JPS61279855A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance light fastness of a magenta dye image and to reduce discolorability by incorporating a specified dye image forming coupler and a specified stabilizer for said dye image in a silver halide emulsion layer. CONSTITUTION:The magenta dye image forming coupler is represented by formula I in which Z is a nonmetallic atomic group necessary to form an N- contg. hetero ring, and X is H or a group to be released by the coupling reac tion with the oxidation product of a color developing agent, and R is H or a substituent. The magenta dye image stabilizer is represented by formula II in which each of R12, R13 is H, alkyl, cycloalkyl, alkenyl, or aryl, each of R14, R15 is halogen, alkyl, cycloalkyl, alkenyl, aryl, or the like, A is 1-6C alkylene, and m, n are each 0-4. The addition of both of formula I and II to the silver halide photographic sensitive material permits the magenta dye image to be made fast against light, heat, and humidity, and to be prevented from yellow discoloring of nonexposed areas.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a halogenated trowel photographic material, and in detail,
This invention relates to a silver halide color photographic light-sensitive material in which a dye image is stable against heat and light, and staining is prevented.

[Background of the Invention] Conventionally, a coupling reaction between an oxidized product of an aromatic primary amine color developing agent and a color former is carried out by imagewise exposing a silver halide color photographic light-sensitive material and performing color development. For example, it is well known that indophenol, indoaniline, indamine, azomethine, phenoxazine, phenazine, and similar dyes are produced and dye images are formed. In such photographic systems, a subtractive color reproduction method is usually adopted, and color forming agents having additional colors, namely yellow and magenta, are added to blue-sensitive, green-sensitive, and red-sensitive light-sensitive silver halide emulsion layers, respectively. A silver halide color photographic light-sensitive material containing a coupler that develops a cyan color is also used.

Couplers used to form the yellow image include, for example, acylacetanilide couplers, and couplers for forming magenta dye images include, for example, pyrazolone, pyrazolobenzimidazole,
Pyrazolotriazole or indacylon couplers are known, and as couplers for forming cyan dye images, for example, phenol or naphthol couplers are commonly used.

It is desirable that the dye image thus obtained does not turn brown even when exposed to light for a long time or stored under high temperature and high humidity. Further, it is desirable that the uncolored areas of the silver halide color photographic light-sensitive material do not turn yellow (hereinafter referred to as Y-stain) by exposure to light or moist heat.

However, with conventional magenta couplers, Y-stain occurs due to light and moist heat in uncolored areas, and browning due to light in dye image areas is more confusing and larger than with yellow couplers or cyan couplers, which often causes problems in terms of color reproduction. ing.

5-pyrazolones are widely used to form magenta dyes. The dye formed from this magenta coupler of 5-pyrazolones has a secondary absorption near 430 nm in addition to the main absorption near 550 ns, which is a major problem in color reproduction, and various methods have been developed to solve this problem. Research has been done.

Magenta couplers having an anilino group at the 3-position of 5-pyrazolones have small side absorption, and are particularly useful for obtaining color images for printing. These techniques are described in, for example, U.S. Patent No. 2,343,703 and British Patent No.
, 059,994@, etc.

However, the above-mentioned magenta coupler has the disadvantage that the image storage property, especially the fastness of the dye image to light, is extremely poor, and furthermore, the Y-stain in the uncolored area is large.

As another means for reducing the side absorption near 430nl of the magenta coupler,
．． Pyrazolobenzimidazoles described in US Pat. No. 612@, indacilones described in US Pat. No. 3,770,447, and US Pat. No. 3,725,067, British Patents 1 and 2
52.418 and 1,334,515, 1-pyrazolo[5,1-C]-]1.2.4-triazole type coupler Research Disclosure (Rese.
arch D 1 closure ) 24531
1H-pyran ON, 5-b described in (1984)]
-]1.2.4-triazole type coupler Research Disclosure v -(Research D 1scl
1 described in 24626 (1984)
-Pyrazolo[1,5-c]-]1.2.3-triazole type coupler JP-A-59-162548, Research φ Disclosure V-(Research D 1s
closure > 24531 1H-imidazo N, 2-bl-pyrazole type coupler described in (above),
Research Disclosure (Research D)
1 sclosure ) 24230 (1984
18-pyrazolo N, 5-b] pyrazole coupler described in Research Disclosure (Resea
rch D 1 closure ) 24220
(1984) 1H-pyrazolo[1,5-d]
The use of magenta couplers such as tetrazole couplers has been proposed. Among these, 1 day - pyrazolo [5,1
-C]-]1.2.4-triazole coupler 1 day-
Pyrazolo[1,5-b]-]1.2.4-triazole coupler 1 day-VirazoD[1,5-O]-]1.2
．． 3-triazole type coupler 1H-imidazo[1,2
-b ] Pyrazole type coupler, 1H-pyrazolo[1,
The dye formed from the 5-b] pyrazole type coupler and the 1-pyrazoloN, 5-d]tetrazole type coupler has a sub-absorption around 430 nl formed from the 5-pyrazolones having an anilino group at the 3-position. It is a coupler that is extremely small compared to other dyes, which is preferable in terms of color reproduction, and it also has the advantage that the occurrence of Y-stin in uncolored areas is extremely small when exposed to light, heat, and humidity.

However, the fastness of azomethine dyes formed from these couplers to light is extremely low, and in addition, the dyes are easily discolored by light, which significantly impairs the performance of color photographic light-sensitive materials, especially for printing. It has not been put to practical use in color photographic materials.

Furthermore, in JP-A-59-125732, a phenol compound or a phenyl ether compound is used in combination with a 1 day-virazo0[5,1-1]-]1.2.4-triazole type magenta coupler. Then, 1 day - pyrazolo [5
, 1-C]-]1.2.4-Triazole type magenta couplers have been shown to have improved light fastness of magenta dye images. However, many of the phenolic compounds or phenyl ether compounds disclosed in JP-A-59-125732 are 18-pyrazolo[5,1-c]-]1,2,4-triazole type magenta compounds. Even when used in combination with a coupler, it is still not sufficient to prevent the magenta dye image obtained from the coupler from fading against light, and the f! ! It was found that the effect of preventing image color in the original image was very small.

In view of the above-mentioned problems, the present inventors conducted extensive research and found that among phenol compounds or phenyl ether compounds, a compound represented by the general formula [XI[] of the present invention has a certain specific structure, 1H- Pyrazolo[5,1-C]-]
It has been found that, when used in combination with a 1.2.4-triazole type magenta coupler, the magenta dye image obtained from the coupler has a specific and large effect not only in preventing fading due to light but also in preventing discoloration.

Roughly speaking, the compound represented by the general formula [XII] of the present invention can be used not only for the magenta dye image obtained from the 1H-pyrazolo[5,1-c]-1,2°4-triazole type magenta coupler but also for the compound represented by the general formula [XII] of the present invention. It has been recognized that the magenta coupler according to [I] exhibits a remarkable effect in preventing the magenta dye image obtained from changing and fading due to light.

The compound represented by the general formula [XI] of the present invention is
9-125132, but in JP-A-59-125732, the compound of general formula [XI] is 1H-pyrazolo[5,1-1]-1°2.4 −
There is no specific description of the fact that when used in combination with a triazole type magenta coupler, the effect of preventing discoloration and fading of dye images is particularly strong.

[Object of the Invention] A first object of the present invention is to provide a silver halide photographic material which has excellent color reproducibility and which has significantly improved light fastness of magenta dye images.

A second object of the present invention is to provide a silver halide photographic material having a magenta dye image with little discoloration due to light.

A third object of the present invention is to provide a silver halide photographic material which is prevented from producing Y-stain in uncolored areas due to light, heat and humidity.

[Structure of the Invention] The above object of the present invention is to provide a silver halide photographic material containing a magenta dye-forming coupler represented by the following general formula [I] and a compound represented by the following general formula [XI]. achieved.

In the following blank general formula [I]

X represents a hydrogen atom or a substituent which is eliminated by reaction with an oxidized product of a color developing agent.

Further, R represents a hydrogen atom or a substituent. ] General formula [X
I[] [wherein R1-L and R+3 each represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group. R14 and RIG are each a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, an alkylthio group, an arylthio group, an acyl group, an acylamimum L sulfonyl group, a sulfonamido group, or a doroxy group. represents a group. - and n each represent an integer from 0 to 4, and when - is an integer from 2 to 4, R+4 may be the same or different. Also, n is 2 to 4
R+5 may be the same or different. A represents an alkylene group in which the straight chain portion has 1 to 6 carbon atoms. ] Hereinafter, unless otherwise specified, the general formula [X
The compound represented by I[ ] is referred to as a magenta dye image stabilizer.

“Invention 0 Specific configuration” 11 Margin below 1 ■ Next, the present invention will be specifically explained.

In the magenta coupler represented by general formula (I) 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, cyano group, spiro compound residue, bridged hydrocarbon compound residue, alkoxy group, aryoloxy group, heterocyclic oxy group, siloxy group , acyloxy group, carbamoyloxy group, amino group,
Acylamino group, sulfonamide group, imide group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkoxycarbonyl group, aryloxycarbonyl group, alkylthio group, aryl l:1・”7° ″″′
1"°"°""'--'1 Examples of the halogen atom include a chlorine atom and a bromine atom, with a chlorine atom being particularly preferred.

R? ! I*tl1771z-11zJf&1,71;
t, carbon number 1~. ．． 32″ is also 0・ak '7: /
lz group,
cycloalkyl group, cyclo: 1゜alkenyl group has 3-T12 carbon atoms, especially 5-7
,,: The latter is preferred, an alkyl group, an alkenyl group, :.

Alkynyl groups may be linear or branched.

Also, 0 ra alky)ゝ group ・A″ke°)′ group ・A)′i
.

Quinyl group, cycloalkyl group, cycloalkenyl
)□::′ group is a substituent [e.g. aryl, cyano, halogen atom,
In addition to heterocycles, cycloalkyl, cycloalkenyl, spiro compound residues, and bridged hydrocarbon compound residues, those substituted via a carbonyl group such as acyl, carboxy, carbamoyl, alkoxycarbonyl, and aryloxycarbonyl; Those substituted through a terror atom (specifically those substituted through an oxygen atom such as hydroxy, alkoxy, aryloxy, heterocyclic oxy, siloxy, acyloxy, carbamoyloxy, nitro, amino (including dialkylamino, etc.) ), those substituted through the nitrogen atom such as sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, acylamino, sulfonamide, imide, ureido, alkylthio, arylthio, heterocyclic thio, sulfonyl,
sulfinyl, sulfamoyl, etc., which are substituted via a sulfur atom, and phosphonyl, which is substituted via a phosphorus atom, etc.).

Specifically, for example, methyl group, ethyl group, isopropyl group, t-butyl group, pentadecyl group, heptadecyl group, 1
-hexylnonyl group,! , 1-dipentylnonyl group,
2-chloro-t-butyl group, trifluoromethyl group, 1
-Ethoxytriacyl group, l-methoxyisopropyl group, methanesulfonylethyl group, 2,4-di-t-amylphenoxymethyl group, anilino group, 1-phenylisopropyl group, 3-m-butanesulfonaminophenoxypropyl group , 3-4·-(α-[4··(p-hydroxybenzenesulfonyl)phenoxidodecanoylamino)phenylpropyl group, 3-(4·-[α-(2··,
Examples include 4...-di-t-amylphenoquine)butanamide]phenyl)-propyl group, 4-[α-(〇-chlorophenoxy)tetradecanamidophenoxy]propyl group, allyl group, cyclopentyl group, cyclohexyl group, etc. .

The aryl group represented by R is preferably a phenyl group, and may have a substituent (eg, an alkyl group, an alkoxy group, an acylamino group, etc.).

Specifically, phenyl group, 4-t-butylphenyl group,
2,4-di-t-amylphenyl group, 4-tetodecaneamidophenyl group, hexadecyloxyphenyl group, 4.
Examples include -[α-(4...-t-butylphenoquine)tetradecanamide] phenyl group.

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

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

Examples of the acyl group represented by R include alkyl carbonyl groups such as acetyl group, phenylacetyl group, dodecanoyl group, α-2,4-di-L-amylphenoxybutanoyl group, benzoyl group, and 3-pentadecyloxybenzoyl group. and arylcarbonyl groups such as p-chlorobenzoyl group.

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

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

The phosphonyl group represented by R includes an alkylphosphonyl group such as a butyloctylphosphonyl group, an alkoxyphosphonyl group such as an octyloxyphosphonyl group, an aryloxyphosphonyl group such as a phenoxyphosphonyl group, and a phenylphosphonyl group. Examples include arylphosphonyl groups such as.

The carbamoyl group represented by R may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc.
For example, N-methylcarbamoyl group, N,N-dibutylcarbamoyl group, N-(2-pen□tadecyloctylethyl)carbamoyl group, N-ethyl-N-dodecylcarbamoyl group, N-(3, -(2,4
-di-t-amylphenoxy)propyl)carbamoyl group, and the like. ; Space below ・The sulfamoyl group represented by R may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc.
For example, N-propylsulfamoyl group, N,N-diethylsulfamoyl group, N-L (2-pentadecyloxyethyl)sulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, N-phenylsulfamoyl group. Examples include moyl group.

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

Examples of the bridged carbonized compound residue represented by R include bicyclo[2,2,1]heptan-1-yl, tricyclo[3
,3,1,l$'? ] Decane-1-yl, 7,7-dimethyl-bicyclo[2,'2.1]hebutan-1-yl, and the like.

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

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

The heterocyclic oxy group represented by R preferably has 5 to 7 heterocyclic rings, and the heterocyclic ring may further have a substituent, for example, 3°4.5.6- Examples include tetrahydropyranyl-2-oxy group and 1-phenyltetrazol-5-oxy group, t, 6°
The siloxy group represented by :R may be further substituted with an alkyl group, and examples thereof include a trimethylsiloxy group, a triethylsiloxy group, a dimethylbutylsiloxy group, and the like.

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 α-chloroacetyloxy group, etc. , benzoyloxy group, etc.

The carbamoyloxy group represented by R may be substituted with an alkyl group, an aryl group, etc., such as an N-ethylcarbamoyloxy group, an N,N-diethylcarbamoyl ookine group, an N-phenylcarbamoyloxy group, etc. Can be mentioned.

The amino group represented by R may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as ethylamino group, anilino group, m-chloroanilino group, 3-pentadecyloxycarbonylanilino group. , 2-
Examples include chloro-5-hexadecaneamide anilino group.

Examples of the acylamino group represented by R include an alkylcarbonylamino group, an arylcarbonylamino group (preferably a phenylcarbonylamino group), and may further have a substituent, specifically an acetamido group, an α- Ethylpropanamide group, N-phenylacetamide group,
Examples include dodecanamide group, 2,4-di-t-amylphenoxyacetamide group, and α-3-t-butyl 4-hydroxyphenoxybutanamide group.
“Rr**tL6XJ)+77i FJ!1L
rl”・7/L=:.

Examples include a kylsulfonylamino group and an arylsulfonylamino group, and may further have a substituent. □
, oh, yu (yo7,7□7.oh,,5aett11,tsuke,!1; silsulfonylamino group, benzenesulfonamide
":t do group, p-toluenesulfonamide group, 2-meth
1□8'xy-5-t-amylbenzenesulfonamide group pa:'□- and the like.
:5゜The imide group represented by R is 1. even if it is an open chain type.

1°"°7""<'i"ff1m I& @ *°゛Pa'1°゛1.1 For example, succinimide group, 3-heptadecylcova, 1.:1:'1 phosphoric acid imide group, phthalimide group, glutarimide
, ;, 1 group, etc. are mentioned.
1jI The ureido group represented by R is an alkyl group, an ali
1. :1L group (preferably phenyl group) etc.
1'rli'rmo J: (e.g., t + t N -
x f Jl/″L/id group, N it
-Methyl-N-decylureido group, N-phenyl
:') ureido group, N-1)-tolylureido group, and the like.

The sulfamoylamino group represented by R is an alkyl group,
It may be substituted with an aryl group (preferably a phenyl group), etc., such as N,N-dibutylsulfamoylamino group, N-methylsulfamoylamino group, N-phenylsulfamoylamino group, etc. .

As the alkoxycarbonylamino group represented by R,
It may further have a substituent, for example, a methoxycarbonylamino group, a methoxyethoxycarbonylamino group,
Examples include octadecyloxycarbonylamino group.

The aryloxycarbonylamino group represented by R may have a substituent, and examples thereof include a phenoxycarbonylamino group and a 4-methylphenoxycarbonylamino group.

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

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

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

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

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

Examples of substituents that can be removed by reaction with the oxidized product of the color developing agent represented by and substituent groups.

In addition to the carboxyl group, examples of groups 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, R1. and R2. are hydrogen (representing an atom, an aryl group, an alkyl group, or a heterocyclic group), a hydroxymethyl group, and a triphenylmethyl group.

Examples of groups substituted via an oxygen atom include alkoxy groups, aryloxy groups, heterocyclic oxy groups, acyloxy groups, sulfonyloxy groups, alkoxycarbonyloxy groups, aryloxycarbonyloxy groups, and alkyloxalyloxy groups. .1114.2-7X/
'r>-Z)'t'i11. ．． A 1'alkoxyoxalyloxy group is mentioned.

The alkoxy group may further have a substituent, such as a 2-cyanoethoxy group, a phenethyloxy group, a p-
Examples include chlorobenzyloxy group.

The aryloxy group is preferably a phenoxy group, and the aryl group may further have a substituent. Specifically, phenoxy group, 3-methylphenoxy group, 3-
Dodecylphenoxy group, 4-methanesulfonamidophenoxy group, 4-[α-(3-pentadecylphenoxy)butanamide] 1;) phenoxy group, hexidecylcarbamoylmethoxy group
:', 1, □ cy group, electro-cyanophenoxy group, 4-methane sulfate
::・War 1χ-honylphenoxy group, l-naphthyloxy group, p
, -methoxyphenoxy group and the like.

The heterocyclic oxy group is preferably a 5- to 7-membered heterocyclic oxy group, which may be a condensed ring or may have a substituent. Specific examples include l-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 arylcarbonyloxy groups such as benzoyloxy groups.

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

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

Examples of the aryloxycarbonyl group include a phenoxycarbonyloxy group.

Examples of the alkyloxalyloxy group include a methyloxalyloxy group.

Examples of the alkoxyoxalyloxy group include an ethoxyoxalyloxy group.

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

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

□ The arylthio group includes phenylthio group, 4-methanesulfonamidophenylthio group, 4-dodecylphenethylthio group, 4-nonafluoropentanamidophenethylthio group, 4-carboxyphenylthio group, 2-ethoxy-5-t- Examples include butylphenylthio group.

Examples of the heterocyclic thio group include 1-phenyl-1,
Examples include 2,3,4-tetrazolyl-5-thio group and 2-benzothiazolylthio group.

Examples of the alkyloxythiocarbonylthio group include a dodecyloxythiocarbonylthio group.

Examples include those represented by the general formula -N. Here, R, and R8 are hydrogen atoms, alkyl groups,
Represents an aryl group, a heterocyclic group, a sulfamoyl group, a carbamoyl group, an acyl group, a sulfonyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, and R4 and R
6. may be combined to form a heterocycle. However, R4・
and R5. are never both hydrogen atoms.

The alkyl group may be linear or branched, and preferably has 1 to 22 carbon atoms. Further, the alkyl group may have a substituent, and examples of the substituent include an aryl group, an alkoxy group, an aryloxy group, an alkylthio group,
Arylthio group, alkylamino group, arylamino group, acylamino group, sulfonamide group, imino group, acyl group, alkylsulfonyl group, arylsulfonyl group,
Carbamoyl group, sulfamoyl group, alkoxy group, trubonyl group, aryloxycarbonyl group,
i'kyloxycarbonylamino group, aryloxy W tocarbonylamino group, hydroxyl group, carboxy
[・'7kK,'/A7M,2,. A: / [-F
M and 9.6ゎ. (Specific examples of the alkyl group include ethyl group, oxytyl group, 2-ethylhexyl group, and 2-chloroethyl group.

As the aryl group represented by R4・ or R6・,
The aryl group has 6 to 32 carbon atoms and is particularly preferably a phenyl group or a naphthyl group, and the aryl group may have a substituent, such as a substituent for the alkyl group represented by R4 or R5 above. Mention may be made of those listed above and alkyl groups. Specific examples of the aryl group include, for example, phenyl group! -naphthyl group, :4-methylsulfonylphenyl group.

The heterocyclic group represented by R6 or R5 is 5
□□ ~6-membered ones are preferred, and may be fused rings,
□□ May have a substituent. Specific examples include 2-furyl group, 2-quinolyl group, 2-pyrimidyl group, 2-benzothiazolyl group, and 2-pyridyl group.

Examples of the sulfamoyl group represented by R4 or R6 include N-alkylsulfamoyl group, N,N-dialkylsulfamoyl group, N-arylsulfamoyl group, N-arylsulfamoyl group,
, N-diarylsulfamoyl group, etc., and these alkyl groups and aryl groups may have the substituents listed for the alkyl groups and aryl groups. Specific examples of the sulfamoyl group include N,N-diethylsulfamoyl group, N-methylsulfamoyl group, N
-dodecylsulfamoyl group and N-p-)dylsulfamoyl group.

The carbamoyl group represented by R4 or R6 is,
Examples include N-alkylcarbamoyl group, N,N-dialkylcarbamoyl group, N-arylcarbamoyl group, N,N-diarylcarbamoyl group, etc., and these alkyl groups and aryl groups can be substituted with the substituents listed above for the alkyl group and aryl group. It may have a group. Specific examples of the carbamoyl group include N,N-diethylcarbamoyl group, N-methylcarbamoyl group, N-dodecylcarbamoyl group, N-p-cyanophenylcarbamoyl group, N-
-p-tolylcarbamoyl group is mentioned.

Examples of the acyl group represented by R4 or Rs' include an alkylcarbonyl group, an arylcarbonyl group, and a heterocyclic carbonyl group, and the alkyl group, aryl group, and heterocyclic group have a substituent. You can leave it there. Specific examples of the acyl group include hexafluorobutanoyl group, 2゜3.4.5.6-pentafluorobenzoyl group, acetyl group, benzoyl group, naphthonyl group, 2-furylcarbonyl group, etc. .

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

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

The alkoxycarbonyl group represented by R4 or R6 may have the substituents listed above for the alkyl group, and specific examples include a methoxycarbonyl group, a dodecyloxycarbonyl group, a benzyloxycarbonyl group, etc. Can be mentioned.

The heterocycle formed by combining R4 and R6 is preferably a 5- to 6-membered ring, and may be saturated or unsaturated, and may or may not have aromaticity, or,
It may be a condensed ring. Examples of the heterocycle include N-phthalimide group, N-succinimide group, 4-N-urazolyl group, 1-N-hydantoinyl group, 3-N-2,4-dioxoxazolidinyl group, 2- N-1,1-dioxo-
3-(2H)-oxo-1,2-benzthiazolyl group,
! -pyrrolyl group, ■-pyrrolidinyl group, 1-pyrazolyl group,! -pyrazolidinyl group, l-piperidinyl group, l-
Pyrrolinyl group, l-imidazolyl group, 1-imidazolinyl group, l-indolyl group, 1-isoindolinyl group, 2
-isoindolyl group, 2-isoindolinyl group, l-benzotriazolyl group, □1-benzimidazolyl group, 1-(1,2,4-triazolyl) group, 1-(1
,2,3-triazolyl) group, 1-(1,
2,3,4-tetrazolyl) group, N-bi1'-morpholinyl group, 1,2,3,4-tetrahydroxy
) 1, Noryl group, 2-oxo-1-pyrrolidinyl group, 21',
1. 1□ -IH-pyridone group, phthaladione group, 2-oxy
) [11,,, So1-Piece'. These groups include ``[ko□
to′ Terocyclic group is an alkyl group, an aryl group, an alkyl group.
:4,・□j↓: Oxy group, aryloxy group, acyl group, sulfony
1, i′1゛ group, alkylamino group, arylamino group, a
:1・ Nidylamino group, sulfonamino group, carbamoyl
,.

Pa:, to group, sulfamoyl group, alkylthio group, ary-E.

1゜ruthio group, ureido group, alkoxycarbonyl group, 1'
・, pararyloxycarbonyl group, imido group, nitro
], ゛・ group, cyano group, carboxyl group, halogen atom, etc.
``□゛B'1 may be substituted.
Examples of the nitrogen-containing heterocycle formed by I, Z or Z. There are many things that can be mentioned.

In addition, substituents on the heterocycle in general formula (1) and general formulas (I[) to [■] described below (for example, R2RI-Rs)
but! moiety (R..., X and Z... have the same meanings as R, X, and Z in the general formula CI). ), it forms a so-called screw-type coupler, which is, of course, included in the present invention.

In addition, the ring formed by Z, Z., Z... and Z described below may further include another ring (for example, a 5- to 7-membered cycloalkene).
may be condensed. For example, R6 and R6 in general formula (V), and R7 and R1 in general formula (W), may be bonded to each other to form a ring (eg, 5- to 7-membered cycloalkene, benzene).

What is represented by the general formula (1) below is more specifically represented by, for example, the following general formulas [11] to [■].

General formula (II) General formula (1) % formula % General formula (IT) N N -NH General formula (V) General formula (VI) N -N -NH General formula [■] General formula (II) - [ ■) R1-R6 and X
has the same meaning as R and X above.

Also, among the general formula CI), the following are preferable:
:1' It is represented by the general formula [■].

General formula [■]
・;:" In the formula, R+, X and Z+B general formula (I') l,, ort
Le R, 'I', □1 Synonymous with 8 and 2, ah.
□”・;= , ゛Magenta represented by the above general formula (n) ~ [■]
-:.

Particularly preferred couplers have the general formula Cn)
It is a magenta coupler represented by '.
:・”.

Regarding the substituents on the heterocycles in general formulas (1) to [■], R in general formulas (T, ) and Ro in general formulas (n) to [■] meet the following conditions l It is preferable that the following conditions [and 2] are satisfied, and more preferable cases are satisfied.
The following condition 1. is particularly preferable.
This is a case where conditions 2 and 3 are satisfied.

Condition 11 The root atom directly connected to the elementary ring is a carbon atom.

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

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

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

General formula (IX) e R1゜-C- I1 In the formula, Rs, R+o and R++ are each a hydrogen atom, /%
Rogen atoms, alkyl groups, cycloalkyl groups, alkenyl groups, cycloalkenyl groups, alkynyl groups, aryl groups, heterocyclic groups, anlu groups, sulfonyl groups, sulfinyl groups, phosphonyl groups, carbamoyl groups, sulfamoyl groups, cyano groups, spiro compounds residue, bridged hydrocarbon compound residue, alkoxy group, aryloxy group, heterocyclic oxy group, siloxy group, acyloxy group, carbamoyloxy group, amino group, acylamino group, sulfonamide group, imide group, ureido group, sulfonyloxy group Famoylamino group, alkoxycarbonylamino group, aryloxyhAt4=t
It7 i / IE,,7tItzya> h /l/
d = 7゜1, stomach □ aryloquine carbonyl group, alkylthio group,
1□ 7 Lee 71z % t!・"7° ring f-I-M in Table 5
・1°・ 1° At least two of R8° and R11 are not hydrogen atoms.
1 piece, ゎ8□□. +R1°-,,U. 1□. ,.

29. E9.1゛R9 and RIG are bonded to form a saturated or unsaturated ring (e.g. lotus).

cycloalkanes, cycloalkenes, heterocycles)
In addition, R11 may be bonded to the ring to form a bridged hydrocarbon compound residue.

The group represented by R9-R11 may have a substituent, and specific examples of the group represented by R8-R11 and the substituents that the group may have include those in general formula CI) described above. Specific examples of the group represented by R and substituents are listed.

Also, for example, a ring formed by combining Ro and R10 and R9
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 above general formula [1]. Specific examples of hydrocarbon compound residues and their substituents are listed.

Among the general formulas (IX), (i) Rs to R
If two of 1□ are alkyl groups, (ii) R- to R
0, for example, R81 is a hydrogen atom, and the other 2
When R, and R8 combine to form a cycloalkyl together with the root carbon atom, further preferable among (i) are R8 to R0.
ivy.

It is.

Two of them are alkyl groups and the other one is hydrogen
;, :1. :, 17/. , 711.2. . 7. . -!
e/I/ink. 1o5: This is an atom or an alkyl group.

Specific examples of the alkyl which may have a substituent, the cycloalkyl, and the substituent thereof include the above general formula, 1
・Alkyl or cycloalkyl represented by R in ゛CI)
[,.

Specific examples of the group and its substituents are listed.
・□1': Below margin: 1, 11゛□・1゜: □ ,゛・ :! : , 1- 1.1 1,.

Aim...'I 1, ( ;1.1 In addition, substituents that the ring formed by Z in general formula (1) and the ring formed by Zl in general formula [■] may have, and general R in formula (If) ~ [■]
1-R8 is preferably represented by the following general formula [X].

General formula (X) -R'-9o, -R'' In the formula, R1 represents alkylene, and R1 represents alkyl, cycloalkyl or aryl.

The alkylene represented by R1 preferably has 2 or more carbon atoms in the straight chain portion, more preferably 3 to 6 carbon atoms, and the straight chain portion has 1 or more carbon atoms.
Regardless of branching. Moreover, this alkylene may have a substituent.

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

Preferred substituents include phenyl.

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

-C1l, C1l, C)11-, -CHCH,C1
1l-, -CHCII, C1l, -, -C1l, CIl
, Cll-CllcoC,H%CJIg (:l1lCIllC11-, (LCLCIltCIh
−+ −cLCIl, cll, cn−.

I The alkyl group represented by R3 may be a linear, monobranched group.

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

The cycloalkyl group represented by R3 is preferably one with 5 to 6 shells, such as cyclohexyl.

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

Specific examples of the aryl represented by R8 include phenyl and naphthyl. The aryl group may have a substituent. Examples of the substituent include linear or branched alkyl, as well as those exemplified as the substituent for R1 described above.

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

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

General formula [Kari] In the formula, R and X have the same meaning as R and X in the general formula CI), and RI, R! is R1°Rt in general formula (X)
is synonymous with

Below margin 2Hs C,H.

cttuts
'C, H.

0′”; Below margin　　　　　　・1 1: i′ ″) , :′ C,U.

C,ll.

ll cm, Cl1m C11ll ff CI2H2 4III CI2H2% Below margin C, 11° C, II CsH1+(t) CIHI! CJI+(Ll C1llte C,H.

58
6'I11 C8゜■ C1(.

□ □ CJ, l j'llC
, 11° or less margin hardness C, H,.

C,IIs C,H.

0CII2CONHCH,CH,OCH.

0CIl, CII, 5O3CI+1 C, lI.

C111゜ 2ns c2n.

C,H.

C,H.

C,H.

C1l.

Below margin C,N.

°“”　　　　　　　　　　,1 C.I.

CI21125 t5 0g Call! Below margin C[+.

H1 Q.C., H.

H1 C+H+t(L) CslLt(t) C1l.

! 27
131 cu, C
J++Ct) H L C, lI.

yHss 111c cIIw □ 4G C! II Margin below □ @ l N
C4J++88N (Mountain N -Jj -N +56 N N -N N N NR N N N11 N N Nu C,1°C,H.

N HNi1 N N Nl1 11110C1 Mountain 5 88□ N -N N 18N N -N -N CJs
Cal Society), Parkin (Perkin)
kin) I (+977), 2047-2052
, U.S. Patent No. 3,725,067, JP-A-59-994
No. 37, JP-A-5142045, JP-A-59-162
No. 548, JP-A-59-171956, JP-A-60-3
The synthesis was carried out with reference to No. 3552 and Japanese Patent Application Laid-Open No. 60-43659.

The couplers of the invention typically contain 1Xl per mole of silver halide.
It can be used in a range of 0-3 mol to 1 mol, preferably 1X10-'' mol to 8X10-' mol.

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

The magenta dye image stabilizing agent used in combination with the magenta dye image-forming coupler represented by the general formula [iJ (hereinafter referred to as the coupler according to the present invention)) prevents fading of the magenta color l#iil image due to light. It is a compound represented by the above general formula [XI[], which not only has an effect but also has an effect of preventing discoloration due to light.

In the general formula [XI[], specific examples of the alkyl group, cycloalkyl group, alkenyl group, and aryl group represented by RIZ and Ra3 include the general formula [IJ
The groups detailed above for R can be mentioned. Halogen atoms, alkyl groups, cycloalkyl groups, alkenyl groups, alkoxy groups, aryl groups, aryloxy groups, alkylthio groups, arylthio groups, acyl groups, acylamimu L sulfonyl groups, and sulfonamide groups represented by RI'+ and Rts- Specific examples include the groups detailed for R in the general formula [IJ].

The above-mentioned algae may each be substituted with other substituents. For example, halogen atom, alkyl group, alkenyl group, alkoxy group, aryloxy group, hydroxy group, flukoxycarbonyl group, aryloxycarbonyl group, alkylamino group, arylamino acylamino group, carbamoyl group, sulfonamide group, sulfamoyl group, etc. can be mentioned.

A represents an alkylene group in which the straight chain portion has 1 to 6 carbon atoms, but this alkylene group may be either a straight chain or a branched one.

Further, this alkylene group may have one or more substituents, and examples of the substituents include an aryl group, a cyano group, a halogen atom, and a hetero group. Ring group, Tsuk. a,
, g) IiM, a) V-, ki, group, nido 1 includes a roxy group, an aryloxy group, and the like.

The alkylene chain itself is cycloalkyl, as in
(□□, work is good. :・
1 Among the compounds represented by the general formula [XII], compounds particularly useful in the present invention are those in which R12 and R+3 are each a hydrogen atom, an alkyl group or a cycloalkyl group, and R1
4 and R+5 are each a hydrogen atom, an alkyl group,
It is a compound in which an alkoxy group or a hydroxy group, and n and n are each an integer of 0 to 2, and A is a substituted or unsubstituted methylene group.

Typical specific examples of these compounds are shown below, but the compounds used in the present invention are not limited thereby.

The following margin-I CsHy(i) A-17 A-18 □ A-25 □ The compound according to the general formula [XII] of the present invention is
No. 31625, JP11! 1 (48-26133, 51-124926), and can be produced according to the synthetic method described. However, in each of the above-mentioned publications, the general formula [XI
It has been described that the compound contained in [I ] '('There is no mention of the fruit.

As a result of a sharp breath test, the present inventors have discovered that the compound represented by the general formula [XII] has an unexpected and specific effect on the retention of magenta dye images obtained from the magenta coupler represented by the general formula [IJ]. They found that it was effective.

The amount of the magenta dye image stabilizer represented by the general formula [XI[] of the present invention used is preferably 5 to 300 mol%, more preferably 10 to 300 mol%, based on the magenta color image forming coupler according to the present invention. It is 200 mol%.

In the silver halide photographic material of the present invention,
□ The magenta dye image stabilizer according to the present invention,
11 Furthermore, other mazenes represented by the following general formula [XI[IJ] 1□ Evening pigment image stabilizers, that is, phenol compounds and phenyl ether compounds can also be used in combination.

1□[XIII] '1. In the formula, RI& is a hydrogen atom, an alkyl group, an alkenyl group.
I[・ Represents a group, aryl group, or heterocyclic group, R1'l
, R, 9, R20-R21 are hydrogen atoms, high i
・0″″″′1″・eFo-4”7M・7/L, *
/L, l!・7 /°'7.

Nyl group, aryl group, aloxy group or acyl
, 1 represents an amino group, and R19 represents an alkyl group, a human U-oxy group, an aryl group or an alkoxy group.

Further, Rib and R1 may be ring-closed with each other to form a 5- or 6-membered ring, in which case Rrq represents a doxy group or an alkoxy group. Further, R16 and RIQ may be ring-closed with each other to form a methylenedioxy ring.

Furthermore, Rrq and Rrq may be ring-closed with each other to form a 5-membered hydrocarbon ring, in which case Rib represents an alkyl group, an aryl group, or a heterocyclic group.

However, this excludes the case where R16 is a hydrogen atom and Rrq is a hydroxy group.

In the general formula [XIIIJ, Rib is a hydrogen atom,
It represents an alkyl group, an alkenyl group, an aryl group, or a polycyclic group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an n-octyl group, a tertyl group, and a tertyl group.
- Straight chain or branched alkyl groups such as -octyl group, benzyl group, I\xadecyl group and the like can be mentioned. Moreover, this alkyl group may have a substituent. Examples of the alkenyl group represented by R76 include allyl, hexenyl, and octenyl groups. In general, examples of the 7-aryl group of Rib include phenyl and naphthyl groups. This aryl group can have a substituent, and specific examples include a methoxyphenyl group and a lylphenyl group.

Furthermore, specific examples of the polycyclic group represented by Rib include a tetrahydropyranyl group, a pyrimidyl group, and the like.

In the general formula [Xlff], Rn, R19s R2
0 and R21 represent a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group, an alkenyl group, an aryl group, an alkoxy group, or an acylamino group.
Examples include the same alkyl groups, alkenyl groups, and aryl groups mentioned above.

Further, examples of the halogen atoms include fluorine, chlorine,
Atoms such as bromine can be mentioned. Further, specific examples of the alkoxy group include a methoxy group, an ethoxy group, a benzyloxy group, and the like. Generally, the acylamino group is represented by R'NHCO-, where R' is an alkyl group (e.g., methyl, ethyl, n-propyl, n-butyl, n-octyl, tert-octyl, benzyl, etc.) , representing an alkenyl group (e.g., allyl, 10,000-cutynyl, oleyl, etc.), an aryl group (e.g., phenyl, methoxynoenyl, naphthyl, etc.) or a heterocyclic group (e.g., pyridyl, pyrimidyl, etc.) I can do it.

In addition, in the general formula [XIIJ-(, RIQ represents an alkyl group, a hydroxy group, an aryl group, or an alkyl group, among which the alkyl group and the aryl group are an alkyl group represented by 4\ with R1&, The same groups as the aryl group can be specifically mentioned.Also, regarding the alkoxy group of Rrq, the above-mentioned R, W, R+2, R2o
and the same alkoxy groups mentioned for R21.

Among the phenolic compounds or phenyl ether compounds represented by the general formula [Xlff] used in combination with the magenta coupler of the present invention, particularly preferred are tetraalkoxybiindane compounds, which are represented by the following general formula LXIV] be able to.

General formula [XrV] In the formula, R>r is alkyl+! & (e.g. methyl, ethyl,
propyl, n-octyl, tert-octyl, benzyl, hexadecyl), alkenyl groups (e.g. allyl,
octenyl, oleyl), an aryl group (eg, phenyl, naphthyl), or a heterocyclic group (eg, tetrahydropyranyl, pyrimidyl). R2
2 and R23 each represent a hydrogen atom, a halogen atom, (e.g., fluorine, chlorine, bromine), an alkyl group (e.g., methyl,
ethyl, n-butyl, benzyl), alkenyl group (e.g. azil, hexenyl, octenyl) or alkoxy group (e.g. methoxy, ethoxy, benzyloxy), Rz+ is a hydrogen atom, alkyl 1! i (for example methyl, ethyl, n-butyl, benzyl), an alkenyl group (for example 2-benyl, hexenyl, octenyl) or an aryl group (for example phenyl, methoxyphenyl, chlorphenyl, naphthyl).

The compound represented by the general formula [XI[I] is disclosed in U.S. Pat. No. 3,935,016, U.S. Pat. No. 145530, British Patent Publication No. 2,077.45
No. 5, No. 2,062,888, Yoneda Toku F 3,764
, No. 337, No. 3,432,300, No. 3,574,
621@, No. 3,573,050, JP-A-52-15
No. 2225, No. 53-20327, No. 53-1772
No. 9, No. 55-6324, British Patent No. 1,347,55
No. 6, Publication No. 2,066.975, Special Publication No. 1972-12
No. 337, No. 48-31625, U.S. Patent No. 3,700
, No. 455 and the like.

Typical specific examples of the compound represented by the general formula [XIIrl according to the present invention are shown below, but the present invention is not limited to these.

Below margin □ H-I H-4 ): P) L-8’□ PH-9 PH-170H.

The phenolic compound or phenyl ether compound represented by the general formula [cxm] of the present invention is represented by the general formula [ :XII] is preferably used in an amount of 200 mol% or less, more preferably 140 mol% or less, based on the magenta dye image stabilizer.

Although many of the phenolic compounds and phenyl ether compounds have the effect of preventing fading of the magenta dye image obtained from the magenta coupler of the present invention, they often have little effect of preventing discoloration.

Therefore, it is not preferable to use an excessive amount of the phenol compound and phenyl ether compound in the magenta dye image stabilizer of the present invention.

Generally speaking, the magenta dye image obtained from the magenta coupler not only fades when exposed to light, but also undergoes significant discoloration due to light, and the color tone of the dye image changes from magenta to yellowish. The magenta dye image stabilizer represented by the general formula [X]I] of the present invention can prevent the magenta dye image obtained from the magenta coupler from i-color and discoloration due to light, as shown in the specific example above. It has effects that cannot be achieved with conventional magenta dye image stabilizers made of phenolic compounds and phenyl ether compounds.

Therefore, when the conventional magenta dye image stabilizers of phenolic compounds and phenyl ether compounds are used in combination with the magenta dye image stabilizers of the present invention represented by the general formula The amount of the conventional phenolic compound and phenyl ether compound magenta dye image stabilizer must be selected to be unobtrusive.

When an appropriate amount of the conventional phenolic compound and phenyl ether compound magenta dye image stabilizer represented by [XIIIJ] is used in combination with the magenta dye image stabilizer of the present invention represented by the general formula [XII], A phase-opening effect may be observed when used together.

Although the magenta coupler of the present invention and the magenta image stabilizer of the present invention are preferably used in the same layer, the stabilizer may be used in a layer adjacent to the layer in which the coupler is present.

The silver halide photographic light-sensitive material of the present invention can be applied to, for example, color negative and positive films, color photographic paper, etc., but the present invention particularly applies when applied to color photographic paper used for direct viewing. 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 photographic light-sensitive materials, in order to perform subtractive color reproduction, a silver halide emulsion layer containing magenta, yellow, and cyan couplers as photographic couplers and a non-light-sensitive layer are usually used. has a structure in which the appropriate number of layers and temperature order are laminated on the support, but vAl
l! The number and temperature may be changed as appropriate depending on the important performance and purpose of use.

The silver halide emulsion used in the silver halide photographic material of the present invention (hereinafter referred to as the silver halide emulsion of the present invention).
Any silver halide used in ordinary silver halide emulsions, such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride, can be used as the silver halide.

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 created. 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
Growth may be performed by controlling H and OAQ and adding them sequentially or simultaneously. Conversion methods may be used to change the silver halide composition of the grains after growth.

When producing the silver halide emulsion used in the present invention, the grain size, grain shape, grain size distribution, and grain growth rate of silver halide grains can be controlled by using a silver halide solvent as necessary.

The silver 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 salt or lead salt in the process of grain formation and/or grain growth. salt, iron salt or complex salt,
Metal ions can be added to the inside of the particles and/or on the surface of the particles by adding metal ions, and reduction-sensitized 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. .

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 C may be added as is. When removing the salts,
This can be carried out based on the method described in Research Disclosure No. 17643.

The silver halide grains used in the silver halide emulsion of the present invention may consist of a uniform layer inside and on the surface.
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 latent images are mainly formed on the surface, or grains in which latent images are mainly formed within the grains.
Particles that are formed in the area may also be used.

The silver halide grains used in the silver halide emulsion of the present invention may have a regular crystal shape or may have an irregular crystal shape such as a spherical shape or a plate shape. In these particles, any ratio of (100) and (111,) planes can be used. □Also, the particles may have a composite form of these crystal forms, or particles of various crystal forms may be mixed.

The silver halide emulsion of the present invention may be a mixture of two or more 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,
Sulfur i with active zeftin! Bad feeling method.

Selenium sensitization method using toselenium compounds, reducing substances
1. Reduction sensitization method using kidney, gold and other noble metal compounds
″:□1 The noble metal sensitization methods used can be used alone or in combination.

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

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

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

The photographic emulsion layer and other hydrophilic colloid layers of the silver halide photographic light-sensitive material of the present invention are hardened by using alone or in combination with a hardening agent that crosslinks binder (or protective colloid) molecules and increases film strength. Ru. It is desirable to add the hardening agent in an amount that can harden the photosensitive material to the extent that it is not necessary to add the hardening agent to the processing solution, but it is also possible to add the hardening agent to the processing solution.

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

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

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

Yellow dye-forming couplers include acylacetamide couplers (e.g., benzoylaceto 7nilides, pivaloylacetanilides); magenta dye-forming couplers include, in addition to the couplers of the present invention, 5-pyrazolone couplers, pyrazolobenzimidazole couplers, Examples include pyrazone triazole, open-chain acylacetonitrile couplers, and cyan dye-forming couplers such as naphthol couplers and phenol couplers.

These dye-forming couplers preferably have a group called a ballast group in the molecule, which makes the coupler non-diffusive and has 8 or more carbon atoms. Also, these dye-forming couplers only require reduction of two silver ions, even if they are 4-equivalent, meaning that four silver ions need to be reduced to form one molecule of dye. Either 2-equivalence may be used.

For hydrophobic compounds such as dye-forming couplers that do not need to be adsorbed onto the silver halide crystal surface, various methods such as solid dispersion, latex dispersion, and oil-in-water emulsion dispersion can be used. It can be appropriately selected depending on the chemical structure of the hydrophobic compound. The oil-in-water emulsion dispersion method can be applied to conventionally known methods for dispersing hydrophobic compounds such as couplers. Usually, a high-boiling point organic solvent with a boiling point of about 150°C or higher is used, and if necessary, a low-boiling point and/or water-soluble compound is added. *WJ* is dissolved in combination with a hydrophilic binder such as an aqueous gelatin solution using a surfactant and dispersion means such as a stirrer, homogenizer, colloid mill, 70-jet mixer, and ultrasonic device. After being emulsified and dispersed, it may be added to the desired hydrophilic colloid layer. A step of removing low-boiling organic WJts simultaneously with the dispersion or dispersion may be included.

Takasu point organic IIs include phenol derivatives, phthalates, phosphates, citric esters, benzoic esters, alkylamides, fatty acid esters, trimesic esters, etc. that do not react with the oxidized form of the developing agent, and have a boiling point of 150'C or higher. An ammonium medium is used.

Anionic surfactants, nonionic surfactants, cations are used as dispersion aids when dissolving a hydrophobic compound in a low boiling point solvent alone or in combination with a high boiling point solvent and dispersing it in water using a machine or ultrasound. A surfactant can be used.

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

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

To prevent fogging due to discharge caused by charging of the photosensitive material in hydrophilic colloid layers such as the retention layer and intermediate layer of the silver halide photographic light-sensitive material of the present invention due to rubbing, etc., and to prevent image deterioration due to UV light. For this reason, it may contain an ultraviolet absorber.

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

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

A lubricant can be added to reduce the sliding friction of the silver halide photographic material of the present invention.

An antistatic agent for the purpose of preventing static electricity can be added to the silver halide photographic material of the present invention. Antistatic agents are sometimes used in the antistatic layer on the side of the support on which the emulsion is not laminated, or they are used to protect the emulsion layer and/or the side other than the emulsion layer on which the emulsion layer is laminated with respect to the support. It may also be used in a colloid layer.

The photographic emulsion layer and/or the silver halide photographic light-sensitive material of the present invention
Or, other hydrophilic colloid layers may contain additives for the purpose of improving coating properties, preventing static electricity, improving slipperiness, emulsifying and dispersing, preventing adhesion, and improving photographic properties (such as accelerating development, increasing contrast, and increasing sensitization). hand,
Various surfactants are used.

The photographic emulsion layer and other layers of the silver halide photographic light-sensitive material of the present invention are a baryta layer or an α-olefin polymer, a flexible reflective support such as paper laminated with a synthetic paper, cellulose acetate, cellulose nitrate, polystyrene, etc. It can be applied to films made of semi-synthetic or synthetic polymers such as polyvinyl chloride, polyethylene terephthalate, polycarbonate, and polyamide, as well as rigid bodies such as glass, metal, and ceramics.゛The silver halide photographic light-sensitive material of the present invention can be prepared by subjecting the surface of the support to corona discharge, ultraviolet irradiation, fire treatment, etc. as necessary, and then directly or adhering the surface of the support.
1. Characteristics, antistatic properties, dimensional stability, abrasion resistance, hardness,
1) Antihalation properties, frictional properties, and/or
) 1 or 2 or more conditions to improve other properties.
l; May be applied via a coating layer
m, □) g・□ When coating the silver halide photographic material of the present invention
11. Even if a thickener is used to improve coating properties.
[;4, good. The coating method is XDOL JOHN COACH-IN, which can coat two or more layers at the same time.
, -g and curtain coatings are particularly useful.

　　　　.

°.

:) The silver halide photographic material of the present invention is
1.-51: The emulsion layer constituting the silver halide photographic light-sensitive material is
It can be exposed using electromagnetic waves in the spectral range that has sensitivity.The light source can be natural light (sunlight),
Excitation by tungsten electric lamps, fluorescent lamps, mercury lamps, xenon arc lamps, carbon arc lamps, xenon flash lamps, cathode ray tube flying spots, various laser lights, light emitting diode lights, electron beams, X-rays, γ-rays, α-rays, etc. Any known light source can be used, such as light emitted from a phosphor.

Exposure times include not only exposure times of 1 millisecond to 1 second commonly used in cameras, but also exposure times shorter than 1 microsecond, such as exposure times of 100 microseconds to 1 microsecond using 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 various color photographic processes. These developers include aminophenol and p-phenylenediamine derivatives. These compounds are generally more stable than the free state and are therefore in the form of salts, e.g. hydrochloride or i
a Used in salt form. Additionally, these compounds generally have a concentration of about 0.117 to about 30 g per color developer 1, preferably about 10 to about 15 g per color developer 1.
Use at a concentration of g.

Examples of the amine phenol developer include 0-7 minophenol, p-aminophenol, and 5-amino-2-
Oxytoluene, 2-amino-3-oxytoluene, 2
-oxy-3-amino-1°4-dimethylbenzene and the like.

Particularly useful aromatic primary amine color developers are N, N'
-Dialkyl-p-phenylenediamine compound, and the alkyl group and phenyl group may be substituted with any substituent. Among them, particularly useful examples include N,N'-diethyl-p-7enylenediamine hydrochloride, N4-methyl-p-phenylenediamine hydrochloride, N
, N'-dimethyl-p-phenylenediamine salt, 2-amino-5-(N-ethyl-N-dodecylamino)-toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl- 4-aminoaniline sulfate,
N-ethyl-N-β-hydroxyethylaminoaniline, 4-amino-3-methyl-N.

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

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

In the present invention, after color development processing, fixing
□Process with a processing liquid that has the fixing ability.
□If the processing solution is a fixing solution, a bleaching process is performed before that. A metal complex salt of an organic acid is used as the bleaching agent in the bleaching process, and the metal complex oxidizes the metallic silver produced by development to convert it into silver halide, and at the same time colors the uncolored part of the color former. It has a warming effect and is composed of aminopolycarboxylic acid or organic acids such as oxalic acid and citric acid coordinated with metal ions such as iron, cobalt, and copper.

Ru. To form metal complexes of organic acids such as
I.

The most preferred organic acids for use include polycarboxylic acids or aminopolycarboxylic acids:
■□Reru. These polycarboxylic acids or aminopoly
,.

Carvone 1 or a water-soluble amine salt may be used.
;,... Specific representative examples of these include the following: (Able to argue.)
,.

ζ [1] Engineered ethylene diamine tetra vinegar M! 1.

1': [2] Nitrilotriacetic acid
.

(,3) Iminodiacetic acid [4] Ethylenediaminetetraacetic acid disodium salt [5] Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt "6" Eblendiamine detraacetic acid tetrasodium salt [7] Nitrilotriacetic acid sodium salt Used bleaching agents contains a metal complex salt of an organic acid as described above as a bleaching agent, and may also contain various additives.Additives include, in particular, alkali halides or ammonium halides, such as potassium bromide, sodium bromide, chloride, etc. It is desirable to contain a rehalogenating agent such as sodium or ammonium bromide, a gold U salt, or a chelating agent.

In addition, H buffering agents such as borates, salts, acetates, carbonates, and phosphates, alkylamines, polyethylene oxides, etc., which are known to be added to normal bleaching solutions, may be added as appropriate. can do.

Furthermore, the constant I1M and bleach-fix solutions contain sulfites such as ammonium nitrite, potassium sulfite, ammonium biel IIIe1, potassium bisulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, and sodium metabisulfite. Various salts such as 4dl acid, mineral sand, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide, etc. IJH laxative consisting of one or two
It can contain more than one species.

When carrying out the process of the present invention while replenishing the bleach-fix solution (bath) with a bleach-fix replenisher, the bleach-fix solution (bath) may contain diosulfate, thiocyanate, sulfite, etc. , the bleach-fixing replenisher may contain these salts and be replenished into the processing bath.
□゛In order to increase the activity of the bleach-fix solution in the present invention, air or oxygen is blown into the bleach-fix bath and the storage tank for the bleach-fix replenisher if desired;

Alternatively, a suitable oxidizing agent,
- For example hydrogen peroxide, bromine M salt, per1iii! Acid salts and the like may be added as appropriate.

The blank spaces below indicate the “specific effects of the invention.”
[In the present invention, a magenta dye image-forming coupler represented by the general formula [I, Ir] and the general formula
According to a silver halide photographic material containing a magenta dye image stabilizer represented by [[XI], 1.
Particularly low fastness to light, heat, and humidity 7 1″
Near, □1, Eng □. Yo l! , mt*Enc+s, )
No discoloration or fading due to light, no resistance to light, heat, or moist heat.
7. 1' The occurrence of Y-stain in the color developing area is well prevented.
Do□ 1・□ Furthermore, a dye image stabilizer represented by the general formula [XI[[]
1. By using a fixing agent in combination, the light fastness of the dye image is improved by i':'.
:□I゛)・ [Example]
).

The present invention will be specifically explained below with reference to Examples.
1::11゛1・”・, but the embodiments of the present invention are limited thereby.
,.

[・1 It's not a thing.
・・・Example 1
p.

Paper support laminated on both sides with 13° polyethylene
Gelatin (15,0111 (+/ 1
00CII+"), the following comparison [(・Magenta coupler a (6,0111+1/100c
Silver bromide emulsion (silver bromide 80-E/L, %, II silver I 3.al
Sample 1 was obtained by coating and drying.

Magenta dye #A in sample 1 above! ! Sample 2 was obtained in which the above-mentioned PH-13 was added as a stabilizer in the same molar amount as the magenta coupler.

Samples 3 and 7.11 were obtained in the same manner except that the magenta coupler in Sample 1 was replaced with magenta couplers 1.44 and 130 according to the present invention, respectively.

In each of the above samples 3.7.11, the above-mentioned "magenta dye image stabilizer PH-13" was added in an equal molar amount to the coupler to obtain samples 4.8.12, respectively, and in addition, in place of PH-13, according to the present invention Samples 5.9 and 13 were obtained by adding the related magenta image stabilizer A-4 in an equal molar amount to the coupler.Also, in the sample 3.7.11, PH-13 and A-4 were added to 1 mol of the coupler.
Added the coupler in a total ratio of 2:2 and the same mole as the coupler, and added each sample to sample 6.
゜10.14 was created.

Comparative magenta coupler a After exposing the sample obtained above through an optical wedge according to a conventional method,
The treatment was carried out in the following steps.

L processing step J processing temperature processing time color development
Bleach and fix at 33°C for 3 minutes and 30 seconds 33
℃ Wash with water for 1 minute 30 seconds 33℃
Dry for 3 minutes 50-80℃
The components of each 2-minute treatment solution are as follows.

Color developer] Benzyl alcohol 12 m (1 diethylene glycol 1 o potassium carbonate 25 iJ Sodium bromide 0.6 g anhydrous sodium sulfite 2.0 g hydroxylamine sulfate a)
Salt 2.5g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 4.5g Water was added to make one sentence, and adjusted to p)-110.2 with NaOH.

[Bleach-fix solution J Ammonium thiosulfate 1201) Sodium metabisulfite 15 Q Anhydrous sodium sulfite 3 g EDTA ferric ammonium salt 65 Q Add water to adjust to 11, pH
Adjusted to 6.1 to 6.8.

The concentrations of Samples 1 to 14 treated above were measured using a densitometer (model KD-7R, manufactured by Konishiroku Photo Industry Co., Ltd.) under the following conditions.

Each of the above-mentioned processed samples was exposed to a xenon fade meter for 10 days to examine the light fastness of the dye image and the Y-stain of the uncolored area, while each sample was exposed to a high temperature and high humidity atmosphere of 60°C and 80% RH. The dye image was left to stand for 14 days, and the moisture resistance of the dye image and the Y-stain of the uncolored area were examined. The results obtained are shown in Table 1.

However, the evaluation of each item of light fastness and moisture fastness of the dye image is as follows.

[Residual rate] Percentage of dye remaining after exposure to light and moisture resistance test at initial density of 1.0.

[The value obtained by subtracting the temperature of Y-Stain before the light and humidity test from the concentration of Y-Stain after the light and humidity test.

[Degree of discoloration] After light test at initial density 1.0 (yellow temperature)/
(magenta density) to (yellow density) before light test /
The value obtained by subtracting the <magenta density> means that the larger this value is, the more likely the color tone changes from magenta to yellowish.

:・Table 1 As is clear from Table 1, sample 3.7.11 prepared using the coupler of the present invention was a conventional 4-equivalent type 3-
Compared to sample 1 made using anilino-1,2-pyrazolo-5-one type coupler, Y-
It can be seen that staining is extremely difficult to occur, but the residual rate and degree of discoloration of the color six image areas in the light exposure test show that the color easily changes and fades when exposed to light. Sample 4.8.12
is a sample prepared by using the coupler of the present invention in combination with the well-known magenta dye image stabilizer PH-13, which certainly greatly improves the fading of the dye image due to light. cannot improve discoloration.

On the other hand, in Samples 5 and 9.13 prepared using the coupler of the present invention and the dye image stabilizer of the present invention, the color change and fading of the dye image were small in the light, heat, and humidity resistance tests, and no color was developed. It can be seen that almost no Y-stin occurs. This is the conventional 4-equivalent type 3-7 Nilino 1.2
-Pyrazolo-5-one type coupler and dye image stabilizer P
This was not possible with the combination with H-13 (sample 2).

Furthermore, in addition to the coupler and magenta dye image stabilizer according to the present invention, Samples 6, 10 and 14, in which a conventional magenta dye image stabilizer was added, further improved the dye residual rate in the light test. I understand that.

Example 2 The coupler and magenta dye image stabilizer combinations shown in Table 2 were coated exactly as in Example 1, and sample 1
5 to 30 were created. Samples 15-30 were processed as described in Example 1. Furthermore, these samples were subjected to a light resistance test and a moisture resistance test in the same manner as in Example 1, and the results shown in Table 2 were obtained.

Note that the comparative magenta coupler b in the table has the following structure.

The following margin comparison magenta coupler is υ”−F ′= +II )] 1.
A combination of 4-equivalent type 3-anilino-1,2-bilan o-5-one type Kab 5~ in combination with the magenta dye image stabilizer of the present invention (sample-15゜16) and the coupler of the present invention When a commonly used magenta dye image stabilizer was used in combination (Samples 19, 20, 21, 22), discoloration and fading in the light control test, Y-stain in the uncolored area, and moisture resistance test were observed. Since it is not possible to improve all aspects of Y-snine, we believe that the above-mentioned improvements can only be achieved by using the magenta dye image stabilizer of the present invention in combination with the present invention. Ru.

Example 3 On a paper support laminated on both sides with polyethylene, the following layers were sequentially coated from the support side to prepare a multicolor halogenated photographic abrasive, which passed Sample F131.

゛1Δ゛Stomach sensitive pager silver emulsion layer
l As a yellow coupler α-gobaloyl-α-
2.4-dioxo-1-benzylimidazolidine-3-
yl)-2-chloro-5-[γ-(2°4-di-t-amylphenoxy)butyramide” acetanilide.
8mg/100cm, blue-sensitive silver chlorobromide emulsion (containing 85 mol% silver bromide) converted to the eye is 3.2mo/1oO
ci+, n-petit/l, 7 talates for 3.5s
a/ 100c+e2 and 13.5-g gelatin
The coating was applied so that the coating amount was 7100CI''.

2nd M = middle layer 2.5-di[-octylhydroquinone 0.5IQ
/ 10001”, dibutyl phthalate 0.5
mg/100cm2 and gelatin at 9. Ou+g
/ 100cII12.

Third layer: green-sensitive silver halide emulsion layer containing the magenta coupler 18 at 3.5 mg/100 cm
, a green-sensitive silver chlorobromide emulsion (containing 80 mol% silver bromide) is converted into silver and has a silver content of 2.51 (1/100C117-petite/L).
, 7 tallate at 3.0-g/100cm and gelatin at 12.0+ag/100CI112.

4th layer: Intermediate layer UV absorber 2-(2-hydroxy-3-8eC-butyl-5-t-7 tylphenyl)benzotriazole at 7.0IQ/100cm, butyl phthalate at 6.011(1/100cm) 12,5-G-
0.5sa/100c of t-octylhydroquinone
m and gelatin 12. The coating was applied so that the OIM was 100 cm.

5th layer: red-sensitive silver halide emulsion layer
1 cyan coupler, 2-α-(2,4-di
1-t-pentylphenoxy)butanamide J
-4,'6-dichloroo-5-ethylphenol 4,
2111 (1/100cm, red-sensitive silver chlorobromide emulsion (
3.0111<
1/100CI11, tricresyl phosphate 3.5sa/100cm and gelatin 11.
It was coated to give 5IQ/100cm.

6th layer: Protective layer Gelatin was coated at 8.0 IQ/100 cm.

In the above sample 31, the magenta dye image stabilizer of the present invention was added to No. 3B in the proportions shown in Table 3 to prepare multilayer sample 32 and 40, which were exposed and processed in the same manner as in Example 1. Afterwards, a light emission test (a xenon fade meter was irradiated for 15 days) was conducted. The results are shown in Table 3.

From these results, the magenta dye image stabilizer of the present invention is
The magenta coupler used in the present invention is effective in stabilizing dye images, and the effect becomes greater as the amount added increases. Moreover, compared to sample 31, samples 32 to 40 showed extremely small discoloration of the dye images in the light emission test. Furthermore, in the samples of the present invention, discoloration and fading of the magenta pigment are extremely small.
After the light exposure test, the overall silver halide color photographic light-sensitive material had good color balance with the yellow and cyan couplers, and maintained extremely good color reproducibility.

Patent applicant Roku Konishi Photo 1: Gyo Co., Ltd., T. Niji 11
- Mino Sai (rf

Claims (1)

[Scope of Claims] A silver halide photographic material comprising a magenta dye image-forming coupler represented by the following general formula [I] and a compound represented by the following general formula [XII]. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. You may. X represents a hydrogen atom or a substituent that can be separated by reaction with an oxidized product of a color developing agent. Further, R represents a hydrogen atom or a substituent. ] General formula [X
II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1_2 and R_1_3 each represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group. R_1_4 and R_1_
5 is a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, an aryl group,
Aryloxy group, alkylthio group, arylthio group,
Represents an acyl group, acylamino group, sulfonyl group, sulfonamide group or hydroxy group. m and n each represent an integer of 0 to 4, and when m is an integer of 2 to 4, R_1_4 may be the same or different. Further, when n is an integer of 2 to 4, R_1_5 may be the same or different. A represents an alkylene group in which the straight chain portion has 1 to 6 carbon atoms. ]