JPS61158330A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a colored photographic material having an improved fastness against light of a Magenta colored image and an excellent color reproducibility by incorporating at least one of specific couplers contg. a nitrogen atom and at least one of specific stabilizers for a colored image contg. an oxygen atom. CONSTITUTION:The titled material contains at least one of couplers shown by formula I and at least one of the compds. shown by formula (XI). In the Magenta coupler (I), R is a substituent such as a halogen atom and a heterocyclic thio group. The halogen atom comprises a chlorine and a bromine atoms, preferably a chlorine atom. The stabilizer for a Magenta colored image joint used with the coupler has an anti-decoloring effect of the Magenta colored image against a light and also an anti-discoloring effect of the Magenta colored image against light and is the compd. shown by formula XI. The additional amount of the Magenta coupler is 1.5X10<-3>-7.5X10<-1>mol, preferably 1X10<-2>-5X10<-1>mol per 1mol of silver.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a silver halide photographic material.
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.

[Prior Art 1] Conventionally, a silver halide color photographic light-sensitive material is imagewise exposed and color developed to cause a coupling reaction between an oxidized product of an aromatic primary amine color developing agent and a color forming agent, for example. It is well known that indophenol, indoaniline, ingumin, 7zomethine, phenoxazine, 7enazine, and similar pigments are produced to form color images. 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 10 dendide color photographic light-sensitive material containing a coupler that develops a cyan color is used.

Couplers used to form the yellow image include, for example, acylacetanilide couplers, and couplers for forming magenta images include, for example, pyrazolone, virazolobenzimigzole,
Pyrazolotriazole or indacylon couplers are known, and as couplers for forming cyan images, for example, phenol or 7-tole couplers are generally used.

It is desirable that the dye image obtained in this way does not change color or fade even when 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, Y-staining due to 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 sub-absorption in the vicinity of nm 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. 1,059,994, etc.

However, the above-mentioned magenta coupler has disadvantages in 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 magenta coupler, British Patent No. 1.047,6
Virazolopengui imiguzole as described in US Pat. No. 12, Inguzolone as described in US Pat.
IH- described in No. 2,418 and No. 1,334,515
Pyrazolo(5,1-c) 1,2,4-triazole coupler, Research Disclosure No. 24,
IH-pyrazolo(1,5-b)-1 described in 531
, 2,4-triazole type coupler, Research Disclosure N.

IH-pyrazolo(1,5-c)- as described in 24.626
1,2,3-) Riazole type coupler, JP-A-59-1
No. 62548, Research Disclosure? -No.

IH-imidazo(t,z-b)- as described in 24.531
Pyrazole coupler, Research Disclosure N
IH-pyrazoel (1,5-b
) Pyrazole coupler, Research Disclosure N.

Magenta couplers such as the IH-pyrazolo(1,5-d)tetrazole type coupler described in 24, 220 have been proposed. Among these, IH-pyrazolo(5,1-c)-
1,2,4-triazole type coupler, IH-pyrazolo.

(1,5-b) -1,2,4-) lyazole type coupler, 1H-pyrazolo(1,5c) -1,2-3) lyazole type coupler, IH-imidazo(1,2-b) pyrazole type Couplers, IH-pyrazolo(1,5-d) pyrazole-type couplers and IH-pyrazolo(1,5-d)
The pigment formed from tetrazole type Kapfu is 430
1 whose subabsorption near nn has an anilino group at the 3-position
, compared to dyes formed from 2-pyrazolo-5-ones, it is more pigmented and smaller, which is preferable in terms of color reproduction, and it also has the desirable advantage of being extremely small in generating Y-stin in uncolored areas when exposed to light, heat, and humidity. It is.

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

Furthermore, JP-A-59-125732 discloses IH-pyrazolo (5,1-e) 1. L4) IH-pyrazolo(5,1-c)-1,2,4-) lyazole-type magenta coupler can be obtained by using the lyazole-type magenta coupler together with a phenol compound or a 7-functional diyl ether compound. Techniques have been proposed to improve the light fastness of magenta dye images. 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.

[Object of the Invention] The present invention has been made in view of the above-mentioned problems, and the first object of the present invention is to provide a color image that has excellent color reproducibility and that has significantly improved light fastness of magenta dye images. The purpose is to provide photographic materials.

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 by light and heat.

[Structure of the Invention J The object of the present invention is to contain at least one coupler represented by the following general formula [I] and at least one compound represented by the following general formula [XI]. This can be achieved using silver halide photographic materials.

General formula (1) 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 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 [revised] In the formula, R1 and R4 are each a hydrogen atom, a denyl atom, an alkyl group, an alkenyl group, an alkoxy group, an alkenyloxy group, a hydroxy group, a 7-aryl group, an aryloxy group, an acyl group, an acylamino group, acyloxy group,
Represents a sulfonamide group or an alkoxycarbonyl group, R2 represents a hydrogen atom, an alkyl group, an alkenyl group, a heptalyl group, an acyl group, a cycloalkyl group, or a heterocyclic group, and R' represents a hydrogen atom, a halogen atom, a furkyl group , alkenyl group, aryl group, aryloxy group, acyl group, acylamide group, acyloxy group, sulfonamide group, cycloalkyl group or alkoxycarbonyl group. Further, R2 and R3 may be ring-closed with each other to form a 5-shell or 6-membered ring, and Y represents an atomic group necessary to form a chroman or coumaran ring.

Hereinafter, unless otherwise specified, the above general formula according to the present invention [
The compound represented by [XI] is a magenta dye image.The present invention will be specifically explained below.

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, a furkyl group, a cycloalkyl group, an alkenyl group, and a cycloalkenyl group. group, alkynyl group, aryl group, heterocyclic group, 7-syl group, sulfonyl group, sulfinyl group, phosphonyl group, carbamoyl group, sulfamoyl group, cyano group, spiro compound residue, organic hydrocarbon compound residue, alkoxy group, aryl Oxy group, heterocyclic oxy group, siloxy group, acyloxy group, carbamoyloxy group, amine 7 group, acylami 7 group, sulfonamide group, imide group, ureido group, sulf 77
Examples include 7 moylamide groups, 7 alkoxycarbonylamide groups, 7 aryloxycarbonylamide groups, 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 groups and cycloalkenyl groups preferably have 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms, and the alkyl groups, alkenyl groups and alkynyl groups may be linear or branched.

In addition, these alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, and cycloalkenyl groups are substituents (e.g., aryl, cyano, halogen atoms, heterocycles, cycloalkyl, cycloalkenyl, spiro compound residues, bridged hydrocarbon compounds) In addition to residues, those substituted via a carbonyl group such as acyl, carboxy, carbamoyl, flukoxylponyl, and aryloxycarbonyl, and those substituted via a heteroatom, specifically hydroxy, alkoxy, and aryl. Oxy, heterocyclic oxy,
Those substituted via an oxygen atom such as siloxy, acyloxy, carbamoyloxy, nitro, 7mino (including noflukylamino, etc.) sul77moylamide/, alkoxycarbonylamino, aryloxycarbonylamino/,
Acylamino, sulfonomino, sulfonamide, imide, ureido, etc. substituted via nitrogen atom, alkylthio, arylthio, heterocyclic group, sulfonyl,
sulfinyl, sulfamoyl, etc., which are substituted through a sulfur atom, and phosphonyl, which is substituted through a phosphorus atom, etc.).

Specifically, for example, methyl group, ethyl group, isopropyl group, t-butyl group, pentadecyl group, heptadecyl group, 1
-hexylnonyl group, 1.1'-nobentyl7yl group,
2-chloro-t-butyl group, tri7fluoromethyl group, 1
-Ethoxytridecyl group, 1-methoxyisopropyl group, methanesulfonylethyl group, 2,4-di-t-7milphenoxymethyl group, anilino group, 1-phenylisopropyl group, 3-Ill-butanesulfonamino 71/ xypropyl group, 3-4'-iα-(4"(p-hydroxybenzenesulfonyl)phenoxy]dodecanoylamino)phenylpropyl group, 314'-(α-(2", 4
"-dimo-amylphenoxy)butanamido]phenyl)-propyl group, 4-[Q-(.

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

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

Specifically, 7enyl group, 4-t-butyl 7enyl group,
2,4-not-7 milphenyl group, 4-tetradecanamidophenyl group, hexadecyloxyphenyl group, 4'
-[α-(4″-t-butylphenoxy)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-thiacyl group, 2-pyrimidinyl group, and 2-benzothiazolyl group.

Examples of the acyl group represented by R include an acetyl group, a phenyl 7cetyl group, a dodecanoyl group, a fulkylcarbonyl group such as a-2,4-cy-monoamylphenoxybuta/yl group, a benzoyl group, and a 3-pentyl group. Examples include 7-aryl carbonyl groups such as decyloxybenzoyl 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-toluenesulfonyl group.

Examples of the sulfinyl group represented by R include an ethylsulfinyl group, an octylsulfinyl group, an alkylsulfinyl group such as a 3-phenoxybutylsulfinyl group, a phenylsulfinyl group, and a 7-arylsulfinyl group such as a m-pentadecylphenylsulfinyl group. Can be mentioned.

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

The carbamoyl group represented by R may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc.
For example, N-methylhydronimoyl group, N,N-butylcarbamoyl group, N-(2-pentadecyloctylethyl)carbamoyl group, N-ethyl-N-dodecylcarbamoyl group, N-13-(2,4-didecylcarbamoyl group) The sulfamoyl group represented by R (-t-7 milphenoxy)propyl) may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as an N-propylsulf 77 moyl group, N,N- Examples include butylcarbamoyl group, N-(2-pentadecyloxyethyl N-ethyl-N-dodecylsulfamoyl group, N-phenylsulfamoyl group), and the like.

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

Examples of the carbonized compound residue represented by R include bicyclo[2.2.1]heptan-1-yl, tricyclo[3
, 3,1.1''']decane-1-yl, 7,7-tumethyl-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 is preferably 7enyloxy, and the aryl nucleus may be further substituted with any of the substituents or atoms listed above for the aryl group,
Examples include phenoxy group, pt-butylphenoxy group, and trans-becitadecylphenoxy group.

The heterocyclic oxy group represented by R preferably has a 5- to 7-membered heterocycle, and the heterocycle may further have a substituent (for example, 3.

4, 5.6-tetrahydropyranyl-2-oxy group, 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-dimethylbutylsiloxy group, and the like.

The acyloxy group represented by R includes, for example, an alkylcarbonyloxy group, an arylcarbonyloxy group, etc., and may further have a substituent, specifically an acetyloxy group, an a-chloroacetyloxy group, etc. , benzoyloxy group, etc.

The carbamoyloxy group represented by R may be substituted with an alkyl group, an ester group, etc. (e.g., N-ethylcarbamoyloxy group, N,N-noethylcarbamoyloxy group, N7zylcarbamoyloxy group). etc.

The amide group represented by R may be substituted with an alkyl group, an aryl group (preferably a 7enyl group), etc., such as ethylamino group, anilino group, m-chloroanily group, 3-pentadecyloxy group, etc. Luponylanili 7 groups, 2-
Examples include 7 chloro-5-hexadecaneamide aniline groups.

Examples of the acylamine 7 group represented by R include alkylcarbonyl 7 groups, arylcarbonyl 7mino groups (preferably phenylcarbonyl 7 groups), and may further have a substituent, specifically, acetamide. group, α-ethylpropanamide group, N-7x nylacetamide group,
Examples include a dodecane 7mido group, a 2,4-di-amylphenoxyacetamide group, and an α-3-t-butyl 4-hydroxyphenoxybutanamide group.

Examples of the sulfone 7mide group represented by R include an alkylsulfonylamino group, an arylsulfonyl 7mide group, and may further have a substituent.

Specifically, 7 methylsulfonylamino groups, pentadecylsulfonylamino groups, benzenesulfonamide groups, p-)
Examples include a luenesulfonamide group and a 2-methoxy-5-t-7 milbenzenesulfonamide 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 a furkyl group, an aryl group (
Preferred examples include N-ethylureido group, N-methyl-N-decylureido group, N-phenylureido group, and N-p-)lylureido group.

The sul77moyl7mi7 group represented by R is a furkyl group,
It may be substituted with an aryl group (preferably a phenyl group), and examples thereof include N, N-diptylsul77moyl7mino group, N-methylsul77moyl7mino group, N-phenylsul77moyl7mino group, etc. It will be done.

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

The aryloxycarbonylamide group represented by R may have a substituent, and examples thereof include phenoxycarbonyl group and 4-methylphenoxycarbonyl group.

The flukoxycarbonyl group represented by R may further have a substituent, such as methoxycarbonyl s, butyloxycarbonyl group, dodecyloxycarbonyl group, octadecyloxycarbonyl group, ethoxymethoxycarbonyloxy group, benzyloxycarbonyl group. Examples include groups.

The 7-aryloxycarbonyl group represented by R may further have a substituent, for example, a 7-enoxycarbonyl group,
Examples thereof include p-chlorophenoxycarbonyl group, p-pentadecyloxyphenoxycarbonyl 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-phenoxypropylthio group.

The arylthio group represented by R is preferably a 7enylthio group and may further have a substituent, such as a phenylthio group,
Examples include p-methoxyphenylthio group, 2-t-octylphenylthio group, 3-octadecylphenylthio group, 2-carboxyphenylthio group, and p-acetaminophenylthio group.

The heterocyclic thio group represented by R is preferably a 5- to 7-shell heterocyclic thio 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-)lyazole-6-thio group.

Examples of substituents that can be separated by reaction with the oxidized product of the color developing agent represented by Examples include groups substituted via.

Groups substituted via a carbon atom include, in addition to carboxyl groups, for example, those of the general formula (R'1 has the same meaning as R, Z' has the same meaning as Z, R2' and R3' are hydrogen atoms, aryl group, an alkyl group, or a heterocyclic group), a hydroxymethyl group, and a tri7enylmethyl group.

Examples of groups substituted via an oxygen atom include an alkoxy group, an aryloxy group, a heterocyclicoxy group, an acyloxy group, a sulfonyloxy group, an alkoxycarbonyloxy group, a 7-aryloxycarbonyl group, a furkyloxalyloxy group, and an alkoxyoxalyloxy group. Examples include groups.

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

The 7-aryloxy group is preferably a phenoxy group, and the aryl group may further have a substituent. Specifically, 7enoxy group, 3-methylphenoxy group, 3-
Dodecyl 7enoxy group, 4-7thanesulfone 7midophenoxy group, 4-[α-(3'-pentadecylphenoxy)butanamido]phenoxy group, hexidecylcarbamoylmethoxy group, 4-cyanophenoxy group, 4-methanesulfonylphenoxy group group, 1-7tyloxy group, p-
Examples include methoxyphenoxy group.

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

The acyloxy group includes, for example, an acetoxy group, a fulkylcarbonyloxy group such as a butazuroxy group, an alkenylcarbonyloxy group such as a cinnamoyloxy group,
Examples include a 7-alcarbonyloxy group 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 7-aryloxycarbonyl group include a 7-ethyloxycarbonyloxy group.

Examples of the alkyloxalyloxy group include a methyloxalyloxy group.

Examples of the alkoxyoxalyloxy group include an ethoxyoxalyloxy group.

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

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

The 7-arylthio group includes a 7enylthio group, 4-methanesulfonamidophenylthio group, 4-dodecyl7enethylthio group, 4-nonafluoropencunamido7enethylthio group, 4-carboxyphenylthio group, 2-ethoxy-5- Examples include t-butylphenylthio group.

Examples of the heterocyclic thio group include 1-722-1.
2.3.4-tetrazolyl-5-thio group, 2-benzothiazolylthio group, and the like.

Examples of the alkyloxythiocarbonylthio group include dodecyloxycarbonylthio group.

Examples of the group substituted via the nitrogen atom include those represented by the general formula -N, such as an aryl group, a heterocyclic group, a sulfonyl group, a carbamoyl group, a sulfonyl group, a sulfonyl group, and an aryl group. It represents an oxycarbonyl group or an alkoxycarbonyl group, and R4' and R5' may be combined to form a petero ring. However, R1' and R5
' cannot both be hydrogen atoms.

The furkyl 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, 7syl 7mi 7 group, sulfonamide group, imino group, acyl group, furkylsulfonyl group, arylsulfonyl group,
Examples include carbamoyl group, sulfamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkyloxycarbonylamine group, aryloxycarbonylamino group, hydroxyl group, carboxyl group, cyano group, and halogen atom.

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

The aryl group represented by R4' or R9' 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 the substituent for the alkyl group represented by R1' or R, and the alkyl group. Specific examples of the aryl group include a phenyl group, a 1-su7tyl group, and a 4-methylsulfonylphenyl group.

The heterocyclic group represented by R4' or R5' is 5 to 6
Shellfish are preferred, and may be a condensed ring or have a substituent. Specific examples include 2-furyl group, 2-quinolyl group, 2-biriminol group, 2-benzothiazolyl group, and 2-bilinol group.

The sulfamoyl group represented by R1' or R5' includes N-furkylsulfamoyl group, N,N-dialkylsulfamoyl group, N-7lylsulfamoyl group, N-furkylsulfamoyl group,
, N-diarylsul 7T moyl group, etc., and these alkyl groups and 7 aryl groups may have the substituents listed above for the alkyl group and aryl group. Specific examples of the sulfamoyl group include, for example: N, N-diethylsulfamoyl group, N-methylsulfamoyl group, N
-dodecylsulfamoyl group, N-p-)lilsul 77
A moyl group is mentioned.

As the carbamoyl group represented by R1' or R, /,
N-furkylcarbamoyl group, N,N-dialkylcarbamoyl group, N-7lylcarbamoyl group, N,N-noarylcarbamoyl group, etc., and these alkyl groups and aryl groups are the same as those mentioned for the furkyl group and aryl group. may have other substituents. Specific examples of carbamoyl groups include N,N-noethyl carbamoyl group, N-methylcarbamoyl group, N-dodecylcarbamoyl a, N-p-thia/phenylcarbamoyl i, N
-p-)lylcarbamoyl group.

Examples of the acyl group represented by R1' or R5' include an alkylcarbonyl group, an arylcarbonyl group, and a heterocyclic carbonyl group, and the alkyl group, aryl group, and heterocyclic group have a substituent. It's okay. Specific examples of the acyl group include hexafluorobuta/yl group, 2゜3.4.5.6-pentafluorobenzoyl cetyl group, benzoyl group, naphthonyl group, 2-
Examples include furyl carbonyl group.

Examples of the sulfonyl group represented by R,' or RS' 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 p-chlorobenzenesulfonyl group, and the like.

The aryloxycarbonyl group represented by R4' or R,' may have any of the substituents listed above for the aryl group, and specific examples thereof include a 71-dicarbonyl group and the like.

The alkoxycarbonyl group represented by R4' or R9' may have the substituents listed for the alkyl group (
Specific examples include methoxycarbonyl group, dodecyloxycarbonyl group, benzyloxycarbonyl group, and the like.

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, or,
It may be a condensed ring. Examples of the heterocycle include N-7 thalimide group, N-succinimide group, 4-N-urazolyl group, 1-N-hyguntoynyl group, 3-N-2,4-dioxoxacylinonyl group, 2- N-1,1-dioxo-
3-(2H)-oxo-1,2-benzthiazolyl group,
1-pyrrolyl group, 1-pyrrolinonyl group, 1-pyrazolyl group, 1-pyrazolinonyl group, 1-piperinonyl group, 1-
Pyrrolinyl group, 1-imidazolyl group, 1-imidazolinyl group, 1-indolyl group, 1-isoindolinyl group, 2
-isoindolyl group, 2-isoindolinyl group, 1-benzotriazolyl group, 1-pencyimigzolyl group, 1-
(1,2,4-)riazolyl) group, 1-(1,2,3-
) riazolyl) group, 1-(1,2,3,4-tetrazolyl) group, N-morpholinyl group, 1,2,3.4-tetrahytomyquinolyl group, 2-oxo-1-pyrrolidinyl group,
2-IH-pyridone group, 7thalathion group, 2-oxo-
These heterocyclic groups include alkyl groups, aryl groups, alkyloxy groups, aryloxy groups, acyl groups, sulfonyl groups, alkylamino groups, arylami 7 groups, 7 silami 7 groups, sulfone 7 groups, etc. Mi7
group, carbamoyl group, sul77 moyl group, alkylthio group, arylthio group, ureido group, narkoxycarbonyl group, aryloxycarbonyl group, imido group, nitro group, cyano group, carboxyl group, halogen atom, etc. good.

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

In addition, the substituents (for example, R1R5 to R1) on the heterocycle in general formula CI) and general formulas (If) to [■] described below 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 general formula (V), R9 and R6 are fused, and in general formula (Vl), R2
and R, are bonded to each other to form 11 (e.g., 5-7 true cycloalkene, benzene) represented by the general formula [I], more specifically, for example, the following general formulas (II) to [ ■
].

General formula (II) General formula (III) General formula (IV) -N-88 General formula (V) General formula (Vl) N -N -NO General formula [■] To the above general formula (U) to [■] In this case, R5 to R8 and VX have the same meanings as R and X above.

Moreover, among the general formula (I), the following general formula [
■].

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

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

Regarding the substituents on the heterocycle in general formulas (1) to [■], R in general formula CI) and R1 in general formulas (n) to [■] satisfy the following condition 1. It is preferable that the following conditions 1 and v2 are satisfied, and it is particularly preferable that the following conditions 1.2 are satisfied.
and 3 are satisfied.

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

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

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

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

General formula ([) % formula % In the formula, RIIRIO and R11 are each a hydrogen atom, a halogen atom, a furkyl group, a dichlorofurkyl group, a fulkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group,
Heterocyclic group, 7-syl 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, 7sil7mi7 group, sulfonamide group, imide group, ureido group, sulfonamido group, sulfonamide group, 7moylamide group, alkoxycarbonyl7mi7 group, aryloxycarbonyl7 group
represents an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylthio group, a 7lylthio group, a heterocyclic thio group, and at least two of R39R3° and R11
One is not a hydrogen atom ~1° Also, the above R,,R,. and two of R8, for example Rs and RI6, may be bonded to form a saturated or unsaturated ring (e.g. dichloroflucan, cycloalkene, heterocycle), and R11 may be further bonded to the ring to form a bridged carbonized ring. The group represented by 6 R9 to R11 which may constitute a hydrogen compound residue may have a substituent, and the following are specific examples of the group represented by R8 to R,-2 and Examples of the substituent that may be used include specific examples of the group represented by R in the above-mentioned general formula (1) and the V substituent.

Also, for example, a ring formed by combining R3 and R10, and R,
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 general formulas (IX), (i) Rq~
When two of R1 are alkyl groups, (ii) R=~R
When one of 1, for example R1, is a hydrogen atom, and the other two R, and R16 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, to Rll are alkyl groups, and one of the groups is a hydrogen atom or an alkyl group.

Here, the alkyl and cycloalkyl may further have a substituent, and specific examples of the alkyl, cycloalkyl and their substituents include the alkyl, cycloalkyl and their substituents represented by R in the general formula (1). Specific examples of the group are listed below.

■ nm CH3 C2) 1° 4H9 12H25 4H9 12H25 CF+3 C2H3 151131 I3 CH.

3 days 0CH2CONHCl (2CH20CIIi0CH2C
H2SO2CH3 2H5 C6H13 C)13 CH3 QC2II.

CH3 CH3 1 (3CCH3 7.5 N -N -N N -N -N N C, Hl ■ ■ N -N -NH Also, the synthesis of the above coupler is published in the Journal of
theChe+eical 5ociety t P
erkin I (1977) t2047-205
2. U.S. Patent No. 3,725,067, JP-A-59-99
The synthesis was carried out with reference to No. 437 and Japanese Patent Application Laid-Open No. 58-42045.

The couplers of the invention typically contain 1Xl per mole of silver halide.
0-' moles to 5 x 10' moles, preferably 1 x 10-' moles
It can be used in a range of 2 mol to 5 x 10-' mol.

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

Furthermore, when the silver halide photographic material according to the present invention is used as a multicolor photographic material, in addition to the coupler of the present invention, yellow couplers and cyan couplers commonly used in this industry are used in the usual manner. be able to. Furthermore, a colored coupler having a color correction effect may be used if necessary. The above couplers can be used in combination of two or more types in the same layer in order to satisfy the characteristics required of a photosensitive material, or the same compound can be used in two or more different layers in combination with the coupler related to the present invention. The image stabilizer is a compound represented by the following general formula [XI], which not only has the effect of preventing the magenta dye image from fading due to light but also has the effect of preventing discoloration due to light.

General formula (XI) (wherein R1 and R4 are a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkenyloxy group, a hydroxy group, an aryl group, an aryloxy group, an acyl group, an acylamine/group, and an acyloxy group, respectively) R2 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an acyl group, a cycloalkyl group, or a heterocyclic group; R3 represents a hydrogen atom, a halogen atom,
It represents an alkyl group, an alkenyl group, an aryl group, a 7-aryloxy group, an acyl group, an acylamide 7 group, an acyloxy group, a sulfonamide group, a cycloalkyl group, or an alkoxycarbonyl group.

Each of the groups listed above may be substituted with other substituents. For example, alkyl group, alkenyl group, alkoxy group, aryloxy group, hydroxy group, alkoxycarbonyl group, aryloxycarbonyl group, acylamide 7
group, carbamoyl group, sulfonamide group, sul77moyl group, and the like.

Further, R2 and R3 may be ring-closed with each other to form a 5-shell or 6-shell ring. Further, R12 and R13 may be ring-closed to form a methylenedioxy ring.

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

The chroman or coumaran ring may be substituted with /10 dene atoms, alkyl groups, cycloalkyl groups, alkoxy groups, alkenyl groups, alkenyloxy groups, hydroxy groups, aryl groups, aryloxy groups or heterocycles,
Furthermore, a spiro ring may be formed.

Among the compounds represented by the general formula [(3)], the compounds particularly useful in the present invention are the general formula (XI) and CXI[I].

It is included in the compounds represented by (XIV), (XV) and (XVI).

General formula [■] General formula (XI[[) General formula [x■] General formula (XV) General formula (XVI) General formula (XI[), (XI[[), (XIV) (XV)
and R l , R2, R3 and R in (XV[)
4 has the same meaning as in the above general formula [(3)], and Rst R'tR7, R', R' and R'' are hydrogen atoms, -) rodene atoms, alkyl groups, alkoxy groups, hydroxy groups, 7 alkenyl group, alkenyloxy group, aryl group, a I - + l less, less ζ I / l ÷ hekoguchida s + husband t
, Furthermore, R5 and R6, R6 and R7, R7 and R8, R8 and R@, and R9 and R10 may be cyclized with each other to form a carbocycle, and furthermore, the carbocycle may be substituted with an alkyl group. good.

The general formula [u], (XI [[), (XIV) (XV)
and (XVI), R1 and R4 are hydrogen atoms, alkyl groups, alkoxy groups, hydroxy groups or cycloalkyl groups, R2 and R3 are hydrogen atoms, alkyl groups, cycloalkyl groups, RS, Rs, R', R', R9 Particularly useful are compounds in which RIO is a hydrogen atom, an alkyl group, or a cycloalkyl group.

Typical specific examples of these compounds are shown below, but these limit the compounds used in the present invention. H3 B-6) B-7) B-8) B-9) B-11> CI.

B-12>B-13> B-14) B-15) B-16) B-17) C view B-18) B-19) B-20) B-21) B-22) B-23) B-24) B-25) B-26) B-27) B-28) B-29) B-30) B-31) B-32) B-33) B-34) B-41) B- 45) B-46) B-47) nt+ B-48) B-49) B-51) B-52) HB-53) C3H7 B-54) The magenta color image stabilizer according to the present invention includes: Tera
herdron * 1970 r vol 26 +
pp. 4743-4751, Journal of the Chemical Society of Japan, 1972,
No. 10. 1987-1990, cheIll,
Lett, 1972 (4) 315-316
JP-A No. 55-139383, and can be synthesized according to the methods described therein.

In the color photographic material of the present invention, the amount of the magenta coupler according to the present invention added is 1.5X per mole of silver.
A range of 10-1 mol to 7.5X 10-' mol is preferred, more preferably 1xto-2 mol-5X10-'
It is in the molar range.

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

In the color photographic material of the present invention, the magenta dye image stabilizer according to the present invention is further added to the following general formula [X
(2) Other magenta dye image stabilizers shown in 1, ie, phenol compounds and phenyl ether compounds, can also be used in combination.

General formula [X■1 In the formula, R1 is a hydrogen atom, an alkyl group, alkeni/14,
Represents an aryl group or a heterocyclic group, R12, R'', R
'5 and R'6 each represent a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group, an alkenyl group, an aryl group, an alkoxy group, or an acylamide group, and R1 represents an alkyl group, a hydroxy group, an aryl group, or an alkoxy group. . Alternatively, R'' and R'2 may be ring-closed with each other to form a 5-shell or 6-shell ring, in which case R1 represents a hydroxy group or an alkoxy group. An oxy ring may be formed.

Furthermore, R'3 and R14 may be ring-closed to form five hydrocarbon rings, in which case R1 represents an alkyl group, an aryl group, or a heterocyclic group. However, the case where R'' is a hydrogen atom and R14 is a hydroxy group is excluded.

In the general formula [X■], R11 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group, and examples of the alkyl group include, for example, a methyl group, an ethyl group, a propyl group, and an n-octyl group. , a tert-octyl group, a benol group, a hexadecyl group, and other linear or branched alkyl groups. Moreover, this alkyl group may have a substituent. Also R 1
Examples of the alkenyl group represented by 1 include 7lyl,
Examples include hexenyl and octenyl groups. Furthermore, R
Examples of the 7-aryl group include phenyl and naphthyl groups. This 7-aryl group can have a substituent, and specific examples include a methoxyphenyl group and a chloro-7enyl group. can.

Furthermore, the heterocyclic group represented by R'' and 1. specifically include a tetrahydropyranyl group, a pyrimidyl group, and the like.

In the general formula [X■], R'2, R'3, R'' and R
``represents a hydrogen atom, a halogen atom, a hydroxy group, a furkyl group, an alkenyl group, an aryl group, an alkoxy group, or an acylamino group. , alkenyl group, and aryl group.

Further, examples of the halogen atoms include fluorine, chlorine,
Examples include bromine. Further, specific examples of the alkoxy group include a methoxy group, an ethoxy group, a benzyloxy group, and the like. Further, the acylamide 7 group is represented by R'NHCO-, where R'
is an alkyl group (e.g. methyl, ethyl, n-propyl,
lobutyl, n-octyl, tert-octyl, benzyl, etc.), alkenyl groups (e.g., allyl, octenyl, oleyl, etc.), aryl groups (e.g., phenyl, methoxyphenyl, naphthyl, etc.), or hetyl groups It can represent a cyclic group (eg, pyridyl or pyrimidyl group).

Furthermore, in the general formula [X I can name specific things. Further, regarding the 8-unit alkenyl group, the al mentioned above for R12, R'co, RI5 and R16.

Among the phenolic compounds or phenyl ether compounds represented by the general formula [X1] used in combination with the pyrazolotriazole type magenta coupler of the present invention, particularly preferred are those that are the same as the xy group. is a tetraalkoxyvining compound and can be represented by the following general formula [X■].

General formula [X
hexadecyl), alkenyl groups (e.g. allyl, octenyl, oleyl), aryl groups (e.g. phenyl,
(naphthyl) or a heterocyclic group (eg, tetrahydropyranyl, pyrimidyl). R′7 and RI″ each represent a hydrogen atom, a halogen atom (e.g., fluorine, chlorine, bromine), an alkyl group (e.g., methyl, ethyl, n-butyl, benol), an alkenyl group (e.g., allyl, hexenyl, octenyl), or an alkoxy a group (e.g. methoxy, ethoxy, pencyloxy, R1
9 is a hydrogen atom, an alkyl group (e.g. methyl, ethyl, n
-butyl, benzyl), alkenyl groups (for example 2-propenyl, hexenyl, octenyl), and Ji717-yl groups (for example phenyl, methoxy7enyl, chlorphenyl, naphthyl).

The compound represented by the general formula [X■1] is disclosed in U.S. Pat.
, No. 935,016, No. 3,982,944, No. 4,
No. 254,216, JP-A No. 55-21004, No. 54
-145530, British Patent Publication No. 2.077.455, British Patent Publication No. 2,062,888, U.S. Patent No. 3,764,33
No. 7, No. 3,432,300, No. 3,574,627
No. 3,573,050, JP-A-52-15222
No. 5, No. 53-20327, No. 53-17729,
No. 55-6321, British Patent No. 1,347,556,
Publication No. 2.086,975, Special Publication No. 54-12337
No. 48-31625, U.S. Patent No. 3,700,45
It also includes compounds described in No. 5 and the like.

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

H-1 Cl yo H-4 H-5 PH-6 PH-7 PH-〇H-10 H-11 ■ H-12 ■ H-13 H-14 H PH H-15 PH-16 PH -17 H3 H-18 PH-22 PH-23 H-24 H-25 C)l, cu= H-26 H-28 H-29 H-30 H-31 H-32 In the above general formula [X■] The 7-functional compound or phenyl ether compound represented by
It is preferably used in an amount of 00 mol% or less, more preferably 140 mol% or less.

The phenol compound and 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 the phenyl ether compound in the magenta dye image stabilizer of the present invention.

In general, the magenta dye image obtained from the magenta coupler exhibits severe discoloration when exposed to light, or is significantly discolored by light, and the color tone of the dye image changes from magenta to yellowish. The magenta dye image stabilizer represented by the general formula [XI] of the present invention is a fish that can prevent the fading and discoloration of the magenta dye image obtained from the magenta coupler due to light, and the stabilizer is a fish that can prevent the magenta dye image obtained from the magenta coupler from fading and discoloration due to light. It has an effect that cannot be achieved with magenta dye image stabilizers made of based compounds and phenyl ether compounds.

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, for example, a color negative film, a one-positive film, or a color photographic paper. The effects of the invented method are effectively exhibited.

The silver halide photographic light-sensitive materials of the present invention, including this color photographic paper, may be for single color or multicolor.In the case of multicolor silver halide photographic materials, subtractive color reproduction is possible. In order to carry out this process, a silver halide emulsion layer containing magenta, yellow, and cyan couplers as photographic couplers usually has a structure in which 1 and a non-light-sensitive layer are laminated on a support in an appropriate number and order of layers. However, the calendar number and layer order 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, and ammonia method. The particles may be grown all at once, or may be grown after seed particles are created. Seed particle (
The method of growing and the method of growing may be the same or different.

In the silver halide emulsion, halide ions and silver ions may be mixed simultaneously, or one may be mixed in the presence of the other. Alternatively, the growth may be carried out by sequentially and simultaneously adding halide ions and silver ions while controlling the l)HvPAg in the mixing pot, taking into account the critical growth rate of /10 silver denride crystals. Converge 5 after growth
The silver halide composition of the grains may be varied using a method of oxidation.

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

The silver halide grains used in the silver halide emulsion of the present invention are prepared in the process of forming and/or growing the grains such as cadmium salt, zinc salt, subsalt, thallium salt, iridium salt or complex salt, rhodium salt or complex salt. , iron salts or complex salts,
Metal ions can be added to the inside of the particles and/or on the surface of the particles, and metal ions can be added to the inside of the particles and/or on the surface of the particles. can.

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

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

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

The silver halide grains used in the silver halide emulsion of the present invention may have a regular crystal shape or may have an irregular crystal shape such as a spherical shape or a plate shape. Any ratio between the (100) plane and the (1113 plane) can be used.

In addition, the particles may have a composite form of these crystal forms (or particles of various crystal forms may be mixed).

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

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

The silver halide emulsion of the present invention can be optically sensitized to a desired wavelength range using a dye known as a sensitizing dye in the photographic industry. The sensitizing dye may be used alone or in combination of two or more, and together with the sensitizing dye, it may be a dye that itself does not have a spectral sensitizing effect, or a compound that does not substantially absorb visible light. In addition, a supersensitizer that enhances the sensitizing action of the sensitizing dye may be included in the emulsion.

The silver halide emulsion of the present invention includes steps for producing light-sensitive materials,
During chemical ripening, and/or at the end of chemical ripening, and/or after the end of chemical ripening, silver halide is used to prevent capri during storage or photographic processing, and/or to maintain stable photographic performance. Compounds known in the photographic industry as anti-capri agents or stabilizers can be added before coating the emulsion.

It is advantageous to use gelatin as the bangu (or protective colloid) in the silver halide emulsion of the present invention, but
In addition, hydrophilic colloids such as gelatin derivatives, graft polymers of gelatin and other polymers, proteins, sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymer substances such as single or copolymers can also be used.

The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material using the silver halide emulsion of the present invention can be formed by using a hardening agent alone or in combination to crosslink the baingu (or protective colloid) molecules and increase the film strength. It is hardened. It is desirable to add the hardening agent in an amount that can harden the photosensitive material to such an 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 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 9-phenylenenoamine 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 j!I); examples of magenta dye-forming couplers include 5-pyrazolone cab, ra, and pyrazolo in addition to the couplers of the present invention; benzimidazole coupler,
Examples include pyrazolotriazole and open-chain acylacetamide couplers, and examples of cyan dye-forming couplers include lotus 7 toll couplers and phenol couplers.

These dye-synthesizing couplers preferably have a group called a ballast group in the molecule, which makes the coupler non-diffusive and has 8 or more carbon atoms. 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. It can be appropriately selected depending on the chemical structure of the hydrophobic compound. The oil-in-water emulsion dispersion method can be applied to conventionally known methods for dispersing hydrophobic additives such as couplers, and is usually mixed with a high boiling point organic solvent having a boiling point of about 150°C or higher, and if necessary, a low boiling point and/or Dissolve it in combination with a water-soluble organic solvent, use a surfactant in a hydrophilic paint such as an aqueous gelatin solution, and use a dispersion means such as a stirrer, homogenizer, colloid mill, 70-noet mixer, or ultrasonic device. After the emulsification and dispersion, a step of removing the low-boiling organic solvent may be added at the same time as the dispersion or dispersion, which may be added to the desired hydrophilic colloid layer.

Examples of high boiling point oils include phenol derivatives that do not react with the oxidized form of the developing agent, heptatarates, phosphates, citricates, benzoates, alkylamides,
Boiling point of fatty acid ester, trinosinate, etc. 150
An organic solvent having a temperature of ℃ or higher is used.

7-ionic active agents, 7-ionic surfactants, Cationic surfactants 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 anti-capri agents are used to prevent deterioration and noticeable graininess.

The anti-capri 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.

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 capri due to discharge caused by charging of the photosensitive material due to friction, etc., and to prevent image deterioration due to UV light. It 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 an anti-halation layer.

These layers and/or the emulsion layer may contain dyes that flow out of the color light-sensitive material or are bleached during development.

The silver halide emulsion layer and V/or other hydrophilic colloid layer of the silver halide photosensitive material using the silver halide emulsion of the present invention are added to reduce the gloss of the photosensitive material and improve the addability.
A matting agent can be added to prevent 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 light-sensitive material using the silver halide emulsion of the present invention.

Antistatic agents are sometimes used in the antistatic layer on the side of the support on which the emulsion is not laminated, or they are used to protect the emulsion layer and/or the side other than the emulsion layer on which the emulsion layer is laminated with respect to the support. It may also be used in a colloid layer.

The photographic emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material using the silver halide emulsion of the present invention may include improved coatability,
Antistatic, improved slipperiness, emulsification and dispersion, prevention of adhesion, and (
Various surfactants are used for the purpose of improving photographic properties (such as accelerating development, increasing contrast, sensitization, etc.).

The photographic emulsion layer of the light-sensitive material using the silver halide emulsion of the present invention, and other layers include a baryta layer or an α-olefin polymer, a visible reflective support such as paper laminated with a synthetic paper, cellulose acetate, cellulose nitrate, etc. ,polystyrene,
It can be applied to films made of semi-synthetic or synthetic polymers such as polyvinyl chloride, polyethylene tere-7-thalerate, polycarbonate, and polyamide, as well as rigid bodies such as lath, 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 additives to improve adhesion, antistatic properties, dimensional stability, abrasion resistance, hardness, anti-scratch properties, friction properties, and/or other properties directly or on the surface of the support. It may be applied through a subbing 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. Silane coatings and curtain coatings are particularly useful.

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 7-lights, xenon flash lamps, cathode ray tube flying spots, various laser lights, light emitting diode lights, electron beams, and X-rays. Any known light source can be used, such as light emitted from a phosphor excited by , gamma rays, a-rays, or the like.

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

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

The aromatic primary amine color developing agents used in the color developing solution of the present invention include known ones that are widely used in various color photographic processes. These developers include aminophenol and l)-phenylenenoamine 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. In addition, these compounds generally have a concentration of about 0.1 g to about 30 g per color developer.
Preferably about 1 g to about 1.5 g per 1 rl of color developer
Use at a concentration of g.

Examples of aminophenol-based developers include 0-7 mino 7 er/-l, p-7 minophenol, 5-7 mino 2-
Oxytoluene, 2-7 minnow 3-oxytoluene, 2
-Oxy-3-7 minnow 1°4-tmethylbenzene and the like are included.

A particularly useful tjS primary aromatic amino color developer is N,
It is an N'-dialkyl-p-phenylenediamine compound, and the furkyl group and 7enyl group may be substituted with any substituent. Among them, examples of particularly useful compounds include N,N'-noethyl-p-phenylenenoamine hydrochloride, N-methyl-p-7enylenediamine hydrochloride, N,
N'-tumethyl-9-phenylenediamine hydrochloride, 2-
7 Minnow 5-(N-ethyl-N-F?'Sylamino)-
Toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-7/aniline sulfate, N-
Ethyl-N-β-hydroxyethylamide/aniline, 4
-7 minnow 3-methyl-N,N'-noethylaniline,
4-7minor N-(2-methoxyethyl)-N-ethyl-3-methylaniline-p-toluenesulfonate, etc.6 The color developing solution used in the treatment of the present invention includes the above-mentioned In addition to the primary aromatic amine color developer, various components normally added to color developers, such as alkaline agents such as sodium hydroxide, sodium carbonate, and potassium carbonate, alkali metal sulfites, and alkali metal bisulfites. salt, alkali metal thiocyanate,
Alkali metal halides, benzyl alcohol, water softeners, thickeners, and the like may optionally be included. The pH value of this color developer is usually 7 or higher, most commonly about 10 to about 13.

In the present invention, after color development processing, processing is performed with a processing solution having a fixing ability, but if the processing solution having a fixing ability is a fixing solution, a bleaching treatment is performed before that.5 Used in the bleaching step As the bleaching agent, a metal complex salt of an organic acid is used, and the metal complex salt has the effect of oxidizing the metallic silver produced by development and converting it into silver halide, and at the same time coloring the uncolored part of the coloring agent. Its composition is one in which metal ions such as iron, cobalt, copper, etc. 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.

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. There are 8 types of bleaching agents used in the bleaching process. A metal complex salt of an acid is used, and the metal complex salt has the effect of oxidizing the metallic silver generated by development and converting it into 7% silver lodenide, and at the same time coloring the uncolored part of the color former, and its composition is as follows: Iron, aminopolycarboxylic acid or organic acids such as oxalic acid and citric acid.
Coordinated with metal ions such as cobalt and copper. The most preferred organic acids used to form such metal complexes of organic acids include polycarboxylic acids and 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] Imi7noacetic acid [4] Ethylenenoaminecytraacetic acid disodium salt [5] Ethylenenoaminecytraacetic acid tetra(trimethylammonium) salt [6] Ethylenenoaminecytraacetic acid Tetrasodium acetate [7] Sodium nitrilotriacetate 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 contains borate, oxalate, acetate, carbonate support, phosphate, etc.
Those known to be added to ordinary bleaching solutions, such as H buffering agents, alkylamines, and polyethylene oxides, can be added as appropriate.

Furthermore, the fixer and bleach-fixer contain ammonium sulfite,
Potassium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, metabisulfite), sulfites such as +7um, boric acid, borax, sodium hydroxide, potassium hydroxide, carbonic acid Sodium, potassium carbonate, sodium bisulfite, sodium bicarbonate, potassium bicarbonate, acetic acid,
It may contain one or more types of pH buffering agents consisting of various salts such as sodium acetate and ammonium hydroxide.

When the process of the present invention is carried out while replenishing the bleach-fix solution (bath) with a bleach-fix replenisher, the bleach-fix solution (bath) is The bath may contain thiosulfate, thiocyanate or sulfite, or the bleach-fixing replenisher may contain these salts 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. are suitably used. [Specific Effects of the Invention] In the present invention, the magenta coupler represented by the general formula [I] and the magenta coupler represented by the general formula (XI) are used. According to a color photographic material containing a magenta dye image stabilizer, the fastness of a magenta dye image, which has conventionally been particularly low in fastness to light, heat, and humidity, has been improved. This effectively prevents Y-stain from occurring in uncolored areas due to humidity.

Furthermore, by using a dye image stabilizer represented by the general formula [X■] in combination, the light resistance of the dye image is greatly improved.

〔Example〕

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 (15,0 mg/100 cn+2) and the following comparative magenta coupler A (6,0 mH/100 cm2) were prepared.
to 2,5-di-tert-octylhydroquinone (0
, 8IIg/100cm") in tricresyl 7m7wet and emulsified and dispersed, and then silver chlorobromide emulsion (silver bromide 8o mol%, coated silver amount 3.8B/100100e)
Sample 1 was obtained by mixing, coating and drying.

The above sample 1 contains the above P as a magenta dye image stabilizer.
Sample 2 in which H-13 and magenta coupler were added in equimolar amounts
I got it.

Samples 3, 7 and 11 were obtained in the same manner except that the magenta coupler in sample 1 was replaced with magenta couplers 1, 5 and v100 according to the present invention, respectively.

In the above Samples 3, 7.11, the magenta dye image stabilizer PH-13 was added in an equal molar amount to the coupler to obtain Samples 4, 8.12, respectively. Samples 5 and 9.13 were obtained by adding magenta image stabilizer B-35 in equimolar amounts to the coupler. Further, in Samples 3 and 7.11, the PH-13 and B-35 were added in a 1:1 ratio and equimolar to the coupler to prepare Samples 6, 10 and 14, respectively.

Comparative magenta coupler A O r1 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 time Color development
Bleach fixing at 33℃ for 3 minutes and 30 seconds
Wash at 33°C for 1 minute and 30 seconds.
Dry at 33℃ for 3 minutes 5
0 to 80°C for 2 minutes The components of each treatment solution are as follows.

[Color developer]

Benzyl alcohol 12.9 Diethylene glycol 10WIQ Potassium carbonate 25° Sodium bromide
O.S.

Anhydrous sodium sulfite 2.0g Hydroxylamine sulfate 2.5g N-ethyl-
N-β-nometasulfonamide ethyl-3-methyl-4-ami/7-niline sulfate 4.5 g was added to make up to 1 liter, and the pH was adjusted to 10.2 with NaOH.

[Bleach-fix solution]

Ammonium thiosulfate 120g Sodium metabisulfite 15g Anhydrous sodium sulfite 3g EDTA ferric ammonium salt 65g Add water to bring IQ to pH 6.7
Adjusted to ~6.8.

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

Each of the above-mentioned processed samples was exposed to a xenon fade meter for 10 days to examine the light fastness of the dye image and the Y-stin of the uncolored area.
The sample was left in a high humidity atmosphere for 14 days, and the moisture resistance of the dye image and the Y-stain of the uncolored area were examined. The obtained result is fJ
Shown in Table S1.

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 concentration of 1.0%.

(YS) Value obtained by subtracting the concentration of Y-stin before the light and humidity test from the concentration of Y-stin after the light and humidity 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), and the larger this value is, the easier it is to change the color tone from magenta to yellowish.

As is clear from Table 1, Sample 3, 7.11 prepared using the coupler of the present invention is a conventional 4-equivalent type 3-anili/-1,2-pyrazolo-5-one. Compared to Sample 1, which was made using a type coupler, it can be seen that YS is extremely unlikely to occur in the light and moisture resistance tests. I know it will fade. Sample 4, 8.12
is a sample prepared by using the coupler of the present invention in combination with the well-known magenta dye image stabilizer PH-13, and it is true that Niko has significantly improved the fading of the dye image due to light. However, it cannot improve discoloration.

On the other hand, in Samples 5 and 9.13 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 was not possible with the conventional combination of a 4-equivalent type 3-7ni/-1,2-pyrazolo-5-one type coupler and a dye image stabilizer (Sample 2).

Furthermore, in addition to the coupler and magenta dye image stabilizer according to the present invention, Samples 6, 10 and 14, in which a conventional magenta dye image stabilizer was added, showed a further significant improvement in the dye residual rate in the light exposure test. I know what to do.

Example 2 The coupler and magenta dye image stabilizer combinations shown in Table 2 were coated exactly as in Example 1, and sample 1
5 to 30 were created. Samples 15-30 were processed as described in Example 1. Further, 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 wS2 were obtained.

In addition, comparative magenta coupler B in the table has the following structure.

Table 2 As is clear from Table 2, the conventionally used
When the magenta dye image stabilizer of the present invention is used in combination with a 4-equivalent type 3-7nilino-1,2-pyrazolo-5-one coupler (Samples-15 and 16), and when the magenta dye image stabilizer of the present invention is used in combination with the coupler of the present invention, When using a magenta dye image stabilizer (Samples 19, 20, 21, 22), all of the discoloration, fading, YS in the uncolored area in the light test, and YS in the moisture resistance test were improved. It can be seen 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.

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 to obtain sample 31.6 First layer: blue a-pivaloyl-α-(2,4
-dioxo-1-benzylimigzolidin-3-yl)
-2-chloro-5-[γ-(2,4-]-1-7 milphenoxy)butyramide 17ceto7 dilide to 8.8I1
g/100cm2, blue-sensitive silver chlorobromide emulsion (silver bromide 85
(containing mol%) converted to silver is 3.2a+g/1010
0e, 3.5-g/100c of di-butyl 7-talate
m'' and gelatin were coated at a coating amount of 13.5 mg/100 cm''.

2nd layer: Middle layer 2.5-1 octyl hydroquinone 0.5mg
/100cm”, Nobutyl 7 Talate 0.5mg/
100cm2 and gelatin 9.0mg7100cm
It was painted so that it became 2.

Third layer: green-sensitive silver halide emulsion layer containing the magenta coupler 74 at 3.5 mg/100ca
+2, blue-sensitive silver chlorobromide emulsion (containing 80 mol% silver bromide) in terms of silver: 2.5II1 g/100cII2, di-butyl 7-thalerate at 3, On+g/100cm2 and gelatin at 12. It was coated to give Omg/100cn+2.

4th N: 2-(2-hydroxy-3-5ee-1 of intermediate layer UV absorber)
+5-t-1 tylphenyl)ben/ ) 177 sol to 7. Omg/100cm2, 6. Omg/ 100cm2.2,5-di-t-
Octylhydroquinone 0.5+H/100cIl
12 and gelatin were coated in an amount of 12.0 mg and 7100 cm2.

5th layer: red-sensitive silver halide emulsion layer 2-[C1-(2,4-no-pentylphenoxy)butanamide]-4,6-dica as cyan coupler
a-5-s chill 7-enol 4.2+H/100C 2-tricrenol aos7ate 3.5B/100C
m2 and gelatin were coated at 11.5 mg/100c++2.

6th layer: Protective layer Gelatin was coated at a concentration of 8.0 mg/10100e.

In the above sample 31, the dye image stabilizer of the present invention was added to the third layer in the proportions shown in Table 3, and multilayer sample 32
-40 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 also shown in Table 3.

Table 3 The results show that the dye image stabilizer of the present invention is effective as a dye image stabilizer for the magenta coupler according to the present invention, and the results increase as the amount added increases. Moreover, compared to sample 31, samples 32 to 40 showed extremely small discoloration of the dye images in the light emission test. Furthermore, it can be seen that in the samples of the present invention, discoloration and fading of the magenta dye are extremely small, 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)

[Claims] At least one coupler represented by the following general formula [I]
and at least one compound represented by the following general formula [X I ]. 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 [X
I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R^1 and R^4 are hydrogen atoms, halogen atoms, alkyl groups, alkenyl groups, alkoxy groups, alkenyloxy groups, hydroxy groups, aryl groups, and aryl groups, respectively. represents an oxy group, an acyl group, an acylamino group, an acyloxy group, a sulfonamide group or an alkoxycarbonyl group, and R^2 represents a hydrogen atom alkyl group, alkenyl group, aryl group, acyl group, cycloalkyl group or heterocyclic group, R^3 represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, an aryloxy group, an acyl group, an acylamino group, an acyloxy group, a sulfonamide group, a cycloalkyl group, or an alkoxycarbonyl group. Further, R^2 and R^3 may be closed to each other to form a 5- or 6-membered ring. Y represents an atomic group necessary to form a chroman or coumaran ring. ]