

Standard processing steps (processing concentration and processing time) [1] Color development 38°C 3 minutes 30 seconds [2] Bleach 33°C 1 minute 30 seconds [3] Washing process
25-30℃ 3 minutes [4] Drying 75-80℃
Approximately 2 minutes [Color developer] Benzyl alcohol 15 ethylene glycol 151Q Potassium sulfite 2.0 (] Sodium bromide
0.7g I.lium chloride
0.2g potassium carbonate
30.0 (]Hydroxylamine sulfate
3.0g polyphosphoric acid (TPPS)
2.5(13-methyl-4-amino-N-(β-methanesulfonamidoethyl)-aniline sulfate 5.5g optical brightener (4,4'-diaminostilbenzsulfonic acid derivative) 1.OQ water Add 2.0 g of potassium oxide water to bring the total amount to 12, and adjust to 11H10 and 20.

[Bleach-fix solution] Ferric ammonium ethylenediaminetetraacetate dihydrate 60 Q ethylenediaminetetraacetic acid M 3゜ammonium thiosulfate (70% solution) 100i ammonium sulfite (40% solution) 27.5㎜ potassium carbonate or glacial acetic acid) Adjust to 87.1 and add water to bring the total volume to 12.

Yellow staining of each sample obtained after the treatment was performed in the following manner.

[Measurement of Yellow Stain] Each sample was stored in a constant temperature bath at 70° C. and 80% relative humidity for 7 days, and the difference between the initial blue density and the blue density after storage was defined as yellow stain.

The results are shown in Table-1.

Margin Table 1 Below: As is clear from Table 1, the yellow stain reduction effect of the samples of the present invention is significant for all magenta couplers.

Example 2 A multicolor silver halide photographic material was prepared by sequentially coating the following layers on a support made of polyethylene-coated paper from the support side.

No. IS: blue-sensitive silver halide emulsion layer as yellow coupler α-bivalyl α-(1-benzyl-2,4-dioxy-imidaridin-3-yl)-
2-chloro-5-[γ-(2゜4-di-t-amylphenoxy)butyramide]-acetanilide at 8 mQ/
dt', 3 ma when converting blue-sensitive silver chlorobromide emulsion into silver
/ dmt, 2,4-di[-butylphenol-3'
, 5'-di-t-amyl-4'-hydroxybenzoate 3m+1/d12, dioctyl phthalate 31
11(+/d, ?) and gelatin at 16mo/(11
'The coating was applied so that it would become the coating bone m.

2nd ffl: Intermediate layer gelatin was coated at a coating density of 4 mg/d12.

Third layer: green-sensitive silver chlorobromide emulsion layer containing the above-mentioned exemplary magenta coupler (MC-1) at 4 ma/d.
m2, green-sensitive silver chlorobromide emulsion converted to silver is 4 m.

/dw2, dibutyl phthalate 4fllll/dt'
And gelatin was coated at a coating amount of 16 mo/dm'.

4th layer: Intermediate layer UV absorber 2-hydroxy-3',5'-G[
-Amyl phenyl)-benzotriazole 3 mg/d
f, 2-(2'-hydroxy-3'.

5'-di-t-butylphenyl)-benzotriazole at 3 mQ/dm', dioctyl phthalate at 41
mg/df and gelatin were coated at a coating amount of 14 mg/dm'. ,.

5th layer: red-sensitive silver chlorobromide emulsion layer 2,4-dichloro-o-3-methyl- as cyan coupler
6-[α-(2,4-di-t-amylphenoxy)butyramide]-phenol lll1g/d v2.2-
(2,3,4,5,6-pentafluorophenyl)acylamino-4-chloro-5-[α-(2,4-di-t
ert-amylphenoxy)pendelamide] at 3 m
g / (1v2, dioctyl phthalate 2mQ /
d12 and red-sensitive silver chlorobromide emulsion converted into silver: 3
The coating was applied in such a manner that the coating amount was that of mMdf.

611th! : 2-(2'-hydroxy-3') as an intermediate layer UV absorber
, 5'-di-t-amylphenyl)-benzotriazole at 2 mQ/df, 2-(2'-human0x-
3',5'-di-t-butylphenyl)-benzotriazole was applied at a rate of 2 mQ/d12, dioctyl phthalate at a rate of 211O/dv2, and gelatin at a rate of 6mMdf.

Seventh layer: Protective layer gelatin was coated at a coating weight of 9II1 g/d12.

The sample thus prepared is designated as sample 9.

Next, Samples 10 to 33, which were the same as Sample 9, were prepared, except that a magenta coupler, a total refraction complex, an organic solvent, and an image stabilizer were added to the third layer of Sample 9 in the combinations shown in Table 2.

However, for Samples 13 to 33, the third layer was coated at a silver concentration of 2 mg/df.

The thus prepared sample was subjected to the same exposure and processing as in Example 1. For each sample obtained after the treatment, yellow stain was measured in the same manner as in Example 1, and light resistance was measured in the following manner.

The results are shown in Table-2.

[Light resistance test] Each sample was exposed to sunlight for 30 days using an underglass outdoor exposure table, and the green light density before and after fading was measured.

The degree of color fading due to light (fading rate) was determined as follows.

Fading rate = (Do −D) /DOX 10G (%) D
o = Concentration before photobleaching D = Concentration made by photobleaching Lower margin platinum m1 body is 1 mol per 1 mol of coupler, high boiling point organic solvent used is the same as the compound represented by the above general formula (1) ff
1 (4mM dr) and 1 mole of both stabilizers were added per 1 mole of coupler.

As is clear from Table 2, it can be seen that the samples of the present invention have improved yellow stain compared to the comparative samples.

In particular, when comparing samples 14 and 16, when a metal complex is used in combination with the magenta coupler represented by the general formula [I], the sample of the present invention significantly reduces yellow stain without impairing light resistance compared to the comparative sample. I know what you did. In addition, in the present invention, sample 3 in which a high boiling point organic solvent with a dielectric constant of 6.0 or less is used in combination with the compound represented by general formula (1)
From 0 to 32, it can be seen that yellow stain is further reduced.

Claims (3)

[Claims] (1) 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 and a compound represented by the following general formula (1). A silver halide photographic material characterized by containing. General formula (1) ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, R_1 and R_2 each represent a hydrogen atom, an aliphatic group, or an aryl group. Also R_1 and R_2
may be combined to form a cycloaliphatic group. R_3 represents an aliphatic group or an aryl group. R_4 represents a hydrogen atom, an aliphatic group, an aryl group, or -(J2)-_nCOOR_5 (R_5 represents an aliphatic group or an aryl group). J_1 and J_
2 each represents a divalent linking group. m and n are
Each represents 0 or 1. ] (2) Claim (1) characterized in that a metal complex is added to a silver halide emulsion layer containing the magenta coupler and the compound represented by general formula (1). silver halide photographic material. (3) The silver halide photographic material according to claim (2), wherein the magenta coupler is a magenta coupler represented by the following general formula [I]. 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. Further, R represents a hydrogen atom or a substituent. ] (4) A patent characterized in that the magenta coupler is added to the silver halide emulsion layer using a compound represented by general formula (1) and a high boiling point organic solvent with a dielectric constant of 6.0 or less. A silver halide photographic material according to claim (1).