JPS62215273A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the titled material capable of stabilizing a color image against a heat and a light, and preventing a generation of stain by incorporating at least one of a coupler capable of forming a specific magenta color image, and at least one of the 1st. specific compd. and at least one of the 2nd. specific compd. to the titled material. CONSTITUTION:The titled material contains at least one of the coupler capable of forming the magenta color image shown by formula I, at least one of the compd. shown by formula II and at least one of the compd. selected from the compds. shown by formula III. In formula I, Z is a non-metallic atom group necessary for forming a nitrogen contg. heterocyclic ring, X is hydrogen atom or a substituted group capable of cleaving by reacting with an oxidant of a color developing agent, R is hydrogen atom or a substituted group. In formula III, R<8>-R<10> are each hydrogen atom or halogen atom, etc., Y is an atomic group necessary for forming an indan ring. The used amount of the stabilizer of the magenta color image is preferably 5-400mol%, more preferably 10-250mol% per the magenta coupler shown by formula I.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a silver halide 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, when a silver halide color photographic light-sensitive material is imagewise exposed and color developed, an oxidized product of an aromatic primary amine color developing agent and a color former undergo a coupling reaction. For example, it is well known that indophenol, indoaniline, indamine, azomethine, phenoxazine, phenazine, and similar pigments are produced to form color images. A color reproduction method using a subtractive color method is adopted, and color formers having an extra color relationship are added to blue-sensitive, green-sensitive, and red-sensitive light-sensitive silver halide emulsion layers, that is,
A silver halide color photographic material containing couplers that develop yellow, magenta and cyan colors is used.

Examples of couplers used to form the yellow image include acylacetanilide couplers, and examples of couplers used to form magenta images include pyrazolone, pyrazolobenzimidazole, pyrazolotriazole, and indacylon couplers. Furthermore, as a coupler for forming a cyan image, for example, a phenol or naphthol coupler is generally used.

It is desired that the dye image obtained in this way does not change color or fade even if it is exposed to light for a long time or stored under high temperature and high humidity. Furthermore, it is desired that the uncolored areas of silver halide color photographic light-sensitive materials do not turn yellow (hereinafter referred to as Y-stain) when exposed to light or moist heat.

However, in the case of magenta couplers, Y-staining due to moist heat in uncolored areas and fading due to light in dye image areas are extremely large compared to yellow couplers and cyan couplers, and often pose a problem.

Couplers commonly used to form magenta dyes are 1,2-pyrazolo-5-ones. This one
, 2-pyrazolo-5-one magenta couplers, in addition to the main absorption around 550 nm, the dye has a wavelength of 430 nm.
Having side absorption near ns is a major problem, and various studies have been conducted to solve this problem.

A magenta coupler having an anilino group at the 3-position of a 1.2-pyrazolo-5-one has a small side absorption and is particularly useful for obtaining a color image for printing. For these techniques, see, for example, U.S. Patent No. 2,343.703;
It is described in British Patent No. 1, No. 059.994, etc.

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

” - British Patent No. 1.0, 17 as another means for reducing the side absorption near 430 nm of magenta couplers.
, 612, indasilones described in U.S. Pat. No. 3,770,447, and U.S. Pat. No. 3,725,067, British Patent No. 1.2.
IH described in Nos. 52,418 and 1,334,515
-Pyrazolo[5,1C1-1,2,4-) lyazole coupler, I H-pyrazolo[1,5-b]-1,2, described in JP-A-59-171956, Research Disclosure Th24,531 4-) Riazole type coupler, IH-pyrazolo[1,5-C-co] described in Research Disclosure Th24,626, 2°3-triazole type coupler, JP-A-59-162548,
1H-imidazo[1,2-bl-pyrazole type coupler described in Research Disclosure 11k124,531, IH-pyrazolo[1°5-bl-pyrazole type coupler described in JP-A-60-43659, Research Disclosure 24,230 , Japanese Patent Publication No. 6033552
No., Research Disclosure 11k124, 220
Magenta couplers have been proposed, such as the IH-pyrazolo[1,5-dl tetrazole type coupler described above.

Among these, 1H-pyrazolo[5,1-cl -1゜2
．． 4-1-lyazole coupler, IH-pyrazolo N,
5-b]-1,2,4-triazole coupler, IH
-Pyrazolo[1,5-CI+ -1゜2.3-triazole coupler, IH-imidazo[L 2-bl Pyrazole coupler, IH-pyrazolo[L 5-d]
Pyrazole-type couplers and I H-pyrazolo “l,
5-d] The dye formed from the tetrazole type coupler has a significantly smaller subabsorption near 430 nm than the dye formed from the 1,2-pyrazol-5-one having an anilino group at the 3-position. This is preferable in terms of reproducibility, and 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 light fastness of azomethine dyes formed from these couplers is extremely low;
The coloring matter is easily discolored by light and significantly impairs the performance of silver halide color photographic materials, especially print-type silver halide color photographic materials, and has not been put to practical use in print-type silver halide color photographic materials. Not yet.

Moreover, in JP-A-59-125732, by using an IH-pyrazolo[5,1-cl-1,2,4-triazole type magenta coupler together with a phenol compound or a phenyl ether compound, IH-pyrazolo c5. Techniques have been proposed to improve the light fastness of magenta dye images obtained from 1 cl L 2+4-triazole type magenta couplers. However, even with the above technology, it has been found that it is still not sufficient to prevent the magenta dye image from fading due to light, and moreover, it is almost impossible to prevent discoloration due to light.

[Purpose of the invention]

The present invention has been made in view of the above problems, and the first object of the present invention is to provide a silver halide photographic light-sensitive material which has excellent color reproducibility and has significantly improved light fastness of magenta dye images. It is about providing.

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.

The third object of the present invention is to reduce Y in uncolored areas against light and moist heat.
- It is an object of the present invention to provide a silver halide color photographic material in which staining is prevented.

[Structure of the invention]

The second object of the present invention is to combine at least one magenta image-forming coupler represented by the following general formula (1) and at least one compound represented by the following general formula [XII],
This can be achieved by using a silver halide photographic material containing at least one compound selected from the following general formulas (X, III).

General formula (1) [In the formula, Z represents a nonmetallic group 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.

Moreover, R represents a hydrogen atom or a substituent. ] General formula (Xr
[) 11 ・History 1',,-'',,,+,,,,',.

In the formula, R', R2 and R3 each represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or a heterocyclic group, and R4 represents an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group. . R5 represents a substituent, and a represents 0 or an integer of 1-4. J is -c
-o'-1-C-1S +1 II 11 and R7 represent a hydrogen atom alkyl group or an aryl group. Also R1 and R
2 may be combined to form a 5- or 6-membered ring. l
When is 2 or more, a plurality of R5s may be the same or different.

Furthermore, R5 may form a 5- to 6-membered ring together with R1 and/or R2 and the nitrogen atom adjacent to R1 and R2.

General formula (XIII RIO [In the formula, R8 and R16 are each 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,
Acylamino group, acyloxy group, sulfonamide group,
Represents a cycloalkyl group or an alkoxycarbonyl group, and R9 is a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, a hydroxy group, an aryl group, an acyl group, an acylamino group, an acyloxy group, a sulfonamide group, a cycloalkyl group, or an alkoxycarbonyl group. represents a group.

Further, R9 and RIO may be ring-closed with each other to form a 5- or 6-membered hydrocarbon ring.

Y represents an atomic group necessary to form an indane ring. ] Next, the present invention will be specifically explained.

In the magenta coupler represented by general formula (1) (CI) according to the present invention, 2 represents a nonmetallic atomic group 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.

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, aryloxy group, heterocyclic oxy group, siloxy group, acyloxy group, carbamoyloxy group, amino group,
Acylamino group, sulfonamide group, imide group, ureido group, sul7amoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkoxycarbonyl group, aryloxycarbonyl group, alkylthio group, arylthio group, heterocyclic thio group Can be mentioned.

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

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

In addition, these alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, and cycloalkenyl groups are substituents [e.g., aryl, cyano, halogen atoms, heterocycles, cycloalkyl, cycloalkenyl, spiro compound residues, bridged hydrocarbon compounds] In addition to residues, fi'? Those that are substituted through an oxygen atom such as hydroxy, alkoxy, acyloxy, heterocyclic oxygen, siloxy, acyloxy, carbamoyloxy, and those that are substituted through an oxygen atom, and those that are substituted through a heteroatom. , Ami7
(including dialkyl amide 7, etc.), sul 7 amoylami 7, etc.
, alkoxycarbonylamino, aryloxycarbonylamino, acylamino, sulfonamide, imide,
``Those substituted through a nitrogen atom such as ``Nraido,'' those substituted through a sulfur atom such as alkylthio, arylthio, heterocyclic thio, sulfonyl, sulfinyl, and sulfamoyl, and those substituted through a phosphorus atom such as bosbonyl, etc.) ].

Specifically, for example, methyl group, ethyl group, isopropyl group, E-butyl group, pentadecyl group, heptadecyl group, 1
-hexylnonyl group, 1,1'-dipentyl7yl group,
2-chloro-7-methyl group, trifluoromethyl group,
1-ethyl)-oxytridecyl group, 1-methoxyisopropyl group, methanesulfonylethyl group, 2,4-di-amyl7ethoxymethyl group, anilino group, 1-phenylisopropyl group, 3-m-butanesulfonamino7 E7xypropyl group, 3-4'-(Q-44''(p-hydroxybenzenesulfonyl)phenoxy]dodecamylamino)phenylpropyl group, 3-(4'-(α-(
2",4"-diE-amylphenoxy)butanamido]phenyl)-propyl group, 4-(Q-(.

-Chlor7e7xy)tetradecanamidophenoxy]
Examples include propyl group, allyl group, cyclopentyl group, and cyclohexyl group.

The aryl group represented by R is preferably a phenyl group, even if it has a substituent (for example, an alkyl group, an alkoxy group, an acylamine group, etc.).

Specifically, phenyl group, 4-t-butylphenyl group,
2.4-di-1-amylphenyl i, 4-tetradecanamidophenyl group, hexadecyloxyphenyl group, 4'
-[α-(4''-t-butyl7eth-7xy)tetradecanamidophenylco, 5, etc., and the like.

The heterocyclic group represented by R is preferably a 5-7 ring group, and may be substituted, J:<, or fused. Specific examples include 2-furyl group, 2-chenyl group, 2-pyrimidinyl group, and 2-benzothiazolyl group.

Examples of the acyl group represented by R include acetyl group, phenylacetyl group, alkylcarbonyl group such as dodecamyl, α-2,4-di[-amyl7ethylbutamyl group, benzoyl group, 3-bentatecyloxy Examples include arylcarbonyl groups such as benzoyl group and 11-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 1)-)luenesulfonyl group.

Examples of the sulfinyl group represented by R include ethylsulfinyl group, octylsulfinyl group, alkylsulfinyl group such as 3-phenoxydibutylsulfinyl group, phenylsulfinyl group, m-bentatecylphenylsulfinyl group, and 717-rusulfinyl group. Can be mentioned.

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

The carbamoyl group represented by R may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc.
For example, N-methylcarbamoyl group, N,N-dibutylcarbamoyl group, N-(2-pentadecyloctylethyl)carbamoyl group, N-ethyl-N-dodecylcarbamoyl group, N15-(2,4-di-t-amyl Examples include phenoxy)propyl 1-carbamoyl group.

The sulfamoyl group represented by the margin R below may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc.
For example, N-propylsulfamoyl group, N,N-diethylsulfamoyl i, N-(2-pentadecyloxyethyl)sulfamoyl group, N-ethyl-N-)'decylsulfamoyl group, N-phenyl Examples include sulfamoyl group.

Examples of spiro compound residues represented by R include spiro[
Examples include 3,31-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
, 3,1,1''']decane-1-yl, 7,7-nomethyl-bicyclo[2,2,1]hebutan-1-yl, and the like.

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

The aryloxy group represented by R is preferably phenyloxy, and the aryl nucleus may be further substituted with the substituents or atoms listed above for the aryl group,
For example, phenoxy group, 1]-t-butylphenoxy group,
Examples include m-pentadecylphenoxy 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-tetrahydrobira. Examples include nyl-2-oxy group and 1-phenyltetrazole-5-oxy group.

The siloxy group represented by R may be further substituted with an alkyl group, and examples thereof include a triethylsiloxy 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 (1, specifically, an acetyloxy group, a-chloroacetyl group, etc.). Examples include oxy group and benzoyloxy group.

The carbamoyloxy group represented by R may be substituted with an alkyl group, an aryl group, etc., such as an N-ethylcarbamoyloxy group, an N,N-diethylcarbamoyloxy group, an N-7xylcarbamoyloxy group, etc. Can be mentioned.

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

Examples of the acylamide 7 group represented by R include an alkylcarbonylamino group, an arylcarbonylamino 7 group (preferably a phenylcarbonylamino 7 group), and may further have a substituent, specifically an acetamide group. , a-ethylpropanamide group, N-phenylacetamide group,
Examples thereof include a dodecanamide group, a 2,4-di-L-amyl 7e/xyacetamide group, and an α-3-t-butyl 4-hydroxyphenoxybutanamide group.

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

The configuration is 7 methylsulfonylamino groups, pentadecylsulfonylamino group, benzenesulfonamide group, p-)
Examples include luenesulfonamide group, 2-7 toxy 5-t-7 milbenzenesulfonamide group, and the like.

The imide group represented by R″C is l! (! Even if it is a chain type,
It may be cyclic and may have a substituent, such as a succinimide group, a 3-heptadecylsuccinimide group, a 7-talimide group, a glutarimide group, and the like.

The ureido group represented by R is an alkyl group, an aryl group (
Preferably, it may be substituted with a phenyl group), etc., such as a triethylureido group, an N-methyl-N-decylureido group, an N-phenylureido group, and an N-p-tolylureido group.

The sul 7 amoylami 7 group represented by R is an alkyl group,
Aryl group (preferably may be substituted with phenyl 1.0, etc., such as N,N-butylsulfamoylamino group, N-methylsulfamoylamino 7 group, N-phenylsul7amoylamino 7 group, etc.) It will be done.

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

The aryloxycarbonylamide 7 groups represented by R may have a substituent, and examples thereof include phenoxycarbonylamide 7 groups and 4-methyl 7e/xycarbonylamide 7 groups.

The alkoxycarbonyl group represented by R may further have a substituent, such as a meFoxycarbonyl group, a butyloxycarbonyl group, a dodecyloxycarbonyl group,
Examples include octatecyloxycarbonyl group, ethoxymethoxycarbonyloxy group, benzyloxycarbonyl group, and the like.

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

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

The 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, 2-1-octylphenylthio group, 3-octadecylphenylthio group, 2-carboxyphenylthio group, and p-acetami/phenylthio group.

The heterocyclic thio group represented by R is preferably a 5-7H heterocyclic thio group.1. <, may further have a fused ring,
It may also have 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 separated by reaction with the oxidized product of the color developing agent represented by Examples include groups substituted via.

In addition to carboxyl groups, examples of the group substituted via a carbon atom include the general formula (R1' has the same meaning as R, Z' has the same meaning as Z, R2' and R3/ are hydrogen atoms, aryl groups, , represents an alkyl group or a heterocyclic group), a hydroxymethyl group, and triphenylmethyl II (.

Examples of groups substituted via an oxygen atom include alkoxy groups, aryloxy groups, heterocyclic oxy groups, acyloxy groups, sulfonyloxy groups, alkoxycarbonyloxy groups, aryloxycarbonyloxy groups, alkyloxalyloxy groups, and alkyloxalyloxy groups. One example is lily.

The alkoxy group may further have a substituent, for example,
Examples include a nidoxy group, a 2-7 enoxyethoxy group, a 2-cyanoethoxy group, a phenethyloxy group, and a 1)-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, 4-7 tansulfonamidophenoxy group, 4-[α-(3'-pentadecylphenoxy)butanamide]phe/oxy group, hexidecylfulbamoylmethoxy group, 4-cyanophenoxy group, 4 -Methanesulfonylphenoxy group, 1-naphthyloxy group, 11
Examples include a 1-medoxy 7-ethyl 7-oxy group and the like.

The heterocyclic oxy group is preferably a 1- or 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.

Examples of the acyloxy group include alkylcarbonyloxy groups such as an acetoxy group and a butazuroxy group, alkenylcarbonyloxy groups such as a cinnamoyloxy group, and arylcarbonyloxy groups such as a benzoyloxy group.

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 7eth7oxycarbonyloxy group.

Examples of the alkyloxalyloxy group include a methyloxalyloxy group.

Examples of the alkoxyoxalyloxy group include a hydroxyoxalyloxy group and the like.

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 7enethylthio group, a benzylthio group, and the like.

The arylthio groups include phenylthio group, 4-methanesulfonamidophenylthio group, 4-dodecylphenethylthio group, 4-7nafluorobencunamide 7enethylthio group, 4-carboxyphenylthio group, 2-ethoxy-5 -[-butylphenylthio group and the like.

Examples of the heterocyclic thio group include 1-7 enyl-1.
2-. Examples include 3.4-tetrazolyl-5-thio group and 2-benzothiazolylthio group.

Examples of the alkyloxythiocarbonylthio group include dodecyloxythiocarbonylthio group.

For example, those represented by the general formula -N represent 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 R5' are bonded. may be used to form a heterocycle. However, R1' 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, alkylami 7 group, arylami 7 group, acylamino group, sulfonamido group, imino group, acyl group, alkylsulfonyl group, arylsulfonyl group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, Examples include 7 alkyloxycarbonylamide groups, 7 aryloxycarbonylamide groups, a hydroxyl group, a carboxyl group, a cyano group, and a halogen atom.

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

The aryl group represented by R, j or R5' preferably has 6 to 32 carbon atoms, particularly a phenyl group or a naphthyl group,
The aryl group may have a substituent, and examples of the substituent include those listed above as a substituent for the alkyl group represented by R2' or R5' and an alkyl group. Specific examples of the aryl group include phenyl group, 1-naphthyl group, and 4-methylsulfonylphenyl group.

The heterocyclic group represented by R1' or R5' 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-x7lyl group, 2-biriminol group, 2-benzothiazolyl group, and 2-pyridyl group.

The sulfamoyl group represented by R4' or R5' includes N-alkylsulfamoyl group, N,N-noarylcarbamoyl group, N-arylsulfamoyl group, N'
, N-noarylsulfamoyl 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 -dodecylcarbamoyl group, l'J -1) -)
Rilsul 7-amoyl group is mentioned.

The carbamoyl group represented by R' or Rs' is
N-alkylcarbamoyl group, N,N-noarylcarbamoyl group, N-arylcarbamoyl group, N,N-noarylcarbamoyl group, etc., and these alkyl groups and aryl groups are It may have the substituents listed above. Examples of carbamoyl group include N,N-diethylcarbamoyl group, N-methylcarbamoyl group, N-dodecylcarbamoyl group, Np-cyanophenylcarbamoyl group, and Np-)lylcarbamoyl group.

Examples of the acyl group represented by R4' or R5' include an alkylcarbonyl group, an arylcarbonyl group, and a heterocyclic carbonyl group. Specific examples of the acyl group include hexafluorobutameyl group, 213.4.5.6-pentafluorobenzoyl group, acetyl group, benzoyl group, naphthonyl group, 2-furylcarbonyl group, etc. can be mentioned.

Examples of the sulfonyl group represented by R4' or R, / include an alkylsulfonyl group, an arylsulfonyl group, and a heterocyclic sulfonyl group, which may have a substituent, and specific examples include an ethanesulfonyl group. , a benzenesulfonyl group, an octanesulfonyl group, a naphthalenesulfonyl group, a 1)-chlorobenzenesulfonyl group, and the like.

The aryloxycarbonyl group represented by R1' or R5j may have any of the substituents listed above for the aryl: l, i; It will be done.

The alkoxycarbonyl group represented by R4' or RS' may have a substituent listed for the alkyl group, and specific examples include a methoxycarbonyl group, a dodecyloxycarbonyl group, and a benzyloxycarbonyl group. Examples include groups.

The heterocycle formed by combining R4' and R5' is preferably one with 5 to 6 shells, and may be saturated or unsaturated, and may or may not have aromaticity. ,
It may be a condensed ring. Examples of the heterocycle include N-7 talimide group, N-succinimide group, 4-N-urazolyl group, 1-N-hyguntoynyl group, 3-N-2,4-nooxooxazolidinyl group, 2 -N-1,1-nooxo-3-(2H)-oxo-1,2-benzthiazolyl group,
1-pyrrolyl group, 1-pyrrolidinyl group, 1-pyrazolyl group, 1-pyrazolidinyl group, 1-biberinonyl group, 1-
Pyrrolinyl group, 1-imidazolyl group, 1-indolyl group, 1-indolyl group, 1-yneindolinyl group, 2-isoindolyl group, 2-isoindolinyl group, 1-benzotriazolyl group, 1-pencyimigzolyl group group, 1-(1
, 2,4,-)riazolyl) group, 1-(1,2,3-triazolyl) group, 1-(1,2,3,4-tetrazolyl) group, N-morpholinyl group, 1.2.3. 4-tetrahydroquinolyl group, 2-oxo-1-pyrrolidinyl group, 2
-I H-pyridone group, 7-thalassion group, 2-oxo-1-piperidinyl group, etc., and these heterocyclic groups include alkyl group, aryl group, alkyloxy group, aryloxy group, acyl group, sulfonyl group, Alkylamino group, 7 arylamino groups, acylamino group, 7 sulfonamide groups, carbamoyl group, sulfamoyl group, alkylthio group, arylthio group, ureido group, alkoxycarbonyl group, aryloxycarbonyl group, imido group, nitro group, n-ano group, carboxyl group , may be substituted with a halogen atom or the like.

Examples of the nitrogen-containing heterocycle formed by Z or Z' include a pyrazole ring, an imidazole ring, a triazole ring, or a tetrazole ring. These include the ones mentioned above.

In addition, in general formula [T) and general formulas (n) to [■] described later, substituents on the heterocycle (for example, R1R1 to Re) are moieties (herein, R'', X and Z II are general formulas (synonymous with R, The ring may be further fused with another ring (for example, a 5- to 7-shell cycloalkene). For example, in the general formula [■], R5 and R6 are R7 and R1 in the general formula (Vl).
may be bonded to each other to form a ring (for example, a 5- to 7-shell cycloalkene, benzene).

More specifically, what is represented by the general formula [I] is represented by, for example, the following general formulas [■] to [■].

General formula (II) General formula (I [[] % formula % General formula (IV) N -N -Ni1 General formula (V) General formula (Vl) N -N - -Ni+ General formula [■] Said general formula ( In 11 to [■], R, -R, and X have the same meanings as R and X above.

Also, among the general formulas (1), those represented by the following general formula [■] are preferred.

General formula [■] In the formula, R, , X and z are R9X in the general formula [,1)
and 2.

Particularly preferred among the magenta couplers represented by the general formulas [■] to [■] is the magenta coupler represented by the general formula 5'-C11).

Regarding the substituents on the heterocycle in general formulas [1] to [■], R in general formula [I] and R3 in general formulas (n) to [■] are as follows. It is preferable that Condition 1 is satisfied, and more preferable that Conditions 1 and 2 below are satisfied.
A stable that satisfies the following condition 1 is particularly preferable.
, 2 and 3 are satisfied.

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

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 [IM:].

General formula (IY) R5 ■ R+[C- In the formula, R, , R, and R1 are each a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a hetero cyclic group, acyl group, sulfonyl group, sulfinyl group,
Phosphonyl group, cal/sjmoyl group, sulfamoyl group, cyano group, spiro compound residue, bridged hydrocarbon compound residue, alkoxy group, aryloxy group, heterocyclic oxy group, siloxy group, acyloxy group, carbamoyloxy group, Amino group, acylami/group, sulfonamide group, imide group, ureido group, sulfamoylamif group, 7 alphkyl carbonyl amine groups, 7 aryl leoquinyl amine groups, alkoxycarbonyl group, aryloxycarbonyl group, alkylthio group , represents an arylthio group, or a heterocyclic thio group, and at least two of R3゜R1゜ and RII are not hydrogen atoms (1.

Furthermore, two of the above Rg, R+o and I'-+1, for example R5 and RIQ, may be combined to form a saturated or unsaturated ring (e.g. cycloalkane, cycloalkene, heterocycle), and further RII may be bonded to the ring to form a bridged hydrocarbon compound residue.

The group represented by R8-R11 may have a substituent, and specific examples of the group represented by R9-RII and the substituents that the group may have include the above-mentioned general formula [I] Specific examples of the group and substituents represented by R are given below.

Also, for example, a ring formed by combining R5 and Rlo and R5
Specific examples of the bridged hydrocarbon compound residue formed from the -R1 mouth and its optional substituents include cycloalkyl, cycloalkenyl, and heterocyclic group represented by R in the above general formula [I]. Specific examples of bridge hydrocarbon compound residues and their substituents are listed.

Among the general formula (IY), (i) Rs~
When two of R11 are alkyl groups, (ii) R, ~
When one of RII, for example R11, is a hydrogen atom, and the other two, R9 and R, combine to form a cycloalkyl together with the root carbon atom, the following is true.

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

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

In addition, substituents which the ring formed by Z in general formula [I] and the ring formed from Z in general formula [■] may have, and R2- in general formulas [rl) to (V[)] R8 is preferably represented by the following general formula [X].

General formula [X] -R'-3o2-R2 In the formula, R1 represents alkylene, 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 the straight chain portion has 1 or more carbon atoms.
Regardless of branching. Further, this alkylene may have a substituent. Examples of the substituent include R in the general formula [1] 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.

-CH2CH2CI+2-, -CIICII□CI+
2-, -CIlC112CI+□-, -C1l□CI
hC11C1l, C2113,C,11,5
-C) 12clI2C1l-, -CI12CI12CI
12CI+2-, -C112CII2CI12C1i.

The alkyl group represented by R2 is a straight chain with no single branch, specifically methyl, ethyl, propyl, 1so-propyl, butyl, 2-ethylhexyl, octyl, dodecyl, tetradecyl, hexadecyl, oftagyl, 2-hexyldecyl. Examples include.

The cycloalkyl group represented by R2 is preferably a cycloalkyl group of 5 to G, such as cycloalkyl.

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

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

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 [X1] In the formula, R and X have the same meanings as R and X in general formula CI), and R1 and R2 are R l in general formula (X).

It has the same meaning as R2.

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

■ CH.

CH:1 2H5 C4119 '53 CI+3 C.If.

C2H.

H3 +13 ■ C, Il, 5 C11゜NIP+ ■ Cr, Il+a - C11゜0CII2CONIC112CI! 20CH30011
□C112SO2C1+3 C2)l! I C,ll.

C.I.

5Ht3 C1] 3 H3 C2II5 H3 ■ CI+3 CI+3 I・ C11゜■ C11゜C71t,! i 13f 113c C1+:+ 16[3 N-N-Nil The above coupler is also described in the Journal of the Chemical
Society (Journal of tl+eCb)
chemical society) t Parkin (
Perkin) 1 (1977), 2047-2
052, U.S. Patent No. 3,725,067, Japanese Patent Application Publication No. 1983-
No. 99437, No. 5B-42045, No. 59-162
No. 548, No. 59-171956, No. 60-3355
It can be synthesized by referring to No. 2, No. 60-43659, No. 60-172982, No. 60-190779, etc.

The couplers of the invention typically contain 1Xl per mole of silver halide.
0-' mol-1 mol, preferably lXl0-2 mol-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 margin below and the synthesis of the above coupler are from the Journal of the Norm.
Journal of t
heChemical 5ociety), Parkin (
Perkin) T (1977).

2047-2052, U.S. Patent No. 3,725,067,
JP-A-59-99437, JP-A-58-42045, JP-A-59-162548, JP-A-59-171.
No. 956, JP-A-60-33552 and JP-A-60-
Synthesis was carried out with reference to No. 43659 and the like.

Moreover, the coupler according to the present invention can also be used in combination with other types of magenta couplers.

One of the two magenta color image stabilizers according to the present invention is at least one compound derived from a P-phenylenediamine compound represented by the general formula [XII], and the other one is a compound derived from a P-phenylenediamine compound represented by the general formula [XII]. It is at least one of the hydroxyindan compounds represented by the general formula (XTII).

Patent Application No. 60-25793 and Patent Application No. 85193-1983
No. 1, the general formula (X
It is described that a hydroxyindan compound represented by III) is effective.

However, in each of the above-mentioned specifications, regarding the stabilization of magenta dye images obtained from the magenta coupler according to the present invention, it is stated that the amount of the hydroxyindan compound represented by the general formula (XTII) according to the present invention ( One of them is at least one compound derived from a P-phenylenediamine compound represented by the general formula (XI) according to the present invention.
There is no mention of the effects of using the two together.

As a result of intensive study, the present inventors have determined that the general formula according to the present invention [
I] together with the magenta coupler represented by the general formula (XU'
When at least one selected from the compounds represented by 1 and at least one selected from the compounds represented by the general formula (X 11) are used in combination, the magenta dye image obtained from the magenta coupler according to the present invention is They found that stability was dramatically improved.

Hereinafter, unless otherwise specified, the general formula (
Xll) and the compound represented by the general formula [Xm] is referred to as a magenta dye image stabilizer according to the present invention.

The magenta dye image stabilizer according to the present invention used in conjunction with the magenta coupler according to the present invention not only has a 1F effect of preventing fading of magenta dye images due to light, but also
It also has the effect of preventing discoloration caused by light. One of them is a compound derived from a P-phenylenediamine compound represented by the following general formula (XIT).

General formula (Xr+) In general formula (XI), specific examples of the alkyl group, cycloalkyl group, alkenyl group, aryl group, and heterocyclic group represented by R''-R2 or R3 include the general formula CI
) Specific examples of the alkyl group, cycloalkyl group, alkenyl group, and aryl group represented by R4 include the groups described for R in general formula [I]. ? "J is -P-0-1-C-N-1-C-N-100R
The same applies to the alkyl group or aryl group 65II6 p6'.

R5 is a substituent that can be substituted on the benzene ring and is not particularly limited, but specifically includes a halogen atom, an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an alkenoxy group, an aryloxy group, an alkylthio group, an arylthio group, an acyl group, Examples include an acyloxy group, an acylamino group, an alkylamino group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, and an alkoxycarbonyl group.

Moreover, each group of R1, R2, R3, and R4 mentioned in -A includes those having a substituent. Examples of the substituent include a hydroxy group, an alkoxy group, an aryl group, an acylamino group, a sulfonamide group, an aryloxy group, a carbamoyl group,
Sulfamoyl group, sulfonyl group, vinylsulfonyl group, nitro group, cyano group, halogen atom, carboxyl group, amino group, alkylamino group, alkoxycarbonyl group, acyl group, arylaminocarbonyloxy group, acyloxy group or heterocyclic group, etc. Specific examples can be mentioned.

Further, in the aryl group, for example, two adjacent groups may cooperate to form a methylenedioxy ring.

Next, typical examples of the compound represented by the general formula [XII] will be shown, but the present invention is not limited thereto.

Margin below (A-1) (A-6) (A-10) (A-14) (A-19) OC4H7 (A-27) (A-31) (A-43) (A-44) (A-48) (A-51) (A-52) (A-53) (A-56) (A-58) (A-60) (A-61) (A-64) (A-68) (A-70) (A-71) (A-72) (A-73) (/l-74)- (A15) (A-76) (A-77) (A-78) (A-79) H (A-84) CH2-c-ocoa (A-89) (A-91) C.I.

Cheer C MiN (A-94) (A-96) ■ (A-98) (A-99) (A-100) (A-102) (A-103) ■ (A-106) ■ (A- 107) (A-108) (A-109) (A-110) Representative synthesis examples of the compound represented by the general formula [X■] used in the present invention are shown below.

Synthesis Example 1 (Synthesis of Exemplified Compound A-50) 13 g of N-(4-amino-2,5-dibutoxyphenyl)-thylpholine hydrochloride and 9 mρ of pyridine were mixed with 200 m of ethyl acetate.
j! Stir and mix inside. While stirring at room temperature, 5.7 g of phenyl chloroformate is added dropwise.

After dropping, the mixture was stirred for 30 minutes to react, poured into 600 mL of water, extracted with ethyl acetate, washed twice with water, dried over anhydrous magnesium sulfate, and ethyl acetate was distilled off under reduced pressure. The obtained deep purple viscous solid was purified by column chromatography and then recrystallized from methanol to obtain 5 g of white crystals. mp57-60℃. The structure was confirmed using FD-mass spectrum and NMR.

Elemental analysis value (as C2SH34N205) Theoretical value:
C (67,85%) Il (7,74%) N (6,
33%) Experimental values: C (67,80%) H (7,7
0%) N (6,34%) Synthesis Example 2 (Exemplary Compound A-5
Synthesis of 6) 25 g of N,N-dimethyl-P-phenylenediamine dihydrochloride and pyridine 11 (m Il, 100 m
Stir and mix in ethyl acetate at t'. Add 26.5 g of Pn-dodecyloxybenzenesulfonyl chloride while stirring at room temperature. Stir for 30 minutes,
Make it react. Pour the reaction solution into 500 ml of water, and add 100 ml of ethyl acetate! is further extracted, washed twice with water, and dried using anhydrous sodium sulfate. Ethyl acetate was distilled off under reduced pressure, and the resulting deep purple viscous oil (n-
300ml of a mixed solvent of (hexane)/(ethyl acetate)-(10/I) was added to precipitate a solid. The resulting solid was recrystallized twice using methanol to obtain 25 g of white flocculent crystals. 111p100-102℃.

The structure was confirmed using FD-mass spectrum and NMR.

Elemental analysis values (Cz611a.N, O, S) Theoretical values: C (67,78%) Il (8,75%) N (
6,08%) Experimental value: C(67,54%)Il(1'
1.73%) N (6,06%) Synthesis Example 3 (Exemplary Compound A
Synthesis of -57) 8.1 g of N,N-dimethyl-P-phenylenediamine dibasic acid and pyridine were combined with ethyl acetate.
m 7! Stir inside to mix. While stirring at room temperature, 14.1 g of 2-butoxy-5-t-octylhenzenesulfonyl chloride is added at once and stirred for 30 minutes to react. After the reaction, the reaction solution is poured into 500 mρ water, washed with water, extracted with ethyl acetate, washed twice with water, dried over anhydrous sodium sulfate, and ethyl acetate is distilled off under reduced pressure. The obtained brown viscous solid was purified by column chromatography and then recrystallized from methanol to obtain 8 g of white crystals. mp: 10R~109℃
. The structure was confirmed using FD-mass spectrum and NMR.

Elemental analysis value (as Cz6[1n.N20.S) Theoretical value: C (67,78%) II (8,75%') N(
60,8%) Experimental value: C (67,77%) 11(
8,76%) N (60,9%) Synthesis Example 4 (Synthesis of Exemplary Compound A-58) 4-(4-dodecyloxybenzenesulfonyl)amino-N,N-dimethylaniline (A
-56) 9.28 and SM 2B (Ctl, ONa's 2
4.6 g of 8 wt % methanol solution) was stirred and dissolved in dimethylformamide 90n+ II. While stirring at room temperature, 3.4 g of methyl iodide is added dropwise. As it is added, it becomes a clear solution. After stirring for 30 minutes, the reaction solution was drained and poured with ethyl acetate 1501III! Extract using. Wash twice with water, dry the solvent using anhydrous magnesium sulfate, and distill off the solvent under reduced pressure. 50 ml of n-hexane was added to the obtained orange-yellow oil to precipitate a precipitate, which was filtered. The obtained precipitate was recrystallized with 2 to 3 times the amount of methanol to obtain 3 g of white sandy crystals.

mp: 59-60°C. The structure was confirmed using FD-mass spectrum and NMR.

Elemental analysis value (as Cz, 1ln2N20aS) Theoretical value: , C(68,31%>11(8,92%)N(5
, 90%) Experimental value F C (68, 27% > 11 (8
,94%) N (5,90%) General formula according to the present invention [x
■] The compound represented by
No. 1200679, Research Disclosure No. 12146, U.S. Patent No. 4060418, Special Publication No. 1983
-14671, 58-14672, JP-A-57-
No. 76543, No. 57-1'79842, No. 5B-1
It contains a precursor of an aromatic primary amine developing agent as described in No. 139 and the like.

However, these compounds have the general formula (
There is no suggestion of increasing the light fastness of magenta dye images obtained from couplers represented by 1).

In addition, the magenta dye image stabilizer used in conjunction with the magenta dye image stabilizer of the general formula [x■] according to the present invention is a hydroxyindan-based compound represented by the following general formula (X I[I) It is.

The following is a blank general formula (X III) RIG [In the formula, R@ and RIS are a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, a hydroxy group, an aryl group, an aryloxy group, an acyl group, respectively.
Acylamino group, acyloxy group, sulfonamide group,
Represents a cycloalkyl group or an alkoxycarbonyl group.

A halogen atom, an alkyl group represented by R8 and RIG,
alkenyl group, alkoxy group, aryl group, aryloxy group, acyl group, acylamino group, acyloxy group,
Specific examples of the sulfonamide group, cycloalkyl group, or alkoxycarbonyl group include the groups detailed for R in general formula (I).

R9 represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, a hydroxy group, an aryl group, an acyl group, an acylamino group, an acyloxy group, a sulfonamide group, a cycloalkyl group, or an alkoxycarbonyl group. R9
Halogen base r1 alkyl group, alkenyl group represented by
Specific examples of the aryl group, acyl group, acylamino group, acyloxy group, sulfonamide group, cycloalkyl group or alkoxycarbonyl group include R in general formula (1).
Examples include the groups detailed in J.

Each of the groups listed in 1-1- may be substituted with other substituents. Examples of the substituent include an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a hydroxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acylamino group, a car'λmoyl group, a sulfonamido group, and a sulfamoylnol group. etc.

Further, R9 and RIG may be ring-closed with each other to form a 5@ or 6-membered hydrocarbon ring. This 5-membered or 6-day hydrocarbon ring may be substituted with a halogen atom, an argyl group, a Schiff 11 alkyl group, an alkoxy group, an alkenyl group, a hydroxy group, an aryl group, an aryloxy group, a 4A group, a heterocyclic nor, etc. good.

Y represents an atomic group necessary for forming an indane ring. This indane ring may be substituted with a halogen atom, -fulgyl group, alkenyl group, alkoxy group, Schiff 11 alkyl group, hydroxy group, aryl group, aryloxy group, or heterocyclic group, and further forms a spiro ring. It's okay.

Among the compounds represented by the general formula CXTII:], compounds particularly useful in the present invention are represented by the general formulas [X1IIa] to [XllIc
] is included in the compound shown.

General formula [Xrlla] RlG ■Tsu 1] General formula [XTIIb) General formula (Xlmc) Re in general formulas [XIIIa] to [XllTc].

R9 and RIG have the same meaning as in general formula [XIII), and R'', R'2.R'', R'4. R” and R
16 represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkenyl group, a hydroxy group, an aryl group, an aryloxy group, or a complex ms, respectively. R11
To R12, R12 To R11, RI3 and R14, R14 and T? 15 and RI5 and R'6 may be ring-closed with R7 to form a hydrocarbon ring, and the hydrocarbon ring may be substituted with an alkyl group.

The general formula [XIIIa] to [Xl! lc],
R8 and RlG are hydrogen atoms, alkyl groups, alkoxy groups, hydroxy groups or cycloargyl groups, R9 is hydrogen atoms, alkyl groups, hydroxy groups or cycloalkyl groups, R", R", R", R eyes.

Particularly useful are compounds in which RI5 and RI6 are hydrogen atoms, alkyl groups or cycloalkyl groups.

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

Hl-3 CI+ CIbHsx HI -4 CHa Cl6H33 H■ -5 C113C113 T-6 C1ls CH3 HI-7Cl Hl-8 C) Is CFI3 CI++ Hr -10 HI -11 CL CHs Hl -12 C)13CH3 l1 4 Hr -15 CH3CHs l-16 CHp Hl ~17 Is CHs Hl-18 CHs CHs Hl-19 CH3CL HI -20 CH3C11s HT-21 HT-22 C113CI+3 T-23 C)1. C113 T-24 H[-25 1 to 2 J1y Hl-30 HT -31 Hl-32 ■Tl-33 Hr-37 l-40 C, +15 Ait according to the present invention represented by the general formula (X III) Magenta dye image stabilizers are described in the Journal of Nor
Michal Society (,1,Chem,Soc,)
, 1962°415-417 Negative, Special Publication Showa 59-3278
No. 5, Piurethane of Chemical Society of Japan (Bul 1.Chem, 5ocja
Pan), 1980, 53.555-556n.

The usage amount of the magenta dye image stabilizer represented by the general formula CXn1l and the general formula [XII] of the present invention is 5 to 400%, respectively, relative to the magenta coupler represented by the general formula CI) according to the present invention. It is preferably mol%, more preferably 10 to 250 mol%, and the total usage amount of both the magenta dye image stabilizer represented by the general formula (Xn) and the general formula [XIl+ 1 according to the present invention] is preferably 10 to 500 mol%, more preferably 20 to 4 (10 mol%) to the magenta coupler according to the present invention.
It is.

Further, the molar ratio of the magenta dye image stabilizer represented by the general formula [XII] and the magenta dye image stabilizer represented by the general formula (XIIT) according to the present invention is 0. 1 to 10 is preferable fl, <, more preferably 0.25
It is in the range of ~4.0.

In the silver halide photographic light-sensitive material of the present invention, in addition to the magenta dye image stabilizer according to the present invention, other magenta dye image stabilizers, such as U.S. Pat.
No. 016, No. 3, 9) (No. 2, 9, 14, No. 4,254)
, No. 216, JP-A-55-21004, JP-A No. 54-14
No. 5530, British Patent Publication No. 2,077.455, No. 2
．． No. 062.888, U.S. Patent No. 3.764.337;
No. 3.432.300, No. 3,574.621, No. 3,573,050, JP-A-52-152225,
No. 53-20327, No. 53-17729, No. 55
-6321, 54-48538, 56-159
No. 644, No. 59-87456, British Patent L347,
No. 556, published 2,066,! No. 1175, Special Publication Showa 5
Phenol compounds or phenyl ether compounds described in No. 11-12337, No. 48-31625, U.S. Pat. Also, JP-A-59-53846, JP-A No. 59-78
Hindant heptamine compounds described in No. 344 can also be used in combination.

The magenta coupler according to the invention and the magenta dye image stabilizer according to the invention are preferably used in the same layer, but 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 color photographic paper intended for direct viewing is used. The effect of the method is effectively demonstrated.

The silver halide photographic material of the present invention, including this color photographic paper, may be for monochrome use or for multicolor use. In the case of multicolor silver halide photographic sensitivity +414,
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 formed on a support in an appropriate number and order. Although it has a laminated structure, the number and order of layers may be changed as appropriate depending on the important performance and purpose of use.

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 emulsions can be used.

The silver halide grains used in the silver halide emulsion according to 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, T:1 gene ions and silver ions may be mixed at the same time, or one may be mixed in the presence of the other. Further, while considering the critical growth rate of silver halide crystals, halide ions and silver ions may be generated by sequentially and simultaneously adding them while controlling PI-1 and PAg in the mixing tank. After growth, a compounding method may be used to change the halogen composition of the particles.

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

The silver halide grains used in the silver halide emulsion according to the present invention are formed by cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts, rhodium salts or Complex salts, iron salts, or complex salts can be used to add metal ions and encapsulate them inside the particles and/or on the surface of the particles. can be given reduction sensitization effect.

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

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

The silver halo 30 grains used in the silver halide emulsion according to the present invention may be grains in which a latent image is mainly formed on the surface, or in which a latent image is mainly formed inside the grain. Particles may be used.

The silver halide grains used in the silver halide emulsion according to the present invention may have a regular crystal shape or may have an irregular crystal shape such as a spherical or plate shape. In these particles, (1,0,0) plane and (1,1,1)
Any surface ratio can be used. Further, the particles may have a composite form of these crystal forms, or particles of various crystal forms may be mixed.

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

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

The silver halide emulsion according to the present invention is used in the photographic industry.
Optical sensitization can be achieved to a desired wavelength range using dyes known as sensitizing dyes. 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. Good too.

The silver halide emulsion according to the present invention may be used during chemical ripening and/or for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of light-sensitive materials, and/or to maintain stable photographic performance. At the end of chemical ripening and/or after the end of chemical ripening and before coating the silver halide emulsion,
Compounds known in the photographic industry as antifoggants or stabilizers can be added.

As the binder (or protective colloid) for the silver halide emulsion according to the present invention, gelatin is advantageously used, but gelatin derivatives, graft polymers of gelatin and other polymers, fluorescent matter, sugar derivatives, Hydrophilic colloids such as synthetic hydrophilic polymeric materials such as cellulose derivatives, monopolymers, 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 light-sensitive material of the present invention may contain a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability.

Between the emulsion layers of the silver halide color photographic light-sensitive material of the present invention (between the same color-sensitive layers and/or between different color-sensitive layers),
Color antifoggants are used to prevent color turbidity, deterioration of sharpness, and noticeable graininess due to migration of oxidized products of developing agents or electron transfer agents.

The color fog preventive agent may be used in the emulsion layer itself, or may be used in a film intermediate layer by providing an intermediate layer between adjacent emulsion layers.

The silver halide color photographic light-sensitive material of the present invention can contain an image stabilizer that prevents deterioration of the dye image.

In order to prevent fogging caused by discharge caused by frictional charging of the photosensitive material in the hydrophilic colloid layers such as the protective layer and intermediate layer of the silver halide photographic light-sensitive material of the present invention, and to prevent image deterioration due to IIV light. It may also contain an ultraviolet absorber.

The silver halide color 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 are washed out or bleached from the color light-sensitive material during development.

A mantle agent is added to the silver halide emulsion layer and/or other hydrophilic colloid layer of the silver halide photographic light-sensitive material of the present invention with the aim of reducing the gloss of the light-sensitive material, increasing the ease of writing, and preventing the light-sensitive materials from sticking together. 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 colloid layers.

The photographic emulsion layer and/or the silver halide photographic light-sensitive material of the present invention
Or other hydrophilic colloid layers have the purpose of improving coating properties, preventing static electricity, improving shearing properties, emulsifying and dispersing, adhesion, and improving photographic properties (such as accelerating development, increasing contrast, sensitization, etc.) As such, various surfactant sides are used.

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

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

When coating the silver halide photographic material of the present invention, a thickener may be used to improve coating properties. Particularly useful coating methods are extrusion coating and curtain coating, which allow two or more layers to be applied simultaneously.

The silver halide photographic light-sensitive material of the present invention can be exposed to electromagnetic waves in a spectral region to which the emulsion layer constituting the light-sensitive material of the present invention is sensitive. As a light source, natural light (
Excitation by sunlight), 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, T-rays, α-rays, etc. Any of a variety of light sources 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 light emission can be used, and exposures longer than 1 second are also possible. The exposure may be carried out continuously or intermittently.

The silver halide photographic light-sensitive material of the present invention can be used to form images by color development as known in the art.

In the silver halide photographic light-sensitive material of the present invention, the aromatic primary amine color developing agent used in the color developing solution includes various kinds that are widely used in various color photographic processes. .

These developers include aminophenol and p-phenylenediamine derivatives. These compounds are generally used in the form of a salt, such as a hydrochloride or a sulfate, as they are more stable than the free form. In addition, these compounds are generally used in color developer II! concentration of about 0.1 g to about 30 g for color developer 1e, preferably about 1 g to about 15 g for color developer 1e.
Use at a concentration of g.

Examples of aminophenol-based developers include 0-aminophenol, p-aminophenol, 5-amino-2-
Oxytoluene, 2-amino-3-oxytoluene, 2
Includes nioxy-3-amino-1°4-dimethylbenzene.

Particularly useful primary aromatic amino-based color development systems include N, N'
-Dialkyl-p-phenylenediamine compound, and the alkyl group and phenyl group may be substituted with any substituent. Among them, examples of particularly useful compounds include N,N"-diethyl-p-phenylenediamine hydrochloride;
N-methyl-p-phenylenediamine hydrochloride, N,N'
-dimethyl-p-phenylenediamine hydrochloride, 2-amino-5-(N-ethyl-N-dobushirua 1))-toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-amino Aniline sulfate, N-ethyl-N-β-hydroxyethylaminoaniline, 4-amino-3-methyl N,N”-diethylaniline, 4-amino-N-(2-methoxyethyl)-N-ethyl-3 -methylaniline-p-') luenesulfonate.

The color developing solution used in the processing of the silver halide photographic light-sensitive material of the present invention contains, in addition to the above-mentioned primary aromatic amine color developing agent, various components normally added to color developing solutions, such as water. Alkali agents such as sodium oxide, sodium carbonate, potassium carbonate, alkali metal sulfites,
Alkali metal bisulfites, alkali metal thiocyanates, alkali metal halides, benzyl alcohol, water softeners, thickeners, and the like may optionally be included. The pH value of this color developing solution is usually 7 or higher,
Most commonly from about 10 to about 13.

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

[1] Ethylenediaminetetraacetic acid [2] Nitrilotriacetic acid (3) Iminodiacetic acid [4] Ethylenediaminetetraacetic acid disodium salt [5] Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt [6] Ethylenediaminetetraacetic acid tetrasodium salt [7] Nitrilotriacetic acid The bleaching agent used in the sodium acetate salt contains, as a bleaching agent, a metal complex salt of an organic acid such as those mentioned above, and may also contain various additives.Additives include, in particular, alkali halides or ammonium halides, such as 9 It is desirable to contain rehalogenating agents such as potassium chloride, sodium bromide, sodium chloride, and ammonium chloride, metal salts, and chelating agents.

Also contains borate, oxalate, acetate, carbonate support, phosphate, etc.
Those known to be added to ordinary bleaching solutions, such as l+ buffers, alkylamines, and polyethylene oxides, can be added as appropriate.

Historically, fixing solutions and bleach-fixing solutions contain ammonium sulfite 11
, potassium sulfite, ammonium bisulfite, potassium bisulfite 1 Jl, sodium bisulfite, ammonium metabisulfite, potassium metabicarbonate, sodium metabisulfite, and other sulfites, boric acid, borax, sodium hydroxide, potassium hydroxide , sodium carbonate, potassium carbonate, bisulfite]-lium, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide, etc., containing one or more pl+buffers. I can do it.

When processing is carried out while replenishing the bleach-fixing solution (bath) with a bleach-fixing replenisher, the bleach-fixing solution (bath) may contain thia-5-osulfate, 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, air or oxygen may optionally be blown into the bleach-fix bath and in the bleach-fix replenisher storage tank, or a suitable oxidizing agent such as hydrogen peroxide may be added. , bromate, persulfate, etc. may be added as appropriate.

[Specific effects of the invention]

The silver halide photographic light-sensitive material of the present invention not only has excellent color reproducibility and less occurrence of Y-stin in uncolored areas against light and moist heat, but also has significantly improved light fastness of macenta dye images. Discoloration due to light is prevented.

Margin 1' [Specific Examples of the Invention] The present invention will be specifically explained below with reference to Examples, but the present invention is not limited thereto.

Example 1 On a paper support laminated on both sides with polyethylene, the following layers were sequentially coated from the support side.

1st layer: emulsion layer 5.0 mg/]0 of magenta coupler 44 according to the present invention
0cm2, silver chlorobromide emulsion (containing 85 mol% silver bromide) converted to silver: 3.5mg/]000cm2, dibutyl phthalate 5.0mg/100cm'' and gelatin 1
The coating was applied in an amount of 3.0 mg/100 cm2.

2nd layer: Intermediate layer (ultraviolet absorber-containing layer) 2-(2-hydroxy-3-sec, -butyl-5) as an ultraviolet absorber
-tert-butylphenyl)hencytriazole 4
．． 0mg/100cm2, 1.3 g of jeepthilphthalene, 1.0mg/100cm2 and 1 g of gelatin.
The coating was applied so that the coating amount was 2.0 mg/100 cm''.

3rd layer: protective layer gelatin 8. On+g/100cm” coating]!
It was painted so that

The sample obtained as described above was designated as sample 1.

Exemplary compounds A-18, A-56°t (I-25,
Samples 2, 3, 4, 5.6, and 7 were obtained in which HT-28 and comparative compounds a and b shown below were added in equimolar amounts as the magenta coupler.

In addition, the six types of magenta dye image stabilizers described in 1.
Sample 8.9.1 using two types in combination as shown in the table.
0.11.12.13.14.15°+6.17.18
and 19 were obtained.

In Samples 8 to 19, the two types of magenta dye image stabilizers used in combination were each used in a molar ratio of 1:1, and the total amount was equimolar to the magenta coupler.

Comparative compound a (compound described in JP-A No. 54-48538) oceo
+t(n) Comparative Compound b (Compound described in JP-A-56-159644) The sample obtained above was exposed to light through an optical pattern according to a conventional method, and then treated in the following steps.

[Processing process] [Processing temperature] [Processing time] Color development 33°C 3 minutes 30 seconds Bleach fixing
Wash with water at 33℃ for 1 minute and 30 seconds
Dry for 3 minutes at 33℃ 50-80
℃ 2 minutes The components of each treatment solution are as follows.

[Color developer] Benzyl alcohol 12ml diethylene glycol 10si potassium carbonate 25 g sodium bromide 0.6 g anhydrous sodium sulfite 2.0 g hydroxylamine sulfate 2.5 g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl- 4- Aminoaniline sulfate Add 4.5g water and make 17! and adjusted to pH 10.2 with NaOH.

[Bleach-fix solution] Ammonium thiosulfate 120 g Sodium metabisulfite 15 g Anhydrous sodium sulfite 3 g EDTA ferric ammonium salt 65 g Add water and prepare 17!
and f) Adjust H to 6.7 to 6.8.

The concentrations of Samples 1 to 19 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 treated samples was exposed to a xenon fade meter for 12 days to examine the light fastness of the dye image.

However, the evaluation of each item of light resistance of the dye image is as follows.

1 only n [Residual rate] Percentage of dye remaining after light fastness and humidity fastness tests at an initial density of 1.0.

[Degree of discoloration] (yellow density) after light fastness test at initial density 1.0/
(magenta density) to (yellow density) before light fastness test /
(magenta density), and the larger this value is, the easier it is to change the color tone from magenta to yellowish.

The results are shown in Table 1.

↓○ri Table 1 (General (m) In Tables 1 to 3, for example, the expression A to 18 + comparative compound a means the combination of both.

From the results in Table 1, it was found that the magenta coupler according to the present invention was prepared by combining the magenta dye image stabilizer which is a p-phenylenediamine derivative according to the present invention and a conventional magenta dye image stabilizer. sample (sample 8, 9, 12.1
3) and samples prepared by using the magenta coupler of the present invention in combination with the hydroxyindan-based magenta dye image stabilizer of the present invention and a conventional magenta dye image stabilizer (Samples 10, 11, 14.15) ), samples (Samples 2 to 7) were prepared by adding a magenta dye image stabilizer to the magenta coupler according to the present invention.
Although the dye image survival rate in the light fastness test is improved compared to that of the original, it is recognized that the degree of discoloration is slightly larger.

On the other hand, samples according to the present invention (Sample 16 to In the case of 19), the light fastness test was unexpectedly high from the samples (Samples 2 to 5) prepared by adding the 7 genta dye image stabilizing layer according to the present invention to the magenta coupler according to the present invention. It can be seen that the residual rate of the dye image is improved, and the degree of discoloration of the dye image in the light fastness test is also extremely small.

As described above, in the case of a sample prepared by combining the coupler according to the present invention with two types of magenta dye image stabilizers according to the present invention, the coupler according to the present invention is combined with one of the magenta dye image stabilizers according to the present invention. It can be seen that the retention rate of the dye image and the degree of discoloration in the light fastness test are greatly improved from the sample prepared using the seeds and the conventional magenta dye image stabilizer.

Example 2 Sample 2 was coated in exactly the same manner as in Example 1 with the coupler and magenta dye image stabilizer combinations shown in Table 2.
0 to 48 were created. Samples 20-48 were processed as described in Example 1. Furthermore, these samples were subjected to a light resistance test in the same manner as in Example 1, and the results shown in Table 2 were obtained.

Table 2 From the results shown in Table 2, the samples prepared by using the magenta coupler according to the present invention together with two types of magenta dye image stabilizers according to the present invention are as follows: It can be seen that the lightfastness is significantly improved over the samples prepared with the addition of either one of the magenta dye image stabilizers alone.

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 silver halide photographic light-sensitive material, and Sample 49 was obtained.

1st layer: Blue-sensitive silver halide emulsion layer α-pivaloyl-α-(2,4
-dioxo-1-benzylimidazolidin-3-yl)
-2-chloro-5-[γ-(2゜4-di-t-amylphenoxy)butyramide 1 acetanilide 6.811
1g/100ca+”, blue-sensitive silver chlorobromide emulsion (containing 85 mol% silver bromide) converted to silver is 3.2 mg/10
0cm”, dibutyl phthalate 3.5n+g/100
cm2 and gelatin at 13. '5mg/100cn+
” It was painted so that it looked like this.

2nd layer: middle layer 2.5-di-t-octino-btz hydroquinone 0,'
5 mg/100cm2, dibutyl phthalate 0.
'5mg/100cm・and gelatin 9. ”Omg/
It was painted so that it was 100c...

3rd layer': green-sensitive silver halide emulsion layer 4.0mg/100c of Mazereta Kaplani 28 from Kihatsu Moe
m2, green-sensitive silver chlorobromide emulsion (containing 80 mol% silver bromide) in terms of silver: 2.5 mg/1'00 cm", dibutyl phthalate: 4.0 mg/100 cm!, and gelatin: 12.0 mg/100 cm+ ' It was painted so that it looked like this.

4th layer: 2-(2-hydroxy-3-'5e as an intermediate layer UV absorber)
c-7'-5-t-butylphenyl)benzotria-)-ol at 4.0 mg/100..., di-butyl phthalate at 4.0 mg/100 cm", 2.5-di-t-
Octylhydroquinone 0.5mg/100cm”
And gelatin was coated at 12.0 mg/100 cm.

5th layer: red-sensitive silver halide emulsion layer l-[α-(2,4-di=1-pentylphenoxy)butanamide]-4゜6-dichloro-5-ethylphenol as a cyan coupler at 4.2mg/100cn+
", red-sensitive silver chlorobromide emulsion (containing 80 mol% silver bromide) in terms of silver: 3.0 mg/100 cm", tricresyl phosphate: 3.5 n+g/100 cm", and gelatin: 11.5 mg/100 cm" It was painted so that it was 100 cm'.

6th layer; middle layer A layer composed of exactly the same composition as No. 4-.

7th-: I-layer gelatin was coated at a concentration of 8.0 mg/100 cn+''.

In the above sample 49, the magenta dye image stabilizer according to the present invention was added to the third layer in the proportions shown in Table 3,
Multilayer samples 50 to 56 were prepared, exposed and processed in the same manner as in Example 1, and then subjected to a light fastness test (1
irradiated for 4 days). The results are also shown in Table 3.

(QO Table 3) From the results in Table 3, it can be seen that when the total use and dosage of the magenta dye image stabilizer according to the present invention is constant, compared to using the magenta dye image stabilizer according to the present invention alone, It can be seen that the light fastness of magenta dye images can be greatly improved by using two types of magenta dye image stabilizers according to the present invention in a suitable ratio.

Furthermore, the silver halide photographic material of the present invention had excellent color reproducibility and little Y-stain occurrence.

Patent applicant: Konishiroku Photo Industry Co., Ltd., agent patent attorney
Toru Takatsuki 19i) Procedural amendment (voluntary) June 15, 1988 Commissioner of the Japan Patent Office Black 1) Akira Akira 1, Indication of the case 1986 Patent side No. 056999 2, Name of the invention Silver halide photographic photosensitive Material 3. Relationship with the case of the person making the amendment Patent applicant address 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name
(127) Roku Konishi photo] Nigyo Co., Ltd. 4, Agent address: 506-6 Dia Palace Niban-cho, 11-9 Niban-cho, Chiyoda-ku, Tokyo 102, Japan Subject of amendment "Scope" column, "Detailed Description of the Invention 1" column.

7. Contents of the amendment As shown in the attached sheet (1) The "Claims" in the description will be amended as shown in the attached sheet.

(2) General formula (XII) on page 11 of the same is amended as follows.

General formula (XII) "(3)", page 12, lines 5-6 [R5 represents a substituent, l represents O or an integer from 1 to 4. -1 as "R5 represents a substituent, l represents O or an integer from 1 to 4, m is 0
or represents l. ” he corrected.

(4) The general formula (Xll) on page 107 of the same publication is corrected as follows.

General formula (XII) N+ or more (amended claims) At least one magenta image-forming coupler represented by the following general formula (1,) and a compound represented by the following general formula (Xll) (1) and at least one compound selected from the following general formula CXn.

General formula (1) [In the formula, Z represents a nonmetallic atomic group 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.

Moreover, R represents a hydrogen atom or a substituent. ] General formula (XI
I) U゛ [wherein R1, R2 and R3 each represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or a heterocyclic group, and R4 represents an alkyl group, a cycloalkyl group, an alkenyl group or Represents an aryl group. R5 represents a substituent, and β represents 0 or an integer of 1-4. m is 0
Or represents 1. J represents, and R6 and R7 represent a hydrogen atom, an alkyl group or an aryl group. Also R1 and R2
may be combined to form a 5- or 6-membered ring. When l is 2 or more, a plurality of R5s may be the same or different. Furthermore, R5 may form 5 to 61 rings together with R1 and/or R2 and the nitrogen atom adjacent to 171.11''.] General formula (X l1l) m [wherein R and RIG are Each 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, and R % represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, a hydroxy group, an aryl group, an acyl group, an acylamino group, an acyloxy group, a sulfonamide group, a cycloalkyl group, or an alkoxycarbonyl group.

Further, R9 and RIG may be ring-closed with each other to form a 5- or 6-membered hydrocarbon ring.

Y represents an atomic group necessary to form an indane ring. ]

Claims (1)

[Scope of Claims] At least one magenta image-forming coupler represented by the following general formula [I], at least one compound represented by the following general formula [XII], and at least one compound represented by the following general formula [XIII] 1. A silver halide photographic material comprising at least one compound selected from the group consisting of: 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. In addition, R represents a hydrogen atom or a substituent] General formula [XII] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, R^1, R^2, and R^3 are each a hydrogen atom,
It represents an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, or a heterocyclic group, and R^4 represents an alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group. R^5 represents a substituent, and l represents 0 or an integer of 1 to 4. J has ▲mathematical formulas, chemical formulas, tables, etc.▼, ▲mathematical formulas,
There are chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and R^6 and R^7 represent a hydrogen atom, an alkyl group, or an aryl group. Further, R^1 and R^2 may be combined to form a 5- or 6-membered ring. When l is 2 or more, multiple R^5s may be the same or different. Furthermore R^
5 may form a 5- or 6-membered ring together with R^1 and/or R^2 and the nitrogen atom adjacent to R^1 and R^2. ] General formula [XIII] ▲ There are mathematical formulas, chemical formulas, tables, etc. group, aryloxy group, acyl group, acylamino group, acyloxy group, sulfonamide group, cycloalkyl group, or alkoxycarbonyl group, and R^9 is a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, a hydroxy group, an aryl group. group, acyl group, acylamino group, acyloxy group, sulfonamide group, cycloalkyl group or alkoxycarbonyl group. In addition, R^9 and R^1^0 are ring-closed with each other to form a 5-membered or 6-membered
may form a membered hydrocarbon ring. Y represents an atomic group necessary to form an indane ring. ]