JPS62182741A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide photographic sensitive material having superior color reproducing characteristic causing small increase of fog by incorporating a specified Magenta coupler into one layer of a silver halide emulsion, incorporating also a metal complex having a specified quenching velocity constant of singlet term oxygen and a specified compd. CONSTITUTION:In at least one layer of the silver halide emulsion, there is contained a Magenta coupler expressed by the formula I, and a metal complex having >=3X10<7>, pref. >=1X10<8>M<-1>.sec<-1> quenching velocity constant of the singlet oxygen, and a compd. expressed by the formula II in the silver halide emulsion layer contg. the Magenta coupler. Preferred content of the metal complex in 1mol Magenta coupler expressed by the formula I is 0.5-1mol. The amt. of the compd. expressed by the formula II to be used is pref. 0.5-1mol per 1mol Magenta coupler expressed by the formula I. The proportion of the metal complex to the compd. II to be used in combination is pref. 1:3-3:1 by molar ratio.

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 color photographic light-sensitive material with improved light fastness.

[Background of the Invention] A method of forming a dye image using a silver halide color photographic light-sensitive material includes a method of forming a dye by a reaction between a photographic coupler and an oxidized color developing agent. As a photographic coupler for color reproduction,
Magenta, yellow, and cyan couplers are used, and an aromatic primary amine color developing agent is used as the color developing agent.Magenta and yellow couplers and an aromatic primary amine color developing agent are used. A dye such as an azomethine dye is formed by the reaction with an oxidized form of an aromatic 7iX11-class amine color developing agent, and a dye such as an indoaniline dye is formed by a reaction between a cyan coupler and an oxidized form of an aromatic 7iX11-class amine color developing agent.

Of these, in order to form a magenta color image, 5
-Pyrazolone, cyanoacetophenone, indacilone,
Pyrazolobenzimidazole, pyrazolotriazole couplers, etc. are used.

Most of the conventional magenta color image forming couplers that have been put into practical use have been 5-pyrazolone couplers.

The color image formed from the 5-pyrazolone coupler has excellent fastness against light and heat, but the color tone of this dye is not sufficient, and there is unnecessary absorption with a yellow component around 430 nm, and there is an unnecessary absorption around 550 nm. The absorption spectrum of visible light is also broad, which causes color smearing and the edges of photographs lack vividness.

U.S. Patent No. 3.72 as a coupler that does not have this unnecessary absorption
No. 5,067, JP-A-59-162548, JP-A-5
1H-pyrazolo[3°2-cl-s-triazole type coupler, 1) described in No. 9-171956 etc.
-1-imidazoN,2-b]-pyrazole type couplers, IH-b pyrazolo[1,5-b]-pyrazole type couplers, or IH-b pyrazolo[1,5-d]tetrazole type couplers, especially It is excellent.

However, the light fastness of dye images formed from these couplers is significantly lower. When these couplers are used in photosensitive materials, particularly color photographic papers for direct viewing, the essential requirements of photographic materials, which are to record and preserve images, are impaired.

Therefore, it was difficult to put it into practical use. Therefore, as a method to improve light resistance, it was proposed to use phenol-based or phenyl ether-based antioxidants.
Although it is described in No. 732, its effect was not sufficient.

On the other hand, the use of metal complexes as anti-fading agents was published in 1983.
-99340, 56-168652, 60-5
It is described in No. 1834, etc. When these metal complexes are applied to dyes formed from pyrazolotriazole couplers, some compounds can be light-fastened to some extent, but compounds that have a relatively large light-fastening effect generally do not work well when preserving unexposed samples. It has the disadvantage that fog increases significantly over time.

Furthermore, among the metal complexes, compounds that showed a small increase in fog when unexposed samples were stored over time had insufficient light fastening effects.

Therefore, it has been difficult to simultaneously improve the light resistance of a silver halide photographic light-sensitive material that uses a pyrazolotriazole-based magenta coupler and a metal complex while preventing fog on storage over time.

[Object of the Invention] An object of the present invention is to provide a silver halide photographic light-sensitive material that has excellent color reproducibility of magenta dye images, improved light fastness, and less increase in fog due to storage of raw samples over time. It is in.

[Configuration 1 of the Invention The above 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 has the following general formula: Contains a magenta coupler represented by [I],
And the silver halide emulsion layer containing the magenta coupler has a singlet oxygen quenching rate constant of 3X 10' M-1
−sec −+ or higher metal complex and the following general formula [a
] This is achieved by providing a silver halide photographic material containing a compound represented by the following.

General Formula [I] [In the formula, 7 represents a group of nonmetallic atoms necessary to form a nitrogen-containing heterocycle, and the ring formed by Z may have a substituent.

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

Further, R represents a hydrogen atom or a substituent.

General formula [a] In the formula, R1 and R2 each represent an alkyl group. R3 is an alkyl group, -NR'R'' group, -3R'
Represents an organic group of 1[]1 on R'L. ), or -c
o Represents OR"or"(R" represents Suiseki atom or 1st character If represents base). m represents an integer from 0 to 3, and -0 [Details of the Invention (J4 Form 1) The present invention will be described in detail below.

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

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

Moreover, R represents a hydrogen atom or a substituent.

Examples of the substituent represented by R include a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a heterocyclic group,
Acyl group, sulfonyl group, sulfinyl group, phosphonyl group, carbamoyl group, sulfamoyl group, sia7 group, spiro compound residue, bridged hydrocarbon compound residue, alkoxy group, aryloxy group, heterocyclic oxy group, siloxy group, Acyloxy group, carbamoyloxy group, amide 7 group,
Acylamino group, sulfonamide group, imide group, threido group, 7 sulfonylamine groups, 7 alfkidicarbonyl 7 groups, 7 lyloxycarbonylamide groups, alkoxycarbonyl group, aryloxycarbonyl group, alkylthio group, arylthio group, Examples include heterocyclic thio groups.

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

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

In addition, these alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, and cycloalkenyl groups include substituents [e.g., aryl, cyano, 7% lodene atom, heterocycle, cycloalkyl, cycloalkenyl, spiro compound residue,
In addition to bridged hydrocarbon compound residues, those substituted via a carbonyl group such as acyl, carboxy, carbamoyl, alkoxycarbonyl, and aryloxycarbonyl, and those substituted via a heteroatom (specifically, hydroxy , alkoxy, 7-aryloxy, heterocyclic oxy, siloxy, acyloxy, carbamoyloxy, etc. substituted via an oxygen atom, nitro, amino (including difurkyl 7-mi/etc.), sulfo-7-amoylamino, alkoxycarbonyl amine/, Those substituted via a nitrogen atom such as 7-aryloxycarbonyl 7-mino, acylamino, sulfonamide, imide, ureido, etc., those substituted via a sulfur atom such as alkylthio, iri-ruthio, heterocyclic thio, sulfonyl, sulfinyl, sulf-7moyl, etc. to be replaced by
[1] such as those substituted via a phosphorus atom such as phosphonyl.

Specifically, for example, methyl group, ethyl group, isopropyl group, t-butyl group, pentadecyl group, heptadecyl group, 1
-hexylnonyl group, 1.1'-cybenthylnonyl group,
2-chloro-1-butyl group, trifluoromethyl group, 1
-Ethoxytridecyl group, 1-nodoxyisopropyl group, methanesulfonylethyl JJ, 2.4-not-7mil7enoxymethyl group, 7nily/group, 1-phenylisopropyl group, 3-Ill-butanesulfonaminophenoxy Propyl group, 3-4'-(α-(4''(p-hydroxybenzenesulfonyl)phenoxy)tokyylami/+phenylpropyl group, 3-+4'-[α-(2
",4"-not-7milphenoxy)butanamide]
phenyl)-propyl i, 4-(α-(0-chloro7e/xy)tetradecanamido72/xy]furobyl group,
Examples include allyl group, cyclopentyl group, and cyclohexyl group.

The 717-l group represented by R'c is preferably a phenyl group, and substituents (for example, alkyl groups, alkoxy groups,
(7 acylamide groups, etc.).

Specifically, phenyl group, 4-t-butyl7enyl group 1
2W4-cyL-7milphenyl group, 4-tetradecanamidophenyl group, hexadecyloxyphenyl group, 4'
-[α-(4″-t-butylphenoxy)tesiladecaneamide] phenyl group and the like.

The heteT:I'R group represented by R preferably has 5 to 7 members, which may be substituted or fused, specifically 2-7yl group, 2- chenyl group, 2-
Examples include pyrimidinyl group and 2-benzthiazolyl group.

Examples of the acyl group represented by R include acetyl group, phenyl 7cetyl group, dodecanoyl group, a-2,4-di-
Furkylcarbonyl groups such as t-7 milphenoxybutanoyl group, benzoyl! , 3-pentadecyloxybenzoyl group, 7-aryl carbonyl group such as p-chlorobenzoyl group, and the like.

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.

Examples of the sulfinyl group represented by R include an ethylsulfinyl group, an octylsulfinyl group, a fulkylsulfinyl group such as a 3-phenoxybutylsulfinyl group, a phenylsulfinyl group, and a chiarylsulfinyl group such as a pentadecyl phenylsulfinyl group. can be mentioned.

The phosphonyl group represented by R includes an alkylphosphonyl group such as a butyloctylphosphonyl group, an alkoxyphosphonyl group such as an octyloxyphosphonyl group, a 717-loxyphosphonyl group such as a 7enoxyphosphonyl group,
Examples include a 7-arylphosphonyl group such as a phenylphosphonyl group.

The carbamoyl group represented by R''Ch may be substituted with a furkyl group, an aryl group (preferably a phenyl group), etc., such as an N-methylcarbamoyl group, N, N-')-
If carbamoyl i, N-(2-pentadecyloctylethyl)carbamoyl M, N-ethyl-N-dodecylcarbamoyl group, N-[3-(2,4-not-t-7milphenoxy)propyl)carbamoyl group, etc. It will be done.

The sulfamoyl group represented by the margin R below may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc.
For example, N-propylsulfamoyl, N,N-diethylsulfamoyl, N-(2-penta-r-syloxyethyl)sulfamoyl, N-ethyl-N-dodecylsulfamoyl! , N-phenylsulfamoyl group, and the like.

Examples of the su and α 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]hebutan-1-yl, tricyclo[3
,3,1,13°)]]decan-1-yl7,7-tumethyl-bicyclo[2,2,1]hebutan-1-yl and the like.

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

The 7-aryloxy group represented by R'c is preferably 7-enyloxy, and the 7-aryl nucleus may be further substituted with any of the substituents or atoms listed above for the aryl group, for example, 7-enyloxy. group, pt-butylphenoxy group,
Examples include m-pencudecylphenoquine group.

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

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

The acyloxy group represented by R includes, for example, an alkylcarbonyloxy group, an arylcarbonyloxy group, etc., and may further have a substituent. Specifically, an acetyloxy group, an a-aryl acetyl Examples include oxy group and benzoyloxy group.

The carbamoyloxy group represented by R'''C may be substituted with an alkyl group, an atomyl group, etc., such as N-ethylcarbamoyloxy group, N,N-diethylcarbamoyloxy group, N-7zni Examples include carbamoyloxy group.

The amine group represented by R''C may be substituted with an alkyl group, a teryl group (preferably a phenyl group), etc., such as a dithylamino group, a 7-nilino group, a chloroanily group, a 3- pentadecyloxylponylanili/i,2-
Examples include cucor-5-hexadecaneamide anilino group.

Examples of the acylamine 7 groups represented by R include alkylcarbonylamino groups, arylcarbonylamino groups (preferably phenylcarbonylamino 7 groups), and may further have a substituent, specifically an acetamido group. , α-ethylpropanamide group, N-7 enyl ace F amide group,
Dodecanamide group, 2,4-ts-amyl 7-functional/xyacetamide group, α-3-L-butyl 4-hydroxy 7
Examples include 27-xybutanamide group and the like.

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

Specific examples include methylsulfonylamide 7 group, pentadecylsulfonyl 7mino group, benzenesulfonamide group, p-toluenesulfonamide group, and 2-methoxy-5-t-7 milbenzenesulfonamide group.

The imide group represented by R may be @1 nodular or cyclic, and may have a substituent, for example, a succinimide group, a 3-heptadecylsuccinimide group, a 7
Talimide groups, glutarimide groups, etc. are included.

The threido group represented by R'c'' may be substituted with an alkyl group, an aryl group (preferably a phenyl group)'*, for example, an N-ethylureido group, an N-methyl-N
-decylureido l' group, N-7 22lureido group, N-
Examples include p-)lylureido group.

The sul 7 amoylami 7 group represented by R is an alkyl group,
It may be substituted with an aryl group (preferably a phenyl group), and examples thereof include N,N-dibutylsul7amoylami/i, N-methylsul7amoylami7 groups, N-phenylsul7amoylamy7 groups, and the like.

The alfkhidicarbonylamide 7 group represented by R is,
It may further have a substituent, for example, a nodoxycarbonylamino group, a methoxyethoxycarbonylamino group,
Examples include 7 octadecyloxycarbonylamide groups.

The aryloxycarbonylamide 7 group represented by R''Ch may have a substituent, for example, the phenoxycarbonylamide 7 group, 4-methylphenoxycarbonylamide 7
Examples include groups.

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

The 7-aryloxycarbonyl group represented by R may further have a substituent, such as phenoxycarbonyl M,
I)-chloro-7enoxycarbonyl group, chlor-pentadecyloxyphenoxycarbonyl group, and the like.

The furkylthio 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″I? is preferably a phenylthio group and may further have a substituent, such as 7-ethyl, nylthio, p-methoxyphenylthio, 2-L-octylphenylthio, 3-octadecyl Phenylthio group, 2
-carboxyphenylthio group, p-7 heptadminophenylthio group, and the like.

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

Examples of substituents that can be separated by reaction with the oxidized product of the color developing agent represented by
Examples include groups that are substituted via an i atom or a nitrogen atom.

In addition to the carboxyl group, examples of the group substituted via a carbon atom include the general formula (R,' is the same as the above R, Z' is the same as the above Z, R2' and R3' are hydrogen atoms, aryl group, an alkyl group or a heterocyclic group, a group represented by ), a hydroxymethyl group, and a phenylmethyl group).

Examples of groups substituted via an oxygen atom include an alkoxy group, a 71-noloxy 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 thereof include a nidoxy group, a 2-phenoxyethoxy group, a 2-Schiff/ethoxy group, a 7enethyloxy group, and a p-chlorobenoloxy group.

The aryloxy group is preferably a 7eth/oxy group, and the 7 +7-yl group may further have a substituent, specifically a phenoxy group, a 3-methyl 7enoxy group,
3-dodecylphenoxy group, 4-notanesulfonamidophenoxy group, 4-[a-(3'-pentadecylphenoxy)butanamido]phenoxy group, hexidenelupamoylmethoxy group, 4-cyanophenoxy group, 4-notane Sulfonylphenoxy group, 1-s7tyloxy group,
Examples include p-methoxyphenoxy group.

The heterocyclic oxy group is preferably a 5- to 7-shell heterocyclic oxy group, which may be a condensed ring or may have a substituent. Specific examples include 1-phenyltetrazolyloxy group, 2-benzothiazolyloxy group, and the like.

The acyloxy group includes, for example, an acetoxy group, an alkylcarbonyloxy group such as a butazuroxy group, an alkenylcarbonyloxy group such as a cinnamoyloxy group,
Examples include a 7-arylcarbonyloxy group such as a benzoyloxy group.

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

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

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

Examples of the alkyloxalyloxy group include a methyloxalyloxy group.

Examples of the flukoxyoxalyloxy 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 furkylthio group include a butylthio group, a 2-cyanoethylthio group, a 7enethylthio group, a bencurthio group, and the like.

The arylthio group includes phenylthio group, 4-methanesulfonamidophenylthio group, 4-dodecyl7enethylthio group, 4-nonafluoropentane7mido7enethylthio group, 4-carboxyphenylthio group, 2-ethoxy-5-t- Examples include butylphenylthio group.

Examples of the heterocyclic thio group include 1-7 enyl-1.
2,3.4-tetracywal-5-thio group, 2-benzothiazolylthio group, etc. are included.

Examples of the alkyloxythiocarbonylthio group include a dodecyloxythiocarbonylthio group.

Examples include those represented by the general formula -N, which represent an aryl group, a heterocyclic group, a sulfamoyl group, a carbamoyl group, an acyl group, a sulfonyl group, an aryloxycarbonyl group, and an alkyl dicarbonyl group, and R1' and R1' are a bond. to form a heterocycle, provided that R1' and R5
' cannot both be hydrogen atoms.

The alkyl group may be linear or branched, and preferably has 1 to 22 carbon atoms. In addition, the alkyl group may have a substituent (for example, an alkyl group, an alkoxy group, an aryloxy group, an alkylthio group,
Arylthio group, alkylami 7 groups, arylami 7 groups, acylami/group, sulfonamide group, imino group, acyl group, alkylsulfonyl group, arylsulfonyl group,
Carbamoyl group, sulfamoyl group, alkyloxycarbonyl group, aryloxycarbonyl group, alkyloxycarbonylamide 7 group, aryloxycarbonylamide 7 group
group, hydroxyl group, carboxyl group, sia group, and halogen atom.

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

The 7-aryl group represented by R, 7 or R5' has 6 to 32 carbon atoms, preferably a phenyl group or a naphthyl group, and the aryl group may have a substituent. Examples of substituents for the alkyl group represented by R4' or R5' include the above-mentioned alkyl groups. Specific examples of the aryl group include a phenyl group, a 1-su7tyl group, and a 4-methylsulfonylphenyl group.

The heterocyclic group represented by R and/or R7' is 5 to 6
A simple ring is preferable, and it may be a condensed ring or may have a substituent. Specific examples include 2-furyl group, 2-quinolyl group, 2-pyrimidyl group, 2-benzothiazolyl group, and 2-pyridyl group.

The sulfamoyl group represented by R, ' or R5' includes N-furkylsulfamoyl group, N,N-noalkylsul7amoyl i, N-7lylsul7amoyl i, N
, N-diarylsulfur, 7-ammoyl group, etc., and these furkyl groups and aryl groups may have the substituents listed for the alkyl groups and aryl groups.
Specific examples of the sulf77moyl group include N,N-diethylsulfamoyl group, N-methylsulfamoyl group,
N-dodecylsulfamoyl group, N-9-)lylsul7
An example is an amoyl group.

As the carbamoyl group represented by R4' or R57,
Examples include N-furkylcarbamoyl group, N,N-dialkylcarbamoyl group, N-7lylcarbamoyl group, N,N-noarylcarbamoyl group, etc., and these alkyl groups and 7-aryl groups are similar to the above-mentioned alkyl and aryl groups. Specific examples of the carbamoyl group which may have the above-mentioned substituents include N,N-noethylcarbamoyl group, N-methylcarbamoyl group, N-dodecylcarbamoyl M, N-p-cyanophenylcarbamoyl group, N
-G+-)lylcarbamoyl group.

Examples of the 7-syl group represented by R or R, 7 include an alkylcarbonyl group, an arylcarbonyl group, and a heterocyclic carbonyl group, and the alkyl group, the 7-aryl group, and the heterocyclic group are substituted as a substituent. Specific examples of the 7-sil group which may have include, for example, hexafluorobutanoyl group, 2゜3.4.5.6-penta7fluorobenzoylcetyl group, benzoyl group, naphthonyl group, 2-
Examples include a 7lylcarbonyl group.

The sulfonyl group represented by R 4' or Rs' is
Examples include an alkylsulfonyl group, a 7-arylsulfonyl group, and a heterocyclic sulfonyl group, which may have a substituent (specific examples include an ethanesulfonyl group, a benzenesulfonyl group, an octanesulfonyl group, a naphthalenesulfonyl group, Examples include p-chlorobenzenesulfonyl group.

The aryloxycarbonyl group represented by R,' or R S' 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 R , i+ or R S' may have the substituents listed above for the furkyl group, and specific examples include a methoxycarbonyl group,
Examples include dodecyloxycarbonyl group and benzyloxycarbonyl group.

The heterocycle formed by combining R4' and RS' is preferably 5 to 6 rings, and may be saturated or unsaturated, and may or may not have aromaticity. , or may be a fused ring. Examples of the heterocycle include N-7 talimido group, N-succinimide group, 4-N-urasili group, 1-N-hyguntoynyl i, 3-N-2.4-)
Oxooxazolidinyl group, 2-N-1.1-dioxo-3-(2H)-oxo-1,2-benzthiazolyl group, 1-pyrrolyl group, 1-pyrrolinonyl group, 1-pyrazolyl group-1-pyrazolidinyl group group, 1-piperidinyl group, 1
-pyrrolinyl group, 1-imidazolyl group, 1-indolyl group, 1-indolyl group, 1-isoindolinyl group, 2-
Isoindolyl group, 2-isoindolinyl group, 1-benzotriazolyl group, 1-benzimidazolyl group, 1-(
1.2,4-)IJ7zolyl) group, 1-(1,2
, 3-)su7zolyl) group, 1-(1,2,3
, 4-tetrazolyl) group, N-morpholinyl group, 1,
2,3.4-tetrahydroquinolyl group, 2-oxo-1
-pyrrolidinyl group, 2-IH-pyridone group, 7-talathion group, 2-oxo-1-piperidinyl group, etc.
These terocyclic groups include alkyl groups, aryl groups, furkyloxy groups, 7-lyloxy groups, 7-syl groups, sulfonyl groups, furkyl-7-mi-7 groups, 7-lylamino-7 groups, acylamino groups, sulfonamide-7 groups, carbamoyl groups, sulfamoyl group,
Alkylthio group, arylthio group, Threido group, flufkidicarbonyl group, 7lyloxycarbonyl group, imido group, nitro group, cyano group, carboxyl group, Ha117
W1 may be replaced by a 5/n atom or the like.

Examples of the nitrogen-containing ring formed by 2 or Z' include a pyrazole ring, an imidazole ring, a triazole ring, or a tetrazole ring, and examples of the substituent that the ring may have include those mentioned above for R. There are many things that can be mentioned.

In addition, general formulas ([) and V, general formulas C'll) to [)T
) on the multi-ring ring (for example, R1R5~R,
) has a moiety (here, R'', X and Z tt have the same meanings as R , X and Z in general formula (1)), it forms a so-called screw type coupler, but is of course included in the present invention. Also, z, z ', z ``Z, yo'' mentioned in vi.
) The formed ring may be further fused with another ring (for example, a 5- to 7-shell cycloalkene).For example, the ring formed by the general formula (V
), R6 and R5 are R6 and R5 are R6 and R5 in the general formula [■].
7 and R8 may be combined with each other to form a ring (for example, 5 to 7 dichloroflukenes or benzene).

Below, what is expressed by the margin general formula [1] is more specifically, for example, tr
It is represented by the following general formulas [U] to [■].

General formula (II) General formula (1 [1) % formula % General formula [■] N -N -Nil General formula [■] General formula [■] N -N -NH General formula [■] Said general formula [`` ] to [■], R1 to R8 and X have the same meanings as R and X above.

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

General formula [■] In the formula, RI-X and z have the same meanings as RlX and Z in the general formula (1).

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

Regarding the substituents on the heterocycle in general formulas (1) to [■], R in general formula [■] and R1 in general formulas [11) to [)τ] meet the following condition 1. It is preferable that the following conditions are satisfied, and more preferable is the case that the following conditions 1 and 2 are satisfied, and particularly preferable is the case that the following conditions 1 are satisfied.
, 2 and 3.

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 R on the heterocycle are those represented by the following general formula (IX).

General formula [I! ] R1 R1゜-C- In the formula, RglR10 and R++ are each a hydrogen atom, and λ
Rodene atom, furkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkynyl group, heptalyl group, heterocyclic group, acyl group, sulfonyl group, sulfinyl group, phosphonyl group, carbamoyl group, sulf-1 moyl group, cyano group , spiro compound residue, bridged hydrocarbon compound residue, alkoxy group, aryloxy group, heterocyclic oxy group, siloxy group, acyloxy group, carbamoyloxy group, amine 7 group, 7 syl amino group, sulfonamide group, imide group , ureido group, 7 sul 7 moyl amine 7 groups, 7 alkoxycarbonyl 7 groups, 7 lyloxycarbonyl 7
represents an alkoxycarbonyl group, an aryloxycarbonyl group, a furkylthio group, an arylthio group, a heterocyclic thio group, and at least two of R91R3° and R11
One is not a hydrogen atom +11° Also, the above R,,R,. and two of Ro, for example R, and R2゜, may be combined to form a saturated or unsaturated ring (e.g. cycloflucane, cycloalkene, heterocycle), and the R eye is further bonded to the ring. The bridged hydrocarbon compound residue may be constructed by

The group represented by R3-R1 may have a substituent,
Specific examples of the groups represented by R9 to R++ and substituents that the groups may have include specific examples of the groups and substituents represented by R in the aforementioned general formula [1).

Also, for example, a moat formed by combining R9 and R3° and R3
Specific examples of the bridged hydrocarbon compound residue formed by -R1 and its optional substituents include cycloalkyl, cycloalkenyl, and heterocyclic groups represented by R in the general formula CI) Specific examples of hydrogen compound residues and their substituents are listed.

Among the general formula [■], (i) when two of Rs to R1+ are alkyl groups, (
ii) When one of Rs to R++, for example R11, is a hydrogen atom and the other two, R9 and R3°, combine to form a cycloalkyl together with the root carbon atom, the following is true.

Furthermore, in (i), it is preferable that two of R9 to R are furkyl groups and the other one is a hydrogen atom or an alkyl group.

Here, the furkyl and the dichlorofurkyl may further have a substituent (specific examples of the alkyl, the cycloalkyl, and the substituent thereof include the alkyl, dichlofurkyl, and the substituent thereof represented by R in the general formula (1)). Specific examples include:

In addition, the substituent that the ring formed by Z in the general formula CI) and the ring formed by Zl in the general formula [■] may have, and R2-R3 in the general formulas (II) to (VI] As such, those represented by the following general formula (X) are preferable.

General formula (X) -R'-5o2-R2 In the formula, R' represents fullkylene and R2 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 straight! !
It does not matter if the alkylene is mono-branched, and even if it has a substituent, examples of the substituent include R in the general formula [1] above.
When is an alkyl group, the substituents that the alkyl group may have include those shown below.

Preferred substituents include phenyl.

One preferred example of alkylene represented by R1 is shown below.

The alkyl group represented by R2 may be a linear, monobranched group.

Specifically, methyl, ethyl, propyl, 1so-propyl, butyl, 2-ethylhexyl, octyl, totyl, tetradecyl, hexadecyl, oftagyl, 2-
Examples include hequinrudecyl.

The cycloalkyl group represented by R2 is preferably 5 to 6 true cycloalkyl groups, such as cyclohexyl.

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

Specific examples of the aryl represented by R2 include phenyl and f7thyl. The aryl group may have a substituent. Examples of the substituent include linear or branched furkyl groups, and 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 CI), particularly preferred are those represented by the following general formula [revised].

General formula [XI] In the formula, R and X have the same meanings as R and X in general formula (1), and R' and R2 are R I in general formula (X).

It is the same as R2.

Specific examples of compounds applicable to the present invention are shown below.

Margin below I C.B.

C.O.

CH.

O CH.

C.B.

■ CH3 2H5 Margin below C4H9 Cl2H25 C4H.

■ CH= H3 C,H,s xHS CH3 C) 13 Te CH3 ■ CH.

CH.

C.H.

C.I.

■ C.H.

CHl 0CH2CONHCl12CII20Cfh0CII2
CH2SO□C111 2H5 C,H6 CH3 ■ CH3 0B Cs)ltm H3 H3 QC2H.

H3 H3 '　LiI)・1 CH.

Hs 12 feet L C.I.

CH.

C7H1'J H3CCH3 4G N -N -N 16FNN
Society (Journal of the Ch)
chemical society) v Parkin (P
erkin) 1 (1977), 2047-2
052, U.S. Patent No. 3,725,067, Patent No. 59-9
No. 9437, No. 58-42045, No. 59-1625
No. 48, No. 59-171956, No. 60-33552
No. 60-43659, No. 60-172982, No. 60-190779, and the like.

The couplers of the present invention typically contain lXl per mole of silver helodenide.
0-' mol-1 mol, preferably lXl0-'' mol to 8
It can be used in the range of X10-' moles.

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

The metal complex according to the present invention is a metal complex having a -single oxygen quenching rate constant of 3×10 7 M −1·sec or more.

The above - quenching rate constant of singlet oxygen is given in the Journal of Physical Chemistry (Journal of Ph.D.
(chemical chemistry) 83. 591
(1979) and others, which measures the 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 test compound is [Q], the concentration of rubrene in the single solution of rubrene after the test is [R], and the concentration of rubrene and the test compound after the test is The concentration of rubrene in the Atsumi solution is [R] stomach.
Then, −the quenching rate constant of singlet oxygen (kl is calculated by

The metal complex according to the present invention has a quenching rate constant of singlet oxygen defined by the above formula of 3 x 107 M''·5 ec-' or more, preferably 1 x 108 M''·5 ec-' or more. The central metal of the metal complex is preferably a transition metal, more preferably Fe, Go, Ni, or Pd.

Each metal atom of P[, particularly preferably a Ni metal atom.

The quenching rate constant of singlet oxygen according to the present invention is 3 x 107M
As the metal complex of -1·5ec-1 or more, those represented by the following general formulas [XI[] to [XV] are preferable.

General formula [XIN] General formula [XI] General formula [XIV] [In general formula [XII], general formula [XI [[] and general formula [XrV], M 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). X3 represents a hydroxyl group or a mercapto group. Y represents an oxygen atom or a sulfur atom. R3, R4, R5 and R6 each represent a hydrogen atom, a halogen atom, a cyan group, or an alkyl group, aryl group, cycloalkyl group or heterocyclic group bonded to a carbon atom directly or via a divalent linking group. Also, R3 and R4 and R5 and R
At least one of the combinations of 6 may form a 5- or 6-membered ring with the carbon atoms connected to each other.

Zo represents a compound capable of coordinating with M or a residue thereof.

General formula [XV] [In the formula, R21, R22, R23 and H2 each represent a hydrogen atom, a halogen atom, a hydroxy group, a cyano group, or a carbon atom on the benzene ring directly or indirectly through a divalent linking group. Represents a bonding alkyl group, aryl group, cycloalkyl group, or heterocyclic group. Further, R21 and R22, R22 and R23, or R23 and R24 may be combined with each other to form a 6-membered 1.

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 represents a totally bent atom. 1 General formula [XI] and general formula [X
IV ], X1 and x2 may be the same or different, but each is an oxygen atom, a sulfur atom or -NR
' - (R' is a hydrogen atom, an alkyl group (e.g. methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, (-butyl group, i-butyl group, benzyl group, etc.)
, represents an aryl group (eg phenyl group, tolyl group, naphthyl group, etc.) or a hydroxyl group. ), preferably an oxygen atom or a sulfur atom, more preferably an oxygen atom.

X3 in the general formula [X IV ] represents a hydroxyl group or a mercapto group, preferably a hydroxyl group.

General formula [XII], general formula [XI [[] and general formula [
X IV ] NoY represents an oxygen atom or a sulfur atom (the two Y's in the general formula [xIv] may be the same or different), preferably a sulfur atom.

General formula [XII], general formula [XI [[] and general formula [
XIV] 17) R3, R'', R5 Oyohi R6 may be the same or different, hydrogen atom, halogen atom (fluorine, chlorine, bromine, iodine), cyano group,
Direct or divalent linking group [e.g. -〇-1-8-, -N
R''-1 (R''' is a hydrogen atom, a hydroxyl group, an alkyl group (e.g. methyl group, ethyl group, n-propyl group, 1
-propyl group, n-butyl group, t-butyl group, 1-butyl group, etc.), aryl group (e.g. phenyl group, tolyl group,
Represents a single stroke group such as naphthyl group, etc. ) , -0CO
-1-CO-1-N HCO-1-CONH-1-CO
O-15O2NH-1-NH8O2-1-8O2-, etc.]
Alkyl groups bonded to carbon atoms via ), aryl groups (e.g. phenyl group, naphthyl group, etc.), cycloalkyl groups (e.g. cyclopentyl group, cyclohexyl group), or heterocyclic groups (e.g. pyridyl group, imidazolyl group, furyl group, chenyl group, pyrrolyl group, pyrrolidinyl group, quinolyl group, morpholinyl group, etc.). Among these, the alkyl group, aryl group, cycloalkyl group, or heterocyclic group bonded to a carbon atom via a divalent linking group is formed with the two linking groups, for example, an alkoxy group (e.g., methoxy (straight chain or branched alkyloxy groups such as ethoxy, lobethyloxy, octyloxy, etc.), alkoxycarbonyl groups (straight chain or branched alkyloxycarbonyl groups such as methoxycarbonylsadecyloxycarbonyl groups), alkyl carbonyl group (e.g. linear or branched alkylcarbonyl group such as acetyl group, valeryl group, stearoyl group), aryl 7J rubonyl group (e.g. benzoyl group etc.), alkylamino group (e.g. N-n-butylamino group, N, Straight chain or branched alkylamino groups such as N-di-rope tylamino group, N,N-di-n-octylamino group), alkylcarbamoyl group (straight chain such as n-butylcarbamoyl n-dodecylcarbamoyl group) or a linear or branched alkylsulfamoyl group such as a branched alkylcarbamoyl n-dodecylsulfamoyl group), an alkylacylamino group (
For example, a straight chain or branched alkylcarbonylamino group such as an acetylamino group or a valmitoylamino group), an aryloxy group (for example, a phenoxy group, a naphthoxy group, etc.),
Aryloxycarbonyl group (e.g. phenoxycarbonyl group, naphthoxycarbonyl group, etc.), arylamino group (e.g. N-phenylamino group, N-phenyl-N-
Examples thereof include methylreaamino groups, etc.), arylcarbamoyl groups (eg, phenylcarbamoyl groups, etc.), arylsulfamoyl groups (eg, phenylsulfamoyl groups, etc.), and arylacylamino groups (eg, benzoylamino groups, etc.).

Further, R3, R4, R5 and R6 of general formula [XII], general formula [XIII] and general formula [XIv] are R3
and R4, or at least one of the combinations of R5 and R6 may form a 5- or 6-membered ring together with the carbon atoms to which they are bonded. In this case, R3 and R4. Examples of the 5- or 6-membered ring formed by at least one of the combinations of B and R5 and R6 together with the carbon atoms to which they are bonded include a cyclopentene ring, a cyclohexene ring, and a benzene ring (however, this benzene ring Hydrocarbon rings having at least one unsaturated bond, such as fused benzene rings (including, for example, naphthalene rings and anthracene rings), heterocycles (for example, nitrogen-containing 5- or 6-membered heterocycles), and the like. When these 5- or 6-membered rings have a substituent, examples of the substituent include a halogen atom (fluorine, chlorine, bromine, iodine), a cyan group, an alkyl group (e.g. methyl group, ethyl group, n- Straight chain or branched alkyl groups having 1 to 20 carbon atoms such as propyl group, n-butyl group, n-octyl group, t-octyl group, n-hexadecyl group), aryl group (e.g. phenyl group, naphthyl group) etc.), alkoxy groups (e.g. methoxy group, n-71
-xy group, straight chain or branched alkyloxy group such as t-butoxy group), aryloxy group (e.g. phenoxy group, etc.), alkoxycarbonyl group (e.g. n-pentyloxycarbonyl group, t-pendeloxycarbonyl group,
Straight chain or branched alkyloxycarbonyl groups such as n-octyloxycarbonyl group and t-octyloxycarbonyl group), aryloxycarbonyl groups (e.g. phenoxycarbonyl group etc.), acyl groups (e.g. straight chain acedel group, stearoyl group etc.) chain or branched alkylcarbonyl groups, etc.), 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 groups, etc.) ), alkylamino group (e.g. N-n-butylamino group, N,
Linear or branched alkylamino groups such as N-diethylamino groups, linear or branched alkylcarbamoyl groups such as n-butylcarbamoyl groups (e.g. N.N-di-n-butylsulfamoyl groups,
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), cycloalkyl group (eg, cyclohexyl group, etc.), and the like.

General formula [x■], general formula [XI[I] and general formula [
X [V] i. t Favorite L < Ha, R3, R4,
At least one of the alkyl group, aryl group represented by R5 and R6, or the combination of R3 and R4J5 and R5 and R6
are selected from the cases where the combinations of R3 and R4 and R5 and R6 together with the carbon atoms to which they are connected and bonded form a 5th or 6th atom, and more preferably, the combinations of R3 and R4 and R5 and R6 are the carbon atoms that are connected and bonded to each other. 6-membered ring with atoms,
Particularly preferred is the case where a benzene ring is formed.

Further, M in general formulas [X, ]I], general formulas [XI[I] and general formulas [XIV] represents a metal atom, preferably a transition metal atom, more preferably a nickel atom, a copper atom, or an iron 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 [XI[l] is preferably an alkylamine having a linear or branched alkyl group, and particularly preferably an alkylamine having a linear or branched alkyl group, and particularly preferably an alkylamine having a linear or branched alkyl group. 2-36, even 3-2
These are dialkylamines and trialkylamines which have 4 alkyl amines, and specific examples thereof include butylamine, octylamine (e.g. [-octylamine), doazylamine (
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 [XII], general formula [XII[] and general formula [
More preferable metal complexes according to the present invention represented by the following general formula [XIV] are represented by the following general formula [XIIal, general formula [XI[[
a ] and a metal complex represented by the general formula [XrVa ].

General formula [XI[a] (R”)w (R”)n General formula [XIua] General formula [>'rVa] General formula [XIIal, general formula [XI[la] and general formula [X■a] , M, XI, X2, X3Y and Zo each have the same meaning as above.

In general formula [XIIal, general formula [XI [[a] and general formula [Xrva], R11, R12, RI3, R
14 is an alkyl group (e.g., methyl group, ethyl group, n-propyl group, n-butyl group, 0-octyl group, octyl group, n-hexadecyl group, etc. having 1 to 1 carbon atoms)
20 linear or branched alkyl groups), aryl groups (
For example, phenyl group, naphthyl group, etc.), alkoxy group (for example, methoxy group, n-butoxy group, (linear or branched alkyloxy group such as -butoxy group), aryloxy group (for example, phenoxy group, etc.), alkoxycarbonyl group (e.g. linear or branched alkyloxycarbonyl groups such as n-pentyloxycarbonyl group, °C-pentyloxycarbonyl group, n-offyloxycarbonyl group, °C-ocdyloxycarbonyl group), aryloxycarbonyl group (e.g. phenoxycarbonyl group, etc.), acyl group (e.g. linear or branched alkylcarbonyl group such as acetyl group, stearoyl group, etc.), acylamino group (
For example, an arylcarbonylamino group such as a linear or branched alkylcarbonylamino group such as an acetamido group), an arylamino group (such as an N-phenylamino group), an alkylamino group (such as an N-n-butylamino group, an N,N - linear or branched alkylamino groups such as -diethylamino group), carbamoyl groups (e.g. linear or branched alkylcarbamoyl groups such as n-bubulcarb7yl), sulfamoyl groups (e.g. N,N-di- straight-chain or branched alkylsulfamoyl groups such as n-butylsulfamoyl group and N-n-dodecylsulfamoyl group), sulfonamide groups (straight-chain or branched alkylsulfonyl groups such as methylsulfonylamino group) amino group, arylsulfonylamino group such as phenylsulfonylamino group), sulfonyl group (for example, linear or branched alkylsulfonyl group such as mesyl group, arylsulfonyl group such as tosyl group)
or cycloalkyl group (e.g. cyclohexyl group, etc.)
represents. m and n each represent an integer of 0 to 4.

General formula [XIIa], [XI[[a], [X Th
A more preferable compound among l a is the compound of the general formula [XI[
la]. General formula cxma ]
The most preferred compound among the compounds represented by is the general formula %
Formula % General formula [XI[[b] ￥゛RIs-N-R” General formula [XI[Ib]
,Y.

R11, R12, m, n are the same as above, R15,
R16 and R+7 represent a hydrogen atom, an alkyl group (eg, butyl group, octyl group, stearyl group, etc.) or an aryl group (eg, phenyl group, naphthyl group, etc.).

However, at least two of R+5, RI6, and R+7 represent an alkyl group or an aryl group.

In the following margin, in the general formula [XV], R2+1 R221R2
The halogen atom represented by 3 and R2 (is a fluorine atom,
Examples include chlorine atom, bromine atom, and iodine atom.

The alkyl group represented by R211R2□, R2, 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 may also have a substituent. include.

R211R221R2) and R24 -
The group is preferably an aryl group having 6 to 14 carbon atoms, including those having a substituent.

The heterocyclic group represented by R211R221R23 and R24 is preferably a five-shell ring or a six-shell ring, and includes those having a substituent.

The cycloalkyl group represented by R211R224R2) and R24 is preferably a five-shelled ring group or a six-shelled ring group, including those having a substituent.

Examples of the six-shell ring formed by bonding R21 and R22 to each other include the following.

The six shell ring formed by bonding R22 and R2) or R2) and R24 to each other is preferably a benzene ring, and this benzene ring also includes one having a substituent, and
They may be combined.

Examples of the alkyl group represented by R211R2□, R2, and R24 include methyl group, ethyl group, propyl group, butyl group, t-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, R2□, R23 and R24 include a phenyl group and a naphthyl group.

The heterocyclic group represented by R2, R2□, R2, and R24 preferably contains at least one nitrogen atom, oxygen atom, or sulfur atom in the ring as a heteroatom.
to 6-shell heterocyclic group, such as furyl group, hydrofuryl group, chenyl group, virolyl group, pyrrolidyl group, pyridyl group, imidazolyl group, pyrazolyl group, chi/lyl group, indolyl group, oxacylyl group, thiazolyl group, etc. can be mentioned.

Examples of the cycloalkyl group represented by R21, R221R2) and R24 include a cyclopentyl group, a cyclohexyl group, a cyclohexenyl group, and a cyclohexagenyl group.

Examples of the hexashell ring formed by bonding R211R221R211 and R24 to each other include a benzene ring, a naphthalene ring, an inbenzothiophene ring, an isobenzofuran ring, and an inton ring.

The alkyl group, cycloalkyl group, aryl group, or heterocyclic group represented by Rx + * R2x v R2x and Rx< above is a divalent linking group, such as an oxy group (-
〇-), thio group (-3-), 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 benzene ring, and some have preferred groups therein.

Examples of the alkyl group represented by R211R22y R23 and R2 bonded to the carbon atom on the benzene ring via the above-mentioned divalent linking group include an alkoxy group (e.g., methoxy group, ethoxy group, butquine group, propoxy group, 2-ethylhexyloxy group, n-decyloxy group, n-dodecyloxy group, or n-hexadecyloxy group), alkoxycarbonyl group (e.g. methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group, n- decyloxycarbonyl group or n-hexadecyloxycarbonyl group), acyl group (e.g. 7
cetyl group, valeryl group, stearyl group, benzoyl group or toluoyl group), acyloxy group (e.g. acetoxy group or hexadecylcarbonyloxy group, etc.),
7 alkyl amide groups (e.g. 7 n-butyl amide groups, N,
N-noethylamide group or N,N-didecylamino group), alkylcarbamoyl group (e.g., butylcarbamoyl group, N,N-diethylcarbamoyl group, or n
-dodecylcarbamoyl group, etc.), alkylsulfamoyl group (e.g., butylsulfamoyl group, N,N-noethylsulfamoyl group, or n-dodecylsulfamoyl group, etc.), sulfonylamine/group (e.g., methylsulfonylamine group), 7 groups, or butylsulfonyl amine 7 groups, etc.),
Sulfonyl group (for example, mesyl group, ethanesulfonyl group, etc.), or acylamide group (for example, acetylamine group, seven valerylamine group, valmityl group, seven valerylamine group,
benzoylamino group, toluoyl amino group, etc.).

R211Rz2t Examples of the cycloalkyl group represented by R21 and R24 bonded to a carbon atom on the ring via the above divalent linking group include a cyclohexyloxy group, a cyclohexylcarbonyl group, a cyclohexyloxycarbonyl group , cyclohexylami7 group, cyclohexenylcarbonyl group, and 1° cyclohexyloxy group.

Examples of aryl groups represented by R21tR2□, R23, and R24 bonded to a carbon atom on the ring via the above-mentioned divalent linking group include an aryloxy group (e.g., phenoxy group or s7toxy group, etc.). ), aryloxycarbonyl groups (e.g., 7e/xycarbonyl group or s7toxycarbonyl group, etc.), acyl groups (e.g., 1f1 benzoyl group or s7toyl group, etc.), anilino groups (e.g., phenylami7 group, N-methylanilino group, etc.), group or N-
7 cetylanili7 groups, etc.), acyloxy groups (e.g.
benzoyloxy group or toluoyloxy group), arylcarbamoyl group (e.g., phenylcarbamoyl group, etc.), arylsulfamoyl group (e.g., phenylsulfamoyl group, etc.), arylsulfonylamide 7 group (e.g., phenylsulfonylamide 7 group) , p-tolylsulfonylamine/group, etc.), arylsulfonyl! (e.g., benzenesulfonyl group, tosyl group, etc.), or acylamide 7
groups (for example, penzoylamide 7 groups, etc.).

The alkyl group, aryl group, heterocyclic group, cycloalkyl group represented by R2, R2□, R2, and R24 above, or R2+ and R22, R22 and R23, or R23
The six-shell ring formed by bonding R24 and R24 to each other is a halogen atom (e.g., chlorine atom, bromine atom, or fluorine atom, etc.), sia/group, alkyl group (e.g., methyl group, ethyl group, i-propyl group). , butyl group, hexyl group, octyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, heptadecyl group, octadecyl group, or methoxyethoxyethyl group), aryl group (for example, phenyl group, tolyl group, naphthyl group, chlorophenyl 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, silyloxy group, naphthoxy group) or methoxy72/oxy group, etc.), alkoxycarbonyl group (e.g., methoxycarbonyl group,
butoxycarbonyl group or 7ethoxycarbonyl group, etc.), aryloxycarbonyl group (for example, 7ethoxycarbonyl group, triloxycarbonyl group, or methoxy7ethoxycarbonyl group, etc.), acyl group (for example, formyl group, acetyl group, valeryl group, stearoyl group, benzoyl group, toluoyl group, naphthoyl group or p-methoxybenzoyl group), acyloxy group (e.g. acetoxy group or acyloxy group etc.), acylami/group (e.g. acetamido group) , benzamide group, or methoxyacetamide group), anilino group (e.g., phenylamino group, N-methylanilino group, N-phenylamino group, or N-7 cetylanili7 group, etc.), alkyl 7mino group (e.g., rope tylamino group), group, N, N-
noethylamino group, 4-methoxy-n-butylamino group, etc.), carbamoyl group [e.g., n-butylcarbamoyl group, N,N-noethylcarbamoyl group, n-butylsul77moyl group, N,N-noethylsul7amoyl group ,
n-dodecylsulfamoyl group, N-(4-7toxic n-butyl)sulfamoyl group, etc.], sulfonylamino group (e.g., methylsulfonylamide 7 groups, phenylsulfonylamide 7 groups, or methoxymethylsulfonylamide 7 groups) ), or a sulfonyl group (eg, mesyl group, tosyl group, methoxymethanesulfonyl group, etc.).

The alkyl groups represented by R25 and 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 part,
For example, methyl group, ethyl group, propyl group, butyl group,
Examples include hexyl group, octyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, heptadecyl group, and octadecyl group.

The aryl group represented by R75 and A includes those having a substituent, and is an aryl group in which the carbon atom of the substituent is removed, preferably having 6 to 14 carbon atoms, 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 it is a transition metal atom. More preferably Cu, Co, and Ni.

Pd, Fe is still Pi, and! j This feminine (Sat N)
It is i. A preferred group for A is a hydroxy group.

Further, among the complexes represented by the above general formula (XV), those preferably used include those in which R21 is an oxy group, a thio group, an alkyl group via a carbonyl group, a cycloalkyl group, an aryl group, or a heterocyclic group; It is a hydroxy group or fluorine, and at least one of the groups represented by R2°, R2ff, or R21 is a hydrogen atom, a hydroxy group, an alkyl group, or an alkoxy group. More preferred among these are those in which R25 is a hydrogen atom, and R25 is a hydrogen atom.
,.

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 HH (4) NH2C8H17(t)↓ H (5) N H2C8H+□
(1) ON i-0 (6) N H2Cs
H+ y↓ 0- N i-〇(force N H2C12
H25↓ 0- N 1-O C1lH17(ri C3HI7(t)(8)
NH2Cl11 H37↓ Cl1H17(t) C3HI7(t)↓ S -Ni -5 (t) C5HIIUOC(,:Riri(,:s Hll(
t) (12) NH2゜8H17(t) ↓ NH(Cd1sOH)2 ↓ (14) N(C4HIIOH)3
↓ 0- Ni -0 ↓ Ni-0 (17) NH(C4H9)2↓ 0-N i-0 (18) NH(C4H9)2↓ 〇-N i-0 (19) N(C2H5)3↓ [ I]H17(t) C3HI7(su(21)
C2H5H-N-CsH17 ↓ HHC500CC00CsH+ 1 (29) NH(C・H・・)・NH(Cl2825)2 C8H,, (Li CB Hl 7(SOC,,H,
.

OCH.

OCR2C)l(C211s)C<ll5(52)
C2115CI.

[84] (8) (ios) (iio) (!23> (12B) Leave a blank space below. Metal complexes represented by the above general formulas [XII] to [XIV] are described in British Patent No. 858. 890, German Patent Application Publication No. 2,042,652, and the like.

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

Wardlaw and K, C, Webster
, J. Chem.

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

The metal complex according to the present invention has a content of 0.1 mol-2-El per 1 mol of the magenta coupler represented by the general formula [I], although it varies depending on the type of metal complex used and the type of coupler used. It is preferably used in a range of 0.5 mol to 1 mol, more preferably in a range of 0.5 mol to 1 mol.

Next, the compound represented by the general formula [a] will be explained.

In the present invention, the alkyl group represented by R1 and R2 in general formula (a) is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 3 to 8 carbon atoms.
It is an alkyl group with a branched position.

Particularly preferred R1 and R2 are t-butyl group or t-pentyl group.

The alkyl group represented by R3 is linear or branched, and includes, for example, methyl, ethyl, propyl, butyl, pentyl, octyl, nonyl, dodecyl, octadecyl, and the like.

These alkyl groups include those having substituents, such as halogen atoms, hydroxyl groups, nitro groups, cyanide groups, aryl groups (e.g. phenyl groups, hydroxyphenyl groups, 3,5-di-t-butyl groups). -4-hydroxyphenyl group, 3°5-di-t-pentyl-4-hydroxyphenyl group, etc.), amino group (e.g. dimethylamino group, diethylamino group, 1,3.5-triazinylamino group, etc.), Alkyloxycarbonyl groups (e.g. methoxycarbonyl group, ethoxycarbonyl group, propyloxycarbonyl group, pentyloxycarbonyl group, octyloxycarbonyl group, nonyloxycarbonyldodecyloxycarbonylcyclocarbonyl group, etc.), aryloxycarbonyl group (e.g. phenoxycarbonyl group), 1.3. ! Examples include heterocyclic groups such as 5-1-riazinyl group. The amino group represented by R3 is, for example, an alkylamino group such as a dimethylamino group, a diethylamino group, or a methylethylamino group, an arylamino group such as a phenylamino group, a droxylphenylamino group, or a cycloalkylamino group such as a cyclohexyl group. , 1.3.

It includes a 5-triazinylamino group, a heterocyclic amino group such as isocyanuryl 1, and the like. The monovalent organic group represented by R' and Rrt is, for example, an alkyl group (for example, a methyl group, an ethyl group, a propyl group, a butyl group, an amyl group, a decyl group, a dodecyl group, a hexadecyl group, an octadecyl group, etc.), an aryl group. (e.g. phenyl group, naphthyl group, etc.),
It includes cycloalkyl groups (for example, cyclohexyl group, etc.) and heterocyclic groups (for example, 1.3.5-triazinyl group, isocyanuryl group, etc.). These compounds include those having substituents, such as halogen atoms (e.g. fluorine, chlorine, bromine, etc.), hydroxyl groups,
Nitro group, cyano group, amine group, alkyl M (e.g. methyl group, ethyl group, i-propyl group, t-butyl group,
-amyl group, etc.), aryl group (e.g., phenyl group, tolyl group, etc.), alkenyl group (e.g., allyl group, etc.), alkylcarbonyloxy group (e.g., methylcarbonyloxy group, ethylcarbonyloxy group, benzylcarbonyloxy group, etc.), Examples include arylcarbonyloxy groups (eg, benzoyloxy groups, etc.).

In the present invention, compounds represented by the general formula (a) are preferably compounds represented by the following general formula [a'].

General formula [a'] [In the formula, R++ and R12 each have 3 carbon atoms
~8 straight-chain or branched alkyl groups, particularly t-butyl and t-pentyl groups. R+3 represents a divalent organic group. k represents an integer from 1 to 6. ] Examples of the monovalent organic group represented by RI3 include methyl group, ethyl group, propyl group, butyl group, pentyl group,
Alkyl groups such as octyl group, hexadecyl group, methoxyethyl group, chloromethyl group, 1,2-dibromoethyl group, 2-chloroethyl group, benzyl group, phenethyl group, alkenyl groups such as allyl group, propenyl group, butenyl group,
polyunsaturated hydrocarbon groups such as ethylene, trimethylene, propylene, hexamethylene, 2-chlorotrimethylene,
Unsaturated hydrocarbon groups such as glyceryl, diglyceryl, pentaerythridel and dipentaerythridel; alicyclic hydrocarbon groups such as cyclopropyl, cyclohexyl and cyclohexenyl groups; phenyl group and p-octylphenyl group; 2.
Aryl groups such as 4-dimethylphenyl group, 2.4-di-t-butylphenyl group, 2.4-di-t-pentylphenyl group, p-chlorophenyl group, 2,4-dibromophenyl group, naphthyl group, 1.2-. 1.3- or 1.4
-Arylene groups such as -phenylene group, 3.5-dimethyl-1,4-phenylene group, 2-t-butyl-1,4-phenylene group, 2-chloro-1,4-phenylene group, naphthalene group, 1. Examples include 3.5-trisubstituted benzene group.

In addition to the above-mentioned groups, R+3 also includes divalent groups bonded to any of the above-mentioned groups via 10-, -3-, or -802- groups.

More preferably R+a is 2,4-di-t-butylphenyl I, 2.4-di-t-pentylphenyl group, p-octylphenyl group, p-dodecylphenyl group, 3.5-
Di[-butyl-4-hydroxylphenyl group, 3,5
-di-t-benzene-4-hydroxyphenyl group.

Preferably, k is an integer of 1 to 4.

Specific compounds represented by the general formula <a) are listed below, but the present invention is not limited thereto.

Margin below (20) CiHs (t) (22] (24) Cane (t) Cs H+ 1 (t) C4H9 (t) Ca & Te C7 HI5 (listening CSSi2 Cs) ht (t) (61] Ca & (j) C1H1t (Bee) C4k
b(L) C1zlb1(8esuC4)3J(t
) CsHti(t)C4几(1) C4H9(j)(8υ(90) Use 1 of the compound represented by the general formula [a] is based on 1 mole of the magenta coupler represented by the general formula [a], The range is preferably 0.1 mol to 2 mol, more preferably 0.5 mol to 1 mol.

Furthermore, the metal complex according to the present invention and the general formula [a]
The combination ratio with the compound represented by is 1:3 to 3 in molar ratio.
:1 is preferable.

The magenta coupler, metal complex, compound represented by general formula [a], etc. according to the present invention can be added to the silver halide photographic material by a solid dispersion method, similar to the method for adding general hydrophobic compounds. Various methods can be used, such as , latex dispersion method, oil-in-water emulsion dispersion method, etc., and these can be appropriately selected depending on the chemical structure of the hydrophobic compound such as the coupler. The oil-in-water emulsion dispersion method can be applied to various methods for dispersing hydrophobic compounds such as couplers. Usually, a high boiling point solvent with a boiling point of about 150°C or higher is used.
If necessary, add a low boiling point and/or water-soluble R solvent to mm
After dissolving and emulsifying and dispersing in a hydrophilic binder such as an aqueous gelatin solution using a dispersion means such as a stirrer, homogenizer, colloid mill, flow jet mixer, or ultrasonic device, it is mixed into a hydrophilic colloid layer covering the target. It can be added to. A step of removing the low boiling point organic solvent may be included simultaneously with the dispersion or dispersion.

Examples of high-boiling organic solvents include phenol derivatives, phthalate esters, phosphate esters, citric acid esters, benzoic esters, alkylamides, fatty acid esters, trimesic esters, etc. that do not react with the oxidized form of mulberry, which has a boiling point of 150°C or higher. of organic solvents are used.

In the present invention, the metal complex according to the present invention and the general formula [
The high boiling point solvent that can be preferably used when dispersing the compound represented by [a] is one having a dielectric constant of 6.
Examples of such compounds include esters such as phthalates and phosphates, organic acid amides, ketones, and hydrocarbon compounds having a dielectric constant of 6.0 or less. Preferably, it is a high boiling point organic solvent having a dielectric constant of 6.0 or less and 1.9 or more and a vapor pressure of 0.5 mmHq or less at 100°C.

Even more preferred are phthalic esters or phosphoric esters in the high-boiling organic solvent. 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.

Phthalic acid esters advantageously used in the present invention include those represented by the following general formula [bl].

General formula [bl In the formula, 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 [b]
The alkyl group represented by may be linear or branched, such as butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, doacyl group, tridecyl group, tetradecyl group, These include a pentadecyl group, hexadecyl group, heptadecyl group, and octadecyl group. The aryl group represented by R+ a 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 M 63J and alkenyl groups include halogen atoms, alkoxy groups, aryl groups, Examples include aryloxy groups, alkenyl groups, alkoxycarbonyl groups, and examples of substituents for aryl groups include halogen atoms, alkyl groups, alkoxy groups, aryl groups, aryloxy groups, alkenyl groups, alkoxycarbonyl groups, etc. I can do it.

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

General Formula [C] (1) In the formula, Ra, R4 and R5 each represent an alkyl group, an alkenyl group or an aryl group.

However, the total number of carbon atoms represented by Ra, R4 and R5 is 24 to 54.

The alkyl group represented by R3, R4 and R5 in the general formula [C] is, for example, a butyl group, a pentyl group, a hexyl group,
heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group,
Pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, etc. Aryl groups include, for example, phenyl group, naphthyl group, etc., and alkenyl groups include, for example, hexenyl group, heptenyl group, octadecenyl group, etc. be.

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 5-1 to lymethylhexyl group, n-nonyl group, n-decyl group, 5ec-decyl group, 5ec-dodecyl group, and [-octyl group.

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

Below are some examples of leading solvents 2Hs 5-12C28S ■ 0C*H19) 0=P OC-HI*(i> 0 C= Hls (i) O-C,H,, (n) O-C,.R2,( i) ■ ○=P-〇-C3゜R211) 0-C6゜H,, (i) 0-C,,H:, (n) 0"P OC,, R2, (nn0 CIQH21(n) S-17 0-C1, H2, (i) o CIz H-s (i) These battering machine solvents have a λ↑ in N'l of the synthetic complex according to the present invention and the compound represented by the general formula [a]. The magenta coupler according to the present invention is generally used in a combination of 5 to 100 N:f1%, preferably 30 to 801N:f1%.The magenta coupler according to the present invention is a compound of the metal complex according to the present invention and the general formula [a] It is preferable to dissolve it in the same oil droplet as the compound represented by.

Anionic surfactants, nonionic surfactants are used as dispersion aids when hydrophobic compounds such as couplers are dissolved in a high boiling point solvent alone or in combination with a low boiling point solvent and dispersed in water using mechanical or ultrasonic waves. Active agents and cationic surfactants can be used.

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. In particular, the present invention The effect of the method is effectively demonstrated.

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

When the silver halide photographic material of the present invention is a multicolor photosensitive material, the specific components include a yellow dye image-forming layer, an intermediate layer, Particularly preferred are magenta dye image-forming layers, interlayer cyan dye image-forming layers, interlayers, and protective layers.

The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention includes conventional halides such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride. Any of those used in silver oxide emulsions can be used.

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, while considering the critical growth rate of silver halide crystals, we added halide ions and silver ions to
H, l) A! It may also be produced using a skewer in which it is added sequentially and simultaneously while controlling It. After growth, a conversion method may be used to change the halogen composition of the particles.

By using a silver halide solvent as necessary during production of the silver halide emulsion of the present invention, it is possible to control the grain amount, shape, grain i-nice distribution, and grain growth rate of silver halide grains.

The silver halide 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 (or complex salts, iron salts or complex salts,
Metal ions can be added to the inside of the particles and/or on the surface of the particles by adding metal ions, and jW original sensitizing nuclei can be added to the inside of the particles and/or on the surface of the particles by placing them in an appropriate reducing atmosphere. I can do it.

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

The cut 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 a spherical shape.
′) It may have an irregular crystal shape such as a plate shape.

In these particles, any ratio of (100) and (111) planes can be used.

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

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

The silver halide emulsion of the present invention is chemically sensitized by a conventional method. That is, compounds containing sulfur that can react with silver ions,
The sulfur sensitization method using activated gelatin, the selenium sensitization method using selenium compounds, the reduction sensitization method using reducing substances, the noble metal sensitization method using precious metal compounds of Kanasoike, etc. can be used alone or in combination. I can do it.

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, a super sensitizer, which is a dye that itself does not have spectral sensitizing function f'f, or a compound that does not substantially absorb visible light, and which enhances the sensitizing effect of the sensitizing dye, is added to the emulsion. It may be included.

The silver halide emulsion of the present invention may be used during chemical ripening for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the photosensitive material 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.

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

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

A dispersion of a water-insoluble or sparingly soluble synthetic polymer (
latex).

In the emulsion layer of the silver halide color photographic light-sensitive material of the present invention, an aromatic primary amine developer (
For example, a dye-forming coupler that forms a dye is used in a coupling reaction with an oxidized product of p-phenylene diamine derivatives, amine phenol derivatives, etc. The dyes are typically selected to form dyes that absorb light in the light-sensitive spectrum, with a yellow dye-forming coupler in the blue light-sensitive emulsion layer and a magenta dye-forming coupler in the green light-sensitive emulsion layer. A cyan dye-forming coupler is used in the red light sensitive emulsion layer. However, depending on the purpose, a silver halide color photosensitive material may be produced using a method different from the above combination.

The cyan dye-forming couplers used in the present invention include:
Typical examples include phenol-based and naphthol-based 4-fold female or 2-terminal cyan dye-forming couplers, specific examples of which are U.S. Pat. Nos. 2.306.410 and 2.356.4.
No. 75, No. 2,362,598, No. 2.367,
No. 531, No. 2.369.929, No. 2.423
．． No. 730, No. 2,474,293, No. 2,47
6.008, 2,498, 466, 2,5
No. 45,687, No. 2.728.660, No. 2.
No. 772.162, No. 2,895,826, No. 2
, 976, 146, 3,002,836, 3.419.390, 3,446,622, 3.476, 563, 3.737.316 ,
British Patent No. 3.758.308, British Patent No. 3,839,044, British Patent No. 478,991, British Patent No. 945.542, British Patent No. 1, 084.480, British Patent No. 1.377, 233.
No. 1.388.024 and No. 1,543.0
40, as well as JP-A No. 47-37425,
No. 50-10135, No. 50-25228, No. 50
-112038, 50-117422, 5
No. 0-130441, No. 51-6551, No. 51-3
No. 7647, No. 51-52828, No. 51-1088
No. 41, No. 53-109630, No. 54-48237
No. 54-66129, No. 54-131931,
It is described in various publications such as No. 55-32071.

Furthermore, cyan dye-forming couplers used in the silver halide emulsion of the present invention include the following general formulas [C-1] and [C
-2] is preferred.

General Formula [C-1] In the formula, 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 being separated by reaction with an oxidized product of an aromatic primary amine color developing agent.

General Formula [C-2] In the formula, R4 represents a linear or branched alkyl group having 1 to 4 carbon atoms, and R5 represents a ballast group.

Z has the same meaning as 7 in general formula [C-1]. Particularly preferred R4 is a straight chain or branched alkyl group having 2 to 4 carbon atoms.

In the present invention, the alkyl group represented by R1 in the general formula [C-1] is a linear or branched one, such as a methyl group, an ethyl group, a 1so-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 group (e.g., methyl group, ethyl group, propyl group, butyl group, dodecyl group, etc.), hydroxyl group, cyan group, nitro group,
Alkoxy groups (e.g., methoxy, ethoxy), alkylsulfonamide groups (e.g., methylsulfonamide, octylsulfonamide, etc.), arylsulfonamide groups (e.g., phenylsulfonamide, naphthylsulfonamide, etc.), Alkylsulfamoyl group (e.g., butylsulfamoyl group, etc.), arylsulfamoyl group (e.g., phenylsulfamoyl group, etc.), alkyloxycarbonyl group (e.g., methyloxycarbonyl group, etc.), aryloxycarbonyl group Group (
For example, phenyloxycarbonyl group, etc.), aminesulfonamide group (for example, N,N-dimethylaminosulfonamide group), acylamino group, carbamoyl group, sulfonyl group, sulfinyl 13, sulfoxy group, sulfo group, aryloxy group, Forms alkoxy groups and carboxyl groups.

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,
These include ethoxy group, propyloxy group, butoxy group, etc.

R3 may combine with R1 to form a ring.

In the present invention, the alkyl group represented by R2 in the general formula [C-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. polyfluoroalkyl'-N'6.

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 are single or ? ! This includes those with two or more substituents; for example, a typical substituent introduced into a phenyl group is a halogen atom (
For example, fluorine, chlorine, bromine, etc.), alkyl groups (
For example, methyl group, ethyl group, propyl group, butyl group, dodecyl group, etc.), hydroxyl group, cyano group, nitro group,
Alkoxy groups (e.g. methoxy groups, ethoxy groups, etc.), alkylsulfonamide groups (e.g. methylsulfonamide groups, octylsulfonamide groups, etc.), arylsulfonamide groups (e.g. phenylsulfonamide groups, naphthylsulfonamide groups, etc.), Alkylsulfamoyl group (
(e.g., butylsulfamoyl group, etc.), arylsulfamoyl group (e.g., phenylsulfamoyl group, etc.), alkyloxycarbonyl group (e.g., methyloxycarbonyl group, etc.), aryloxycarbonyl group (e.g.,
phenyloxycarbonyl group, etc.), aminosulfonamido group, acylamino group, carbamoyl group, sulfonyl group, sulfinyl group, sulfooxy group, sulfo group, aryloxy group, alkoxy group, carboxyl group, alkylcarbonyl group, arylcarbonyl group, etc. I can do it. 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, or cyano group as a substituent.

In the present invention, general formula [C-1. ] Preferably, the cyan dye-forming coupler represented by the following general formula [C-3]
It is a compound represented by

General Formula [C-3] In General Formula [C-3], R6 represents a phenyl group. This phenyl group includes those having single or multiple substituents, and typical examples of the substituents introduced are halogen atoms (e.g., fluorine, chlorine, bromine, etc.)
, 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 (
For example, methylsulfonamide group, octylsulfonamide group, etc.), arylsulfonamide group (for example, phenylsulfonamide group, naphthylsulfonamide group, etc.), alkylsulfamoyl group (for example, butylsulfamoyl group, etc.), arylsulfamoyl group Examples include groups (eg, phenylsulfamoyl group, etc.), alkyloxycarbonyl groups (eg, methyloxycarbonyl group, etc.), and aryloxycarbonyl groups (eg, phenyloxycarbonyl group, etc.). Two or more of these substituents may be substituted with a phenyl group. Preferred groups represented by R6 include phenyl group, halogen atom (preferably fluorine, chlorine, and bromine atoms), alkylsulfonamide group (preferably 0-methylsulfonamide group, p-octylsulfonamide group, 0-methylsulfonamide group, p-octylsulfonamide group, -dodecylsulfonamide group), arylsulfonamide group (preferably phenylsulfonamide group), alkylsulfamoyl group (preferably butylsulfamoyl group), arylsulfamoyl group (preferably phenylsulfamoyl group), Alkyl group (preferably methyl group, trifluoromethyl group), alkoxy group (preferably methoxy group,
It is a phenyl group having one or more ethoxy groups 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.), alkylsulfomyl group (e.g., butylsuno, nonmoyl group, etc.), arylsulfamoyl group (e.g., phenylsulfamoyl group, etc.), alkyloxy carbonyl group (e.g. methyloxycarbonyl group etc.), aryloxycarbonyl group (e.g. phenyloxycarbonyl group etc.), aminosulfonamide group (e.g. dimethylaminosulfonamide group etc.), arylcarbonyl group, arylsulfonyl group, alkylcarbonyl group, arylcarbonyl group,
Examples include an aminocarbonylamide group, a carbamoyl group, and a sulfinyl group. These substituents are 2
More than one species may be introduced.

Preferred groups represented by R7 are an alkyl group when n=0 and an aryl group when n1=1 or more. More preferable groups represented by R7 include n
When +=o, 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 it is nl-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 dimethylaminosulfonamide group), or an alkyloxycarbonyl group (preferably methyloxycarbonylcarbonyl M) as a substituent.

R8 represents an alkylene group. It represents a straight chain 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 O or a positive integer, preferably O or 1
It is.

X is 10-, -〇〇-, -COO-, -OCO-, -SO2NR-, -NR'S○2NR''
-, -S-, -S〇-, or -SO2- represents a divalent group. Here, R' and R'' represent an alkyl group, and R'
, R'' each includes a substituent. X is preferably a -0-1-S-1-SO-1-3O2- group.

Z has the same meaning as 7 in general formula [C-1].

In the present invention, the linear or branched alkyl group having 11 to 4 carbon atoms represented by R4 in the general formula [C-2] is, for example, an ethyl group, a propyl group, a butyl group, a 1so-
A propyl group, a 1so-butyl group, a 5ec-butyl group, or a tcrt-butyl group, including those having a substituent. Examples of the substituent include an acylamino group (eg, acetylamino group), an alkoxy group (eg, methoxy group), and the like.

R4 is preferably an alkyl group having 2 to 4 carbon atoms.

The ballast group represented by R5 is an organic group having a rough shape that imparts sufficient bulk to the coupler molecule to substantially prevent the coupler from diffusing from the layer to which it is applied to other layers.

Typical ballast groups include alkyl or aryl groups having 8 to 32 total carbon atoms.

These alkyl groups or aryl groups also include those having substituents. Examples of substituents for aryl groups include alkyl groups, aryl groups, alkoxy groups, aryloxy groups, carboxy groups, acyl groups, ester groups, hydroxy groups, cyano groups, nitro groups, carbamoyl groups, carbonamide groups, and alkylthioamide groups. , a sulfamoyl group, and a halogen atom. Furthermore, examples of substituents for the alkyl group include the substituents listed above for the aryl group except for the alkyl group.

Particularly preferred as the ballast group is one represented by the following general formula [C-4].

General formula [C-4] 1CH-0-Ar 10 R+o represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, Ar represents an aryl group such as phenyl, and this aryl group has no substituent. Including those who have. Examples of the substituent include an alkyl group, a hydroxy group, and an alkylsulfonamide group, but the most preferred one is t-
It is a branched alkyl group such as a butyl group.

In the general formulas [C-1], [C-2] and [C-3], the groups each represented by Z that can be separated by reaction with the oxidized product of the aromatic primary amine color developing agent are This method is well known to those in the industry and modifies the reactivity of the coupler.
Alternatively, it separates from the coupler and acts advantageously in the coating layer or other layers containing the coupler in the silver halide color photographic light-sensitive material by performing functions such as development inhibition, bleaching inhibition, and color correction. Typical examples include halogen atoms represented by chlorine and fluorine, substituted and unsubstituted alkoxy groups, aryloxy groups, arylthio groups, carbamoyloxysulfonamide groups, heteroylthio groups, and heteroyloxy groups. It will be done. Particularly preferred Z is:
It 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. 48-3689
No. 4, U.S. Patent No. 3,47G, 563, U.S. Patent No. 3, 7
37, 316, 3,227, and 551.

Typical specific examples of the Et cyan coupler represented by the general formula [c-1] are shown below in the margins, but the invention is not limited to these.

(n) CxsL3SOzNH C4I (9(n) C12 5(n) C-3'2 Next, specific examples of the coupler represented by the general formula EC-2] will be shown, but the invention is not limited thereto.

As the yellow dye-forming coupler used in the present invention, compounds represented by the following general formula [Yl] are preferred.

General formula [Yl In the formula, R++ 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 R+
2 represents an aryl group, and Yl represents a hydrogen atom or a group that is eliminated 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, R13 represents a halogen atom, an alkoxy group, or an aryloxy group, and R+4, 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, sulfonyl group, carboxyl group, alkoxycarbonyl group, carbamylsulfonamide group, acylamido group, ureido group or amino group, and Yl has the above-mentioned meaning.

These include, for example, U.S. Pat. No. 2,778,658, U.S. Pat.
No. 73, No. 3,227, 155, No. 3, 227
, No. 550, No. 3, 253, 924, No. 3
, 265, 506, 3, 277, 155
No. 3,341, 331, No. 3, 369,
No. 895, No. 3, 384, 657, No. 3, 4
No. 08, 194, No. 3,415,652, No. 3
, 447, 928, 3,551,155, 3,582,322, 3,725, 072
No. 3, 894, 875, etc., German Patent Publication No. 1,547,868, German Patent Publication No. 2,057, Ri 4
No. 1, No. 2, 462, 899, No. 2, 16
3, 812, same No. 2, 213.461, same No. 2,
No. 219,917, No. 2,261,361, No. 2
．． No. 263.875, Special Publication Showa 49-1357 June, Machibu Ro! No. 148-29432, No. 4g-66834, No. 49-10731;, No. 49-122335, No. 50
-28834, a3, and 50132926, etc.

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

Margin P Below Margin Color turbidity occurs due to the migration of the oxidized form of the developing agent or the electron transfer agent between the emulsion layers of the color photographic light-sensitive material of the present invention (between the same color-sensitive layers and/or between different color-sensitive layers). Color anti-fogging agents are used to prevent blurring, 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.

Examples of the color antifogging agent preferably used in the present invention include compounds represented by the following general formula [HQ].

General formula [HQ] In the formula, R31, R32, R33 and R33 are hydrogen atoms, halogen atoms, alkyl groups, alkenyl groups, aryl groups, cycloalkyl groups, alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, and acyl groups, respectively. , alkylacylamino group, arylacylamino group, alkylcarbamoyl group, arylcarbamoyl group, arylsulfonamide group, alkylsulfamoyl group, arylsulfamoyl group, alkylsulfonyl group, arylsulfonyl group, It represents a cyano group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an alkylacyloxy group, or an arylacyloxy group.

In the general formula [HQ], R3+, R32, R3
3, and the atom or group represented by R34,
Examples of halogen atoms include fluorine, chlorine, and bromine atoms, and examples of alkyl groups include methyl, ethyl, n-propyl, i-propyl, n-butyl,
t-butyl, n-amyl, 1-amyl, n-octyl,
Examples include n-dodecyl and n-octadecyl groups,
Particularly preferred is an alkyl group having 1 to 32 carbon atoms.

Examples of the alkenyl group include allyl, octenyl, and oleyl groups, and alkenyl groups having 2 to 32 carbon atoms are particularly preferred.

Examples of the aryl group include phenyl and naphthyl groups.

Examples of the acyl group include acetyl, octanoyl, and lauroyl groups.

Examples of the cycloalkyl group include cyclohexyl and cyclopentyl groups.

Examples of the alkoxy group include methoxy, ethoxy, and dodecyloxy groups, examples of the aryloxy group include phenoxy, and examples of the alkylthio group include methylthio, lobethylthio, n-
Examples of the arylthio group include dodecylthio groups, and examples of the arylthio group include phenylthio groups.
Examples of cylamino groups include acetylamino groups, arylacylamino and benzoylamino groups, examples of alkylcarbamoyl include phenylcarbamoyl, and examples of alkylsulfonamide groups include methylsulfone, etc. Examples of the arylsulfonamide group include a phenylsulfonamide group, examples of the alkylsulfamoyl group include a methylsulfamoyl group, and examples of the arylsulfamoyl group include an amide group. Examples of the alkylsulfonyl group include a phenylsulfamoyl group, examples of the alkylsulfonyl group include a methylsulfonyl group, examples of the arylsulfonyl group include a phenylsulfonyl group, and examples of the alkyloxycarbonyl group include, Examples of the aryloxycarbonyl group include a phenyloxycarbonyl group, examples of the alkyloxycarbonyl group include an acetyloxy group, and examples of the aryloxycarbonyl group include, for example, an acetyloxy group. Examples include benzoyloxy group.

These groups include those with substituents, such as alkyl groups, aryl groups, aryloxy groups, alkylthio groups, cyanogen groups, acyloxy groups, alkoxycarbonyl groups, acyl groups, sulfamoyl groups, and hydroxy groups. , a nitro group, an amino group, a heterocyclic group, and the like.

Among the compounds represented by the general formula [HQ] used in the present invention, compounds represented by the following general formula [HQ'] are particularly preferably used in the present invention.

General formula [HQ'] In the formula, R35 and R36 each represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an acyl group, a cycloalkyl group, or a heterocyclic group;
are never both hydrogen atoms.

In the general formula [HQ'], R35 and R36
Examples of the alkyl group represented by include methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, n-amyl, 1-amyl, n-octyl, n-dodecyl, n--A phtadecyl. and the like, with alkyl groups having 1 to 32 carbon atoms being particularly preferred.

Examples of the alkenyl group include allyl, A-cutinyl, and oleyl groups, and alkenyl groups having 2 to 32 carbon atoms are particularly preferred.

Examples of the aryl group include phenyl and naphthyl groups.

Examples of the acyl group include acetyl, octanoyl, and lauroyl groups.

Examples of the cycloalkyl group include cyclohexyl and cyclopentyl groups.

Examples of the heterocyclic group include imidazolyl, furyl, pyridyl, triazinyl, and deazolyl groups.

In the general formula [HQ'], it is more preferable that the atoms or groups represented by R35 and R36 have a total number of carbon atoms of 8 or more and are a group that imparts non-diffusibility.

Specific examples of the compound represented by the general formula [HQ] used in the present invention are listed below, but of course the compound is not limited thereto.

Below F margin (HQl) □H O) 1 (HQ-6) oH (HQ-11) oH H H H (IQ-21) OR (HQ-26) (HQ-27) (HQ-29) (HQ- 30) (HQ-31) (HQ-32) (HQ-33) H (HQ-34) (HQ-3,1) (HQ-36) (HQ-37) H (HQ-King) OH These compounds For example, Research Disclosure, No. 176 (1978), Section 17643, VI
It is described in 1.

The silver halide photographic material of the present invention may contain an image stabilizer that prevents deterioration of the dye image. Image stabilizers preferably used in the present invention include the following general formulas [A] to [H], [J], and [K].

General formula [AI, where R is a hydrogen atom, an alkyl group, an alkenyl group,
R1, R,, R,%
R1 each represents a hydrogen atom,)) a rodene atom, a hydroxy group, an alkyl group, an alkenyl group, an aryl group, an alkoxy group, or an acylamide/group; R1 represents an alkyl group, a hydroxy group, an aryl group, or an alkoxy group; represent.

Further, R and R2 may be ring-closed with each other to form a 5-shell or 6-shell ring, in which case R4 may have a hydroxy group or an alkoxy group, or R3 and R may be ring-closed to form a 5-shell hydrocarbon ring. A ring may be formed, in which case Ro is an alkyl group, a 7-aryl group, or a vl ring group, provided that R
Except when 1 is a hydrogen atom and R1 is a hydroxy group.

In the general formula [AI, R8 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, Lert
- Straight chain or branched alkyl groups such as octyl group and hexadenyl group can be mentioned. Examples of the alkenyl group represented by R3 include allyl, hexenyl, and octenyl groups. Furthermore, examples of the aryl group for R1 include phenyl and naphthyl groups. Further, specific examples of the heterocyclic group represented by R3 include a tetrahydropyranyl group and a pyrimidyl group. Each of these groups can have a substituent, for example, an alkyl group having a substituent such as a bennol group, a nidoxymethyl group, and an aryl group having a substituent such as a methoxy7enyl group, a chlorophenyl group, a -hydroxy-3,5-dibutylphenyl group and the like.

General formula [In A1, R2, R1, R1 and R51
Examples include earth hydrogen atoms, halogen atoms, hydroxy groups, alkyl groups, alkenyl groups, 7-aryl groups, furfoxy groups, and acylamino groups. Among these, alkyl groups, alkenyl groups, and aryl groups include the alkyl groups mentioned above for R1. , alkenyl group, and aryl group. 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. ′! - and the acylamino group is represented by R'CONH-, where R' is an alkyl group such as 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, etc.), or heterocyclic groups (e.g., pyridyl, torimicle groups). be able to.

In addition, in the general formula [A], % R4 is an alkyl group,
It represents a hydroxy group, an aryl group, or an alkoxy group, and among these, for a furkyl group and an aryl group, the above R
The same alkyl groups and aryl groups as shown in , can be specifically mentioned. As for the alkenyl group for R1, the same alkoxy groups mentioned above for R2, R3, Rs, and R1 can be mentioned.

Examples of the ring formed by R and R2 together with a benzene ring include chroman, coumaran, and methylenedioxybenzene.

Furthermore, examples of the ring formed by Rff and R2 together with a benzene ring include bean. These rings may have substituents (eg alkyl, alkoxy, aryl).

In addition, a spiro compound may be formed as a spiro atom in the ring formed by R, and R2, or R5 and R4, or a bis compound may be formed by using R2, R4, etc. as a linking group. Good too.

Among the phenolic compounds or phenyl ether compounds represented by the general formula [A], preferred are R
O- group (R is an alkyl group, alkenyl group, aryl group,
or 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, terL-octyl, benzyl, hexadecyl), an alkenyl group (e.g. allyl, octenyl, oleyl), an aryl group (e.g. , phenyl, naphthyl) or a heterocyclic group (e.g., tetrahydropyranyl, pyrimidyl), R3 and RIG each represent a hydrogen atom, a halogen atom, (e.g., fluorine, chlorine, bromine), an alkyl group (e.g., methyl, ethyl, lobethyl, benzyl), alkoxy groups (e.g., allyl, hexenyl, octenyl), or alkoxy groups (e.g., allyl, hexenyl, octenyl);
For example, methoxy, ethoxy, benzyloxy),
R11 is a hydrogen atom, an alkyl group (e.g. methyl, ethyl, n-butyl, benzyl), an alkenyl group (e.g. 2
-propenyl, hexenyl, octenyl), or an aryl group (eg phenyl, nodoxyphenyl, arylphenyl, 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 Z, 077.455
No. 2,062, No. 888, U.S. Patent No. 3,764
, 337, No. 3.432300, No. 3,574,
No. 627, No. 3,573,050, JP-A-52-1
No. 52225, No. 53-20327, No. 53-177
No. 29, No. 55-6321, British Patent No. 1,347,
No. 556, Publication No. 2fO66,975, Special Publication No. 1973-
No. 12337, No. 4B-31625, U.S. Patent No. 3,
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.

Typical specific examples of compounds reduced by the general formula [A] are shown below.

Type (1) OR' Type (2) Type (3) Type (4) Type (5) Type (6) Type (7) Type (2) Below margin type (4) Below margin type ( 5) The following margin type (6) The following margin A-7 The following margin General formula [B] (In the formula, R and R4 are each hydrogen atom, 7% lodene atom, alkyl group, alkenyl group, alkoxy group, alkenyloxy group, a hydroxy group, an aryl group, an aryloxy group, an acyl group, an acylamino group, an acyloxy group, a sulfonamido group, a cycloalkyl or alkyl carbonyl group, and R2 is a hydrogen atom, an alkyl group, an alkenyl group, or a 7-aryl group. group, 7-syl group, cycloalkyl group or heterocyclic group, R2 is a hydrogen atom,
Includes halogen atom, alkyl group, alkenyl group, aryl group, aryloxy group, acyl group, acyloxy group, sulfonamide group, cycloalkyl group, or alkoxycarbonyl group.

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 hydroxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heptadylamine group, an acyloxy group, a carbamoyl group, a sulfonamide group, and a sulfamoyl group.

Furthermore, R2 and R5 may be linked together to form a five-shell or six-shell ring. Examples of the ring formed by Rz and R1 when closed 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.

The chroman or coumaran ring is a halogen atom, a furkyl group, a dichlorofurkyl group, an alkoxy group, an alkenyl group,
May be substituted with an alkenyloxy group, a hydroxy group, a 7-aryl group, an 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 general formulas [B-1], [B-2], [B
-33, [B-4], and [B-5].

General formula [B-1] 1'11 General formula [B-2] General formula [B-3] General formula [B-4] General formula [B-5] K' General formula [B-1], [B -2], [B-3], [B
-41 and [B-5], R1, R2, R and R1 have the same meanings as in the above general formula [B], and Rs%R, Rt, R1, R1 and R3 are hydrogen atoms and halogen atoms. , an alkyl group, an alkoxy group, a hydroxy group, a fulkenyl group, an alkenyloxy group, an aryol group, an aryyloxy group, or a heterocyclic group.

Furthermore, R8 and Rs, Ri and R7, R1 and R5, R, and R
R1 and Rto from 9 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-21, [B-3],
[B -4lfiyo VI IB 51nib iteR+
g, I/R4 is a hydrogen atom, a furkyl group, an alkoxy group,
Hydroxy group or dichlorofurkyl group, Rs, R6%
Particularly useful are compounds in which Rt, R6, R5 and R2° are hydrogen atoms, alkyl groups, or cycloalkyl groups.

The compound represented by the general formula [B] is
trahedron), 1970. vo126,474
B-4751 page, Journal of the Chemical Society of Japan, 1972. No.10,
098fu-1990 page, Chemical (chem, Lett
), 1972 (4) pp. 315-31f3, Japanese Patent Application Publication No. 1983.
-139383, and can be synthesized according to the methods described therein.

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

Typical specific examples of these compounds are shown below.

The following is a blank general formula [CI RI R'' General formula [D] RI In the formula, R1 and VR2 are a hydrogen atom, a halogen atom, a furkyl group, an alkenyl group, an alkoxy group, an alkenyloxy group, a hydroxy group, an aryl group, an aryloxy group , an acyl group, an acylamide group, an acyloxy group, a sulfonamide group or an alphkyl dicarbonyl group.

Each of the groups listed above may be substituted with other substituents, such as halogen atoms, alkyl groups, alkenyl groups,
Alkoxy group, aryloxy group, hydroxy group, alkoxycarbonyl group, aryloxycarbonyl group, acylamino group, Cal.

Examples include a moyl group, a sulfonamide group, and a sulfamoyl group.

Y represents the atomic group necessary to form a nochroman or dicumafun ring with the benzene ring.

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

Among the compounds represented by the general formulas [CI and [D], the compounds particularly useful in the present invention are the general formulas ['C-1] and [C-
23, [D-1] and [D-2].

General formula [C-1] General formula [C-21 General formula [D-1] General formula [D-2] General formula [C-13, [C-2], [D-1] and [
D-2] and R2 are represented by the general formula [CI
and have the same meaning as in [D,], Rco, R
4, R6, R6, R1 and R$ represent a hydrogen atom, an atom, an alkyl group, an alkoxy group, a hydroxy group, an alkenyl group, an alkenyloxy group, an aryl group, an aryloxy group or a heterocyclic group, and R1
and R4% R1 and R1, R1 and R6, R6 and R7 and R
1 and R8 may be cyclized with each other to form a carbocycle,
Furthermore, the carbocycle may be substituted with an alkyl group.

In the general formulas [C-1], [C-2], [D-1] and [D-2], R and VR are hydrogen atoms, alkyl groups, alkoxy groups, hydroxy groups or cyclo A compound in which the alkyl group, R1, R4, R8, R8, R2, and VRm are a hydrogen atom, an alkyl group, or a cycloalkyl group, is a Mitsubishi Arizuki.

Compounds represented by the general formulas [C] and [D] are published in the Journal of the Chemical Society of Japan (J, Cbem, Soe, part C) 19
68. (14), pp. 1937-18, Journal of Japan Society of Synthetic Chemistry 1970.28 (1), pp. 60-65, Tetrabedron Letters
1973, (29), pp. 2707-2710, and can be made into synthetic leather according to the methods described therein.

Note: The amount of the compound represented by the general formulas [C] and [D] to be used is 5-3 for the magenta coupler according to the present invention.
00 mol% is preferable, more preferably 10-200 mol%.

Specific representative examples of these compounds are shown below.

Below is a blank space below: General formula [E] In the formula 1 (+ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an acyl group, a cycloalkyl group, or a heterocyclic group, and R3 is a hydrogen atom, a halogen atom, an alkyl group, alkenyl group, aryl group, 7-aryloxy group,
Acyl group, 7-sylami/group, 7-syloxy group, sulfonamide group, cycloalkyl group or 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 another substituent, such as an alkyl group, an alkenyl group, an alkoxy group, a 7-aryl group, an aryloxy group, a hydroquine group,
Examples include an alkoxycarbonyl group, an aryloxycarbonyl group, an acylamide group/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 this case, R3 and R4 are hydrogen atoms, halogen atoms, alkyl groups, alkenyl groups, alkoxy groups, alkenyloxy groups, hydroquine groups, aryl groups, aryloxy groups, acyl groups, 7-sylami-7 groups, 7-syloxy groups, sulfonamide groups. Or reward an alkoxycarbonyl group.

Y represents a chroman et al. L< represents an atomic group necessary to form a coumaran ring.

Riman or coumaran ring is a halogen atom, an alkyl group, a dichlorofurkyl group, an alkoxy group, an alkenyl group,
It may be substituted with an alkenyloxy group, a hydroquine group, an aryl group, an allinyloxy group or a heterocyclic group, and may further form a spiro ring.

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

(E-2), (E-3), (E-4) and (E-5)
It is included in the compound represented by.

General formula (E-1) OR+ General formula (E-2) OR+ General formula (E-3) General formula (E-4) R book General formula (E-5) R I in general formulas (E-1) to (E-5).

R2, R3 and VR' have the same meaning as the throat in the above general formula (E), and Hs, R&, Rt, Ra
, R * and R'' are hydrogen atoms, halogen atoms, alkyl groups, alkoxy groups, hydroxy groups, alkenyl groups,
An alkenyloxy group, an aryl group, an aryloquine group, or a heterocyclic group, furthermore, R1 and R', R1 and Rγ, R' and R'', Ra and R', R' and R16 are cyclized with each other, and R A bare ring may be formed, and the two carbon rings may be substituted with a furkyl group.

In the general formula (E-1)-(E-53, R1, R
”, R3 and R4 are a hydrogen atom, a furkyl group, or a dichlorofurkyl group, in the general formula (E-5), R3
R4 is a hydrogen atom, an alkyl group, an alkoxy group, a hydroxy group, or a cycloalkyl group, and in the general formulas (E-1) to (E-5), R', R', R',
Compounds in which R', R' is a hydrogen atom, a furkyl group, or a cycloalkyl group are particularly useful.

The compound represented by the general formula [E] is tetrahedron (
Tetrahedron Letters) 1965
．． (8L pages 457-460 Journal of the Chemical Society of Japan (J, Che
@, Sac, part C) 1966° (22)
, pp. 2013-2016, CZh, Org, Kbi
+*) 1970. (6).

Compounds described on pages 1230 to 1237,
And write these down! It can be synthesized according to the method described.

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

Specific representative examples of these compounds are shown below.

The following is a blank general formula CF) In the formula, R1 is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an acyl group, a cycloalkyl group, or a hetero group:
R2 represents a 1-ring group, and R2 is a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, an aryloxy group, an acyl group, an acylamino group, an acyloxy group, a sulfonamide group, a cycloalkyl group, or an alkoxycarbonyl group. Hail to the foundation.

R3 represents a hydrogen atom, a halogen atom, a furkyl 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, a 7-syl group, an acylamino group, an acyloxy group, a sulfonamide group, or an alkoxy Hail carbonyl group.

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 hydroxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acylamide group, a carbamoyl group, a sulfonamide group, and a sulfamoyl group.

Further, R1 and R2 may be ring-closed with each other to form a 5-shell or 6-shell ring, in which case R1 and R1 are a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkenyloxy group, a hydroxy group, 71J -ru group, 71
J-ruoxy group, acyl group, acyl group, acyloxy group, sulfonamide group, or alkoxycarbonyl group.

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

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

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

Below are the blanks General formula (F-11 General formula (F-2) General formula (F-3) 1 to υ General formula (F-4) General formula [F-5] General formula [F-1] and [F- R1 and R2 in [5]
, Ri and R4 have the same meanings as in the above general formula [F], and R3, R6, R1, R,, Rt and R8
゜ represents a hydrogen atom, an alkyl group, an alkoxy group, a hydroxy group, an alkenyl group, an alkenyloxy group, an aryl group, an aryloxy group, or a heterocyclic group.

Furthermore, R1 and R,, R, and R7, R7 and R3, R1 and R
1 and VRg and Ro. may be cyclized with each other to form a carbocycle (furthermore, the carbocycle may be substituted with an alkyl group).

Also [F-3], [F-4J# upper v[F-5]1:
In this case, the two R8-R8 degrees may be the same or different.

The general formula [F-1], [F-2], [F-3],
[F-4] and I/[F-5] R1, R2,
and VF6 is a hydrogen atom, a furkyl group, a cycloalkyl group, R1 is a water'X: atom, an alkyl group 5, an alkoxy group,
hydroxy group or cycloalkyl group, further R3, R
Compounds in which 6, R2, R1, R5 and R1° are hydrogen atoms, alkyl groups, or cycloalkyl groups are particularly interesting.

The compound represented by the general formula [F] is tetrahedron (
Tetrabedron Letters) 1970
．． Vol 26, pages 4743-4751, Journal of the Chemical Society of Japan 1972. Ha, 10. pp. 1987-1990,
Synthesis 1975. V
ol 6t pp. 392-393, (Bul Sac, C
hime Be1g) 1975. Vo184 (
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] used is 5 to 300 mol% based on the magenta coupler according to the present invention.
is preferable, and more preferably 10 to 200 mol%.

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

Below is a general formula (Gl R'R in which R1 and R3 are each a hydrogen atom)) a loden atom, an alkyl group, an alkenyl group, an alkoxy group, a hydroxy group, an aryl group, an aryloxy group, a 7-syl group, an acyl amino group. -7 group, acyloxy group, sulfonamide group,
Represents a Schiff-furkyl group or an alkoxycarbonyl group.

R2 represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, a hydroxy group, an aryl group, an acyl group, an acylamide 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, a luoquine group, a hydroxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a 7-sylamine group, a carbamoyl group, a sulfonamide group, a sulfamoyl group, and the like.

± R2 and R3 may be ring-closed with each other to form a 5- or 6-shell hydrocarbon ring, and these 5 or 6 hydrocarbon rings may be a halogen atom, an alkyl group, a dichlorofurkyl 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 the fi atoms necessary to form the kidney ring,
The green bean ring may be substituted with a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, a cycloalkyl group, a hydroxy group, an aryl group, an aryloxy group, a heterocyclic group, etc. to form a spiro ring. You may.

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-33.

The following are blank general formula (G-1) 81 General formula (G-2) General formula (G-3) R1, R2 and V in general formula (G-13 to (G-3))
R31 has the same meaning as in general formula [G], and R4
, R5, R6, Rfu, Ra and VR5 are Soh? h
Hydrogen atom, halogen atom, alkyl group, alkoxy group,
Represents an alkenyl group, a hydroxy group, an aryol group, a 7q-ruoxy group, or a heterocyclic group R4 and R', Rs and R
', R' and R1, R7 and R', and R'' and R'' may be ring-closed with each other to form a hydrocarbon ring, and furthermore, the hydrocarbon ring is an alkyl group and r! It may be &.

In the general formulas (G-1) to (G-3), R1 and R3 are a hydrogen atom, an alkyl group, an alkoxy group, a hydroxy group, or a cycloalkyl group, and R2 is a hydrogen atom, an alkyl group, a hydroxy group, or a cycloalkyl group. 907 has a kill group, R', R
Compounds in which S, R', Rff, R'' and R'' are hydrogen atoms, alkyl groups or dichlorofurkyl groups are particularly valuable.

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 general formula (H) R'' in which R1 and R2 are a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, an acyl group,
Acylamino group, acyloxy group, sulfonamide group,
Represents a cycloalkyl group or an alkoxycarbonyl group.

R5 represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, a hydroxy group, an aryl group, an aryloxy group, an acyl group, an 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 a narkyl group, an alkenyl group, an alkoxy group,
Examples include an aryl group, a 7-aryloxy group, a hydroxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acylamide 7 group, a cal, an imoyl group, a sulfonamide group, a sulf 7 moyl group, and the like.

Furthermore, R1 and R2 and R2 and R3 may be ring-closed with each other to form five or six hydrocarbon rings (the hydrocarbon rings may be halogen atoms, alkyl groups, cycloalkyl groups, alkoxy groups, alkenyl groups). , hydroxy group, aryl group,
It may be substituted with an aryloxy group, a heterocyclic group, etc.

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

Among the compounds represented by the general formula (H), the most useful compounds for the present invention are included in the compounds represented by the general formula [H-1]-[H-2].

General formula (H-1) General formula [H-2] General formula (H-3) General formula [R1 in H-13 to (I-1-3). R2
and R3 have the same meaning as in general formula (H), and R
4, R', R', R', R"AI, rR' is soh-v
h Represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a hydroxy group, an alkenyl group, an aryl group, an aryloxy group, or a heterocyclic group, and R' and R'%
R' and R', R' and R7, R' and R', and R1 and R1 may be combined with each other to form a hydrocarbon ring, and the hydrocarbon ring may be further substituted with an alkyl group. .

In the general formula (H-1)-(H-3), R' and R2 are each a hydrogen atom, an alkyl group or a cycloalkyl group, %R' is a hydrogen atom, an alkyl group, an alkoxy group,
Hydroxy group or dichlorofurkyl group, R', R5, R
Particularly useful are compounds in which each of ', R7, R'' and R' is a hydrogen atom, an alkyl group, or a cycloalkyl group.

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

Ber, 1972.95(5), 1673-16
74 pages, Chemist-ry Letters,
1980, pp. 739-742.

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

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

Below is the general formula [J] - or an aryl group, and Y represents a group of nonmetallic atoms necessary to form a bicyclic ring with 5 to 7 shells together with the nitrogen atom, provided that the heterocyclic ring is Among the nonmetallic atoms containing nitrogen atoms that form,
When there are two or more heteroatoms, at least two heteroatoms are not in FA contact with each other. ] Examples of the aliphatic group represented by R' include a saturated alkyl group which may have a substituent, and an unsaturated alkyl group which may have a V substituent. As f@sum alkyl group,
For example, methyl group, ethyl group, butyl group, octyl group,
Examples of the unsaturated alkyl group include a dodecyl group, a tetradecyl group, and a hexadecyl group. Examples of the unsaturated alkyl group include an ethynyl group and a propenyl group.

Examples of the cycloalkyl group subjected to the R'''r wave include a 5- to 7-shell cycloalkyl group which may have a substituent, such as a cyclopentyl group and a cyclohexyl group.

The aryl group represented by R't' represents a phenyl group or a naphthyl group, each of which may have a substituent.

Substituents for the aliphatic group, cycloalkyl group, and aryl group represented by Rγ include alkyl groups, aryl groups, alkoxy groups, carbokol groups, carbamoyl groups, and acylamine 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 (J), Y together with the nitrogen atom is 5 to 7
The nonmetallic atomic groups necessary to form the bicyclic ring are praised, and at least two of the nonmetallic atomic groups containing nitrogen atoms forming the bicyclic ring must be heteroatoms, Also,
The at least two heteroatoms must not be adjacent to each other. In the heterocycle of the compound represented by general formula (J), if all the heteroatoms are adjacent to each other, l as magenta dye image stabilization 1 'j! It is not desirable because it does not allow one to fully understand Noh.

The 5- to 7-shell heterocycle of the compound represented by the general formula (J) may have a substituent, and examples of the substituent include an alkyl group, an aryl group, a heptadyl group, a carbamoyl group, an alkoxycarbonyl group, a sulfonyl group, a sulfamoyl 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 to form a spiro ring.

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 (I) 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 ■ 12H25 Among the compounds represented by the general formula (J), piperazine compounds and homopiperazine compounds are particularly preferred,
More preferably, the following general formula (J-1) or (J-
This is a compound represented by 2).

General formula (J-1) General formula [J-2] In the formula, R2 and R1 each represent a hydrogen atom, an alkyl group, or an aryl group, provided that R2 and R3 do not become hydrogen at the same time, R4- R'' represents a hydrogen atom, an alkyl group or an aryl group, respectively.

In the general formulas (J-1) and (J-2), R2 and V
R' represents a hydrogen atom, an alkyl group, or a heptadyl group, respectively, and examples of the alkyl group represented by R2 or R1 include a methyl group, an ethyl group, a butyl group, an octyl group, a dodecyl group, and a tetradecyl group. , hexadecyl group,
Examples of the aryl group represented by R2 or R3 include an octadecyl group, and a phenyl group.
The alkyl group and aryl group represented by R2 or R3 may have a substituent, and examples of the substituent include a halogen atom,
Examples include a furkyl group, an aryl group, an alkoxy group, an aryloxy group, and a heterocyclic group.

The total number of carbon atoms of R2 and R'' (including the rrL substituent) is preferably 6-40.

In the general formula [J-1] or (J-2), R4
~R1' each represents a hydrogen atom, an alkyl group, or an aryl group, and examples of the alkyl group represented by R4 to R11 include a methyl group and an ethyl group.

Examples of the aryl group represented by R4 to R+s include a phenyl group.

Specific examples of the compounds represented by the above general formula (J-13 or [J-2] include the above-mentioned exemplary piperazine compounds (J-
1)-(J-30) and exemplary 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 77 tons of 100 mQ 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 8 reactions. After pouring the reaction solution into 500 TIIQ water, ethyl acetate 5001. Extracted with lu. After drying the ethyl acetate with magnesium sulfate, the ethyl acetate was distilled off to obtain the desired product as white crystals. Recrystallization was performed with 300 ml of acetone to obtain 34 g of white scaly crystals (yield: 70%).

Melting temperature: 55-58°C Synthesis Example-2 (Synthesis of Compound J-34) 18 g of 4-morpholinoaniline was dissolved in 100 m of ethyl acetate (
After dissolving the mixture in 1:1, 12-acetic anhydride was added little by little while keeping the reaction solution at 20°C under stirring. After adding acetic anhydride, the mixture was cooled with water, the precipitated crystals were collected by filtration, and then recrystallized with ethyl acetate to obtain white powdery crystals 16-5K (yield 75%).

Melting point: 207-210°C General formula CK) In the formula, R' represents an aliphatic group, a cycloalkyl group, or an aryl group, and Y is a simple bond necessary to form a 5- to 7-shell heterocycle with the nitrogen atom. R'', R'', R', which represents a divalent hydrocarbon group.

R5, R", and R7 each represent a hydrogen atom, an aliphatic group, a cycloalkyl group, or an aliphatic group. However, R2 and R4 and R2 and R6 bond with each other to form a simple bond and form a nitrogen atom. Atom, together with Y, may form an unsaturated 5-7 shell ring. Also, when Y is a simple bond, R' and R7 combine with each other to form a simple bond. may be formed to form an unsaturated five-shell heterocycle with the nitrogen atom and Y.Also, when Y is not a simple bond, R5 and YSR' and Y or Y itself may form an unsaturated bond. may form an unsaturated 6-shell or 7-shell heterocycle together with the nitrogen atom and Y.

Examples of the aliphatic group represented by R''''C include a saturated furkyl group which may have a substituent, and an unsaturated alkyl group which may have a substituent. Examples of the saturated alkyl group include:
For example, methyl group, ethyl group, butyl group, octyl group,
Examples of the unsaturated alkyl group include a dodecyl group, a tetradecyl group, and a hexadecyl group. Examples of the unsaturated alkyl group include an ethynyl group and a propenyl group.

The cycloalkyl group represented by R1 includes 5 to 7 cycloalkyl groups which may have substituents, such as a schifbentyl group and a cyclohexyl group.

The aryl group represented by R'''C' represents a phenyl group or a naphthyl group which may have a substituent.

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

In the general formula (K), Y together with the nitrogen atom is 5 to 7
It represents a simple bond or a divalent hydrocarbon group necessary to form the heterocycle of the shell ring, but when Y is a simple bond, R5 and R7 further combine with each other to form a simple bond. 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. may form an unsaturated hexacyclic heterocycle. In the case of an ethylene group, R5 and Y, R' and Y, or Y itself may form an unsaturated bond, forming an unsaturated hexacyclic heterocycle. Further, the divalent hydrocarbon group represented by YT, which may form a 7-shell heterocycle, is FL
It may have a substituent, and examples of the substituent include an alkyl group, a carbamoyl group, an alkyloxycarbonyl group, an acylamino group, a sulfonamide group, a sulf7moyl group, an aryl group, and a heterocyclic group.

In the general formula (K), R2gR1yR4Rs.

R' and R7 each represent a hydrogen atom, an aliphatic group, a dichlorofurkyl group, or an aliphatic group, and the aliphatic group represented by R2-R7 is a saturated furkyl group which may have a substituent. and unsaturated furkyl groups which may have 1/fi substituents. Examples of saturated alkyl groups include methyl group, ethyl group, butyl group, octyl group, dodecyl group, tetradecyl group, hexadecyl group, etc., and examples of unsaturated alkyl groups include ethynyl group, propenyl group, etc. It will be done.

The cycloalkyl group represented by 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 oryl group represented by R1-R7 include a phenyl group and a naphthyl group which may have a substituent.

Substituents for the aliphatic group, cycloalkyl group, and aryl group represented by R2 to R7 above include an alkyl group, a 7-aryl group, an alkoxy group, a carbonyl group, a carbamoyl group, an acylamide group, a sulfamoyl group, and a sulfone group. basis,
Examples include carbonyloxy group, alkylsulfonyl group, arylsulfonyl group, hydroxy group, heterocyclic group, and alkylthio group.

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

In the following, NJN of the compound represented by the general formula [K) is preferably 5-:jOO mol%, more preferably 10 to 200% by mole, based on the magenta coupler represented by the general formula CI) of the present invention. It is mole%.

Typical specific examples of compounds reduced by the above general formula (K) are shown below.

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

Synthesis Example-1 (combination of -14 to compound f1) 1 Perazine 9.
60T in which 0g and 28g of myristyl bromide were dissolved.
6.0 g of anhydrous potassium carbonate was added to 11Q of acetone, and the mixture was boiled and refluxed for 20 hours to react.

After the reaction, the reaction solution was poured into 300 m (l) of water,
Extracted with ethyl acetate 300ITIQ. After drying the ethyl acetate layer with magnesium sulfate, the ethyl acetate was distilled off.
The desired product was obtained as white crystals. Acetone 100TII!
! 12 g of white flaky crystals (yield: 43
%) was obtained.

Melting point: 175-180°C To prevent fogging due to discharge caused by friction of the photosensitive material in the hydrophilic colloid layers such as the retention layer and intermediate layer of the photosensitive material of the present invention, and to prevent image deterioration due to UV light. may contain an ultraviolet absorber.

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

The silver halide emulsion layer and/or other hydrophilic colloid layer of a silver halide photosensitive material using the silver halide emulsion of the present invention is added to reduce the gloss of the photosensitive material and improve the addability.
A matting agent can be added to prevent the sensitive materials from sticking together.

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

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

Antistatic agents are sometimes used in the antistatic layer on the side of the support on which the emulsion is not laminated, or they are used to protect the emulsion layer and/or the side 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 other hydrophilic colloid layer of the light-sensitive material using the silver halide emulsion of the present invention may include improved coatability,
Antistatic, improved slipperiness, emulsification and dispersion, prevention of adhesion, and (
Various surfactants are used for the purpose of improving photographic properties (such as accelerating development, increasing contrast, sensitization, etc.).

A light-sensitive material using the silver halide emulsion 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, etc. Films made of semi-synthetic or synthetic polymers such as cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, polyamide, glass, metal, I! ? It can be applied to rigid bodies such as vessels.

The silver halide photosensitive material of the present invention can be produced by subjecting the surface of the support to corona discharge, ultraviolet irradiation, flame treatment, etc., if necessary, and then directly or The coating may be coated via one or more subbing layers (to improve properties such as hardness, abrasion resistance, hardness, antihalation properties, frictional properties, and/or other properties).

When coating a photographic light-sensitive material using the silver halide emulsion 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 light-sensitive material of the present invention can be exposed to electromagnetic waves in the spectral range to which the emulsion layer of the present invention is sensitive. Examples of light sources include natural light (sunlight), tungsten electric lamps, and fluorescent lamps. Light emitted from phosphors excited by , mercury lamps, xenon arc lamps, carbon arc lamps, xenon flash lamps, cathode ray tube flying spots, various laser beams, light emitting diode light, electron beams, X-rays, γ-rays, α-rays, etc. Any known light source can be used.

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 cathode ray tubes and xenon flash lamps.
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 as known in the art.

The aromatic primary amine color developing agents used in the color developing solution of the present invention include known ones that are widely used in color photographic processes.

These phenomenon agents include amine phenolic and p-phenylene diamine derivatives. These compounds are T.I.
Since it is more stable than the separated state, it is generally used in the form of a salt, such as a hydrochloride or a sulfate. Additionally, these compounds are generally present in a concentration of about 0.1 g to about 30% for color developer 1y, preferably about 1 g to about 15% for color developer 12.
(Use at + concentration.

Examples of aminophenol-based developers include 0-aminephenol, p-aminephenol, 5-amino-2-
Oxytoluene, 2-amino-3-oxy1-toluene,
2-oxy-3-amino-1,4-dimethylbenzene and the like are included.

Particularly useful primary aromatic amine color developers are N, N'
-Dialkyl-p-phenylenediamine type compound, and the alkyl group and phenyl group may be replaced with arbitrary substituents. Among them, examples of particularly useful compounds include N,N'-diethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine fgM salt, N
, N'-dimethyl-p-phenylenediamine mR salt,
2-amino-5-(N-ethyl-N-doacylamino)
-Toluene, N-ethyl-N-β-methanesulfinamidoethyl-3-methyl-4-aminoaniline @acid, N-ethyl-N-β-hydroxyethylaminoaniline, 4-amino-3-methyl- N.

N'-diebruaniline, 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 contains various components that are normally added to color developers, such as sodium hydroxide and carbonate. ~Alkaline agents such as thulium potassium carbonate, alkali metal sulfites, alkali metal binitritettr
It is also possible to optionally contain t+ acid salts, alkali metal thiocyanates, alkali metal halides, benzyl alcohol, water softeners, thickeners, and the like. The l)H value of this color developer is usually 7 or more, most commonly about 10 to about 13.

In the present invention, the protein that has been subjected to color development processing is treated with a processing liquid having a fixing ability. If the processing liquid having a fixing ability is a fixing liquid, the seedling is subjected to a bleaching treatment. FJ<
As a bleaching agent used in the whitening process, a metal complex salt of an R acid is used, and the metal complex salt oxidizes the metallic silver produced by development and converts it into silver halide, and at the same time colors the uncolored part of the color former. It is composed of aminopolycarboxylic acid or organic acids such as oxalic acid and citric acid, and contains iron,
Coordinated with metal ions such as cobalt and copper. The most preferred IFIf used to form such IM metal complexes include polycarboxylic acids or aminopolycarboxylic acids. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts.

Specific representative examples of these include the following.

[1] Ethylenediaminetetraacetic acid [2] Nitrilotriacetic acid [3] Iminodiacetic acid [4] Ethylenediaminetetraacetic acid disodium salt [5] Ethylenediaminetetraacetic acid tetra(trimethylane72lcum) salt [6] Ethylenediaminetetraacetic acid tetrasodium salt [7] Sodium nitrilotriacetic acid salt The bleaching agent used contains the above-mentioned allotropic salt of oleaginous acid as a bleaching agent, and may also contain various additives. As additives, it is particularly desirable to include rehalogenating agents, metal salts, and chelating agents such as alkali halides or ammonium halides, such as potassium bromide, sodium bromide, sodium chloride, and ammonium bromide.

In addition, pH buffering agents such as I/I salts, oxalates, acetates, carbonates, and phosphates, alkylamines, polyethylene oxides, and other substances known to be added to ordinary bleaching solutions may be added as appropriate. be able to.

Furthermore, the fixer and bleach-fixer contain ammonium sulfite,
Sulfites such as potassium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, sodium metabisulfite, U5 acid, borax, sodium hydroxide, potassium hydroxide , 1-lium carbonate, potassium carbonate, 1-lium bisulfite, 1-helium bicarbonate, potassium bicarbonate, r
It may contain a single pHvffi agent or two or more types of pHvffi agents consisting of various salts such as It acid, sodium acetate, and ammonium hydroxide.

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

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

[Effects of the Invention] As explained above, according to the halogenated photographic material of the present invention, the color reproducibility of the magenta dye image is improved, the light fastness is improved, and fogging does not increase due to storage of raw samples over time. Less is.

[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 A comparison magenta coupler was placed on a support made of polyethylene-coated paper at 4 mg/dB2 and a green-sensitive silver chlorobromide emulsion was placed on a support made of polyethylene-coated paper at an amount of 4 m! ] / 6m2. 4 m of dioctyl phthalate (1/du' and 15 mg/dm of gelatin)
The coating was applied so that the coating amount was t5.

Furthermore, 9 m of gelatin (1/d+i') was coated on top of the gelatin to give a coating of 1 x 1 M.

The sample thus prepared is referred to as sample 1. Next, the above sample 1
Table 1 shows the combinations of couplers, metal complexes, and compounds represented by the general formula [a] in the coupler-containing layer.
Samples 2 to 17', which were the same as sample 1, were prepared except for the changes shown in FIG. However, for samples 5 to 17', the coating @good was set to 2rr1g/d12. Incidentally, the metal name and the compound represented by the general formula [a] were added to the solvent together with the magenta coupler.

These samples were measured using a sensitometer (Konishi Roku Photo Industry Co., Ltd. (Taisei KS-7)).
After performing wedge exposure of green light using a mold), the following processing was performed.

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°C 3 minutes [4] Drying 75-80'C
Approximately 2 minutes [Color developing solution] Benzyl alcohol 15. , +2 Ethylene Glycol 1511R Potassium Sulfite 2.00 Sodium Bromide o7g Sodium Chloride
0.2 (1 potassium carbonate
30.0 (J Hydroxylamine 5FtW salt
3o9 polyphosphoric acid (TPPS>
2.5! ]3-Methyl-4-amino-N-(β-methanesulfonamidoethyl)-aniline sulfate 5.59 Fluorescent brightener (4,4'-diaminostilbenzsulfonic acid derivative) 1.0g Potassium hydroxide 2 Add .0g water to bring the total sweat to 12 and adjust the pH to 10.20.

[Bleach-fix solution] Ferric ammonium ethylenediaminetetraacetate dihydrate 60 Q Ethylenediaminetetraacetic acid R 3g Ammonium thiosulfate (70% solution) 100. ,
Q Ammoniumite (40% solution) 27.5d
Adjust the pH to 7.1 with potassium carbonate or glacial acetic acid, and add water to bring the total volume to 12.

A light resistance test was conducted on each sample obtained after the treatment in the following manner.

[Light resistance test 1] Each section 11 was exposed to sunlight for 30 days and the degree of green light Ω before and after fading was measured using an underglass outdoor stand.

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

D〇 - Temperature before photobleaching - Density after photobleaching The results are shown in Table-1.

Margin below Table-1 The amount was 0.05 mol per 1 mol of coupler, respectively.

Comparative magenta coupler (-! From the results in Table 1, it can be seen that when the metal complex according to the present invention and the compound represented by the general formula [a1] are used in combination with the magenta coupler, the light resistance is significantly improved. It can be seen that the effect of improving the light resistance of the dye formed from the magenta coupler represented by the general formula [I] is large. In addition, the sample using the magenta coupler represented by the general formula [I] of the present invention The dye has a low 01 absorption density and excellent color reproducibility.

Example 2 On a support made of polyethylene-coated paper, the following layers were sequentially coated from the support side to prepare a multicolor halogenated limited photographic light-sensitive material.

1st layer: blue-sensitive silver halide emulsion layer α-pivalyl-α-(1-benzyl-2,4-dioxyimidarizin-3-yl)- as a yellow coupler
8 m (1
/ d, 2, 3 m in terms of silver of blue-sensitive silver chlorobromide emulsion
g/d-12,2,4-'';-1-butylphenol-3',5'-di-t-amyl-4'-hydroxybenzoate at 3111 g/di', dioctyl phthalate at 3 mg/d'd3 and 1611 gelatin
10/d]::'.

Second layer: Intermediate layer gelatin was coated in a coating amount of 4 mg/6.2.

Third layer: green-sensitive JW bromide-limited emulsion layer containing the above-mentioned exemplary magenta coupler 44 at 4 mg/d1. +, 2 mg/(It2,
Dioctyl phthalate was applied at a coating amount of 4 m (1/d, ?) and gelatin was applied at a coating amount of 16111!+/di'.

4th layer: Intermediate layer UV absorber 2-hydroxy-31,51-di[-amylphenyl)-benzotriazole at 3 mg/d, 2
．． 2-(2'-tnitroxy-3'.

5'-di-t-butylphenyl)-benzo1-lyazole at 3 m(+/di2, dioctyl phthalate-1-4In(17d12) and gelatin at 14 mg/dl
The coating was applied so that it was coated with lt and m.

5th layer: red-sensitive silver chlorobromide emulsion layer 2,4-dichloro-3-methyl- as cyan coupler
6-[α-(2,4-di[-amylphenoxy)butyramide]-phenol at 1 mo/d i2.2-(
2,3,4,5,6-pentafluorophenyl)acylamino-4-chloro-5-[α-(2,4-diter
3 mg/d of t-amylphenoxy)pentylamide 1
, z, 2 mg/dB2 of dioctyl phthalate and 3 mQ/dII2 of red-sensitive silver chlorobromide emulsion in terms of silver were coated.

6th m: 2-(2'-hydroxy-3' as an intermediate layer UV absorber)
, 5'-di[-amylphenyl)-benzotriazole at 2mg/dB' , 2111 g/d of dioctyl phthalate, 2 and 6 m of gelatin (
The coating was applied so that the amount of coating was +/(l TQi).

7th Layer 2 Protective Layer Gelatin was coated to give a coating G of 9 mg/dv'.

The sample thus prepared is designated as sample 18.

Next, a magenta coupler, a metal complex, and a compound represented by the general formula [a] are added to the third layer of Sample 18 (the metal complex and the compound represented by the general formula [a] are added to the coupler 1).
Added at a ratio of 0.5 mole to each mole)
Samples 19 to 32, which were the same as sample 18, were prepared except that the combinations shown in 2 were added.

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

In addition, a test for increasing the fog value due to storage of raw samples over time was conducted in the following manner.

[Test for increase in fog value due to storage of raw samples over time] Each coated tl was stored in a constant temperature bath at 77° C. without humidification for 6 days.

These samples were exposed to light in the same manner as described above, and the green light reflection density of the white portion of each sample was measured.

The difference from the green light reflection temperature of the white part of the sample treated before being stored in a constant temperature bath was taken as the increased concentration of fog value.

The results are shown in Table-2.

From the results in Margin Table 2 below, it can be seen that adding a synthetic mirror to magenta 7J blur (one sample) has an effect on the light fastness Q, but the fog 11 during raw storage is very large, and the magenta coupler When a compound represented by the general formula [a] is added to the sample 2 (sample 20), the increase in fog during raw storage is almost 2, but the effect of improving light resistance is insufficient.

On the other hand, it can be seen that samples 21 to 32 according to the present invention have a remarkable effect of improving f and property, and moreover, the increase in car during raw storage is very small.

Example 3 The gold FA R< and the specific solvent added to the magenta coupler-containing layer were changed as shown in Table 3, and in addition to this, an antioxidant (addition base was 0.
Sample F121 of Example 2 except that 5 mol) was newly added.
The same sample 3:40 was prepared. Examples of each of these samples: Turnip 1 in the same way for light resistance and storage of raw samples
Measurements were made.

The results are shown in Table-3.

) to Table 3 Comparative gold
-1-sec-') As is clear from the results in Table 3, C33-3 of the present invention has extremely good light resistance;
It can be seen that the increase in fog during raw storage was very small, and that samples 37 to 39 [4] in which antioxidants were used in combination showed that the optical properties were synergistically improved.

Further, when comparing Samples 21.33 to 36, it can be seen that when an organic solvent with a 1-low dielectric constant is used, the light resistance [1 effect] is high.

Claims (2)

[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 has the following general formula [I]
The silver halide emulsion layer containing the magenta coupler represented by the formula has a singlet oxygen quenching rate constant of 3 x 10^7 M^-^1 sec^.
A silver halide photographic material, characterized in that it contains one or more metal complexes and a compound represented by the following general formula [a]. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. It's okay. 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. ] General formula [a
] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1 and R_2 each represent an alkyl group. R_3 is an alkyl group, -NR'R'' group, -SR'
group (R' represents a monovalent organic group), or -COO
R'' group (R'' represents a hydrogen atom or a monovalent organic group). m represents an integer from 0 to 3. ] (2) A patent characterized in that the metal complex and the compound represented by general formula [a] are added to the silver halide emulsion layer using a high-boiling organic solvent with a dielectric constant of 6.0 or less. A silver halide photographic material according to claim 1.