JPS61184543A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve light fastness of a magenta dye image by incorporating a specified dye forming coupler and a specified compd. in a photographic sensitive material. CONSTITUTION:The magenta dye forming coupler to be used in an amt. of 1.5X10<-3>-7.5X10<-1>mol per mol of silver halide is represented by formula I (Z being a nonmetallic atomic group necessary for forming an N-contg. option ally substd. hetero ring, X being H or a group to be released by the coupling reaction with the oxidation product of a color developing agent, and R being H or a substituent), and the compd. to be used for stabilizing a magenta dye image in an amt. of 5-300mol% of said coupler is represented by formula II, each of R1-R3 being H, halogen, alkyl, alkenyl, hydroxy, aryl, acyl, acyamino, acyloxy, sulfonamide, cycloalkyl, alkoxycarbonyl, or the like, thus permitting image fastness to be improved.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide color photographic light-sensitive material. 6 Regarding silver halide color photographic light-sensitive materials [Prior art] Conventionally, silver halide color photographic light-sensitive materials are imagewise exposed and color developed to form an oxidized form of an aromatic primary amine color developing agent and a color forming agent. It is well known that by carrying out a coupling reaction, for example, indo7er/-el, indoaniline, indamine, azomethine, phenoxanone, 7enazine, and similar pigments are produced, and a color image is formed. be. 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.

Examples of couplers used to form the above-mentioned yellow image include acylacetanilide couplers, and examples of couplers used to form magenta images include pyrazolone, virazolobenzimiguzole, pyrazolotriazole, and ingzolone. Coupler is known, and as a coupler for forming a cyan image, for example, a 7-er or 7-tole 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. It is also desired that the uncolored areas of silver halide color photographic materials (hereinafter referred to as color photographic materials) do not turn yellow (hereinafter referred to as Y-stain) when exposed to light or heat.

However, in the case of magenta couplers, fading of color by light in uncolored areas, Y-stain due to heat, and dye image areas due to light is extremely large compared to yellow couplers and cyan couplers, and often poses a problem.

Couplers commonly used to form magenta dyes are 5-pyrazolones. The dye formed from this magenta coupler of 5-pyrazolones is 550nw
In addition to the main absorption in the vicinity, a major problem is that it has a secondary absorption in the vicinity of 430 nUa, and various studies have been conducted to solve this problem.

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. Regarding these technologies, for example, U.S. Patent No. 2,343°703, British Patent No. 1,
No. 059,994, etc.

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

As another means for reducing the side absorption near 430 nm of the above magenta coupler, British Patent No. 1゜047.6
Virazolobenzimidazoles described in US Pat. No. 12, Inguzon a described in US Pat.
IH-pyrazolo[5゜1-cl-1,2,4=) lyazole coupler described in No. 418 and No. 1,334,515, Re5earch D 1sclosu
IH-pyrazolo[1,5-bl-1,2,4-) lyazole coupler described in RE 24531 (1984), Research D 1 closure 24
626 (1984) IH-pyrazo a [1,5
-cl-1,2,3-) lyazole coupler, JP-A-59-162548, Research D 1s
IH-imidazo [1,2-bl-pyrazole type coupler described in Closure 24531 (described in Iiff), Research D 1 closure 242
30 (1984), IH-pyrazolo[1,5-b
l Pyrazole type coupler, Research D 1
IH described in sciosure24220 (1984)
A magenta coupler of the -pyrazolo[1,5-d]tetrazole type coupler has been proposed. Among these, IH
-pyrazolo[5,1-cl -1,2,4) lyazole coupler, IH-pyrazolo[1,5-bl-1,2,
4-) Lyazole couplers, IH- and LazoC7[1,
5cl 1゜2.3-)su7sol type coupler, 1H
-Imigzo[1,2-bl pyrazole type coupler, IH
The dye formed from the -virazo o[l,5-b] pyrazole type coupler and the IH-pyrazolo[1,5-dl tetrazole type coupler has a subabsorption near 430 nm, and the 5- Compared to dyes formed from pyrazolones, it has a smaller color, 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 light fastness of the azomethine dyes formed from these couplers is rather low, and moreover, the dyes are susceptible to discoloration upon exposure to light, which traditionally impairs the performance of color photographic materials, especially printed color photographic materials. However, it has not been put to practical use in printed color photographic materials.

In addition, JP-A-59-125732 discloses the use of an IH-pyrazolo[5,1cl 1,2,4) lyazole type magenta coupler in combination with a 7-functional 7-l compound or a 7-functional diyl ether compound. Accordingly, a technique has been proposed for improving the light fastness of magenta dye images obtained from IH-pyrazolo[5,l cl 1,2.4 ) lyazole type magenta couplers. However, it has been recognized that even the above techniques are 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 a first object of the present invention is to provide a color photographic material with excellent color reproducibility and improved light fastness of magenta dye images. There is a particular thing.

A second object of the present invention is to provide a color photographic material having a magenta dye image that is less discolored by light.

A third object of the present invention is to provide a color photographic material in which the generation of Y-styrene in uncolored areas is prevented from being exposed to light, heat, and humidity.

[Structure of the invention]

The above object of the present invention is to provide a silver halide color photographic photosensitive material containing a magenta dye-forming coupler represented by the following general formula (1) and a compound represented by the following general formula (II). Achieved by materials.

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

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

Moreover, R represents a hydrogen atom or a substituent.

General formula [II] R' R In the formula, R1 and R3 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, an acylamino group, an acyloxy group , represents a sulfone 7mido group, a cycloalkyl group or an alkoxycarbonyl group, and R
2 represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, a hydroxy group, an aryl group, an acyl group, an acylamide group, an acyloxy group, a sulfonamide group, a cycloalkyl group, or an alkoxycarbonyl group.

Further, R2 and R3 may be ring-closed with each other to form a 5-shell or 6-shell hydrocarbon ring.

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

In the magenta coupler represented by the general formula (1) according to the present invention, 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, Ryl group, heterocyclic group, acyl group, sulfonyl group, sulfinyl group,
Phosphonyl group, carbamoyl group, sulfamoyl group, cyano group, spiro compound residue, bridged hydrocarbon compound residue,
alkoxy group, aryloxy group, heterocyclic oxy group,
Siloxy group, acyloxy group, carbamoyloxy group,
ami 7 groups, acylami 7 groups, sulfonamide group, imido group, ureido group, sulfonyl amine 7 groups, alkoxycarbonyl 7 mino groups, aryloxycarbonyl amine 7 groups
group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylthio group, an arylthio group, and a heterocyclic thio group.

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

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

In addition, these alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, and cycloalkenyl groups include substituents [e.g., aryl, cyano, halogen atoms, heterocycles, cycloalkyl, cycloalkenyl, spiro compound residues, and aromatic hydrocarbon compound residues. In addition to groups, those substituted through a carbonyl group such as acyl, carboxy, carbamoyl, alkoxycarbonyl, and 7-aryloxycarbonyl, and those substituted through a hetero atom (specifically hydroxy, alkoxy, aryloxy , heterocyclic oxy,
Those substituted through an oxygen atom such as siloxy, acyloxy, carbamoyloxy, nitro, 7mino (including dialkylamino, etc.), sul77moylamino, alkoxycarbonylamino, aryloxycarbonylamino, acylamino, sulfonamide, imide, ureido those substituted through the nitrogen atom such as alkylthio, arylthio, heterocycle, sulfonyl, sulfinyl,
(such as those substituted via a sulfur atom such as sulfamoyl, and those substituted via a phosphorus atom such as phosphonyl).

Specifically, for example, methyl group, ethyl group, isopropylene 71
4, t-butyl group, pentadecyl group, heptadecyl group,
1-hexylnonyl group, i,i'-noventylnonyl group, 2-chloro-t-acyl group, trifluoromethyl group,
1-Ethoxytridecyl group, 1-methoxyisopropyl group, methanesulfonylethyl group, 2,4-not-7mil7ethyl/oxymethyl group, anilino group, 1-phenylisopropyl group, 3-II+-butanesulfonaminophenoxy Propyl group, 3-4'-iα-(4''(p-hydroquinebenzenesulfonyluami7)7enylprobyl group, 3-i4'-(α-(
2”,4”-di-t-amylphenoxy)butane 7)
') phenyl)-propyl group, 4-(α-(0-chloro7enoxy)tetrazodicane7mido72/xy]propyl group, allyl group, cyclopentyl group, cyclohexyl group, etc.

The aryl group represented by R is preferably a phenyl group, which may have a substituent (eg, an alkyl group, an alkoxy group, a 7-sylami-7 group, etc.).

Specifically, phenyl group, 4-t-butyl 7-enyl group,
2.4-di-t-7mylphenyl group, 4-tetradecanamidophenyl group, hexadecyloxyphenyl group, 4'
-[α-(4″-t-butyl7enoxy)tetradecanamidophenyl group and the like.

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

Specific examples include 2-furyl group, 2-chenyl group, 2-biriminonyl group, and 2-pentthiazolyl group.

Examples of the acyl group represented by R include acetyl group, phenylacetyl group, dodecanoyl group, fulkylcarbonyl group such as α-2,4-monoamyl72/xybutanoyl group, benzoyl group, and 3-pentadecyl group. Examples include arylcarbonyl groups such as oxybenzoyl group and p-chlorobenzoyl group.

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

The sulfinyl group represented by R includes a fulkylsulfinyl group such as an ethylsulfinyl group, an octylsulfinyl group, a 3-72/xybutylsulfinyl group, and 7!
Nilsulfinyl group 1. -Pentadecylphenylsulfinyl group, chiarylsulfinyl group, and the like.

The phosphonyl group represented by R includes an alkylphosphonyl group such as a butyloctylphosphonyl group, an alkoxyphosphonyl group such as an octyloxyphosphonyl group, an aryloxyphosphonyl group such as a 7e7xyphosphonyl 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-pentadecyloctylethyl)carbamoyl group, N-ethyl-N-F? 'dylcarbamoyl group, Ni3-(2,4-not-7-milphenoxy)propyl)carbamoyl group, and the like.

The sulfamoyl group represented by R is often substituted with an alkyl group, an aryl group (preferably a phenyl group), etc.
For example, N-propylsulfamoyl group, N,N-diethylsulfamoyl group, N-(2-pentadecyloxyethyl)sulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, N-phenylsulfamoyl group Examples include groups.

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

Examples of the bridged hydrocarbon compound residue represented by R include bicyclo[2,2,1]hebutan-1-yl, tricyclo[3,3,1,1''ldecane-1-yl, 7,7 -nomethyl-bicyclo[2,2,1]heptane-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''C is preferably a 7-enyloxy group, and the aryl nucleus may be further substituted with any of the substituents or atoms listed above for the aryl group, such as a phenoxy group, p- Examples include t-butylphenoxy group and lll-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-tetrahydro. Examples include biranyl-2-oxy group and 1-phenyltetrazole-5-oxy group.

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

The acyloxy group represented by R includes, for example, a furkylcarbonyloxy group, an arylcarbonyloxy group, etc., and may further have a substituent, and specifically, an acetyloxy group, an α-chloro7cetyloxy group, etc. group, benzoyloxy group, and the like.

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

The amino group represented by R may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as an ethyl group, anilino group, ffl-chloroanili group, 3-pentadecyloxy carbonylanilino group,
Examples include 7 groups of 2-chloro-5-hexadecaneamide aniline.

Examples of the acylamine 7 groups represented by R include 7 alkylcarbonylamide groups, 7 arylcarbonylamide groups (preferably 7 phenylcarbonylamide groups), and may further have a substituent. Cetamide group, α-ethylpropanamide group, N-7x nylacetamide group,
Dodecanamide group, 2,4-di-t-amylphenoxyacetamide group, α-3-t-butyl 4-hydroxy 7
Examples include 7-xybutanamide group.

Examples of the sulfonamide group represented by R include 7 alkylsulfonylamide groups and 7 arylsulfonylamide groups, and may further have a substituent.

Specifically, methylsulfonyl 7 groups, bentatecylsulfonyl 7 groups, benzenesulfonyl 1' groups, p-
Examples include toluenesulfonamide group and 2-methoxy-5-t-amylbenzenesulfonamide group.

The imide group represented by R may be open-chain or cyclic, and may have a substituent, such as a succinimide group, a 3-heptadecylsuccinimide group, a 7-talimide group, Examples include glutarimide group.

The ureido group represented by R is an alkyl group, an aryl group (
Preferably, it may be substituted with a 7enyl group), and examples thereof include an N-ethylureido group, an N-methyl-N-decylureido group, an N-phenylureido group, and an N-p-)lylureido group.

The sul77moylamide7 group represented by R is an alkyl group,
It may be substituted with an aryl group (preferably a phenyl group) or the like (eg, N,N-dibutylsul7amoylami7 groups, N-methylsul7amoylami7M, N-phenylsul7amoylamy7 groups, etc.).

The phenoxycarbonylamide 7 group represented by R is:
It may further have a substituent, for example, 7 toxycarponylamino groups, 7 methoxyethoxycarbonylamino groups,
Examples include octadecyloxycarbonyl 7-7 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, 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, a -pentadecyloxy7e/oxycarbonyl group, and the like.

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 3-7ethylthio 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-t-octylphenylthio group, 3-octadecylphenylthio group, 2-carboxyphenylthio group, and p-7cetaminophenylthio group.

The heterocyclic group represented by R is preferably a 5- to 7-shell heterocyclic group, which may further have a condensed ring or a substituent. Examples include 2-pyridylthio group, 2-benzothiazolylthio group, and 2,4-nophenoxy-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 Examples include groups substituted via.

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

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

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

The aryloxy group is preferably a phenoxy group, and the aryl group may further have a substituent.

Specifically, 71/oxy group, 3-methylphenoxy group, 3
-dodecyl 7eth/oxy group, 4-methanesulfonamide 7
2/oxy group, 4-[α-(3'-pentadecyl 7ヱ/xy)butanamide] 7eth/oxy group, hexydecylcarnoimoylmethoxy group, 4-cya/phenoxy group, 4-methanesulfonyl 7enoxy group, 1-s7tyloxy group,
Examples include p-7toxy-7enoxy group.

The following margins are as follows. The heterocyclic oxy group is preferably a 5- to 7-shell heterocyclic oxy group, which may be a condensed ring or may have a substituent. Specific examples include -phenyltetrazolyloxy group and 2-benzothiazolyloxy group.

Examples of the acyloxy group include acetoxy group, fulkylcarbonyloxy group such as butanoyloxy group, alkenylcarbonyloxy group such as cinnamoyloxy group, and arylcarbonyloxy group such as benzoyloxy group.

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

As the alkoxycarbonyloxy group, for example,
Examples include a 4dicarbonyloxy 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 ethoquinoxalyloxy group.

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

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

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

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

Examples of the alkyloxythiocarbonylthio group include a dodecyloxythiocarbonylthio group.

Examples of the group substituting via the nitrogen atom are as follows. Here, R1' and R5' are a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a sulfamoyl group, a carbamoyl group,
It represents an acyl group, a sulfonyl group, an aryloxycarbonyl group, or an alkoxycarbonyl group, and R1' and R5' may be combined to form a heterocycle. However, R, 7 and RS'
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, a 7-aryloxy group, an alkylthio group,
Arylthio group, 7 alkylamides, 7 arylamides, 7 acylamides, sulfonamide group, imino group, acyl group, alkylsulfonyl group, arylsulfonyl group,
Carbamoyl group, sulfamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkyloxycarbonylamide 7 group, aryloxycarbonylamide 7 group
group, hydroxyl group, carboxyl group, sia/group, and halogen atom.

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

The 7-aryl group represented by R and/or RS' preferably has 6 to 32 carbon atoms, particularly a phenyl group or a naphthyl group,
The aryl group may have a substituent (substituents include those listed above as substituents for the alkyl group represented by R, 7 or R5', and a furkyl group. Specific examples of the group include phenyl group, 1-s7tyl group, and 4-methylsulfonylphenyl group.

The heterocyclic group represented by R% or Rs' is preferably one with 5 to 6 shells, may be a condensed ring, and may have a substituent. Specific examples include 2-furyl group, 2-quinolyl group, 2-biriminol group, 2-benzothiazolyl group,
Examples include 2-bilinol group.

The sulfamoyl group represented by R1' or R5' includes N-furkylsulfamoyl group, N,N-noalkylsul7Tmoyl group, N-7lylsul7amoyl group,
, N-diarylsulfamoyl group, etc., and these alkyl groups and v7 aryl groups may have the substituents listed for the alkyl groups and aryl groups. Specific examples of the sulfamoyl group include N, N-noethylsulfamoyl group, N-methylsulfamoyl group, N
-dodecylsulfamoyl group, Np-)lylsul7-amoyl group.

As the carbamoyl group represented by R, 7 or R5',
N-furkylcarbamoyl group, N,N-dialkylcarbamoyl group, N-7arylcarbamoyl group, N,N-diarylcarbamoyl group, etc., and these alkyl groups and aryl groups are the same as those mentioned for the alkyl group and 7aryl group. may have other substituents. Specific examples of the carbamoyl group include N,N-noethylcarbamoyl group, N-methylcarbamoyl group, N-dodecylcarbamoyl group, Np-thia/phenylcarbamoyl group,
p) Lycarbamoyl group can be mentioned.

Examples of the acyl group represented by R, 7 or R5' include an alkylcarbonyl group, a 7-arylcarbonyl group, and a heterocyclic carbonyl group, and the alkyl group, aryl group, and heterocyclic group have a substituent. You may do so. Specific examples of the acyl group include hexafluorobuta/yl group, 2゜3.4.5.6-pentafluorobenzoyl group, acetyl group, benzoyl group, naphthonyl group, 2-furylcarbonyl group, etc. It will be done.

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

The 7-aryloxy carbonyl group represented by R or Rs' may have any of the substituents listed above for the aryl group, and specific examples thereof include a 7-ethyl carbonyl group and the like.

The alkoxycarbonyl group represented by R1' or R5' may have a substituent listed for the alkyl group, and specific examples include a methoxycarbonyl group, a dodecyloxycarbonyl group, a benyloxycarbonyl group, etc. can be mentioned.

The heterocycle formed by R4J and R, / is preferably one with 5 to 6 shells, and may be saturated or unsaturated, and may or may not have aromaticity, or,
Examples of the heterocycle, which may be a condensed ring, include N-7 talimide group, N-succinimide group, 4-N-urazolyl group, 1-N-hyguntoynyl group, and 3-N-2,4-nooxooxazoli. Dinyl group, 2-N-1,1-dioxo-
3-(2H)-oxo-1,2-benzthiazolyl group,
1-pyrrolyl group, 1-pyrrolidinyl group, 1-pyrazolyl group, 1-pyrazolidinyl group, 1-piperidinyl group, 1-
Pyrrolinyl group, 1-imidazolyl group, 1-indolyl group, 1-indolyl group, 1-isoindolinyl group, 2-isoindolyl group, 2-isoindolinyl group, 1-benzotriazolyl group, 1-benzotriazolyl group, l −(
1,2,4-)riazolyl) group, 1-(1,2,3-)
riazolyl) group, l-(1,2,3,4-tetrazolyl) group, N-morpholinyl group, 1,2,3.4-tetrahydroxyl group, 2-oxo-1-pyrrolidinyl group,
2-IH-pyridone group, 7thalathion group, 2-oxo-
1-piperidinyl group, etc., and these heterocyclic groups include alkyl groups, aryl groups, alkyloxy groups, aryloxy groups, acyl groups, sulfonyl groups, 7 alkylamides, 7 arylamides, 7 acylamides, and 7 sulfonamides.
group, carbamoyl group, sulfamoyl group, alkylthio group, arylthio group, Vreido group, alkoxycarbonyl group, aryloxycarbonyl group, imido group, nitro group, cyano group, carboxyl group, 7% lodene atom, etc. .

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

In addition, general formula [I] and general formula [ll] to (IM
) on the heterocycle (e.g., RlR, -R,
) has a partial R'', X and Z j 7 have the same meanings as R , X and Z in general formula (I),
Although it forms a so-called screw type coupler, it is of course included in the present invention. Further, the ring formed by z, z', z'' and 21 described below may be further fused with another ring (for example, a cycloalkene with 5 to 7 shells).For example, the ring formed by the general formula (Vl
), R2 and R6 are R2 and R6 in the general formula [■]
7 and R8 may be bonded to each other to form a ring (for example, 5 to 7 cycloalkenes, benzene).

More specifically, what is represented by the general formula (1) is represented by, for example, the following general formulas (1) to [■].

General formula (I[] General formula (IV) N -N -N General formula [■] N -N -NH General formula (Vl) General formula [■] N -N --NH General formula [■] The above general formula In [■] to [■], R1-R8 and X have the same meanings as R and [/X] above.

Also, among the general formula (1), the following general formula C is preferable.
II).

General formula CII) in which R, , X and 2. has the same meaning as R9X and Z in general formula (1).

Among the magenta couplers represented by the general formulas (II-[■]), particularly preferred are magenta couplers represented by the general formula CI [[].

Regarding the substituents on the heterocycle in general formulas (I) and (Ill) to (IX), R in general formula [I] and R3 in general formulas CI3 to (IXI) meet the following conditions 1. It is preferable that the following conditions are satisfied, more preferable is the case that the following conditions 1 and 2 are satisfied, and particularly preferable is the case that the following conditions 1, 2 and 3 are satisfied.

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

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

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

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

General formula (X) R5 ■ R5゜-〇- R1゜In the formula, R9fR1O and RII 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,
heterocyclic group, acyl group, sulfonyl group, sulfinyl group, phosphonyl group, carbamoyl group, sulfamoyl group,
Cyano group, spiro compound residue, bridged hydrocarbon compound residue, alkoxy group, aryloxy group, heterocyclic oxy group, siloxy group, acyloxy group, carbamoyloxy group, ami7 group, acylamino group, sulfonamide group, imide R9゜R, represents a ureido group, a sulfamoylaminyl group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylthio group, an arylthio group, a heterocyclic thio group, . At least two of RII and RII are hydrogen atoms.

Also, the above R5, R,. and two of RII such as R3
and R1° may be combined to form a saturated or 1i-unsaturated ring (e.g., cycloalkane, cycloalkene, heterocycle), and R1 is further bonded to the ring to form a bridged hydrocarbon compound residue. may be configured.

The groups represented by R4 to R11 may have a substituent, and specific examples of the group represented by R3 to R1 and the substituents that the group may have include the above-mentioned general formula [I Specific examples of the group represented by R in ] and substituents are listed.

Also, for example, a ring formed by combining Rs and R1゜ and R3
Specific examples of the bridged hydrocarbon compound residue formed by ~R1+ and its optional substituents include specific examples of the cycloalkyl, cycloalkenyl, and heterocyclic groups represented by R in the aforementioned general formula (1). Examples and substituents thereof are listed.

Among the general formulas (IX), (i) Rs~
When two of R1 are alkyl groups, (ii) Rs~
When one of RI+, for example R1, is a hydrogen atom, and the other two R, and Rto combine to form a cycloalkyl together with the root carbon atom, the following is true.

Furthermore, it is preferable among (i) that two of R9 to R11 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.

Typical specific examples of the magenta dye image-forming coupler according to the present invention are shown below.
-, JT"1, here;'lower reading'/゛\, ---l 2H5 CI.

■ H3 2H5 A-13 A-14 C,H.

C4H.

A-29 A-3O H3 A-43 A-44 A-4F L;4i19 A-59 A-6O H3 H3 QC2H.

A-75 A-7ro CH3 C? H15 HIC CH3 L; 2H5 A-8F A-91 A-92 N -N -N -N-NH A-106 rN Js ■ ■ A-126 N -N -NH A-143 The synthesis of the above coupler is Journal of t
heChes+1cal 5ociety w
Perkin I (1977) t204
No. 7-2052, U.S. Patent No. 3,725,087, No. 11
1@59-99437 and JP-A-58-42045, etc. The magenta dye image stabilizer used in conjunction with the magenta coupler of the present invention has the effect of 'preventing fading of magenta dye images due to light. In addition, it also has the effect of preventing discoloration due to light, and it has the effect of preventing discoloration due to light. It is a -1,1'-spirobiindane compound.

General formula (If) R' R In the formula, R1 and R3 are each a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, a hydroxy group, an aryl group, a 717-ruoxy group, an acyl group,
Represents a silami7 group, an acyloxy group, a sulfonamide group, a cycloalkyl group, or an alphkidicarbonyl group.

Yahidene atom used for R1 and R3, furkyl group,
Alkenyl group, alkoxy group, aryl group, aryloxy group, acyl group, 7-sylami 7 group, acyloxy group,
Specific examples of the sulfonamide group, cycloalkyl group, or alkoxycarbonyl group include the groups detailed for R in general formula (1).

R2 represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, a hydroxy group, an aryl group, an acyl group, an acylamide group, an acyloxy group, a sulfonamide group, a cycloalkyl group, or an alkoxycarbonyl group. Halogen atom, alkyl group, alkenyl group used for R2,
Specific examples of the aryl group, acyl group, acylamino group, 7-syloxy group, sulfonamide group, cycloalkyl group or alkoxycarbonyl group include R in general formula (1).
Mention may be made of the groups detailed in .

The groups listed above may each be substituted with other substituents. Examples of substituents include alkyl groups, alkenyl groups,
Examples include an alkoxy group, an aryl group, a 7-aryloxy group, a hydroxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acylamino group, a carbamoyl group, a sulfonamide group, and a sulfamoyl group.

Further, R2 and R3 may be ring-closed with each other to form a 5-shell or 6-shell hydrocarbon ring. This 5-membered or 6-membered true hydrocarbon ring is a halogen atom, an alkyl group, a cycloalkyl group,
Alkoxy group, alkenyl group, hydroxy group, 717-
may be substituted with a group such as an aryl group, an aryloxy group, a heterocyclic group, or the like.

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

Among the compounds represented by the general formula (II), compounds particularly useful in the present invention are represented by the general formula [°C] to (XI [[)]
Xl] to 1 General formula (n) General formula (XI) R I , R in general formulas (XI) to (XI[I)
2 and R3 have the same meaning as in general formula (II), R', R5tR'tR'tR"l and R'li, +reP
h Represents a hydrogen atom, halogen atom, furkyl group, alkoxy group, alkenyl group, hydroxy group, aryl group, aryloxy group or heterocyclic group aR4 and Rs, R5 and R6, R@ and R7, Rf and R8 and R1 and R9 may be bonded to each other to form a hydrocarbon ring, and furthermore, the hydrocarbon ring may be substituted with an alkyl group.

In the general formulas (n) to (XI[[), R1 and R
3 is a hydrogen atom, an alkyl group, an alkoxy group, a hydroxy group, or a cycloalkyl group, R'' is a hydrogen atom, an alkyl group, a hydroxy group, or a cycloalkyl group, R4, R'
, R'', R'.

Particularly useful are compounds in which R1 and R9 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.

HI-1 HI-2 l-3 HI-4 t-5 l-6 HI-7 HI-8 HI-9 l-10 l-11 HI-12 HI-13 HI-14 l-15 HI-16 l- 17 l-18 l-19 l-20 HI-21- HI-22 l-23 l-24 HI-25 l-26 l-27 l-28 HI-29 HI-30 HI-31 l-32 l-33 l-34 l-35 l-36 HI-3F l-38 l-39 l-40 l-41 HI-42 l-43 l-44 l-45 General formula (II) above, C revision] ~ (XI The method for synthesizing the 1-zenta dye image stabilizer of the present invention represented by [[] is known, and is described in J. Chem, Soc, 1962.4.
pp. 15-417, Special Publication No. 59-32785, Bul
l, Chem, S oc.

Japan, 1980v 5L, pages 555-556.

The magenta dye image stabilizer of the present invention is disclosed in Japanese Patent Publication No. 59-32
No. 785, it is used as a stabilizer for magenta dye images obtained from pyrazolone, indashilon or shea 7-acetyl type magenta couplers, and is particularly useful as a magenta dye image stabilizer obtained from 5-pyrazolone type magenta couplers. It is stated that

However, there has been no suggestion that the magenta coupler of the present invention, which has a different structure from the magenta coupler described above, is useful as a stabilizer for magenta dye images. It was found that the hydroxyindan compound represented by the general formula [II] exerts an unexpected and specific effect on the preservation of magenta dye images obtained from the magenta coupler represented by the general formula (1). It started.

In the color photographic material of the present invention, the amount of the magenta coupler represented by the general formula (1) of the present invention added is as follows:
1,5X 10-' to 7,5X10-1 per mole of silver
A molar range is preferred, more preferably a range of 1 x 10-2 moles to 5 x 10-' moles.

The amount of the magenta dye image stabilizer represented by the general formula (11) of the present invention used is preferably 5 to 300 mol% relative to the magenta coupler represented by the general formula (()) of the present invention, More preferably, it is 10 to 200 mol%.

In the color photographic material of the present invention, the magenta dye image stabilizer of the present invention is further compounded by the following general formula (XIV):
Other magenta dye image stabilizers shown in (1), ie, phenol compounds and phenyl ether compounds, can also be used in combination.

General formula (XIV) In the formula, R4 represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and R5, R6, R6, and R9 each represent a hydrogen atom, a hydroxy group, an alkyl group, an aryl group,
It represents an alkoxy group or an acylamide 7 group, and R7 represents a furkyl group, a hydroxy group, a 7-aryl group, or an alkoxy group. In addition, R4 and R5 are ring-closed to each other to form a 5-shell or a 6-shell ring.
A shell ring may be formed, in which case R7 represents a hydroxy group or an alkoxy group. Furthermore, R4 and R5 may be ring-closed to form a methylenedioxy ring. Furthermore, R6 and R7 may be ring-closed to form a five-shell carbon ring, in which case R4 represents an alkyl group, an aryl group, or a heterocyclic group.

The compound represented by the general formula [XIV] is disclosed in US Pat.
, No. 935,016, No. 3,982,944, No. 4,
No. 254,216, Special Ill No. 1983-21004,
No. 54-145530, British Patent Publication No. 2,077.4
No. 55, No. 2,062,888, U.S. Patent No. 3,764
．． No. 337, No. 3,432,300, No. 3,574,
No. 627, No. 3,573.050, JP-A-52-15
No. 2225, No. 53-20327, No. 53-1772
No. 9, No. 55-6321, 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.

Specific examples of the compound represented by the general formula [X1] are shown below. -111, below □ bottom margin PH-1 PH-2 H-3 CH.

H-4 P 1-5 H-6 H-7 H-8 PH-10 H-11 ■ H-12 H-13 H-14 H PH-15 PH-16 H-17 H3 PH-18 The phenolic compound represented by the general formula [X■] or the phenyl ether compound accounts for 200 mol% or less of the magenta dye image stabilizer represented by the general formula [II] of the present invention. Preferably, it can be used in an amount of 140 mol% or less.

The 7 ether compound and the phenyl ether compound have the effect of preventing fading of the magenta dye image obtained from the magenta coupler of the present invention, but have almost no effect of preventing discoloration.

Therefore, it is not preferable to use an excessive amount of the phenol compound and 1/' phenyl ether compound in the magenta dye image stabilizer of the present invention.

In general, the magenta dye image obtained from the magenta coupler of the present invention not only exhibits ν1 fading when exposed to light, but also undergoes 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 [II] of the present invention can prevent the fading and discoloration of the magenta dye image obtained from the magenta coupler due to light, compared to the conventional heptagonal compound. It also has effects that cannot be achieved with magenta dye image stabilizers made of phenyl ether compounds.

Therefore, when the conventional magenta dye image stabilizers of phenolic compounds and heptadyl ether compounds are used in combination with the magenta dye image stabilizer represented by the general formula [II] of the present invention, The amount of the magenta dye image stabilizer of the conventional phenol compound and phenyl ether compound must be selected to such an extent that the color change due to light is not noticeable.

The magenta dye image stabilizing agent of the present invention represented by the general formula (n) is mixed with an appropriate amount of the conventional magenta dye image stabilizer of the 7-functional compound and the phenyl ether compound represented by the above (XIV). When used in combination with other agents, a mutually beneficial effect may be observed because they compensate for each other's shortcomings.

Although it is preferred that the magenta couplers of the invention and the magenta dye image stabilizers of the invention are used in the same layer, the stabilizers may be used in layers adjacent to the layer in which the couplers are present. 77. -2, hereinafter □Lower margin-' The silver halide photographic light-sensitive material of the present invention can be, for example, color negative and positive films, color photographic paper, etc., but is particularly suitable for direct viewing. The effects of the method of the present invention are effectively exhibited when color photographic paper is used.

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 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 layers are laminated on a support in an appropriate number and order of layers, but 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 used in silver emulsions can be used.

The silver halide grains used in the silver halide emulsion of the present invention may be obtained by any of the acid method, neutral method, or ammonia method, and the grains may be grown all at once. Alternatively, seed particles may be produced and then grown. The method for creating seed grains and the method for growing them may be the same or different. (For 1° silver halide emulsion) Even if 1-ride ions and silver ions are mixed at the same time, in the presence of either one, , the other may be mixed. Alternatively, the growth may be performed by sequentially and simultaneously adding S ride ions and silver ions while controlling the pHlpAg in the mixing pot, taking into consideration the critical growth rate of the silver dendecide crystal. After the growth, a conversion method may be used to change the silver halide composition of the grains (by using a silver halide solvent as necessary during the production of the silver halide of the present invention). Particle size of silver particles, particle shape,
Particle size distribution and particle growth rate can be controlled.

The silver halide grains used in the silver halide emulsion of the present invention are prepared by adding cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts, rhodium salts, Alternatively, metal ions can be added using complex salts, iron salts, or complex salts to be included inside the particles and/or on the particle surfaces, and in an appropriate reducing atmosphere (by which the metal ions can be incorporated inside the particles and/or on the particle surfaces). Reduction-sensitizing nuclei can be added to the surface.

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

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

The silver lodenide grains used in the silver halide emulsion of the present invention may be grains in which a latent image is mainly formed on the surface, or grains in which a latent image is mainly formed inside the grains.

The silver halide grains used in the silver halide emulsion of the present invention may have a regular crystal shape or may have an irregular crystal shape such as a spherical or plate shape. In these particles, any ratio of the f1001 plane to the 11111 plane can be used. Further, the particles may have a composite form of these crystal forms, or particles of various crystal forms may be mixed.

The silver halide emulsion of the present invention may be a mixture of two or more kinds of separately formed silver halide emulsions. The silver halide emulsion of the present invention is chemically sensitized by a conventional method. That is,
Sulfur sensitization method using active gelatin or a compound containing sulfur that can react with silver ions, selenium sensitization method using selenium compounds, reduction sensitization method using reducing substances, and noble metal sensitization method using gold or other noble metal compounds. These 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. Good too.

The silver halide emulsion of the present invention includes steps for producing light-sensitive materials,
During chemical ripening for the purpose of preventing capri during storage or photo processing and/or maintaining stable photographic performance,
and/or at the end of the chemical ripening, and/or after the end of the chemical ripening, before coating the S silver lodenide emulsion, compounds known in the photographic industry as anticapri agents or stabilizers can be added. .

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

In the photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material using the silver halide emulsion of the present invention, a hardening agent is used alone or in combination to crosslink binder (or protective colloid) molecules and increase film strength. The membrane is hardened from this. The hardening agent is
Although it is desirable to add an amount of the photosensitive material that can be hardened to such an extent that there is no need to add a hardening agent to the processing solution, it is also possible to add a hardening agent to the processing solution.

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

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

In the emulsion layer of the silver halide color photographic light-sensitive material of the present invention, an aromatic primary amine developer (
For example, a dye-forming coupler is used that forms a dye by performing a coupling reaction with an oxidized product of p-phenylenediamine derivatives, aminophenol derivatives, etc.). 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 for the blue light-sensitive emulsion layer. However, 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 color photographic materials may be produced using different combinations from the above.

Examples of yellow dye-forming couplers include acylacetamide couplers (e.g., benzoylaceto 7nilides, pivaloylacetanilide Jii); examples of magenta dye-forming couplers include, in addition to the couplers of the present invention, 5-pyrazolone couplers, pyrazolobenzimidazole couplers, pyrazolotriazole, w14 nod 7 sylacetrinitrol coupler, etc., and as a cyan dye-forming coupler, hasu 7
There are tall couplers, phenol couplers, etc.

These dye-synthesizing couplers preferably have a group called a pallast group in the molecule, which makes the coupler non-diffusive and has 8 or more carbon atoms. In addition, even if these dye-forming couplers are 4-equivalent, in which 4 molecules of silver ions need to be reduced in order to form 1 molecule of dye, only 2 molecules of silver ions need to be reduced. Either equivalence is fine.

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. can be appropriately selected depending on the chemical structure of the hydrophobic compound, etc. The oil-in-water type emulsification dispersion method can be applied using conventionally known methods for dispersing hydrophobic additives such as couplers, and is usually mixed with a commercial boiling point organic solvent having a boiling point of about 150°C or higher, and if necessary, a low boiling point and/or a commercial boiling point organic solvent. Or, by dissolving it in combination with a water-soluble organic solvent, using a surfactant in a hydrophilic binder such as an aqueous gelatin solution, and using a dispersion means such as a stirrer, homogenizer, colloid mill, 70-diet mixer, or ultrasonic device. After emulsification and dispersion, it may be added to the desired hydrophilic colloid layer. A step of removing the low boiling point organic solvent may be included simultaneously with the dispersion or dispersion.

High boiling point oils include phenol derivatives that do not react with the oxidized form of the developing agent, 7-talic acid ester, phosphoric acid ester, citric acid ester, fA fragrance 1! ! Boiling point 1 of esters, furkylamides, fatty acid esters, trimesic acid esters, etc.
An organic solvent having a temperature of 50° C. or higher is used.

Anionic active agents, /ionic surfactants, cations are used as dispersion aids when hydrophobic compounds are dissolved in a low boiling point solvent alone or in combination with a high boiling point solvent and dispersed in water using machines or ultrasonic waves. A surfactant can be used.

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

The color anti-capri agent may be used in the emulsion layer itself, or in an intermediate layer provided between adjacent emulsion layers.

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

A UV absorber is added to the hydrophilic colloid layers such as the protective layer and intermediate layer of the photosensitive material of the present invention in order to prevent fogging caused by discharge caused by charging of the photosensitive material due to friction, etc., and to prevent image deterioration due to UV light. may be included.

A color light-sensitive material using the silver halide emulsion of the present invention can be provided with auxiliary layers such as a filter layer, an antihalation layer, and/or an anti-ilanoation 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.

The silver halide emulsion layer and/or other hydrophilic colloid layer of a silver halide photosensitive material using the silver halide emulsion of the present invention is added to reduce the gloss of the photosensitive material and improve the addability.
A capping agent can be added for the purpose of preventing photosensitive materials from sticking to each other.

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

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

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

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

The silver halide photosensitive material of the present invention is prepared by subjecting the surface of the support to corona discharge, ultraviolet irradiation, flame treatment, etc. as necessary.
one or more substrates to improve adhesion, antistatic properties, dimensional stability, abrasion resistance, hardness, antihalation properties, frictional properties, and/or other properties directly or on the surface of the support. It may be applied via a coating layer.

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

The light-sensitive material of the present invention can be exposed using electromagnetic waves in a spectral region to which the emulsion layer constituting the light-sensitive material of the present invention is sensitive. Light sources include natural light (sunlight), tungsten electric lamps, fluorescent lamps, mercury lamps, xenon arc lamps, carbon arc lamps, xenon flash lamps, cathode ray tube flying tubes, various laser lights, light emitting diode lights, electron beams,
Any known light source can be used, such as light emitted from a phosphor excited by X-rays, γ-rays, α-rays, or the like.

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, or longer exposures of 1 second or more are possible. The exposure may be performed continuously or intermittently.

An image can be formed using the silver halide photographic material of the present invention 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 used in the form of salts, such as hydrochlorides or sulfates, since they are more stable than in the free state. These compounds are also generally used in concentrations of from about 0.1 g to about 30 g per color developer IQ, preferably from about 1 g to about 1.58 g per color developer.

Examples of Ami77 E7-el based developer include 〇-Ami7
7 7-el, p-7 mil/7 er 7-el, 5-7 mil/-2-
Oxytoluene, 2-ami/-3-oxytoluene, 2
-Oxy-3-amino/-1°4-tmethylbenzene and the like are included.

Particularly useful primary aromatic amino color developers are N, N'
-Dialkyl-p-phenylenediamine compound, and the alkyl group and phenyl group may be substituted with any substituent. Among them, examples of particularly useful compounds include N,N'-noethyl-p-phenylenenoamine hydrochloride;
N-methyl-p-phenylenediamine hydrochloride, N,N'
-tmethyl-p-7 2-2-diamine hydrochloride, 2-amino-5-(N-ethyl-N-dodecylami7)-toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4 -Aminoaniline sulfate, N-ethyl-N-β-hydroxyethylaminoaniline, 4-7mi/-3-methyl-N,N'-diethylaniline, 4-7
Minnow N-(2-methoxyethyl)-N-ethyl-3-
Examples include methylaniline-p-toluenesulfonate.

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, Alkaline agents such as potassium carbonate, alkali metal sulfites, alkali metal bisulfites,
Alkali metal thiocyanates, alkali metal halides, alcohol, water softeners, thickeners, and the like can also be optionally contained. The pH value of this color developer is usually 7 or higher, most commonly about 10 to
It is about 13.

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

Specific representative examples of these include the following.

[I] Ethylenediaminetetraacetic acid [2] Nitrilotriacetic acid [3] Imi7noacetic acid [4] Ethylenediaminetetraacetic acid disodium salt [5] Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt [6] Ethylenediaminetetraacetic acid Tetrasodium Salt (7) Di) Lilotriacetic Acid Sodium Salt The bleaching agent used contains the above-mentioned metal complex salt of an organic acid as a bleaching agent, and may also contain various additives. As additives, it is particularly desirable to include rehalogenating agents, metal salts, and chelating agents such as alkali halides or ammonium halides, such as potassium bromide, sodium bromide, sodium chloride, and ammonium bromide.

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

Furthermore, the fixing solution and the bleach-fixing solution contain 7 ammonium sulfite,
Sulfites such as potassium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, sodium metabisulfite, boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, carbonic acid A pH buffering agent consisting of various salts such as potassium, sodium bisulfite, potassium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide may be contained alone or in combination of two or more.

When carrying out the process of the present invention while replenishing the bleach-fixer 1 (bath) with a bleach-fix replenisher, the bleach-fixer (bath) may contain a naosulfate, thiocyanate, sulfite, etc. These salts may be added to the bleach-fixing replenisher to replenish the processing bath.

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

[Specific effects of the invention]

According to the color photographic material containing the magenta coupler of the present invention and the magenta dye image stabilizer represented by the general formula (II), conventional magenta dye images that have low fastness to light, heat, and humidity have been improved. Fastness, specifically, good prevention of discoloration and fading when exposed to light, and generation of Y-stain in uncolored areas when exposed to light, heat, and humidity.

[Specific embodiments of the invention]

The present invention will be specifically explained below with reference to Examples, but the embodiments of the present invention are not limited thereto.

Example 1 On a paper support laminated on both sides with polyethylene, gelatin (15, O+ag/100 cm2), comparative magenta coupler (1) shown below (6, OnH/100
100e and 2.5-di-tert-octylhydroquinone (0.8u+g/100c+++2) were dissolved and emulsified in dibutyl 7 tallate (5.0mff/100cI112), and then a silver chlorobromide emulsion (silver bromide 80 mol%, silver bromide 80 mol%, Sample 1 was obtained by mixing with coated silver f13.8mg/100c+a2), coating, and drying.

The above sample 1 contains the above P as a magenta dye image stabilizer.
Sample 2 was obtained in which H-13 was added in the same molar amount as the magenta coupler.

Samples 3.6.9 were obtained in the same manner, except that the magenta couplers in Sample 1 were replaced with magenta couplers A-5, A-7, and A-98 of the present invention, respectively.

In the above sample 3.6.9, PH-13 was added as the magenta dye image stabilizer in an equal molar amount to the coupler to obtain samples 4 and 7.10, respectively, and further PH-1
Samples 5 and 8.11 were obtained by adding the magenta image stabilizer HI-3 of the present invention in place of Sample No. 3 in an amount equal to that of the coupler.

Comparative coupler (1) After exposing the sample obtained above through an optical wedge according to a conventional method,
The treatment was carried out in the following steps.

[Processing process] Processing temperature Processing VF dark color development 33℃ 3 minutes 30 seconds Bleach fixing
Wash with water at 33℃ for 1 minute and 30 seconds
33°C 3 divisions drying 50-80
℃ 20 The components of each treatment solution are as follows.

[Color developer]

Bennol alcohol 12. Q diethylene glycol io, potassium 1 carbonate 25g sodium bromide
0.6g anhydrous sodium sulfite
2.0g hydroxylamine sulfate
2.58N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-7mino7niline sulfate 4.5g Water was added to make IQ, and the pH was adjusted to 10.2 with NaOH.

[Bleach-fix solution]

Ammonium Naosulfate 120g Sodium metabisulfite 158 Anhydrous sodium sulfite 3g EDTA ferric ammonium salt 65g Add water to adjust to IQ and adjust pH to 6.7
Adjusted to ~6.8.

The concentrations of Samples 1 to 11 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 irradiated with a xenon 7-ade meter for 10 days to examine the light fastness of the dye image and the Y-stin 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.

〔Survival rate〕

Percentage of dye remaining after exposure to light and moisture resistance test for initial density of 1.0.

[YS]

From the concentration of Y-steine after light resistance and moisture resistance tests, it was determined that
The value after subtracting the concentration of Y-stin before the moisture resistance test.

[Degree of discoloration]

(Yellow density) after light emission test at initial density 1.0/
(magenta density) to (yellow density) before light test /
(magenta density), the larger this value is, the more yellowish the magenta becomes. As shown, sample 3.6.9 prepared using the coupler of the present invention is a conventional 4-equivalent type 3-
Compared to Sample 1 prepared using a 7nilino 5-pyrazolone type coupler, it can be seen that Y-stain is extremely less likely to occur in the light fastness and humidity tests; It can be seen that the color easily changes and fades when exposed to light. Samples 4, 7, and 10 were prepared by using the coupler of the present invention in combination with the well-known magenta dye image stabilizer PH-13, which certainly prevented the dye image from fading due to light. is significantly improved, but discoloration cannot be improved.

On the other hand, in samples 5 and 8.11 prepared using the coupler and dye image stabilizer of the present invention, the color change and fading of the dye image were small in the resistance test against light, heat, and humidity, and the Y - It turns out that Stin also doesn't occur.

This is a combination of a conventional 4-equivalent type 3-7-nili-7-5-pyrazolone coupler and a dye image stabilizer (sample 2).
) could not have been done.

Example 2 The coupler and magenta dye image stabilizer combinations shown in Table 2 were coated exactly as in Example 1, and sample 1
2 to 27 were created. Samples 12-27 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.

Comparative coupler (2) Table 2 (In Table 2, Samples 25, 26 and 27 used a HI compound and a PH compound in a molar ratio of 2:1, and the total amount of dye image stabilizer was the same as that of other samples. The number of moles is the same as that of the dye image stabilizer used in
When the magenta dye image stabilizer of the present invention is used in combination with a 4-equivalent type 3-7 nilino-5-pyrazolone coupler (Samples-12 and 13), and when the magenta dye image stabilizer conventionally commonly used in the coupler of the present invention is used. When used together with a chemical agent (
Samples 16, 17, 18, 19) showed discoloration and fading in the light test, Y-stain in the uncolored area, and Y-stain in the moisture resistance test.
It can be seen that it is not possible to improve all stains, and that all of the above-mentioned improvements can only be achieved by using the coupler of the present invention in combination with the magenta dye image stabilizer of the present invention.

Further, when the coupler of the present invention is used in combination with the dye image stabilizer of the present invention and a conventional dye image stabilizer (Sample-25,
26, 27), the degree of discoloration in the light test increases slightly, but the phase-opening effect due to combined use is clearly recognized in terms of survival rate.

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 28 was obtained.

1st layer: blue-sensitive silver halide emulsion layer α-pivaloyl-a-(2,4
-dioxo-1-bennolimidazolidin-3-yl)
6.8 m
g/100cm2, blue-sensitive silver chlorobromide emulsion (silver bromide 85
(containing mol%) converted to silver is 3.2+H/100cm
2. Dibutyl 7 tallate at 3.5+H/100c+s
2 and gelatin: /wo 13.5B/100cm2 coating amount.

2nd layer: middle layer 2.5-not-t-octylhydroquinone at 0.5ta
g/100cm+2, 0.5m of dibutyl 7 tallate
g/100cTa” and gelatin at 9.0mg/10
The coating was applied so that the concentration was 0ca2.

Third layer: green-sensitive silver denride emulsion layer containing the magenta coupler A-36 at 3.5111g/100CI112
, green-sensitive silver chlorobromide emulsion (containing 80 mol% silver bromide) in terms of silver is 2.5 B/100 cm2, dibutyl 7-thalet is 3.0 + ag/100 cm2, and gelatin is 12
．． The coating was applied so that the weight was 0II1g/100cn+2.

14th layer: Intermediate layer UV absorber 2-(2-hydroxy-3-see-butyl-5-t-butylphenyl)benzotriazole 7.0 mg 7100 cm2, di-butyl 7 talate 6
．． 0mg/100cm'', 2,5-cy, monooctylhydroquinone at 0.5a+H/10100e, and gelatin at 12.O+ng/100cm2.

5th layer: Red-sensitive silver halide emulsion layer 2-[α-(2,4-not-pentyl 7ethyl 7ethyl)butanamide]-4,6-dichloro-5-ethyl 7ethyl as cyan coupler 4.2mg/100e I
II 2, red-sensitive silver chlorobromide emulsion (containing 80 mol% silver bromide) in terms of silver: 3.0 mg/100 cm2, tricresyl phos-7-2, 3.5111 g/100 c111
2 and gelatin were coated to give 11.5B/100cu+2.

6th layer: Protective layer Gelatin was coated to a thickness of 8.0B/100C+A2.

In the above sample 28, the dye image stabilizer of the present invention was added to the third layer in the proportions shown in Table 3, and multilayer sample 29
-37 were prepared, exposed and processed in the same manner as in Example 1, and then subjected to a light emission test (irradiated with a xenon fade meter for 15 days). The results are summarized below.Table 3: From the results, the dye image stabilizer of the present invention is effective in stabilizing the dye image of the magenta coupler of the present invention, and as a result, the amount added is increased. It gets bigger.

In addition, Samples 29 to 37 showed extremely small discoloration of the dye images in the light emission test compared to Sample 28. Furthermore, in the sample of the present invention, the discoloration and fading of the magenta dye are extremely small, and the overall color balance with the yellow and cyan couplers as a color photographic material is good (and the color reproducibility is extremely good). .

Claims (1)

[Scope of Claims] A silver halide color photographic light-sensitive material comprising a magenta image-forming coupler represented by the following general formula [I] and a compound represented by the following general formula [II]. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. It's okay. X represents a hydrogen atom or a substituent that can be separated by reaction with an oxidized product of a color developing agent. Moreover, R represents a hydrogen atom or a substituent. ] General formula [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R^1 and R^3 are hydrogen atoms, halogen atoms, alkyl groups, alkenyl groups, alkoxy groups, hydroxy groups, aryl groups, respectively. It represents an aryloxy group, an acyl group, an acylamino group, an acyloxy group, a sulfonamide group, a cycloalkyl group, or an alkoxycarbonyl group, and R^2 is a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, a hydroxy group, an aryl group, or an acyl group. group, acylamino group, acyloxy group, sulfonamido group, cycloalkyl group or alkoxycarbonyl group. Further, R^2 and R^3 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. ]