JPS62180366A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve the color reproducibility of a silver halide photographic sensitive material and the light fastness of a magenta dye image by incorporating a specified magenta coupler and two kins of specified compounds into at least one of the silver halide emulsion layers. CONSTITUTION:This silver halide photographic sensitive material having one or more silver halide emulsion layers on the support contains a magenta coupler represented by formula I, a compound represented by formula II and a compound represented by formula III in at least one of the silver halide emulsion layers. In the formula I, Z is a group of nonmetallic atoms required to form a heterocyclic ring contg. N, the formed ring may have a substituent, X is H or a substituent eliminable by a reaction with the oxidized product of a color developing agent and R is H or a substituent. In the formula II, each of R1 and R2 is alkyl, R3 is alkyl, -NR'R'', -SR' (R' is a univalent org. group) or -COOR'' (R'' is H or a univalent org. group) and m is an integer of 0-3. In the formula III, each of R21 and R22 is H, alkyl or the like and each of R23-R26 is H, halogen or the like. The coupler is used by 1X10<-3>-1mol, preferably 1X10<-2>-8X10<-1>mol per 1mol silver halide. The compound represented by the formula II is used by 5mu10<-2>-3mol per 1mol coupler. The compound represented by the formula III is preferably used by 1X10<-3>-1mol per 1mol coupler.

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a silver halide photographic light-sensitive material.
The present invention relates to a silver halide photographic material which has a stable dye image against heat and light, good leg gradation, and prevents staining. [Background of the Invention] Conventionally, a coupling reaction between an oxidized product of an aromatic primary amine color developing agent and a color former is carried out by imagewise exposing a silver halide color photographic light-sensitive material and performing color development. For example, it is well known that indophenol, indoaniline, indamine, azomethine, phenoxazine, phenazine, and similar 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, magenta and A silver halide color photographic material containing a coupler that develops cyan color is used. Examples of couplers used to form the yellow image include acylacetanilide couplers, and examples of couplers used to form magenta images include pyrazolone, pyrazolobenzimidazole, pyrazolotriazole, and indacylon couplers. Furthermore, as a coupler for forming a cyan image, for example, a phenol or naphthol coupler is generally used. It is desired that the dye image obtained in this way does not change color or fade even if it is exposed to light for a long time or stored under high temperature and high humidity. Furthermore, it is desired that the uncolored areas of silver halide color photographic materials (hereinafter referred to as color photographic materials) do not turn yellow (hereinafter referred to as Y-stain) due to light or moist heat.However, magenta couplers In the case of magenta dyes, the fading of uncolored areas by light, Y-stain due to moist heat, and color fading of dye image areas by light is extremely large compared to yellow couplers and cyan couplers, and is often a problem. Widely used to form magenta dyes. The couplers used are 1,2-pyrazol-5-ones.
．． In addition to the main absorption near 550 nm, the dye formed from magenta couplers of 2-pyrazolo-5-ones has an absorption 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. These techniques are described, for example, in U.S. Patent No. 2,343,70.
No. 3, British Patent No. 1,059,994, etc. However, the above-mentioned magenta coupler has the disadvantage that image stability, especially the fastness of the dye image to light, is extremely poor, and Y-stin in the uncolored area is large. As another means for reducing the a-absorption near 430na+ of the magenta coupler, British Patent No. 1, 04
Pyrazolobenzimidazoles described in U.S. Pat. No. 7.612, indasilones described in U.S. Pat. No. 3,770.447, and U.S. Pat. Magenta couplers such as pyrazolotriazoles described in U.S. Pat. No. 1,334,515 have been proposed. Dyes formed from these couplers have a significantly smaller side absorption near 430 nm than dyes formed from 1,2-pyrazol-5-ones having an anilino group at the 3-position, and are preferred in terms of color reproduction. Moreover, the occurrence of Y-stin in uncolored areas due to light, heat, and humidity is extremely small, which is a desirable advantage. However, the fastness of azomethine dyes formed from magenta couplers such as the pyrazolotriazoles to light is extremely low, and magenta tin (
M-stin (hereinafter referred to as M-stin) occurs, which significantly impairs the performance of color photographic materials, especially print-type color photographic materials, and has not been put to practical use in print-type color photographic materials. In addition, JP-A-59-125732 discloses that a 1-day-virazolo-[3,2-C]-s-triazole type magenta coupler is used in combination with a phenol compound or a phenyl ether compound. Day - Villazoro -
[Techniques have been proposed to improve the light fastness of magenta dye images obtained from magenta couplers of the 3,2-C1-s-triazole type. 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. Furthermore, the pyrazolotriazole-based magenta couplers tend to have softer gradations, particularly in the leg portions, than conventional 1,2-pyrazolo-5-ones. Therefore, when applied to color photosensitive materials, red-sensitive layer,
The gradation balance of the three layers, the green photosensitive layer and the blue photosensitive layer, is disrupted, and the magenta color becomes particularly noticeable in highlighted areas. For this reason, in photosensitive materials for color printing, for example, the sky and clouds appear pink, and snow appears pink instead of white, resulting in a so-called highlight pink phenomenon. The human eye discerns these subtle changes, especially at low densities, and interprets them as undesirable color print results. Therefore, when designing color photosensitive materials, great efforts are made to balance the three layers, especially in the low density areas. Therefore, the phenomenon of softening of the tones caused by the pyrazolotriazole magenta coupler causes a significant decrease in commercial value due to the highlight pink tendency, and it is no exaggeration to say that it is a fatal drawback. Various methods for controlling the gradation of silver halide photographic materials have been studied. For example, commonly used methods include increasing or decreasing the amount of silver halide applied, increasing the amount of coupler applied,
A method of reducing and changing the ratio of coated silver halide m and coupler 5, or for example, JP-A-50-713
Particle sizes and sensitization methods described in 20@, 53-44016, 56-78831, 57-58137%, 57-150841, 57-178235, 58-14829, etc. A method of mixing two or more types of silver halide emulsions with different values, and furthermore, a commonly used method in which silver halide grains are chemically sensitized or color sensitized, and conditions are set so that the tones are softened. , a method of selecting additives, etc., and furthermore, for example, JP-A-52-11029, JP-A-52-18310@, British Patent No. 1,535,018
There is a method in which a water-soluble Odium salt is added when forming silver halide grains, as described in US Pat. No. 3,448,709 and the like. However, these methods not only increase the gradation of the target leg area but also increase the gradation of the shoulder area, soften the gradation due to storage over time, or affect other photographic performance, such as sensitivity. For the above-mentioned pyrazolotriazole-based magenta couplers that cause fogging, adverse effects on exposure characteristics, etc., the prior art is an effective means to sharpen only the leg gradation without affecting other performance. The current situation is that it has not been found. Furthermore, there is a method of controlling gradation using a compound such as that described in Item 17643, Section 1 of Research Disclosure Magazine No. 176 (1978). However, when these compounds are used in combination with the magenta coupler represented by the general formula [I] of the present invention, the gradation can be controlled, but on the other hand, the fastness to light is impaired and the gradation balance is impaired. The shortcoming was that it was still not sufficient. Therefore, it is desired to develop a silver halide photographic light-sensitive material that utilizes the above-mentioned excellent properties of the azole-based magenta coupler and further improves image storage stability, leg gradation, and stain. [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 halogenated image with excellent color reproducibility and significantly improved light fastness of magenta dye images. Our objective is to provide silver photographic materials. A second object of the present invention is to provide a silver halide photographic material which improves the softness of the leg gradations, which is a drawback of the azole magenta couplers, and at the same time improves the gradation balance. A third object of the present invention is to provide a silver halide photographic material in which the occurrence of M-stain in uncolored areas is prevented. A fourth object of the present invention is to provide a silver halide photographic material in which the occurrence of Y-stain in uncolored areas due to moist heat is prevented. [Structure of the Invention] The above object of the present invention is to provide a silver halide photographic material having at least one silver halide emulsion layer on a support, in which at least one of the silver halide emulsion layers comprises:
A magenta coupler represented by the following general formula [I], a compound represented by the following general formula [a ] and the following general formula [
This is achieved by providing a silver halide photographic material containing a compound represented by [b]. General formula [I] In formula E, 7 represents a group of nonmetallic atoms necessary to form a nitrogen-containing heterocycle, and the ring formed by 2 may have a substituent. X represents a hydrogen atom or a substituent that can be separated by reaction with an oxidized product of a color developing agent. Further, R represents a hydrogen atom or a substituent. General formula [a
] to 1 [wherein R1 and R2 each represent an alkyl group. R3 is an alkyl group, -NR'R'' group, -8R' group (
R' represents a monovalent organic group. ), or −〇 〇
〇 Represents an R″ group (R″ represents a hydrogen atom or a monovalent organic group). m represents an integer of 0 to 3,] General formula [b] [wherein R21 and R22 each represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an acyl group, a cycloalkyl group, or a heterocyclic group, R23, R24, R
25 and R26 are each a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, a cycloalkyl group, an alkoxy group, an aryloxy group, an alkylthio group,
Arylthio group, acyl group, alkylacylamino group,
arylacylamino group, alkylcarbamoyl group, arylcarbamoyl group, alkylsulfonamide group, arylsulfonamide group, alkylsulfamoyl group,
It represents an arylsulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group, a nitro group, a cyano group, an alkyloxycarbonylbonyl group, an alkylacyloxy group, or an arylacyloxy group. However, when R23, R24, R25 and R26 are hydrogen atoms at the same time, R2+ and R22
are never hydrogen atoms at the same time. ] [Specific details of the invention] The present invention will be specifically explained in the following margin. In the magenta coupler represented by general formula (1) and general formula CI) according to the present invention, Z represents a nonmetallic atomic group necessary to form a nitrogen-containing bicyclic ring, and the ring formed by Z represents may have a substituent. X represents a hydrogen atom or a substituent that can be separated by reaction with an oxidized product of a color developing agent. Moreover, R represents a hydrogen atom or a substituent. Examples of the substituent represented by R(7) include a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an acyl group, a sulfonyl group, a sulfinyl group, and a phosphonyl group. , carbamoyl group, sulfo moyl group, cyano group, spiro compound residue, bridged hydrocarbon compound residue, flukoxy group, aryloxy group, heterocyclic oxy group, siloxy group, acyloxy group, carbamoyloxy group, amine 7
group, acylamino group, sulfone 7 mido group, imido group, 9
Reid group, 7 amoylamino group, 7 alkoxycarbonyl amine groups, 7 ryoryloxy luponyl amine groups, alkoxy carbonyl group, aryloxy carbonyl group,
Examples include 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 furkyl group represented by R has 1 to 32 carbon atoms, and the alkenyl group and alkynyl group have 2 to 3 carbon atoms.
2, cycloalkyl groups and cycloalkenyl groups preferably have 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms, and the alkyl groups, alkenyl groups and alkynyl groups may be linear or branched. In addition, these alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, and cycloalkenyl groups are substituents [for example, aryl, cyano, 7X rodene atom, heterocycle, dichlorofurkyl, cycloalkyl, spiro compound residue, bridged hydrocarbon compound In addition to residues, those substituted via a carbonyl group such as acyl, carboxy, carbamoyl, alkoxycarbonyl, and aryloxycarbonyl, and those substituted via a heteroatom (1) Specifically, hydroxy, alkoxy , aryloxy, heterocyclic oxygen,
Those substituted via an oxygen atom such as siloxy, acyloxy, carbamoyloxy, nitro, amino (including qualkyl 7, etc.), sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, acylamino, sulfone 7, Imide, ureido, etc. substituted via nitrogen atom, furkylthio, 7
Those substituted through a sulfur atom such as lylthio, heterocyclic thio, sulfonyl, sulfinyl, sulfamoyl, etc.
(e.g., those substituted via a phosphorus atom such as phosphonyl)]. Specifically, for example, methyl group, ethyl group, isopropyl group, t-butyl group, pentadecyl group, heptadecyl group, 1
-hexylnonyl group, 1.1'-noventylnonyl group,
2-chloro-t-butyl group, tri7fluoromethyl group, 1
-Ethoxytridecyl group, 1-methoxyisopropyl group, methanesulfonylethyl i, 2.4-sheet t-7mil7e/oxymethyl group, anilino group, 1-phenylisopropyl group, 3-Ill-butanesulfonamino 7 Dynoxypropyl group, 3-4'-iα-[4"(p-hydroxybenzenesulfonyl)phenoxy]dodecanoylamino)phenylpropyl i, 3-+4'-(α-(2"
, 4''-not-t-amylphenoxy)butane 74F) phenyl)-propyl!, 4-(α-(〇-chlorophenoxy)tetradecanamide 7 e/xy]propyl group, 7
Examples include a lyl group, a cyclopentyl group, a cyclohexyl group, and the like. The 71)-l group represented by R″c is preferably a phenyl group, and a substituent (for example, an alkyl group, an alkoxy group,
(7 acylamide groups, 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-butylphenoxy)tetradecanamide] phenyl group, etc. The heterocyclic group represented by R″t′ is preferably a 5- to 7-shell group, and may be substituted. Examples of A-isomers which may be condensed include 2-furyl group, 2-chenyl group, 2-pyrimidinyl group, and 2-benzothiazolyl group. Examples of the acyl group represented by R include an acetyl group, a phenylacetyl group, a dodecamyl group, a fulkylcarbonyl group such as an α-2,4-not-t-7 methylphenoxybutanoyl group, a benzoyl group, and a 3-pentamethyl group. Examples include arylcarbonyl 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 a benzenesulfonyl group, a 9-benzene sulfonyl group, and the like. The sulfinyl group represented by R"C' includes a furkylsulfinyl group such as an ethylsulfinyl group, an octylsulfinyl group, and a 3-phenoxybutylsulfinyl group,
Phenylsulfinyl i%m-pentadecylphenylsulfinyl group m! 717-rusulfinyl group and the like. The phosphonyl group represented by Rt' includes an alkylphosphonyl group such as butyloctylphosphonyl group, an alkoxyphosphonyl group such as octyloxyphosphonyl group,
7-aryloxyphosphonyl group such as xyphosphonyl group,
Examples include arylphosphonyl groups such as phenylphosphonyl groups. The carbamoyl group represented by R''Ch may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as an N-methylcarbamoyl group, N, N-')-
f-thylcarbamoyl i, N-(2-pentadecyloctylethyl)carbamoyl group, N-ethyl-N-dodecylcarbamoyl group, N-(3-(2,4-not-t-7milphenoxy)propyl)carbamoyl group, etc. Can be mentioned. The sulfamoyl group represented by the margin R below may be substituted with an alkyl group, a 7-aryl group (preferably a phenyl group), etc.
For example, N-propylsulfamoyl group, N,N-noethylsulfamoyl group, N-(2-pentadecyloxyethyl)sulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, N-phenylsulfamoyl group etc. Examples of spiro compound residues represented by R include spiro[
3,3]heptane-1-yl and the like. Examples of the bridged carbonized compound residue represented by R include bicyclo[2,2,1]hebutan-1-yl, tricyclo[
3,3,1,1co°)]decan-1-yl7,7-dimethyl-bicyclo[2,2,ljheptan-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 7-enyloxy, and the aryl nucleus further has ra to the 79-l group.
The substituents may be substituted with the atoms listed above, such as phenoxy group, pt-butyl 7eth/oxy group,
-1bentadecylphenoxy group and the like. The heterocyclic oxy group represented by R preferably has 5 to 7 heterocycles, and the heterocycle may further have a substituent, for example, 3゜4.5.6-tetrahydro. Examples include pyranyl-2-oxy group and 1-phenyltetrazol-5-oxy group. The siloxy group represented by R″Ch may be further substituted with a furkyl group, etc., for example, a trimethylsiloxy group,
Examples include triethylsiloxy group and trimethylbutylsiloxy group. The acyloxy group represented by R includes, for example, a furkylcarbonyloxy group, a 7-arylcarbonyloxy group, etc., and may further have a substituent, and specifically, an acetyloxy group, an a-chloro 7 Examples include cetyloxy group and benzoyloxy group. RF! The carbamoyloxy group is an alkyl group, 7
It may be substituted with a lyl group, and examples thereof include JrN-ethylcarbamoyloxy group, N,N-diethylcarbamoyloxy M, and N-phenylcarbamoyloxy group. The amide group represented by R1' may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as an ethyl amine group, anilino group, a chloraniline group, a 3-pentadecyloxy group, and a 3-pentadecyloxy group. 7 units, 2-
Examples include chloro-5-hexadecane 7mide 7nily7 groups. Examples of the 7-sylamine group to be reduced by R″C include a furkylcarbonylamino group, a carbonylamino group (preferably a phenylcarbonylamino group), and may further have a substituent. Specifically, acetamido group, a-
Ethylpropane 7mido group, N-phenyl 7ceto7mido group, dodecanamide group, 2,4-di-t-7milphenoxyacetamide group, (1-3-t-butyl 4-hydroxyphenoxybutanamide group, etc.) Examples of the sulfone 7 mido group represented by R include a furkylsulfonylamino group, an arylsulfonylamino 7 group, and may further have a substituent.Specifically, methylsulfonylamino 7 group, pentadecylsulfonylamide group, benzenesulfonamide i, p) luenesulfonamide group, 2-methoxy-5-t-7 milbenzenesulfonamide group, and the like. The imide group represented by R″t′ may be open-chain or cyclic (and may have a substituent (for example, a succinimide group, a 3-heptadecylsuccinimide group,
Examples include a 7-talimide group, a glutarimide group, and the like. The ureido group represented by R is an alkyl group, a 7-aryl group (
Preferred examples include N-ethylureido group, N-methyl-N-decylureido group, N-phenylureido group, and N-p-)dylureido group. The sul 7 amoylami 7 group represented by R is a furkyl group,
It may be substituted with an aryl group (preferably a phenyl group), etc., such as N,N-diptylsul77moylamy7 group, N-methylsul77 moylamy7! , , N-phenylsulfo T-moylamide 7 groups, and the like. As the flukoxyluponylamine 7 group represented by R,
Furthermore, it may have a substituent, for example, methoxycarbonyl amine 7 groups, notoxyshetoxy group 7 groups,
Examples include 7 octadecyloxycarbonylamide groups. The 7 aryloxycarbonyl amide groups represented by R may have a substituent, and examples thereof include 7 phenoxycarbonyl amine groups and 7 4-methyl 72 carbonyl amine groups. The flukoxycarbonyl group represented by R may further have a substituent, such as methoxycarbonyl group, butyloxycarbonyl group, dodecyloxycarbonyl group, octatecyloxycarbonyl group, ethoxymethoxycarbonyloxy group, benzyloxy Examples include carbonyl group. The aryloxycarbonyl group represented by R″C may further have a substituent, for example, a 7-ethyloxycarbonyl group, a p-chlorophenoxycarbonyl group, a m-bentate°
Examples include syloxy 7-enoxycarbonyl group. The alkylthio group represented by R may further have a substituent, and examples thereof include an ethylthio group, a dodecylthio group, an octadecylthio group, a 7enethylthio group, and a 3-7e/xypropylthio group. The arylthio group represented by Rt' is preferably a phenylthio group and may further have a substituent, such as a phenylthio group, p-methoxyphenylthio group, 2-t-octylphenylthio group, 3-octadecylphenylthio group, 2 -carboxyphenylthio group, p-7cetaminophenylthio group, etc. 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 the substituent which 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 (R8' is the same as the above R, Z' is the same as the above Z, R2' and R3' are a hydrogen atom, an aryl group , a group represented by ) representing an alkyl group or a heterocyclic group, a hydroxymethyl group, and a )+7 phenylmethyl group. Examples of groups that exchange 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. Examples include groups. The alkoxy group may further have a substituent, for example,
Examples include ethoxy group, 2-phenoxyethoxy group, 2-thia7ethoxy group, 7enethyloxy group, p-chlorobenoloxy group, and the like. The aryloxy group is preferably a 7-eth/oxy group, and the aryl group may further have a substituent. Specifically, 7e/oxy group, 3-methyl 7e/oxy group, 3-
Dodecylphenoxy group, 4-notanesulfonamide 72/xy! , 4-(α-(3′-pentadecylphenoxy)butanamide]7e/oxy group, hexidecylcarbamoylmethoxy group, 4-cyanophenoxy group, 4-methanesulfonylphenoxy group, 1-su7tyloxy group, p −
Examples include methoxyphenoxy group. The heterocyclic oxy group is preferably a 5- to 7-shell heterocyclic oxy group, which may be a condensed ring or may have a substituent. Specific examples include 1-phenyltetrazolyluoquine group and 2-benzothiazolyloxy group. The acyloxy group includes, for example, an acetoxy group, an alkylcarbonyloxy group such as a butazuroxy group, an alkenylcarbonyloxy group such as a cinnamoyloxy group,
Examples include arylcarbonyloxy groups such as benzoyloxy groups. Examples of the sulfonyloxy group include a butanesulfonyloxy group and a methanesulfonyloxy group. Examples of the alkoxycarbonyloxy group include an ethoxycarbonyloxy group and a benyloxycarbonyloxy group. Examples of the aryloxycarbonyl group include a 7-ethyloxycarbonyloxy group. Examples of the alkyloxalyloxy group include a notyloxadyloxy group. Examples of the alphoxyoxadyloxy group include an ethoxyoxalyloxy group. Examples of the group substituting via the sulfur atom include an alkylthio group, an alkylthio group, a heterocyclic thio group, and an alkyloxythiocarbonylthio group. Examples of the alkylthio group include a butylthio group, a 2-cyanoethylthio group, a 7enethylthio group, a benzylthio group, and the like. The 7-arylthio group includes phenylthio group, 4-methanesulfonamidophenylthio group, 4-dodecyl7enethylthio group, 4-nonafluoropentane7mido7enethylthio group, 4-carboxyphenylthio group, 2-ethoxy-5-t -butylphenylthio group and the like. The heteaML thio group is, for example, 1-722-1
．． 2.3.4-tetrazolyl-5-thio group, 2-benzothiazolylthio group, and the like. Examples of the alkyloxythiocarbonylthio group include a dodecyloxythiocarbonylthio group. For example, those represented by the general formula -N represent an aryl group, a heterocyclic group, a sulfamoyl group, a carbamoyl group, a 7-syl group, a sulfonyl group, a 7-aryloxycarbonyl group, an alkoxycarbonyl group, and R,' and R5 ' may be combined to form a heterocycle, provided that R4' and R6
′ are never both 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, a furkylthio group,
Arylthio group, 7 alkylamides, 7 arylamides, 7 acylamides, sulfonamide group, imino group, acyl group, alkylsulfonyl group, arylsulfonyl group,
Examples include a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a fluoryloxycarbonylamine group, an aryloxycarbonylamino group, a hydroxyl group, a carboxyl group, a cyano group, and a halogen atom. Specific examples of the alkyl group include ethyl group, oxytyl group, 2-ethylhexyl group, and 2-chloroethyl group. The aryl group represented by R4' or R1' 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 as the substituent for the furkyl group represented by R1' or R5' above, and an 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 R (or R1' is 5 to 6
A true one is preferable, and it may be a fused ring or have a substituent. Specific examples include 2-furyl group, 2-quinolyl group, 2-pyrimidyl group, 2-benzothiazolyl group, and 2-pyridyl group. The sulfamoyl group represented by R4' or Rs7 includes N-furkylsulfamoyl group, N*N-noalkylsulfamoyl group, N-717-rusul7amoyl group,
N,N-diarylsulfamoyl groups, etc., and these furkyl groups and aryl groups may have the replacement groups listed for the furkyl groups and aryl groups,
Specific examples of the sulfamoyl group include N,N-quethylsulfamoyl group, N-methylsulfamoyl group,
N-dodecylsul 77 moyl M, N-p-tolylsul 7
A 7 moyl group is mentioned. The carbamoyl group represented by R4' or R5' is
N-furkylcarbamoyl group, N,N-dialkylcarbamoyl group, N-7lylcarbamoyl group, N,N-)
Examples of carbamoyl groups include N,N-noethyl groups, etc., and these alkyl groups and aryl groups may have the substituents listed above for the alkyl groups and aryl groups. Rubamoyl group, N-methylcarbamoyl group, N-dodecylcarbamoyl group, N-p-cyanophenylcarbamoyl group, N
-p-) Zylcarbamoyl group. Examples of the acyl group represented by R1' or R9' 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 hexafluorobutanoyl group, 2゜3.4.5.6-pentafluorobenzoyl group, acetyl group, benzoyl group, naphthonyl group, 2-7lylcarbonyl group, etc. It will be done. Examples of the sulfonyl group represented by R,' or R,7 include an alkylsulfonyl group, a 7-arylsulfonyl group, and a heterocyclic sulfonyl group, which may have a substituent, such as ethane. Examples thereof include a sulfonyl group, a benzenesulfonyl group, an octanesulfonyl group, a naphthalenesulfonyl group, and a p-chlorobenzenesulfonyl group. The aryloxycarbonyl group represented by R, 7 or R5' may have any of the substituents listed above for the aryl group, and specific examples thereof include phenoxycarbonyl group and the like. The alkoxycarbonyl group represented by R and/or R5' may have a substituent listed for the alkyl group, and specific examples include a methoxycarbonyl group, a dodecyloxycarbonyl group, a benzyloxycarbonyl group, etc. can be mentioned. The heterocycle formed by combining R% and R, 7 is 5
~6 shellfish are preferred, and may be saturated or unsaturated,
Further, it may or may not have aromaticity, and may be a condensed ring. Examples of the heterocycle include N-7 talimide group, N-succinimide group, 4-N-furazodyl group, 1-N-hydantoinyl group, 3-N-2,4-nooxooxazolicinyl group, 2- N-1,1-nookin-3
-(2H)-oxo-1,2-benzthiazolyl group, 1
-pyrrolyl group, 1-pyrrolifnyl 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-bencyimigzolyl 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 -tetrahydroquinolyl group, 2-oxo-1-pyrrolidinyl group, 2-I
Examples include H-pyridone group, 7-thalassion group, 2-oxo-1-piperidinyl group, etc., and these heterocyclic groups include alkyl groups, aryl groups, alkyloxy groups, aryloxy groups, acyl groups, sulfonyl groups, and alkylamino groups. group, arylami 7 groups, acylami 7 groups, sulfonami 7 groups, carbamoyl group, sulfamoyl group, alkylthio group, arylthio group, ureido group, alphkidicarbonyl group,
It may be substituted with an aryloxycarbonyl group, an imide group, a nitro group, a cyano group, a carboxyl group, a halogen atom, or the like. 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, the substituents on the heterocycle (for example, R1R3 to Rs) in the general formula (r) and the general formulas [■] to [■] described later are moieties (herein, R'', X and Z II are the general formula (synonymous with R , The ring may be further fused with another ring (for example, a 5- to 7-shell cycloalkene). For example, in the general formula CV), R3 and R6 are R7 in the general formula (VIE).
and R8 may be combined with each other to form m (for example, 5 to 7 dichloroflukenes, benzene). What is represented by the general formula [I] below is more specifically represented by, for example, the following general formulas (II) to [■]. General formula (U) General formula (111) General formula (mV) N -N -Ni1 General formula (V) General formula (Vll General formula [■]] Rl-R in the general formulas (If) to [■] # and X
has the same meaning as R and X above. Moreover, among the general formula (I), the following general formula [
■]. General formula [■] In the formula, R1X and Zl have the same meanings as RlX and Z in the general formula ('I). Among the magenta couplers represented by the general formulas (IF) to [■], particularly preferred is the magenta coupler represented by the general formula (II). Regarding the substituents on the bicyclic rings in general formulas (1) to [■], R in general formula [I] and R3 in general formulas (II) to [■] satisfy the following condition 1. It is preferable that the conditions 1 and 2 below are satisfied, and more preferable.
The following conditions 1 and 1 are particularly preferred.
This is a case where conditions 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 bonds between the carbon atom and adjacent atoms are single bonds. The most preferable substituents R and 1/''R on the heterocycle are those represented by the following general formula (IX). ,R,. and R11 are each a hydrogen atom, !1
0 den atom, alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkynyl group, 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, aryoloxy group, heterocyclic oxy group, siloxy group, acyloxy group, carbamoyloxy group, amine 7 group, acylami 7 group, sulfonamide group, imide group , represents a ureido group, 7 sul7amoylamino groups, an alkoxycarbonylamino group, 7 aryloxycarbonylamino groups, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylthio group, an arylthio group, a heterocyclic thio group, and R91R3° and Rl 1 At least two of them must be hydrogen atoms). Also, the above R,,R,. and two of RII, for example R1
and Rlo may be combined to form a saturated or unsaturated ring (e.g., cycloheptalykane, cycloalkene, heterocycle), and the R port is further bonded to the ring to form a bridged hydrocarbon compound residue. You may. The group represented by R9 to R11 may have a substituent, and specific examples of the group represented by R3 to RII and the substituent that the group may have include the above-mentioned general formula [I] Specific examples of the group represented by R and substituents are listed. Also, for example, a ring formed by combining R3 and R3゜ and R3
Specific examples of the bridged hydrocarbon compound residue formed by ~R11 and its optional substituents include cycloalkyl, cycloalkenyl, and heterocyclic group represented by R in the general formula CI). Specific examples of hydrogen compound residues and their substituents are listed. Among the general formula (IX), (i) R1 to R
When two of 1+ are alkyl groups, (ii) Rs to R
One of 11, for example R1, is a hydrogen atom, and the other 2
When R3 and RIG combine to form a cycloalkyl together with the root carbon atom, the following is true. Furthermore, it is preferable among (i) that two of R and 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 [1] above. Specific examples of the group are listed below. In addition, substituents that the ring formed by Z in the general formula [CHI] and the ring formed by Z- in the general formula [~I] may have, and R2- in the general formulas CHI) to (VI) R3 is preferably represented by the following general formula [X]. General formula [χ] -R'-3Q2-R2 In the formula, R1 represents alkylene, and R2 represents alkyl, cycloalkyl or aryl. The alkynyl group represented by R1 preferably has 2 or more carbon atoms in the straight chain portion, more preferably 3 to 6 carbon atoms, and does not matter whether the straight chain is monobranched or not, and this alkylene may have a substituent. Examples of the substituent include R in the above general formula [I]
When is an alkyl group, the substituents that the alkyl group may have include those shown below. Preferred substituents include phenyl. Preferred specific examples of alkylene represented by R' are shown below. -CLCLCII-, -C112C)12CH2Ct1
2-1-CHzCHzC)I2CH-. The alkyl group represented by R2 may be a straight chain with 9 branches. Specific examples include methyl, ethyl, propyl, 1so-propyl, butyl, 2-ethylhexyl, octyl, dodecyl, tetradecyl, hexadecyl, oftagyl, 2-hexyldecyl, and the like. The cycloalkyl group represented by R2 is preferably one with 5 to 6 shells, such as cyclohexyl. The alkyl and cycloalkyl represented by R2 may have a substituent, and examples thereof include those exemplified as the substituent for R1 above. Specific examples of the aryl represented by R2 include phenyl and naphthyl. The aryl group may have a substituent. Examples of the substituent include linear or branched alkyl, as well as those exemplified as the substituent for R1 described above. Moreover, when there are two or more substituents, those substituents may be the same or different. Among the compounds represented by the general formula [I], the most preferred are those represented by the following general formula (XI). General formula (XI) In the formula, R and X have the same meanings as R and X in general formula (I), and R' and R2 are R I in general formula (X). It has the same meaning as R2. Specific examples of compounds used in the present invention are shown below. Below margin Cl2H2≦I3 I13 CH3 10・CH. CH. C) +3 2H5 Below margin CH3 CH Yo CH. C.H. Js CH. CH. CHl C11°CI. CJ+s C6H13 CH. 0C■2CO Cl2CH20CH3 0Cfh (JhSOzCH3 C, 11s ■ CH3 2115 6H13 CHl H3 oc2n. C)13 - C)13 L:81'11F (1) Hot L C■. L (:l, t,:,u,
)(t)■ CH. Station CHl ■ 7H15 If3CCH3 0 (CH2hUL; tzizs N -N -N H-N-N) 1 N C, [I. H N -N -N H The above coupler is also used in the Journal Op the Chemical
Society (Journal of the Ch)
chemical 5ociety) *Parkin (P
erkio) I(197)), 2047-205
2. U.S. Patent No. 3,725,067, No. 1, 1983-1989
No. 437, No. 58-42045, No. 59-16254
No. 8, No. 59-171956, No. 60-33552, No. 60-43659, No. 60-172982, No. 60-190779, and the like. The couplers of the invention are typically 1x1 per mole of silver halide.
0-Comole 1 mol, preferably lXl0-'' mol to 8
It can be used in the range of X10'-' moles. The couplers of the present invention can also be used in combination with other types of magenta couplers. In the following margin, the compound represented by the general formula [a] will be explained. In the present invention, the alkyl group represented by R+J'3 and R2 in general formula (a) preferably has 1 to 12 carbon atoms.
an alkyl group, more preferably an alkyl group having 3 to 8 carbon atoms and branched at the α position. Particularly preferred for R1 and R2 is a [-butyl group or a [-pentyl group]. The alkyl group represented by R3 is a straight chain or branched alkyl group, such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, an octyl group, a nonyl group, a dodecyl group, an octadecyl group, and the like. These alkyl groups include those having substitutions, and these substituents include halogen atoms, hydroxyl groups, nitro groups, cyano groups, aryl groups (e.g. phenyl groups, hydroxyphenyl groups, 3.5-di-t-dibru 4-hydroxyphenyl group, 3°5-di-t-benzene-4-hydroxyphenyl group, etc.), amino group (e.g. dimethylamino group, diethylamino group, 1,3.5-1-riazinylamino group, etc.), alkyloxycarbonyl groups (e.g. methoxycarbonyl group, ethoxycarbonyl group, propyloxycarbonyl group, butoxycarbonyl group, pentyloxycarbonyl group, octyloxycarbonyl group,
nonyloxycarbonyl group, dodecyloxycarbonylcarbonyl group, etc.), aryloxycarbonyl group (e.g., phenoxycarbonyl group, etc.), carbamoyl group (e.g., alkylcarbamoyl group such as methylcarbamoyl group, ethylcarbamoylcarbamoyl group, heptylcarbamoyl group, phenyl Examples include arylcarbamoyl groups such as carbamoyl groups, cyclohexylcarbamoyl groups, etc.), isocyanudyl groups, and polycyclic groups such as 1.3.5-i-riazinyl groups. The amino group represented by R3 is, for example, a dimethylamino group, a diethylamino group,
Alkylamino groups such as methyl ethyl 7mino group, arylamino groups such as phenylami LL hydroxyl phenylamino group, cycloalkylamino groups such as cyclohexyl group, 1.3. It includes a 5-triazinylamino group, a polycyclic amino group such as an isocyanudyl group, and the like. The monovalent organic group represented by R' and R11 is, for example, an alkyl group (e.g., methyl group, ethyl group, propyl group, butyl group, amyl group, decyl group, dodecyl group, hexadecyl group, octadecyl group, etc.), aryl group, etc. groups (e.g. phenyl group, naphthyl group, etc.)
, cycloalkyl groups (for example, cyclohexyl group, etc.), and heterocyclic groups (for example, 1,3.5-triazinyl group, isocyanudyl group, etc.). These organic groups include those having substituents, such as halogen atoms (e.g., fluorine, chlorine, bromine, etc.), hydroxyl groups, nitro groups, cyano groups, atomyl groups, alkyl groups (e.g., methyl groups, ethyl group, 1-11] biru group,

[-butyl group
, [-amyl group'6), aryl group (e.g. phenyl group)
, tolyl group, etc.), alkenyl group (e.g. allyl group, etc.),
Alkylcarbonyloxy groups (e.g. methylcarbonyl
Oxy group, ethylcarbonyloxy group, benzylcarbo
nyloxy group), arylcarbonyloxy group (e.g.
Examples include benzoyloxy groups, etc.). In the present invention, preference is given to compounds represented by the general formula (a>).
Preferably, it is a compound represented by the following general formula [a'].
Ru. General formula [a'] [In the formula, Rt+ and R12 each have 3 carbon atoms
~8 straight-chain or branched alkyl groups, especially [-butyl
group, t-pentyl group. R13 has a value of
Was. k represents an integer from 1 to 6. ] k expressed by R+a (as the IIM of ilIi,
For example, methyl group, ethyl group, propyl group, butyl group,
del group, octyl group, hexadecyl group, methoxyethyl group
group, chloromethyl group, 1,2-dibromoethyl group, 2
- Aluminum groups such as chloroethyl group, benzyl group, phenethyl group, etc.
Alkyl groups such as kill groups, allyl groups, propenyl groups, butenyl groups, etc.
Kenyl group, ethylene, trimebrene, propylene, hexyl group
Polyunsaturated carbon such as samedilene, 2-chlorotrimethylene, etc.
Water f(W, glyceryl, diglyceryl, pentaerys
Unsaturated hydrocarbons U such as lytyl and dipentaerythrityl,
Cyclopropyl, cyclohexyl, cyclohexenyl group
alicyclic hydrocarbon groups such as phenyl groups, p-octylphenyl groups, etc.
Nyl group, 2.4-dimethylphenyl group, 2.4-di-t
-butylphenyl group, 2,4-di-t-pentylphenyl group
p-chlorophenyl group, 2,4-dibromophenyl group, p-chlorophenyl group,
1.2-. 1.3-
or 1,4-phenylene group, 3,5-dimethyl-1,
4-phenylene group, 2-t-butyl-1,4-phenylene
2-chloro-1,4-phenylene group, naphthalene group
Arylene groups such as 1,3,5-trisubstituted benzene groups
etc. In addition to the above groups, R+3 is any group among the above groups.
to which is bonded via 10-+ -5-1-302~ group
valent organic groups. R+3 is more preferably 2,4-c[-butylphene]
Nyl group, 2,4-di(-pentylphenyl group, p-o
cutylphenyl group, p-dodecylphenyl group, 3.5-
Di[-butyl-4-hydroxylphenyl group, 3.5
-di[-pendel-4-hydroxyphenyl group
. Preferably, k is an integer of 1 to 4. Specific compounds represented by the general formula (a) are shown below.
However, the present invention is not limited thereto. Below is the margin C4 mountain (1) C5HH (t) BMIlj C4Hj (
t) (20) C4H, (t) 04 Hs(L) S Ct Le(24) [26] (28 N(3g (32) C4Hs(t) CsHo(t) C4 Le(1) CsHsteCsHll(L ) CxH7(i) Cs)ht(t) (60〕 (63) ctfan(1) C4H9(t) C5上jll (
Bee) The compound represented by the above general formula [a] is a general
For the magenta coupler 1T nyl represented by the formula [d1]
5X10-2 to 3 moles, furthermore 1X10-1 to 2 moles.
It is preferable to use it in a proportion of . Next, the compound represented by the general formula [b] will be explained.
Ru. In the general formula [b], represented by R2+ and R22
Examples of alkyl groups include methyl, ethyl, n
-propyl, i-propyl, n-butyl, [-butyl,
n-amyl, i-amyl, n-octyl, n-dodecyl
, n-octadecyl, etc., especially those with 1 carbon number
~32 alkyl groups are preferred. Examples of alkenyl groups include allyl, octenyl, and octenyl.
Examples include each group of leyl, especially an alkyl group having 2 to 32 carbon atoms.
Kenyl group is preferred. Examples of aryl groups include phenyl and naphthyl groups.
etc. Examples of acyl groups include acetyl, octanoyl,
Examples include uroyl groups. Examples of the cycloalkyl group include cyclohexyl,
Examples include each group of clopentyl. Examples of the heterocyclic group include imidazolyl, furyl, and pyri.
Examples include zyl, triazinyl, thiazolyl groups, etc.
. These groups include those with substituents, and as substituents
For example, an alkyl group, an aryl group, an aryloxy group,
Alkylthio group, cyano group, acyloxy group, alkoxy group
Cycarbonyl group, acyl group, sulfamoyl group, hydro
Examples include xyl group, nitro group, amino group and heterocyclic group.
It will be done. In the general formula [b], R23, R24, R25 or
The halogen atom represented by R26 and R26 is, for example,
, fluorine, chlorine, and bromine atoms, and alkyl groups
For example, methyl, ethyl, n-propyl, i-
Propyl, n-butyl, t-butyl, n-amyl, i-
amyl, n-octyl, n-dodecyl, n-octadecy
In particular, alkyl groups having 1 to 32 carbon atoms are mentioned.
Groups are preferred. Examples of alkenyl groups include allyl, octenyl, and oleyl.
yl groups, etc., especially alkylene groups having 2 to 32 carbon atoms.
Nyl group is preferred. Examples of aryl groups include phenyl and naphthyl groups.
etc. Examples of acyl groups include acetyl, octanoyl,
Examples include uroyl groups. Examples of the cycloalkyl group include cyclohexyl,
Examples include each group of clopentyl. As the alkoxy base, for example, methoxy, ethoxy, do
Examples include decyloxy groups, and aryloxy groups.
Examples of such groups include phenoxy groups, and alkylthio groups.
Examples of the group include methylthio, n-1 methylthio, 0-
Examples include dodecylthio, and arylthio groups.
Examples of such groups include phenylthio groups, etc.
Examples of the cylamino group include an acetylamino group.
Examples of the arylacylamino group include benzene.
Examples include zoylamino group, alkylcarbamoyl group, etc., and arylcarbamoyl includes, for example,
Examples include phenylcarbamoyl groups, and alkyl sulfonyl groups.
Examples of the amide group include methylsulfonamide group, etc.
Examples of the arylsulfonamide group include
Examples include phenylsulfonamide groups, etc.
Examples of the 1-moyl group include methylsulfamoyl
The arylsulfamoyl group includes, for example,
Examples include phenylsulfamoyl groups,
As the sulfonyl group, for example, methylsulfonyl group
etc., and examples of the arylsulfonyl group include
Examples include phenylsulfonyl groups, and alkyloxycarbonyl groups.
As a carbonyl group, for example, a methyloxycarbonyl group
etc., and the aryloxycarbonyl group is,
Examples include phenyloxycarbonyl groups,
As the kylacyloxy group, for example, an acetyloxy group
etc., and examples of the arylacyloxy group include
Examples include benzoyloxy group. These groups include those with substituents, and as substituents
is the same substitution as mentioned for the groups R21 and R22 above.
The following groups can be mentioned. Compounds represented by the above general formula [b] used in the present invention
Among the compounds, the compound represented by the following general formula [b'] is included in the present invention.
It is particularly preferably used in In the formula, R31 and R32 are a hydrogen atom and an alkyl atom, respectively.
group, alkenyl group, aryl group, acyl group, cycloal
Represents a kill group or a '7fI ring group, but R31 and
Neither R32 is a hydrogen atom. In the general formula [b'], R31 and R32 are
Examples of the alkyl group include methyl, ethyl,
n-propyl, i-propyl, n-butyl, t-butyl
, n-amyl, 1-7 mil, n-octyl, n-dodecyl
and n-octadecyl groups, etc., especially those having a carbon number
1 to 32 alkyl groups are preferred. Examples of alkenyl groups include allyl, octenyl, and oleyl.
yl groups, etc., especially alkylene groups having 2 to 32 carbon atoms.
Nyl group is preferred. Examples of aryl groups include phenyl and naphthyl groups.
etc. Examples of acyl groups include acetyl, octanoyl,
Examples include uroyl groups. Examples of the cycloalkyl group include cyclohexyl,
Examples include clopendel groups. Examples of the heterocyclic group include imidazolyl, furyl, and pyri.
Jill! - Examples include riazinyl and thiazolyl groups.
Ru. In the general formula [b'], R3j and R32 represent
The total number of atoms or carbon atoms in each group is 8 or more and is non-containing.
It is most preferable that the group is a group that imparts diffusibility. Compound represented by the above general formula [b] used in the present invention
Specific examples of things are listed below, but of course they are not limited to these.
It's not something you can do. H (HQ-6) OH OH (IQ-11) OH OH OH (HQ 16) OH OH (HQ-21). □ H (HQ-26) (HQ-27) (HQ-28) (HQ-29) H (HQ-30) (HQ-31) (HQ-32) These compounds are
- Magazine, No. 176 (1978) (7) Section 17643
(7) It is described in the work of V[. The compound represented by the general formula [bl] used in the present invention
The amount of addition depends on the silver halide emulsion used and
Depends on the type of magenta coupler, there are no particular restrictions.
but preferably i x per mole of magenta coupler
i o-a mole - 1 mole, more preferably I
10-2 mol-5X 10-1 mol. Magenta coupler according to the present invention, general formula <a) and
Silver halide photographic material of the compound represented by (b)
The general method of adding hydrophobic compounds to
solid dispersion method, latex dispersion method, oil droplet in water
Various methods can be used, such as type emulsion dispersion method, which is
Select as appropriate depending on the chemical structure of the hydrophobic compound such as coupler.
You can choose. The oil-in-water emulsion dispersion method uses coupler
Various methods can be applied to disperse hydrophobic compounds such as
, usually necessary for high-boiling point solvents with a boiling point of about 150'C or higher.
If necessary, use a low boiling point and/or water-soluble organic solvent.
and dissolved in a hydrophilic binder such as an aqueous gelatin solution.
Stirrers, homogenizers, colloids using surfactants
Dispersion means such as mills, 70-git mixers, ultrasonic devices, etc.
After emulsifying and dispersing the desired hydrophilic colloid using
It can be added to the hard layer. dispersion or at the same time low
A step of removing the boiling point organic solvent may be included. As a high boiling point organic solvent, it does not react with the oxidized form of the developing agent.
phenol derivatives, phthalate 1, phosphoric acid esters
Stell, citric acid ester, rest 1M ester, alkyl
amide, fatty acid ester, trimesic acid ester, etc.
An organic solvent having a boiling point of 150° C. or higher is used. In the present invention, represented by general formulas (a) and (b),
It can be preferably used when dispersing compounds that are
The high boiling point organic solvent used is a compound with a dielectric constant of 6.0 or less.
For example, heptatalic acid ester with a dielectric constant of 6.0 or less.
Esters such as alcohol, phosphate ester, etc., 83! chuamide
compounds, ketones, hydrocarbon compounds, etc. Preferably
The vapor pressure at 100°C is 6.0 or less and 1.9 or more.
It is a high boiling point organic solvent of 0.5 mm11 or less. Also more
Preferably, phthalate esters in the high-boiling organic solvent
Or phosphoric acid esters. Furthermore, the high boiling point paid melt
The medium may be a mixture of two or more types. Note that the dielectric constant in the present invention refers to the dielectric constant at 30°C.
It shows the rate. Phthalate esters advantageously used in the present invention as J3
Examples include those represented by the following general formula [C]
. General formula [C] In the formula, R16 and R17 are an alkyl group and an alkyl group, respectively.
Represents a lekenyl group or an aryl group. However, R+s
The total number of carbon atoms in the groups represented by and R+7 is 8 to
It is 32. More preferably, the total number of carbon atoms is
16 to 24. In the present invention, R+s and R+ of the general formula [C]
The anoσ-kyl group represented by 7 can be linear or branched.
For example, butyl group, pentyl group, hexyl group,
butyl group, octyl group, nonyl group, decyl group, undecyl group
group, dodecyl group, tridecyl group, tetradecyl group,
tadecyl group, hexadecyl group, heptadecyl group, octane
Such as a tacyl group. represented by R+6 and R17
Aryl groups are, for example, phenyl groups, naphthyl groups, etc.
, alkenyl group is, for example, hexenyl group, heptenyl group
, octadecenyl group, etc. These alkyl groups, a
alkenyl and aryl groups can have single or multiple substitutions.
May have a substituent, alkyl group and alkenyl
Examples of substituents include halogen atoms, alkoxy
group, aryl group, aryloxy group, alkenyl group,
Examples include alkoxycarbonyl groups, and substitution of aryl groups.
Examples of the group include a halogen atom, an alkyl group, and an alkyl group.
xy group, aryl group, aryloxy group, alkenyl group
, an alkoxycarbonyl group, and the like. Phosphate esters advantageously used in the present invention
Examples include those represented by the following general formula [d]. General formula [d] Mountain R,,0-P-OR,. 0R,. In the formula, R+8, R+s and R20 are each alkyl
represents an alkenyl group, an alkenyl group or an aryl group. However, carbon atoms represented by R+a, R+s and R20
The total number of children is 24 to 54. Represented by R+a, R+9 and R20 of general formula [d]
Examples of alkyl groups include butyl, pentyl, and hexyl groups.
Syl group, heptyl group, octyl group, nonyl group, decyl group
, undecyl group, dodecyl group, tridecyl group, tetrade
Cyl group, pentadecyl group, hexadecyl group, heptadecy
aryl group, octaacyl group, nonadecyl group, etc.
Examples of the group include phenyl group, naphthyl group, etc.
, and alkenyl groups include, for example, hexenyl group, hexenyl group,
These include a putenyl group and an octadecenyl group. These alkyl, alkenyl and aryl groups are
, may have single or multiple substituents. Like
Or R+a, R+s and R20 are alkyl groups
, for example, 2-ethylhexyl group, n-octyl group, 3
．． 5.5-trimethylhexyl group, n-nonyl group, n-
Decyl group, 5ec-decyl group, 5ec-dodecyl group, [
-octyl group and the like. Typical specific examples of organic solvents used in the present invention are shown below.
However, the present invention is not limited to these. Examples of organic solvents in the margin below - 2O These organic solvents are represented by general formulas (a) and (b).
5 to 100% by weight of the compound to be mixed.
Q? Mashukuke 30 to 80 moves m%
be. In addition, the magenta coupler according to the present invention is of the general type mentioned above.
The same oil as the compound represented by formulas (a) and (11)
Preferably, it is dissolved in drops. Hydrophobic compounds such as couplers can be mixed with high boiling point solvents alone or with low boiling points.
Dissolved in a solvent and used mechanically or ultrasonically
Anionic interface is used as a dispersion aid when dispersing in water.
Active agent, nonionic surfactant, cationic surfactant
can be used. The silver halide photographic light-sensitive material of the present invention can be used, for example, in a color network.
negative and positive films, color photographic paper, etc.
but especially for direct viewing.
The effects of the present invention are effectively exhibited when color photographic paper is used.
be done. Silver halide of the present invention including this color photographic paper
Photographic materials, whether for single color or multicolor,
stomach. In the case of multicolor silver halide photographic materials, color reduction
In order to reproduce normal colors, it is usually used as a photographic coupler.
Contains magenta, yellow, and cyan couplers.
A silver halide emulsion layer and a non-photosensitive layer are formed on the support.
It has a groove path laminated in an appropriate number of layers and phase order, but the
The calendar number and phase order may be changed as appropriate depending on the important performance and purpose of use.
It's okay. The silver halide photographic light-sensitive material of the present invention is a multicolor light-sensitive material.
In some cases, the specific layer structure may include a support layer on the support body.
Sequentially from the body side: yellow dye image forming layer, intermediate layer, magenta
Dye image forming layer, intermediate layer, cyan dye image forming layer, intermediate
Particularly preferred are layers and protective layers. Halogen used in the silver halide photographic material of the present invention
The silver halide emulsion (hereinafter referred to as the silver halide emulsion of the present invention) contains silver bromide, silver iodobromide, and iodide salts as silver halides.
Common silver halide milks such as silver chloride, silver chlorobromide, and tin chloride
Any material used in agents can be used. Silver halide grains used in the silver halide emulsion of the present invention
The particles can be obtained by either the acidic method, neutral method, or ammonia method.
It may also be something that has been removed. The particles may be grown all at once, or
, seed particles may be produced and then grown. Seed particle
Even if the method of harvesting and the method of growing are the same, they are different.
Also good. Silver halide emulsion contains halide ions and silver ions at the same time.
Even if they are mixed together, if one is present, the other is mixed.
May be combined. Also, the critical growth rate of silver halide crystals
While considering the above, the halide ions and silver ions are
in-+, sequentially and simultaneously while controlling pAo
It may also be generated by adding it. Combination after growth
By changing the halogen composition of the particles using the
Also good. When producing the silver halide emulsion of the present invention, if necessary,
By using a silver halide solvent, silver halide grains can be
Particle size, particle shape, particle size distribution, particle growth
You can control the speed. Silver halide grains used in the silver halide emulsion of the present invention
In the process of particle formation and/or growth,
, cadmium salt, zinc salt, lead salt, thallium salt, iridium
rhodium salt or trumpet W, rhodium JP or complex salt, iron salt or complex salt,
Add metal ions to the interior of the particles and/or
It can be encapsulated on the child surface and also in a suitable reducing atmosphere.
By placing the
It can give you a feeling of emotion. The silver halide emulsion of the present invention is characterized by the growth of silver halide grains.
After the completion of the process, unnecessary soluble salts may be removed or
Otherwise, it may be left as is. When removing the salts,
, those listed in Research Disclosure No. 17643
It can be done according to the law. Silver halide grains used in the silver halide emulsion of the present invention
The child may consist of a uniform layer inside and on the surface,
It may consist of different layers. Silver halide grains used in the silver halide emulsion of the present invention
A particle whose latent image is mainly formed on its surface.
may be formed mainly inside the particles.
Particles may also be used. Silver halide grains used in the silver halide emulsion of the present invention
The crystals may have regular crystal shapes, spherical or plate shapes.
It may also have an irregular crystal shape such as a shape. these
In a particle, the ratio of (1oo) plane to (111) plane is arbitrary.
You can use whatever you want. Also, it may have a composite form of these crystal forms, and various crystal forms may be used.
Crystalline particles may also be mixed. The silver halide emulsion of the present invention comprises two or more types formed separately.
A mixture of silver halide emulsions may be used. The silver halide emulsion of the present invention is chemically sensitized by a conventional method.
Ru. That is, compounds containing sulfur that can react with silver ions,
Sulfur sensitization method using activated gelatin, using selenium compound
selenium sensitization method using reducing substances, reduction sensitization method using reducing substances,
Noble metal sensitization methods using other compounds may be used alone or
can be used in combination. The silver halide emulsion of the present invention is widely used in the photographic industry for sensitized color.
Light is transmitted to the desired wavelength range using a known dye.
It can be scientifically sensitized. Sensitizing dyes may be used alone, but
Two or more types E may be used in combination. with sensitizing dye
A dye that itself has no spectral sensitizing effect or visible light
A compound that does not substantially absorb sensitizing dyes.
A supersensitizer that enhances the effect may be included in the emulsion. The silver halide emulsion of the present invention includes steps for producing light-sensitive materials,
Preventing fog during storage or photo processing and/or
In order to maintain stable photographic performance, during chemical ripening and
and/or at the end of chemical ripening and/or at the end of chemical ripening.
After that, by the time silver halide emulsion was applied, the photographic industry
Compounds known as antifoggants or stabilizers
can be added. The binder (or
It is advantageous to use gelatin as a protective colloid.
However, in addition to gelatin derivatives, gelatin and other high
Graft polymers of molecules, proteins, sugar derivatives, cellulose
Synthetic hydrophilic polymers such as gas derivatives, single or copolymers
Hydrophilic colloids such as child substances can also be used. The photographic emulsion layer of the silver halide photographic light-sensitive material of the present invention;
The other hydrophilic colloid layer is a binder (or protective colloid).
d) vj! crosslinks molecules and increases membrane strength! Membrane agent alone
Or, it can be hardened by using it together. Hardener is a processing liquid
Harden the photosensitive material to the extent that there is no need to add a hardening agent inside.
Yes, it is desirable to add a hardening agent to the processing solution.
It is also possible to add. Silver halide emulsion of the silver halide photographic light-sensitive material of the present invention
to increase the flexibility of the layer and/or other hydrophilic colloid layers.
A plasticizer can be added to the material. Photographic emulsion layer and others of the silver halide photographic light-sensitive material of the present invention
The purpose of this is to improve the dimensional stability of the hydrophilic colloid layer.
Dispersions of water-insoluble or poorly soluble synthetic polymers (latex)
) can be included. The emulsion layer of the silver halide photographic light-sensitive material of the present invention contains color-forming
In the development process, an aromatic primary amine developer (e.g.
p-phenylenediamine derivatives and aminophenol derivatives
Coupling reaction with oxidized material (conductor, etc.) to form dye
A dye-forming coupler is used. The pigment-forming cap
The sensitivity spectrum of the emulsion layer is determined for each emulsion layer.
Usually selected to form pigments that absorb light.
The blue light-sensitive emulsion layer contains a yellow dye-forming color.
The green light-sensitive emulsion layer contains a magenta dye-forming color.
The red light-sensitive emulsion layer contains a cyan dye-forming cap.
ra is used. However, the above combinations can be used depending on the purpose.
Silver halide color photography in different ways than combination
You can also make the materials. The cyan dye-forming couplers used in the present invention include:
Phenol-based, naphthol-based 4-equivalent or 2-equivalent type
Typical examples are cyan dye-forming couplers.
U.S. Patent No. 2,306,410, U.S. Patent No. 2,356,4
No. 75, No. 2,362,598, No. 2.367,
No. 531, No. 2.389.929, No. 2.423
．． No. 730, No. 2,474,293, No. 2,47
6.008, 2.498, 466, 2.5
No. 45.687, No. 2.728.660, No. 2,
No. 772.162, No. 2,895,826, No. 2
, No. 976.146, No. 3.002.836, No. 976.146, No. 3.002.836, No.
No. 3,419.390, No. 3.446.622, No. 3,446.622, No.
No. 3.476, 563, No. 3,737, 316,
Same No. 3.758.308, Same No. 3.839.044
, British Patent No. 478.991, British Patent No. 945,542
, same No. 1.084.480@, same No. 1,377.233
No. 1.388.024 and No. 1,543.0
40, as well as JP-A No. 47-37425,
No. 50-10135, No. 50-25228, No. 50
-112038, 50-117422, 50
-130441, 54-6551, 51-37
No. 647, No. 51-52828, No. 51-10884
No. 1, No. 53-109630, No. 54-48237
No. 54-66129, No. 54-131931,
It is described in various publications such as No. 55-32071. Furthermore, the cyan dye type used in the silver halide emulsion of the present invention
Examples of couplers having the following general formulas [CC-11 and [
CC-2] is preferred. General Formula [CC-1] In the formula, R1 does not represent an alkyl group or an aryl group. R2 is an alkyl group, a cycloalkyl group, an aryl group or
represents a heterocyclic group. R3 is a hydrogen atom, a halogen atom,
Represents an alkyl group or an alkoxy group. Also, R3 is R
It may be combined with 1 to form a ring. Z is a hydrogen atom or
For reaction with oxidized product of aromatic primary amine color developing agent
Represents a more releasable group. General formula [CC-2] In the formula, R4 is a straight chain or branched atom having 1 to 4 carbon atoms.
The alkyl group and R5 represent a ballast group. Z has the same meaning as 7 in general formula [CC-1]. R4 especially
Preferably straight chain or branched alkyl having 2 to 4 carbon atoms
is a group. In the present invention, represented by R1 of the general formula [CC-11]
The alkyl group may be straight chain or branched, e.g.
For example, methyl group, ethyl group, iso-propyl group, butyl group,
ru group, pentyl group, octyl group, nonyl group, tridecyl group
The aryl group is, for example, a phenyl group, a
Such as phthyl group. These groups represented by R1 may have a single or multiple groups.
Including those with 4% u, for example, introduced into phenyl group
Typical substituents include halogen atoms (
For example, fluorine, chlorine, bromine, etc.), alkyl groups
(For example, methyl group, ethyl group, propyl group, butyl group
, dodecyl group, etc.), hydroxyl group, cyano group, nitro
group, alkoxy group (e.g. methoxy group, ethoxy group)
, alkylsulfonamide groups (e.g. methylsulfone
(amide group, octylsulfonamide group, etc.), aryls
sulfonamide group (e.g., phenylsulfonamide group,
(naphthylsulfonamide group, etc.), alkylsulfamoyl
(e.g., butylsulfamoyl group, etc.), aryl group (e.g., butylsulfamoyl group, etc.)
Sulfamoyl group (e.g. phenylsulfamoyl group)
etc.), argyloxycarbonylbonyl group, etc.), aryloxycarbonyl group (e.g.,
phenyloxycarbonyl group, etc.), aminosulfonamide
group (for example, N,N-dimethylaminosulfonamide)
), acylamino group, carbamoyl group, sulfonyl group, etc.), acylamino group, carbamoyl group,
group, sulfinyl group, sulfoxy group, sulfo group,
A lyloxy group, an alkoxy group, and a carboxyl group are formed. Two or more of these substituents are introduced into the phenyl group.
It's okay. The halogen atom represented by R3 is, for example, fluorine, salt
Each atom such as hydrogen, bromine, etc., and an alkyl group is
Tyl group, ethyl group, propyl group, butyl group, dodecyl group
etc., and the alkoxy group is, for example, a methoxy group,
These include ethoxy group, propyloxy group, butoxy group, etc. R3 may combine with R1 to form a ring. In the present invention, represented by R2 of the general formula [CC-1]
Examples of alkyl groups include methyl, ethyl, butyl
group, hexyl group, tridecyl group, pentadecyl group, hep
The so-called polyphenyl group substituted with tadecyl group and fluorine atom
Such as a fluoroalkyl group. The aryl group represented by R2 is, for example, a phenyl group, a
It is a phthyl group, preferably a phenyl group. R2
The heterocyclic group represented by is, for example, a pyridyl group, a 7-ran group
etc. The cycloalkyl group represented by R2 is, for example,
Examples include cyclopropyl group and cyclohexyl group. child
These groups represented by R2 have one or more substituents.
It also includes those with groups, for example, those introduced into phenyl groups.
Typical substituents include halogen atoms (e.g.
fluorine, chlorine, bromine, etc.), alkyl groups (e.g.
Methyl group, ethyl group, propyl group, butyl group, dodecyl group
hydroxyl group, cyano group, nitro group, alkaline group, etc.), hydroxyl group, cyano group, nitro group,
Koxy group (e.g. methoxy group, ethoxy group, etc.), alkyl
sulfonamide group (e.g. methylsulfonamide group,
octylsulfonamide group, etc.), arylsulfone 7 group
do group (e.g. phenylsulfonamide group, naphthyls
sulfonamide group, etc.), alkylsulfamoyl group (e.g.
(butylsulfamoyl group, etc.), arylsulfamoyl group, etc.
group (e.g., phenylsulfamoyl group, etc.),
(e.g., methyloxycarbonyl)
aryloxycarbonyl group, etc.), aryloxycarbonyl group (e.g., phenylene group),
Nyloxycarbonyl group, etc.), aminosulfonamide group
, acylamino group, carbamoyl group, sulfonyl group, sulphate
Rufinyl group, sulfooxy group, sulfo group, aryl group
xy group, alkoxy group, carboxyl group, alkyl group
Bonyl group, arylcarbonyl group, etc.
Wear. In these substituents, 213i or more leads to a phenyl group.
It may be included. Preferred groups represented by R2 include polyfluoro
alkyl group, phenyl group or halogen atom, alkyl group
, alkoxy group, alkylsulfonamide group, aryl
Sulfonamide group, alkylsulfamoyl group, aryl
Rusulfamoyl group, alkylsulfonyl group, aryl
Sulfonyl group, alkylcarbonyl group, arylcarbo
One or two nyl or cyano groups as substituents
It is a phenyl group having the above. In the present invention, cyan represented by the general formula [CC-11]
The dye-forming coupler preferably has the following general formula [CC-3
] It is a compound represented by. General formula [CC-31] In general formula [CC-3], R6 represents a phenyl group.
Was. This phenyl group has single or multiple substituents.
Typical substituents to be introduced include those with
However, halogen atoms (e.g. fluorine, chlorine, bromine, etc.)
), alkyl groups (e.g. methyl, ethyl, propylene)
), butyl group, octyl group, dodecyl group, etc.), hydro
xyl group, cyano group, nitro group, alkoxy group (e.g.
methoxy group, ethoxy group, etc.), alkylsulfonamide
groups (e.g. methylsulfonamide group, octylsulfone group)
amide group, etc.), arylsulfonamide group (for example) I
Nylsulfonamide group, naphthylsulfonamide 1, etc.)
, an alkylsulfamoyl group (e.g. 1 mole of butylsulf
arylsulfamoyl group (e.g. phenyl group), arylsulfamoyl group (e.g.
rusulfamoyl group, etc.), alkyloxycarbonyl j
l (VAλ is methyloxycarbonyl group, etc.), aryl
Oxycarbonyl U (e.g. phenyloxycarbonyl
etc.). These substituents are 2
More than one species may be replaced with phenyl groups. Table with R6
Preferred bases to be beaten include phenyl U or halo.
Gen atom (0, preferably fluorine, chlorine, and bromine atoms)
, an alkylsulfonamide group (preferably 0-methylsulfonamide group)
Rubonamide v, 'p-octylsulfonamide group, 0
-dodecylsulfonamide group), arylsulfonamide group
Do M (preferably phenylsulfonamide group), alkyl
0 mole of rusulfamoyl (preferably 1 mole of butylsulfur)
), arylsulfuryl moyl group (preferably phenyl group),
rusulfamoyl group), alkyl ζ group (preferably methyl
Le! j, trifluoromethyl), ゛alkoxy group (preferably
Preferably, one substituent (methoxy group, ethoxy group)
Or it is a phenyl group having two or more. R7 is an alkyl group or an aryl group. Alkyl group
or the aryl group can be substituted with single or multiple 1i substituents.
Typical examples of this substituent include
rogene atoms (e.g. fluorine, chlorine, bromine, etc. atoms),
Hydroxyl group, carboxyl group, alkyl group (e.g.
Methyl group, ethyl group, propyl 1J, butyl group, octyl group
aralkyl group, dodecyl group, etc.), aralkyl group, cyano group, nitro group, etc.
group, alkoxy group (e.g. methoxy group, ethoxy group)
, aryloxy group, alkylsulfonamide group (e.g.
Methylsulfonamide group, octylsulfonamide group
etc.), arylsulfonamide groups (e.g. phenylsulfonamide groups),
(honamide group, naphthylsulfonamide group, etc.), alkyl
Rusulfamoyl group (e.g. butylsulfamoyl group, etc.)
), arylsulfamoyl groups (e.g. phenylsulf
amoyl spheres, etc.), alkyloxycarbonyl groups (e.g.
(methyloxycarbonyl group, etc.), aryloxycarbo
Nyl group (e.g. phenyloxycarbonyl group, etc.), amino
Nosulfonamide group (e.g. dimethylaminosulfonate)
(mido group, etc.), alkylsulfonyl group, arylsulfonyl group
group, alkylcarbonyl group, arylcarbonyl group,
Examples include aminocarbonylamide group, carbamoyl, and the like. Two or more of these substituents
May be introduced. Preferred groups represented by R7 include when nl=0
is an alkyl group, and when nl −1 or more, it is an aryl group.
Ru. More preferable groups represented by R7 include:
When nl = 0, the alkyl of carbon v11~22flI]
group (preferably methyl group, ethyl group, propyl group, butyl group)
tyl group, octyl group, dodecyl group), and n1=1 or more.
In the above case, phenyl group or alkyl group (preferably
[-butyl group, t-amyl group, octyl group), alkyl
Sulfonamide group (preferably butylsulfonamide group)
, octyl sulfonamide group, dodecyl sulfonamide
), arylsulfonamide group (preferably phenyl
sulfonamide group), aminosulfonamide group (preferably
or dimethylaminosulfonamide group), alkyl quaternary
Ni-dicarbonyl group (preferably methyl A-oxycarbonyl
group, butyloxycarbonyl group) as a substituent.
or a phenyl group having two or more. R8 represents alkylene. Straight chain or branched carbon atom
Alkyl having 1 to 20 children and even 1 to 12 carbon atoms
Represents a ren group. R9 is a hydrogen atom or a halogen atom (fluorine, chlorine, odor
Represents each atom (such as elemental or iodine). Preferably a hydrogen source
It is a child. 01 is O or a positive integer, preferably O or 1
It is. x bar o-, -CO-, -COO-, -OCO-,
-SO2 NR-, -NR'302NR"-, -S-
, -SO- or -SO2- represents a divalent group. here
where R' and R'' represent an alkyl group, and R' and R'' are
Each includes substituents. X preferably
, -0-, -S-, -SO-, -SO2- groups. Z has the same meaning as 7 in the general formula [CC-11]. In the present invention, R4 in the general formula [CC-2]
Straight chain or branched alkyl group having 1 to 4 carbon atoms
is, for example, an ethyl group, a propyl group, a butyl group, an iso-
Propyl group, iso-butyl group, sec-butyl group, or
or tert-butyl group, which has a substituent
There are also things that are S. Substituents include acylamino groups (e.g.
acetylamino group), alkoxy group (e.g. methoxy group)
) etc. R→ is preferably an alkyl group having 2 to 4 carbon atoms.
Ru. The ballast L (represented by R5 is the coupler applied)
The coupler cannot substantially diffuse from the layer to other layers.
If we give the coupler molecule enough bulk to make it
It is an organic group that has the size and shape of a roller. Typical ballast groups include those with a total carbon number of 8 to 32.
Examples include alkyl groups and aryl groups. These alkyl or aryl groups have substituents
Including things. Examples of substituents for aryl groups include alkaline
Kirkudzu, aryl group, alkoxy group, aryloxy 1
1 Carboxy group, acyl group, ester group, hydroxy group
, cyano group, nitro group, carbamoylamide Ht, sulfamoyl group, and halogen atom.
It will be done. In addition, as a direct substituent for an alkyl group, an argyl group is used.
The substituents listed above for the aryl group to be excluded may be mentioned. Particularly preferred as the ballast group are the following general groups.
It is represented by the formula [CG-4]. General formula [CC-4 1 -CH-0-Ar Rho is a hydrogen atom or C 1 to C 12 Al 4
represents a nyl group, and Ar represents a 7-aryl group such as a phenyl group.
However, this aryl group also includes those having substituents. Place
Substituents include alkyl groups, hydroxy groups, and alkyl sulfur groups.
Examples include phonamide group, but the most preferred one is t
-A branched alkyl group such as a butyl group. General formulas [CG-11, [CC-2] and [CC-31
, aromatic primary amines each represented by 2
The group that can be separated by reaction with the oxidized form of color developing agent is
, which are well known to those skilled in the art and modify the reactivity of the coupler.
or detach from the coupler, silver halide color
Coating layers or other layers containing couplers in photographic materials
functions such as development suppression, bleaching suppression, color correction, etc.
It works advantageously by fulfilling the following. Typical
Examples include halogens such as chlorine and fluorine.
Gen atom, substituted/unsubstituted alkoxy group, aryloxy group
cy group, arylthio group, carbamoyloxynyloxy group, sulfonamide group or heteroylthio group
group, heteroyloxy group, etc. Particularly preferred Z is a hydrogen atom or a chlorine atom.
Ru. More specifically, Japanese Patent Application Laid-open No. 50-10135 and 5G-
No. 120334, No. 50-130441@, No. 54-4
No. 8237, No. 51-146828, No. 54-147
No. 36, No. 47-37425, No. 50-123341
No. 58-95346, Special Publication Showa 48-36894@
, US IN rF3, 47G, No. 563, liil
No. 3, 737, 316, No. 3.2271551
It is stated in each publication. Below, in the margin, the cyan cuffler represented by the general formula (mouth)-1.
Typical specific examples are shown, but are not limited to these (n)C
xcHnSOzNH C4H9(n) Crz□5LnJ C-32 Next, a specific example of the coupler represented by the general formula [cc-2]
However, it is not limited to these. The yellow dye-forming coupler used in the present invention is
, a compound represented by the following general formula [Yl is preferred. General formula [Yl OY'0 In the formula, R++ is an alkyl group (e.g. methyl group, ethyl group
, propyl group, butyl group or aryl group (e.g.
phenyl group, p-methoxyphenyl, etc.), and R1
2 represents an aryl group, Yl is a hydrogen atom or a color developing
Represents a group that leaves during the image reaction process. Additionally, it is particularly preferred as a yellow dye-forming coupler.
A compound represented by the following general formula [Y'] is preferred.
Yes. General formula [Y'] In the formula, R13 is a halogen atom, an alkoxy group, or an aryl group.
represents a roxy group, R+4, R+5, and R+6 are
hydrogen atom, halogen atom, alkyl group, alkyl group, respectively.
Nyl group, alkoxy group, aryl group, aryloxy group,
Carbonyl group, sulfonyl group, carboxyl group, alkyl group
Coxycarbonyl carbamyl sulfonamide group, acylamide group, ureido base or
represents an amino group, and Yl has the above-mentioned meaning. These include, for example, U.S. Pat. No. 2,778,658;
No. 2,875,057, No. 2,908,573,
Same No. 3,227, 155, Same No. 3,227,550
, No. 3,253,924, No. 3,265,506
No. 3,277, 155, No. 3,341, 3
No. 31, No. 3, 369, 895, No. 3, 38
No. 4,657, No. 3,408. No. 194, No. 3,
No. 415,652, No. 3,447, 928, No. 3
, 551, 155@, same No. 3, 582, 322
No. 3,725,072, No. 3,894,875
German Patent Publication No. 1,547,86
No. 8, No. 2,057,941, No. 2,162,8
No. 99, No. 2, IO 2,812, No. 2, 213
, No. 461, No. 2,219,917, No. 2,26
No. 1,361, No. 2,263,875, Tokukosho
No. 49-13576, JP 48-29432@, 4
No. 8-66834, No. 49-10736, No. 49-1
No. 22335, No. 50-28834, and No. 50-
It is described in Publication No. 132926 and the like. The yellow dye-forming capacitor represented by the general formula [Yl] is shown below.
Typical specific examples of ra are shown, but are limited to these
isn't it. Below Margin Y-3 Below Margin The silver halide photographic light-sensitive material of the present invention has defects in dye images.
Both stabilizers can be used for the purpose of preventing oxidation. Image quality stabilizer that can be preferably used in the present invention
As, the following general formulas [A] to [H] and [J], [K
] Compounds represented by the following can be mentioned. Below is the general formula [AI], where R is a hydrogen atom, a furkyl group, an alkenyl group, 7
Ryl group or heterocyclic group, R2, R,, R,, R
@ is a hydrogen atom, a 7% loden atom, and a hydroxyl group, respectively.
, furkyl group, alkenyl group, 7-aryl group, alkoxy
group or 7sylami7 group, R4 is furkyl
group, hydroxy group, 7-aryl group or alkoxy group
. Also, R3 and R2 close each other to form a 5-shell or 6-shell ring.
In this case, R4 may be a hydroxy group or an alkyl group.
Oxy group is added, and R7 and R1 form an M ring, and carbonization of 5 shells occurs.
A hydrogen ring may be formed, in which case R1 is a furkyl group.
, represents an aryl group, or a heterocyclic group, provided that R,
except when is a hydrogen atom and R4 is a hydroxy group
. In the general formula [AI, R, is a hydrogen atom, furkyl
group, alkenyl group, aryl group or heterocyclic group.
However, among these, as a furkyl group, for example, a methyl group
, ethyl group, propyl group, n-octyl group, tert-
Linear or branched chains such as octyl and hexadecyl groups
Mention may be made of the alkyl group. Hail again to R.
Examples of alkenyl groups include allyl, hexenyl,
Examples include octenyl group. @ et al., R1 7 Lee
Examples of the group include phenyl and naphthyl groups.
. Furthermore, as the heterocyclic group represented by R3, tetrahydro
Specific examples include ropyranyl group, pyrimidyl group, etc.
. Each of these groups can have a substituent, for example a substituent
As a furkyl group having a benzyl group,
Methyl group, as a group having a substituent,
xy7enyl group, chlorphenyl group, 4-hydroxy-
Examples include 3,5-butylphenyl group. In the general formula [AI, R2, R3, R1 and R6 are
Hydrogen atom, herodene atom, hydroxy group, alkyl group,
Alkenyl group, 7-aryl group, alkoxy group or 7-syl group
There are 7 groups of 7 groups, but among these, furkyl group, alkyl group,
Regarding the nyl group and the 7-aryl group, as described above for R6.
The same as an alkyl group, an alkenyl group, and a 7-aryl group
Can be mentioned. As the main herodene atom, for example, 7
Examples include 7 elements, chlorine, and bromine. further back
Examples of the alkoxy group include methoxy group, ethoxy group, etc.
can be specifically mentioned. In addition, the acyl 7mi
/ group is denoted by R'CONH-, where R
a is a furkyl group (e.g. methyl, ethyl, n-propyl
, n-butyl, n-octyl, tert-octyl, pen
groups such as acyl), alkenyl groups (e.g.
groups such as ctenyl and oleyl), 7-aryl groups (e.g.
each group such as phenyl, methoxy7dinyl, naphthyl),
or hesenkuchi ring groups (e.g. pyrinol, pyrimidyl groups)
) can be mentioned. In addition, in the general formula [AI, % R4 is a furkyl group,
Represents a hydroxy group, aryl group or alkoxy group
, among these, for the furkyl group and the 7-aryl group, the above-mentioned R
Contains the same alkyl group and aryl group shown in 3.
It can be mentioned physically. Also, for the alkenyl group of R1
Regarding R2, R=, Rs and R& mentioned above,
The same alkoxy groups can be mentioned. R1 and R2 close each other to form a benzene ring
Examples of rings include chroman, coumaran, and metelencho.
Examples include xybenzene. Also, R1 and R4 are ring-closed to form a benzene ring.
Examples of the ring include kidney bean. these
The ring may contain substituents (e.g. alkyl, alkoxy, aryl).
). Also, if R1 and R2 or R3 and R2 form a w1 ring,
A spiro compound is formed by using the atom in the ring as a spiro atom.
Alternatively, R2, R1, etc. may be used as linking groups to form a bis body.
may be formed. A phenolic compound represented by the general formula [A] or
Among the phenyl ether compounds, preferred are R
O- group (R is a furkyl group, an alkenyl group, an aryol group,
Or a biingonization having 4 ) which weakens the hetero m group
A compound of the following general formula [A-11] is particularly preferable.
You can make wheat. General formula [A-1] In the formula, R is a furkyl group (e.g. methyl, ethyl, propyl
, n-octyl, tert-octyl, pencil, hex
sadecyl), alkenyl groups (e.g., 7lyl, octenyl),
oleyl, oleyl), 7-aryl groups (e.g. phenyl, naphyl),
) or heterocyclic groups (e.g., tetrahydropyrani)
R3, pyrimidyl), R3 and
R+a is a hydrogen atom, a halogen atom, (for example, a fluoride atom,
element, chlorine, odor @), alkyl group (e.g. methyl, ethyl
, n-butyl, benol), alkoxy groups (e.g. ali
hexenyl, octenyl), or alkoxy groups (
For example, ethoxy, ethoxy, benzyloxy),
R11 is a hydrogen atom, an alkyl group (e.g. methyl, ethyl
% n-decyl, benzyl), alkenyl groups (e.g.
2-7-robenyl, hexenyl, octenyl), and
is an aryl group (e.g. phenyl, nodoxyphenyl,
lorphenyl, naphthyl). The compound represented by the general formula [A] is disclosed in U.S. Patent No. 3.
No. 9:15,016, No. 3,982,944, No. 9:15,016, No. 3,982,944, No.
4.254,216, JP-A-55-21004, same.
No. 54-145530, British Patent Publication No. 2,077.45
No. 5, No. 2,062, No. 888, U.S. Patent No. 3,76
4,337, No. 3.432300, No. 3.574
, No. 627, No. 3,573,050, Japanese Unexamined Patent Publication No. 1973-
No. 152225, No. 53-20327, No. 53-17
No. 729, No. 55-6321, British Patent No. 1,347
．． No. 556, Publication No. 2.066.975, Special Publication No. 1973
-12337, No. 48-31625, U.S. Patent No. 3
, 700, 455 and the like. The monthly usage amount of the compound weakened by the general formula [A] is mazen.
It is preferably 5 to 300 mol% based on Tacoupler, and more
Preferably it is 10-zoo mol%. Typical examples of the compound represented by the general formula [A] are shown below.
Give an example. Type (1) Type (2) Type (3) Type (4) Type (5) Type (6) Type (7) P K″l Type (2) Below margin type (4) Type ( 5) Type (6) Below margin A-7 Below margin General formula [B] In formula c, R1 and R1 are a hydrogen atom and a halogen atom, respectively.
child, alkyl group, alkenyl group, flukoxy group, alke
Nyloxy group, hydroxy group, aryl group,
Kishi flea, acyl group, 7 silami 7 groups, acyloxy group,
Sulfone 7mido group, cycloalkyl or alkoxyca
Rubonyl group, R2 is hydrogen atom, alkyl group,
Alkenyl group, aryl group, acyl group, cycloalkyl group
group or heterocyclic group, R3 is a hydrogen atom, halo
Gen atom, alkyl group, alkenyl group, aryl group,
lyloxy group, acyl group, 7syloxy group, sulfone
Amide group, cycloalkyl group or alkoxycarbonyl group
Hail to you. Each of the groups listed above may be substituted with other substituents.
For example, a furkyl group, an alkenyl group, a flukoxy group,
7 aryl group, aryloxy group, hydroxy group, alco
oxycarbonyl group, aryloxycarbonyl group, 7-carbonyl group
Ruamino group, acyloxy group, carbamoyl group, sulfonate group
Examples include amide group, sulfamoyl group, and the like. In addition, R2 and R1 close each other to form a 5-shell or 6-shell ring.
may form, R2 and Rx are ring-closed together with the benzene ring.
For example, the ring formed is a chroman ring, methylene oxy
One example is a benzene ring. Y is necessary to form a coumaran ring in Taloman's opinion.
Hail atomic groups. Chroman or coumaran ring is a halogen atom, furkyl
group, dichlorofurkyl group, alkoxy group, fulkenyl group,
Flukenyloxy group, hydroxy group, 7-lyl group, 7-lyl group
(,
Furthermore, a spiro ring may be formed. Among the compounds represented by the general formula [B], those particularly suitable for the present invention
Useful compounds have general formulas [B-1], [B-2], [B-3]
], [B-4], [B-5l]
be done. General formula [B-1] General formula [B-2] General formula [B-31 General formula [B -41 General formula [B-51] 1 General formula [B-1], [B -2], [B -3], [B
-4] R2, R control to [B -5]
and R4 have the same meaning as in the general formula [B] above.
Wait, R1, R2, Rs, R- and R1
゜ is hydrogen atom, halogen atom, alkyl group, alkoxy
group, hydroxy group, flukenyl group, flukenyloxy group
, 7-aryl group, aryloxy group or heterocyclic group
Alas. Furthermore, Rs and R, , R, and R1, R1 and R1, R1 and R
1 and R1 and R1° are cyclized with each other to form a carbocyclic ring
Furthermore, the carbocycle may be substituted with an alkyl group.
Good too. The general formula [B-13, [B-2], [B-33, [
B-4] Onozo [R1 and R1 in B-53
is hydrogen atom, furkyl group, alkoxy group, hydroxy group
or cycloalkyl group, R,, R1, R,, R,
and R8° is a hydrogen atom, an alkyl group, or a diclofyl group.
Particularly useful are compounds that are alkyl groups. The compound degraded by general formula [B] is tetrahedron (Te
trabedron), 1970. vo126,474
3-4751, Journal of the Chemical Society of Japan, 1972. No.10.
pp. 0987-1990, Chemical (cbem, Lett
), 1972 (4) pp. 315-316, Japanese Patent Application Publication No. 1987-
Represents and includes a compound described in No. 139383,
and synthetic leather according to the method described in these.
I can do it. The monthly usage amount of the compound represented by the general formula [B] is as follows.
5 to 300 for the magenta coupler according to the emulsion of the present invention.
Mol% preferably, more preferably 10 to 200 mol%
It is. Representative examples of these compounds are shown below. The following is a blank general formula [CI 8 section R'' General formula [D] In the formula, R1 and R1 are hydrogen atoms, halogen atoms,
ru group, flukenyl group, flukoxy group, alkenyloxy
group, hydroxy group, aryl group, aryloxy group, a
Syl group, 7-syl amino group, 7F, ruoxy group, sulfone
7 mido group or flukoxycarbonyl group. Each of the groups listed above may be replaced with other substituents.
6 For example, halogen atom, alkyl group, fulkenyl group,
Flukoxy group, aryloxy group, hydroxy group, flu
Coxycarbonyl group, aryloxycarbonyl group,
Silami 7 groups, carbamoyl group, sulfonamide Y group,
Examples include rufuamoyl group. Y is a benzene ring and a dichroman or dicoumaran ring
List the atomic groups necessary to form b. Taloman or coumaran ring is a halogen atom, an alkyl
group, dichlorofurkyl group, alkoxy group, alkenyl group,
Alkenyloxy group, hydroxy group, aryl group, aryl group
may be substituted with a ruoxy group or a heterocyclic group,
Furthermore, a spiro ring may be formed. Among the compounds represented by the general formula [CI and [DI], this
Compounds particularly useful in the invention have general formulas [C-1] and [C-2
], [D-1] and [D-2]
included in General formula [C-1] General formula [C-21 81 General formula [D-11 General formula [D-21 General formula [C-13, [C-2], [D-13 Ascend [D
R1 and R2 in the general formula EC] and
and have the same meaning as in [D,], Ryu, R4
%R6, R6, R7 and R1 are hydrogen atoms, halogen atoms
child, alkyl group, alkoxy group, hydroxy group, alke
Nyl group, alkenyloxy group, 7-aryl group, aryl group
xy group or heterocyclic group, and R1 and R
R4 and R6, R9 and R6, R6 and R2 and R1
R1 may be cyclized with each other to form a carbocyclic ring, and
The carbocycle is an alkyl group and r! ! may be replaced. The general formula [C-1], [C-2], [D-1] and
[D-2] R and R2 are hydrogen atoms,
Alkyl group, alkoxy group, hydroxy group or cyclo
Alkyl group, R1, R1, R6, R2 and R3 are
is a hydrogen atom, an alkyl group, or a cycloalkyl group
Compounds are particularly useful. Compounds represented by the general formula [CI, ID] are those of the Chemical Society of Japan.
Magazine (J, Che+s, Soc, part C) 1
968. (14) * pp. 1937-18, Arimo 1 synthesis
Academic Society Journal 1970.2B(1), pp. 60-65, Tet
Rahedron (Tetrahedron Letters)
) 1973, (29), 2707-2710 Makotoki $
Contains the compounds listed in 2 and are listed in these.
Method I: Therefore, it can be synthesized. The amount of the compound represented by the general formula [CI, [DI] is
, 5 to 30 for the magenta coupler according to the present invention.
Preferably 0 mol%, more preferably 10-200 mol%
%. Specific representative examples of these compounds are shown below. Below is the general formula (E) in which R1 is a hydrogen atom, an alkyl group, an alkenyl group, an ali
group, acyl group, dichlorofurkyl group or heterocycle
s R' is a hydrogen atom, a halogen atom, an alkyl
group, alkenyl group, aryl group, aryloxy group,
Acyl group, acylami 7 group, 7 syloxy group, sulfone
Amide group, cycloalkyl group or alkoxycarbo
Depletes the nyl group. R2 and VR' are hydrogen atoms, halogen atoms, alkyl groups
, alkenyl group, aryl group, acyl group, acylami/
group, sulfonamide group, cycloalkyl group or alkyl group
Represents a koxycarbonyl group. Each of the groups listed above is substituted with other substituents.
1 For example, alkyl group, alkenyl group, alkoxy
group, aryl group, aryloxy group, hydroxy group, aryl group,
Rukoxycarbonyl group, Roxycarbonyl group,
Acyl 7mi7 group, carbamoyl group, sulfonamide group,
Examples include sulfamoyl group. In addition, R1 and R2 close each other to form a 5-shell or 6-shell ring.
may be formed. At that time, R1/'R' is a hydrogen atom, a halogen atom,
Furkyl group, alkenyl group, alkoxy group, alkenyl
Oxy group, hydroxy group, aryl group, 7-aryloxy
group, acyl group, 7syl amino group, 7syloxy group, sulfur
Hon7 represents a mido group or an alkoxycarbonyl group
. Y is necessary to form a chroman or coumaran ring
Make a group of atoms. Chroman or coumaran ring is a halogen atom, furkyl
group, cycloalkyl group, alkoxy group, alkenyl group,
Alkenyloxy group, hydroxy group, 7-aryl group, 7-aryl group
il! with a ruoxy group or a heterocyclic group! has not been replaced
or may further form a spiro ring. Among the compounds represented by the general formula [E], *particularly applicable to the invention
The compound used is general formula (E-1). (E-2), (E-3], (E-4) and (E-5)
It is included in the compound represented by. General formula (E-1) R1 81 General formula (E-23 OR+ General formula (E-3) W 8゛-OR' General formula (E-4) General formula (E-5) General formula (E- 1) to (R in E-53 1%1(2
, R3 and R4 are the same as in the above general formula [E]
with meaning, Rs, Ha, Rt, Ra, Rs and RI
a is hydrogen atom, halogen atom, furkyl group, alkoxy
cy group, hydroxy group, alkenyl group, alkenyloxy
group, aryl group, 7-aryloxy group or heterocyclic group
Rf and R6, R6 and R7, R1 and R”
, R" and R'(/"R' and RI 11 are mutually ring
may be converted into a carbocyclic ring, and furthermore, the carbocyclic ring may be
May be substituted with a kill group. In the general formulas (E-1) to (E-5), R', R
", R' and (/"R' is a hydrogen atom, an alkyl group, or
is a cycloalkyl group, in the general formula (E-5),
R' and R4 are hydrogen atoms, furkyl groups, alkoxy groups
, a hydroxy group or a cycloalkyl group;
General formula [E-1] to (E-5) Nioite, R', R', R
Fu-R' s R' *yo [/R" is a hydrogen atom, an alkyl
Compounds with a group of 1 or cycloalkyl are particularly useful.
It is. The compound represented by the general formula [E] is tetrahedron (
Tetraheclron Letters) 196
5. (8), pp. 457-460 Journal of the Chemical Society of Japan (J, C
hew, Soc, part C) 1966° (2
2), pp. 2013-2016, (Zb, Org,
Kbim) 1970. (6) -1230~1237 true
Contains compounds listed in and listed in these
It can be synthesized according to the method described. The amount of the compound represented by the general formula [E-1] is
5 to 300 moles for the magenta coupler according to the present invention.
preferably 10 to 200 mol%.
be. Specific representative examples of these compounds are shown below. The following is a general formula (F) in which R is a hydrogen atom, a furkyl group, an alkenyl group, or a 7-aryl group.
L group, 7-syl group, and dichlorofurkyl group are also L (heterocyclic
represents a group, R2 is a hydrogen atom, a halogen atom, a furkyl group
, alkenyl group, aryl group, 7-aryloxy group, 7-silyl group
group, 7 sylamine/group, 7 syloxy group, sulfone 7 group
group, cycloalkyl group, or alkoxycarbonyl group
Hail to you. R is a hydrogen atom, halo, dene atom, alkyl group, alke
Nyl group, aryl group, 7yl group, acylamino group, sulfur group
Hon7mir group, dichlorofurkyl group or alkoxycarboxylic acid
List the carbonyl group. R4 is a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group.
group, alkoxy group, alkenyloxy group, hydroxy
group, 7-lyl group, Ryoruokine group, 7-syl group, 7-syl group
Ami/group, 7syloxy group, sulfone 7mido group, or
represents an alkoxycarbonyl group. Each of the groups listed above may be substituted with other substituents.
For example, furkyl group, alkenyl group, alkoxy group
, 7-aryl group, aryloxy group, hydroxy group, alkyl group
Koxycarbonyl group, aryloxycarbonyl group, 7
sil7mi7 group, carbamoyl group, sulfonamide group,
Examples include a 7-moyl group. Also, R and R close each other to form a 5-shell or 6-shell ring.
In that case, R3 and R1 are hydrogen atoms, halogen atoms.
atom, alkyl group, alkenyl group, alkoxy group,
rukenyloxy group, hydroxy group, aryl group, 7-ary
7-syloxy group, 7-syl group, 7-syl-7mino group, 7-syloxy group
group, sulfonamide group, or alkoxycarbonyl
Destroy the base. Y is necessary to form a chroman or coumaran ring
Hail atomic groups. Chroman or coumaran ring is a halogen atom, alkyl
group, cycloalkyl group, alkoxy group, fulkenyl group,
alkenyloxy group, hydroquine group, aryl group, aryl group
may be substituted with a hydroxyl group or a heterocyclic group.
Furthermore, a spiro ring may be formed. Among the compounds represented by the general formula [F], those particularly suitable for the present invention
Useful compounds have general formulas [F-1] and [F-2]. Indicated by [F-3], [F-41 and [F-5]
Included in compounds. The following are blank general formulas (F-11 General formula [F-2] General formula CF-3) General formula [F-4] General formula (F-5) General formula [R1, R2 in F-11 and IF-51
, R, and R1 are the same as in the above general formula [F]
with meaning, Rs=Rs, R7, R1, R3 and R3
゜ is hydrogen atom, halogen atom, alkyl group, alkoxy
group, doroquine group, fulkenyl group, alkenyloxy group
, 7-aryl group, aryloxy, I-t' I+
Hesenro-style certain net gets fat during h-further R5 and R R1 and R7
, R7 and R1, R8 and Rs, and R9 and Rla are mutually
may be cyclized to form a carbocycle, and furthermore, the R ring is
It may be substituted with an alkyl group. Also, [F-31, [F-41 upper tF[F-5]1
: The two R1-RB are the same or different.
You can stay there. The general formula [F-11, [F-21, [F-31, [
F-4] and V[F-5], R2, and
R3 is a hydrogen atom, a furkyl group, a dichlorofurkyl group, R1
is hydrogen atom, alkyl group □, alkoxy group, hydroxy
a base or a cycloalkyl group, further R5, R,, R1,
R1, R9 and R1° are hydrogen atoms, furkyl groups, or
Compounds having a dichlorofurkyl group are particularly useful. The compound degraded by the general formula [F] is tetrahedron (
Tetrahedron Letters) 197G
, Vol 26, 4743-4751'! X1 Japaneseization
Academic journal 1972. No.lQ, 1987-199
Page 0, Synthesis 19F5
．． Vol 6゜pages 392-393, (Bul 5
oCp Chime Be1g ) 197L
Vol 84 ()), pages 747-759.
Contains compounds that are present and listed in these! ! the way it is
It can be synthesized according to The usage amount of the compound represented by the general formula [F] is determined according to the above book.
5 to 300 mol% based on the magenta coupler according to the invention
is preferable, more preferably 10 to 200 mol%
. Specific representative examples of compounds weakened by general formula [F] are shown below.
show. The following is a blank general formula [G] R' R] In the formula, R' and R2 are each a hydrogen atom, and
child, furkyl group, fulkenyl group, flukoxy group, hydro
xy group, aryl group, 7-aryloxy group, 7-syl group, a
Cylamino group, acyloxy group, sulfone 7-mido group, cylamino group
Represents a chloroalkyl group or an alkoxycarbonyl group. R2 is a hydrogen atom, a halogen atom, an alkyl group, or a fluorine atom.
1 acyl group, hydroxyl group, 7 aryl group, acyl group
Mi7 group, acyloxy group, sulfonamide group, diclof
alkyl or flukoxycarbonyl groups. Each of the groups listed above may be substituted with other substituents.
I-5! As a substituent, for example, a furkyl group, a flukenyl group
, flukoxy group, aryl group, aryloxy group, hydrogen
Roxy group, flukoxycarbonyl group, aryloxycarbonyl group
carbonyl group, acyl amino group, carbamoyl group, sulfur
Examples include a phon7mido group and a sulfamoyl group. In addition, R2 and R) are ring-closed with each other, and carbonization of 5 or 6 shells occurs.
These 5 or 6 hydrocarbons may form hydrogen rings.
Bare rings include halogen atoms, furkyl groups, cycloalkyl groups,
Alkoxy group, alkenyl group, hydroxy group, aryl
substituted with a group, an aryloxy group, a heterocyclic group, etc.
Good too. Y represents the atomic group necessary to form an indane ring,
The Ndan ring is a halogen atom, a furkyl group, an alkenyl group,
Alkoxy group, cycloalkyl group, hydroxy group, ali
Substituted with a ring group, a 7-aryloxy group, a heterocyclic group, etc.
or may further form a spiro ring. Among the compounds represented by general formula (G), particularly useful for the present invention
Compound I is represented by the general formula [G-13 to [G-3]
Included in compounds. The following are blank general formulas (G-1) K' General formula (G-2) General formula (G-3) R1 and R2 in general formulas (G-1) to (G-3)
R3C± is the same a as in general formula (G), and R'
, R', R', R', R'' and R'j!, 7t1-?!
'L hydrogen atom, halogen atom, alkyl group, alkoxy
group, alkenyl group, hydroxy group, 7-aryl group, aryl group
R4 and R1% R representing a fluoroxy group or a heterocyclic group
5 and Ra, K' and R1, R' and R1, and R'' and K' are mutually exclusive.
The ring may be closed to form a hydrocarbon ring, and the
Hydrogen rings may be substituted with alkyl groups. In the general formulas (G-1) to (G-3), R', i
f/R' is a hydrogen atom, an alkyl group, an alkoxy group, a hydride
Roxy group or dichlorofurkyl group, R2 is a hydrogen atom,
alkyl group, a hydroxy group, or a kyl group at 907, R'
, R', R", Rf, RaXvR"bt hydrogen atom, Al
Compounds that are kill or cycloalkyl groups are particularly useful.
It is. The amount of the compound represented by the general formula [G]
5-300 mol% based on zenta coupler is preferred;
More preferably, it is 10 to 200 mol%. Typical specific examples of compounds represented by general formula [G] are shown below.
show. The following is a blank general formula [H] R2, where R' and R2 are each a hydrogen atom, and
child, alkyl group, alkenyl group, aryl group, acyl group
, acylamino group, acyloxy group, sulfonamide group
, represents a dichlorofurkyl group or an alkoxycarbonyl group.
vinegar. R3 is a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group
group, alkoxy group, hydroxy group, aryol group, aryl group,
yloxy group, 7yl group, acylamide 7 group, acyloxy group
cy group, sulfonamide group, cycloalkyl group or alkyl group
Decreases Fukidicarbonyl group. Each of the groups listed above may be substituted with other substituents.
For example, an alkyl group, an alkenyl group, an alkoxy group,
7-aryl group, 7-aryloxy group, hydroxy group, alco
oxycarbonyl group, aryloxycarbonyl group, acyloxycarbonyl group,
7 groups, carbamoyl group, sulfonamide group, sulfonamide group,
Examples include a 77 moyl group. In addition, R1 and R1 and (/R'' and R3 are ring-closed with each other, and 5 shells
Alternatively, a six-shell hydrocarbon ring may be formed, and the hydrocarbon
The ring is a halogen atom, a furkyl group, a dichlorofurkyl group, or an atom.
Rukoxy group, alkenyl group, hydroxy group, 7-aryl group
, may be substituted with an aryloxy group, a heterocyclic group, etc.
. Y represents an atomic group necessary to form a kidney bean ring, and
The bean ring is substituted with a substituent that can di-convert the above hydrocarbon ring.
or may further form a spiro ring. Among the compounds represented by the general formula (H), most useful for the present invention
Compounds represented by general formulas (H-1) to (H-2) are
included in the compound. General formula (H-13 General formula (H-23 General formula (H-3) General formula (H-1) - (R l, R2 and
and R3 have the same meanings as in general formula (H), and R4
,R8,R',R',R"l[/R"ji,+hrhwater
Elementary atoms, halogen atoms, furkyl groups, alkoxy groups,
Droxy group, fluganyl group, aryol group, aryloxy group
represents a group or a hetero R group, and also R' and R'% R'
and R', R' and R', R' and R'' and FR' and R1 are mutually
may be ffl[ to form a hydrocarbon ring, and further the carbon may be
The hydrogenated ring may be substituted with a furkyl group. In the general formulas ()f-1) to (H-3), 11j
l and R2 are hydrogen atoms, furkyl groups, or
Dichlorofurkyl group R3 is a hydrogen atom, a furkyl group, an alkyl group
Koxy group, hydroxy group or cycloalkyl group, Ra
, Rs, p, a, Rt, Ra and R are respectively water
Elementary atoms 1. A radical that is a furkyl group or a dichlorofurkyl group
Compounds are particularly useful. The method for synthesizing the compound reduced by the general formula [H] is known.
No. 3,057,929, Chell. Ber, 1972.95(5), 1673-16
741. Che! Jist-ry L etter
s, 1980, pp. 739-742.
Ru. The compound magenta coupler represented by the general formula [H]
It is preferably 5 to 300 mol%, more preferably 1
It is 0 to 200 mol%. Specific representative examples represented by the general formula [H] are shown below. The following blanks represent the general formula (J) -- or a 7-aryl group, and Y represents a nitrogen atom and 5 to 7 shell rings.
decomposes in the nonmetallic atoms necessary to form the heterocycle of
and the nonmetallic atom containing the nitrogen atom forming the atom ring.
If there are two or more heteroatoms in the molecule, at least two
The heteroatoms of are heteroatoms that are not adjacent to each other. ] The aliphatic group represented by R' may have a substituent.
unsaturated alkyl groups, and unsaturated alkyl groups that may have substituents.
Examples include alkyl group. Examples of saturated alkyl groups include
For example, methyl group, ethyl group, butyl group, octyl group, dode
Examples include sil group, tetradecyl group, hexadecyl group, etc.
, unsaturated alkyl groups include, for example, ethynyl group,
Examples include a lopenyl group. As the cycloalkyl group represented by R1''Ch, the substituent
A cycloalkyl group of 5-7 shells which may have, for example,
Examples include cyclopentyl group and cyclohexyl group. As the R1t'R3h71J- group, each
Represents a phenyl group or naphthyl group that may have a substituent. R't'i aliphatic group, cycloalkyl group, aryl
Examples of substituents for the group include alkyl groups, aryl groups, and
Koxy group, carbonyl group, carbamoyl group, acylamide
7 groups, sulfone 77 moyl group, sulfone 7 mido group, carbonyl group
group, alkylsulfonyl group, arylsulfony group
group, hydroxy group, heterocyclic group, alkylthio group,
These include lylthio groups, and these substituents can be further substituted.
It may have a substituent. In the general formula [J], Y together with M atoms is 5 to 7
Represents a group of nonmetallic atoms necessary to form the bilobed ring of a shellfish ring.
is a group of nonmetallic atoms containing nitrogen atoms forming the multi-chain ring.
At least two must be heteroatoms, the main,
These at least two heteroatoms must not come into instant contact with each other.
In the heterocyclic ring of the compound represented by the general formula (J)
If all the heteroatoms are in instant contact with each other, mazen
It is possible to exhibit selectivity as a dye image stabilizing specific gravity.
I don't like it because there isn't. The 5 to 7 rings of the compound represented by the general formula (J)
The heterocycle may have a substituent, and the M substituent is
Kyl group, teryl group, 7yl group, carbamoyl group, alkyl group,
Koxycarbonyl group, sulfonyl group, sulfamoyl group
etc., and may further have a substituent, and 5 to 7
Kaikan's f! A monocyclic ring may be saturated, but a saturated atom ring may be saturated.
A ring is preferable, and a benzene ring or the like is combined with the heterocycle.
or may form a spiro ring. The amount of the compound represented by the general formula (J) of the present invention is
, a magenta coupler attenuated by the general formula (1) of the present invention
It is preferably 5 to 300 mol% based on L (more preferably
is 10 to 200 mol%. A specific example of a vicarious decay using the general formula (J) will be shown below. Margin R1-C below) J-69 J-70 ■ ■ ■ ctzllzs Among the compounds represented by the previous general formula (J), piperazine
type compounds and homopiperazine type compounds are highly preferred;
More preferably, the following general formula (J-1) or (J-
This is a compound represented by 2). General formula (J-13 General formula (J-2) In the formula, R2 and R3 are a hydrogen atom and an alkyl group, respectively.
or represents an aryl group, provided that R2 and R1 are simultaneously water
Each of R4 to R+i is a hydrogen atom.
represents a child, an alkyl group, or an aryl group. A compound represented by the general formula (J-13 or [J-2])
A specific example of the compound is the above-mentioned exemplified piperazine compound I# (J
-1)-(J-30) and exemplary homopiperazine compounds
As described in item (J-51)-(J-62)
be. Next, a representative matrix of the present invention represented by the general formula (J)
An example of synthesis of a zenta dye image stabilizer is shown. Synthesis Example-1 (Synthesis of Compound J-2) 9.0 g of piperazine and 55 g of myristyl bromide
In 77 tons of dissolved 100.9, anhydrous potassium carbonate
15 g was added and the mixture was boiled and refluxed for 10 hours to react. After the reaction, the solution was poured into 500 mG of water, and then the acetic acid solution was poured into 500 mG of water.
Chill 500ml! Extracted with. The ethyl acetate layer was diluted with sulfuric acid.
After drying with magnesium and distilling off the ethyl acetate, a white crystal appears.
The desired crystalline product was obtained. acetone ao o ml
Recrystallize to obtain 34 g of white scaly crystals ([rate 70%)]
I got it. Melt j: L55-58°C Synthesis Example-2 (Compound P: Synthesis of !JJ-34) A-x
n, -b n p -fu - It'i
10- + 1'k Continued-< ,-So to Dissolved in 〇
After that, add anhydrous vinegar while stirring and keeping the reaction solution at 20°C.
Acid 12- was added in portions. After adding acetic anhydride, cool with water,
After filtering the precipitated crystals, recrystallize with ethyl acetate to obtain a white
16.5 g (yield: 7596) of colored powder crystals were obtained. Melting point 207-210°C R2 and
VR' is a hydrogen atom, an alkyl group, or a hydrogen atom, respectively.
represents a furkyl group represented by R2 or R3.
For example, methyl group, ethyl group, butyl group, octyl group, etc.
Tyl group, dodecyl group, te)labyl group, hexadecyl group
, octadecyl group, etc. Represented by R2 or R3
Examples of the 7-aryl group include phenyl group.
The furkyl group and aryl group represented by Hz or R3 are
It may have a substituent, and examples of the substituent include
child, furkyl group, aryl group, alkoxy group, 7 aryl
Examples include oxy group and heterocyclic group. The total number of carbon atoms of R2 and R' (including substituents) is 6 to
40 is my favorite. In the general formula (J-13 or (J-2)!-1,
R4-fl12 is a hydrogen atom, an alkyl group or
represents a 79-yl group;
Examples of the group include methyl group, ethyl group, etc.
It will be done. The aryl group represented by R4 to R1 is
Examples include nyl group. General formula [K] In the formula, R' is an aliphatic group, a dichlorofurkyl group, or an aryl group.
% Y represents a heterocyclic ring with 5-7 shells together with a nitrogen atom.
Mere bonds or divalent hydrocarbons needed to form
R", R", R4゜R5, R~R7 representing a group is that
hydrogen atom, aliphatic group, cycloalkyl group or aliphatic group, respectively
represents a group, provided that R2 and R4 and R3 and R6 are mutually
to form a simple bond, and together with the nitrogen atom and Y
May form an unsaturated 5-7 shell heterocycle;
When Y is a simple bond, Rs and Ht bond to each other.
forms a simple bond and forms an unsaturated nitrogen atom with Y.
May form an i-element ring of 5 shell rings, or Y may be a mere bond.
If it is not a hand, use R1 and Y, R' and Y, or Y itself.
Forms an unsaturated bond L-1”Nitrogen atom, unsaturated with Y
6 members or 7 true 1! May form an elementary ring. The aliphatic group represented by R' may have a substituent.
unsaturated alkyl groups, and unsaturated alkyl groups that may have substituents.
Examples include alkyl group. Examples of saturated alkyl groups include
For example, methyl group, ethyl group, butyl group, octyl group, dode
Examples include sil group, tetradecyl group, hexadecyl group, etc.
, unsaturated alkyl groups include, for example, ethynyl group,
Examples include robenyl group. The dichlorofurkyl group represented by R1 has a substituent.
For example, Schiff
Examples include a bentyl group and a cyclohexyl group. As the 7-lyl group honored by R1, even if it has a substituent,
Represents a good phenyl group or naphthyl group. jIlIJJ group group represented by R1, cycloalkyl group,
As a substituent for the aryl group, an alkyl group, an aryl group
, alkoxy group, carbonyl group, carbamoyl group, acyl
7 groups, sulfamoyl groups, sulfonami) groups,
Rubonyloxy group, Furkylsulfonyl group, Ryoriichirusu
Suitable for sulfonyl group, hydroxy group, heterocyclic group, and furkyl group.
group, 7-arylthio group, etc., and these substituents include
It may further have a substituent. In the general formula (K), Y together with the nitrogen atom is 5 to 7
A simple bond or
It represents a divalent hydrocarbon group, but when Y is just a bond,
, furthermore, Hs and R1 combine with each other to form a simple bond.
may form an unsaturated pentagonal heterocycle, or
When Y is a divalent monovalent hydrogen group, that is, when it is a methylene group,
In this case, R5 and Y or R1 and Y form an unsaturated bond.
However, it may form an unsaturated hexacyclic heterocycle, and
In the case of a tyrene group, R1 and Y, R' and Y or Y itself
to form an unsaturated bond and form an unsaturated heptad bilobal ring.
Furthermore, the divalent hydrocarbon group represented by Y may be substituted with
It may have a substituent, and this r! The l substituent includes an alkyl group
, carbamoyl group, alkyloxycarbonyl group, 7-carbonyl group,
7mino group, 1″ group, sulfamoyl group,
Examples include an aryl group and a heterocyclic group. In the general formula (Kl), R", R3, R4, R%. Rg and R7 are a hydrogen atom, a WI aliphatic group, respectively.
Represents a loalkyl group or an aryl group, but % R''-R'
So 2! The aliphatic group may have a substituent.
Saturated alkyl groups and unsaturated alkyl groups that may have substituents
Examples include ru groups. As the saturated furkyl group, for example,
Methyl group, ethyl group, butyl group, octyl group, dodecyl group
group, tetofdecyl group, hexadecyl group, etc.
Examples of saturated furkyl groups include ethynyl group, bucobe
Examples include nyl group. 9 with R2-R7. As the dichlorofurkyl group,
A 5- to 7-ring cycloalkyl group that may have a substituent,
For example, cyclopentyl group, cyclohexyl group, etc.
I can ride. The R2-R7 group has a substituent.
Examples include a phenyl group, a naphthyl group, and the like. Aliphatic group, cycloalkyl group attenuated by R2 to Rd above
, as substituents for aryl groups, alkyl groups, aryl
group, flukoxy group, carbonyl group, carbamoyl group,
cylamino group, sulfone 77 moyl group, sulfone 7 mido group,
Carbonyloxy group, alkylsulfonyl group, aryl
Sulfonyl group, hydroxy group, heterocyclic group, alkyl group
Examples include O groups. The compound represented by the general formula (K) has 5 to 7 shell rings.
It is preferable that the compound has the same heterocyclic ring as the unsaturated one.
stomach. The amount of the compound represented by the general formula (K) below is as follows:
Magenta coupler of the present invention represented by the above general formula (I)
It is preferably 5 to 300 mol%, more preferably
It is 10 to 200 mol%. Typical specific examples of the compound represented by the general formula (K) are shown below.
vinegar. In the margin below -34 to -35 to -36 to -37 to -38 to -39 to -40 to -41 Next, a preliminary synthesis of the compound represented by the above general formula (K)
Give an example. Synthesis Example-1 (Synthesis of Compound -14) Piperazine 9.0. and 28g of myristyl bromide
Dissolved 60. Anhydrous potassium carbonate 6 in acetone of Q
．． 0 g was added, and the mixture was boiled and refluxed for 20 hours to react. After the reaction, the reaction solution was poured into 300 mQ of water, and then added with vinegar.
Extracted with 300 tIlu of ethyl acid. Ethyl acetate layer
After drying with magnesium sulfate, ethyl acetate is distilled off.
The desired product was obtained as white crystals. Acetone 100 all
12g of white scaly crystals (yield: 43%)
) was obtained. rI&! :F, 175-180°C Protective layer, intermediate layer, etc. of the silver halide photographic material of the present invention
The hydrophilic colloid layer of the photosensitive material is charged with 1"I1.i etc.
Prevents fogging due to discharge caused by UV light in the image
Contains ultraviolet absorber to prevent deterioration caused by
Also good. The silver halide photographic light-sensitive material of the present invention includes a filter layer.
, antihalation layer, and/or anti-irradiation layer.
An auxiliary layer such as a stop layer can be provided. In these layers and
/or in the emulsion layer, from the color light-sensitive material during the development process.
Contains dyes that run off or bleach
Also good. Silver halide emulsion of the silver halide photographic light-sensitive material of the present invention
layer and/or other hydrophilic colloid layer of photosensitive material.
Prevents mutual scratching of sensitive materials to reduce gloss and improve retouchability
A matting agent can be added with the aim of preventing Reducing sliding fJ friction of the silver halide photographic light-sensitive material of the present invention
A lubricant can be added to increase the The purpose of the silver halide photographic light-sensitive material of the present invention is to prevent static electricity.
Antistatic agents can be added. The antistatic agent is
It may also be used as an antistatic layer on the side where emulsion is not laminated.
However, the emulsion layer is a VS layer with respect to the emulsion layer and/or the support.
Used in protective colloid layers other than the emulsion layer on the side where
It's okay. The photographic emulsion layer and/or the silver halide photographic light-sensitive material of the present invention
Or, the hydrophilic colloid layer has improved coating properties and antistatic properties.
, improved slipperiness, emulsification and dispersion, prevention of adhesion, and (promotion of development)
, high contrast, sensitization, etc.) for the purpose of improving photographic characteristics, etc.
Various surfactants are used. The silver halide photographic light-sensitive material of the present invention includes a photographic emulsion layer, and
Other layers are baryta paper or α-olefin polymerer, etc.
Flexible reflective support such as paper laminated with synthetic paper, vinegar
Acid cellulose, nitrate cellulose, polystyrene, polysalt
vinyl chloride, polyethylene terephthalate, polycarbonate
Fibers made of semi-synthetic or synthetic polymers such as carbon fibers, polyamides, etc.
Can be applied to rigid bodies such as film, glass, metal, and ceramics.
Ru. The silver halide photographic photosensitive material of the present invention may be provided as necessary.
The surface of the holding body is subjected to corona discharge, ultraviolet irradiation, flame treatment, etc.
After that, directly or (adhesiveness, antistatic property, dimensional
degree stability, wear resistance, hardness, antihalation, friction
1 or to improve the properties and/or other properties.
or two or more undercoat layers). When coating the silver halide photographic light-sensitive material of the present invention,
A thickener may be used to improve fabric properties. Application method and
It is an extruder that allows you to apply two or more layers at the same time.
Doll silicone coating and curtain coating
Particularly useful. The silver halide photographic light-sensitive material of the present invention is composed of
Electromagnetic radiation in the spectral region to which the emulsion layer is sensitive
Exposure can be done using waves. As a light source, natural light (sunlight)
, tungsten electric lamp, fluorescent lamp, mercury lamp, xenon arc
lamp, carbon arc lamp, xenon flash lamp, J344 line
Tube flying spot, various laser lights, light emitting diode
Excited by light, electron beam, xrA, γ rays, α rays, etc.
Any known light source, such as light emitted from a phosphor
It can be used. The exposure time is usually between 1 millisecond and 1 second, which is used in cameras.
Of course, exposure time is shorter than 1 microsecond, for example, in the shade.
100 microseconds to 1 using polar ray tube or xenon flash lamp
Microsecond exposures can be used, or even longer than 1 second.
Longer exposures are also possible. The exposure is carried out continuously.
It may also be performed intermittently. The silver halide photographic light-sensitive material of the present invention can be prepared using a silver halide photographic material known in the art.
An image can be formed by color development. Aromatic primary atom used in color developer in the present invention
Min-based color developing agents are used in various color photographic processes.
This includes well-known and widely used methods. These developers are aminophenolic and p-phenylene
Contains diamine derivatives. These compounds are free
generally in salt form, e.g. hydrochloride or
(illFi! is used in the form of salts. Also, these compounds
The compound is generally about 0.1 g to about
Concentration of 30 g, preferably about 1 per 12 chromogenic liquid
g to about 15 (l). As the amine phenol developer, for example, O-amino
Phenol, p-aminophenol, 5-amino-2-
Oxytoluene, 2-amino-3-oxytoluene, 2
-oxy-3-amino-1,4-dimethylbenzene, etc.
is included. Particularly useful primary aromatic amine coloring agents include N, N'
-Dialkyl-p-phenylenediamine compound
, alkyl groups and phenyl groups are substituted with any substituents.
You can leave it there. Among them, examples of particularly useful compounds include
, N,N'-diethyl-p-phenylenediamine hydrochloride
salt, N-methyl-p-phenylenediamine hydrochloride, N,
N'-dimethyl-p-phenylenediamine hydrochloride, 2
-amino-5-(N-ethyl-N-dodecylamino)-
Toluene, N-ethyl-N-β-methanesulfonamide
Ethyl-3-methyl-4-aminoaniline sulfate, N-
Ethyl-N-β-human O-oxyethylaminoaniline, 4
-amino-3-methyl-N. N'-diethylaniline, 4-amino-N-(2-meth
xyethyl)-N-ethyl-3-methylaniline-p-
Examples include toluene sulfonate. The color developing solution used in the processing of the present invention includes the above-mentioned
Color development in addition to primary aromatic amine color developer
Various components normally added to liquids, such as sodium hydroxide
Alkali such as carbonate, sodium carbonate, potassium carbonate, etc.
agent, alkali metal ithite, alkali metal hyposulfite,
Alkali metal thiocyanates, alkali metal halides
substances, benzyl alcohol, water softeners and thickeners, etc.
It can also be included arbitrarily. This coloring liquid p
The H value is usually 7 or higher, most commonly about 10 to about
It is 13. In the present invention, after color development processing,
However, the processing liquid that has the fixing ability is used for fixing.
If it is a liquid, it is bleached first. The bleaching
The bleaching agent used in the process is organic acid gold l1fi salt.
The metal complex salt is the metallic silver produced by development.
At the same time, the coloring agent is not released.
It has the effect of coloring the colored part, and its composition is
Iron can be removed with organic acids such as nopolycarboxylic acid, oxidized acid, and citric acid.
Coordinated with metal ions such as , cobalt, and copper. It is used to form such a metal complex salt of
The most preferable acid is polycarboxylic acid or
Examples include aminopolycarboxylic acids. These polycarbonate
Rubonic acid or aminopolycarboxylic acid is an alkali metal salt
may be an ammonium salt or a water-soluble amine salt.
stomach. Specific representative examples of these include the following:
I can do it. [IJ Ethylenediaminetetraacetic acid [2] Nitrilotriacetic acid [3] Iminodiacetic acid [4] Ethylenediaminetetraacetic acid disodium salt [5] Ethylenediaminetetraacetic acid tetra(trimethyl
ammonium) salt [6] ethylenediaminetetraacetic acid
um salt [7] Sodium nitrilotriacetate The bleaching agent used contains a metal complex salt of t1M as mentioned above.
In addition to containing it as a bleaching agent, it also contains various additives.
I can do it. As additives, especially alkali halides or
are ammonium halides, such as potassium bromide and sodium bromide.
Thorium, sodium chloride, ammonium bromide, etc.
It is desirable to contain a halogenating agent, metal salt, or chelating agent.
Delicious. See you again! salts, oxalates, acetates, carbonates, phosphates, etc.
pHm1 agent, alkylamines, polyethylene oxy
Items known to be added to normal bleaching solutions such as
can be added as appropriate. Furthermore, the fixer and bleach-fixer contain ammonium sulfite,
Potassium sulfite, ammonium bisulfite, potassium bisulfite
Um, m-a1ii! tlI? Sodium, metabisulfite
Ammonium, potassium metabisulfite, sodium metabisulfite
Sulfites such as thorium, boric acid, borax, thorium hydroxide
, potassium hydroxide, sodium carbonate, potassium carbonate, heavy
Sodium sulfite, sodium bicarbonate, potassium bicarbonate
, acetic acid, sodium acetate, ammonium hydroxide, etc.
Contains one or more pH buffers consisting of salts of
I can do it. While replenishing the bleach-fixing solution (bath) with bleach-fixing replenisher,
When performing brightening treatment, thiosulfuric acid is added to the bleach-fixing solution (bath).
It may contain salts, thiocyanates, sulfites, etc.
However, the bleach-fixing replenisher contains these salts.
The treatment bath may be replenished. In the present invention, in order to increase the activity of the bleach-fix solution,
as desired in the white fixing bath and in the bleach fixing replenisher storage tank.
Blow in more air or oxygen.
or a suitable oxidizing agent such as hydrogen peroxide, bromine
vi salt, persulfate, etc. may be added as appropriate. The following margin [Effect of the invention] The silver halide photographic material of the present invention has excellent color reproducibility.
, and the light fastness of the magenta dye image is significantly improved,
Moreover, azole magenta couplers, especially Bilan 0
Lung gradation is a drawback of triazole magenta couplers
At the same time, the softness of the image has been improved, and the gradation balance is also excellent.
Furthermore, M-stin and Y-stin in the uncolored area
Occurrence has been prevented. [1 Practical FF Example] The present invention will now be described in more detail with reference to Examples. <Example-1> Magenta coupler or bottom according to the present invention shown in Table-1
The comparative magenta coupler-1 is shown as 40+7 and Table-1.
The compound of general formula (a) according to the present invention or the following ratio
Comparison compound (A) was added to each magenta coupler at 5
C) t% and the general formula (b) according to the present invention shown in Table 1
) compound 2gt high boiling point organic solution tsS -230vQ and
Dissolve 1 sli of acid in 100 d of ethyl (7) mixed solvent.
A solution containing sodium dodecylbenzenesulfonate
After adding to 5% gelatin aqueous solution 30G, Q, ultrasonic
Disperse with a homogenizer, and the resulting dispersion is shown below.
It is mixed with a green-sensitive silver chlorobromide emulsion to form the composition shown below.
It was coated on a polyethylene-coated paper support and dried.
Samples 1 to 18 shown below were obtained. The following margin (ratio (exchange deficiency)) Blur 1) Of (comparative compound) (8) (Compound q described in JP-A-54-48538: J>0
C4H. Preparation method of silver chlorobromide emulsion>I'Ag7.3, pH 3,
of each of the silver salt solution and halide solution while keeping it constant at 0.
Particle growth is performed while controlling the amount of addition, and the growth is completed.
After completion, the pl was adjusted to 16.0 and washed with demineralized water using a conventional method.
. The silver chlorobromide emulsion prepared in this way was as shown in the table below.
The emulsion was composed of tetrahedral grains. This emulsion was then divided into sulfur and color sensitized parts. (Constitution conditions) Gelatin 1.5 (1/TI'
Silver chlorobromide emulsion 0.2 o/i [70
Mol% of A(l Br-containing magenta coupler 0.4(1/1"-
General formula (a) compound 50 mol% based on the coupler General formula (b) compound 0.02Ql f high boiling point
point i melt 1 G, 3 U/f these
Samples 1 to 18 were measured using a sensitometer (manufactured by Konishiroku Photo Industry Co., Ltd.
Light wedge exposure was performed using green light using a KS-7 model.
After that, the following treatments were performed. Standard treatment process (treatment temperature and treatment time) [I] Color development m 38°C 3 minutes 30 seconds [2] Bleaching
White fixing 33℃ 1 minute 30 seconds [3] Washing process 2
5-30℃ 3 minutes [4] Drying 75-80℃
Approximately 2 minutes Processing liquid composition (colored liquid) Benzyl alcohol 15th grade ethylene
Glycol 151Q Potassium Sulfite
2.0g potassium bromide
0.7゜Sodium chloride
0.2g potassium carbonate
30.0Q human O-xylamine sulfate 3.
0g polyphosphoric acid (TPPS) 2.5 (
13-Methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl)-aniline sulfate 5.5g Fluorescence enhancement
Whitening agent (4,4'-diaminostilbenzsulfonic acid derivative) 1.0 (J water
Potassium oxide 2.0g Add water
Set the total n to 12 and adjust to pl-110,20. (Bleach-fix solution) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60 (1 step
Diaminetetraacetic acid 3g Ammonium thiosulfate (70% solution) 100d
Ammonium sulfate (40% solution) 27.5112
Adjust the pH to 7.1 with potassium carbonate or glacial acetic acid and add water.
The total number of sets is 12. Optical thermometer (Photograph by Roku Konishi)
Magenta is produced using Kogyo Co., Ltd.'s IPDA-65 model).
Measure color pigment density and gamma value of 81 degrees 0.8 to 1.8
(taken as γ1), density 0.3 to 0.8 as leg gradation
The gamma value (referred to as γ2) was determined. Rough M stain, light fastness, moisture resistant Y stain, spectral absorption
The yield characteristics were determined as follows. MS stain (MS)> Measure the green density Dq of the uncolored part of the sample after the above treatment.
, expressed as a relative value with the value of comparative sample No. 17 as 100.
did. The level of comparative sample No. 17 is within the range without any problem.
be. High humidity resistance
Yellow stain (blue stain) in uncolored area when left for 4 days
The difference ΔDs in color density before and after the test was measured. <Light fastness test> Using an underglass outdoor exposure table, expose to sunlight for 7 days.
7-day irradiation for initial 1 degree Qo = 1.0
It is expressed as the residual rate of concentration after irradiation. Spectral absorption characteristic test〉 The spectral reflection spectrum of the mapinta coloring sample obtained was colored.
-Using Analyzer Model 607 (Hitachi 'l'F Office! 4)
It was measured using At this time, the absorption spectrum in the visible region of each sample is
The maximum concentration was normalized to 1.0 and measured. 42 of each sample
The reflection density at 0 nm is used as a sub-absorption index of color purity.
did. These results are shown in Table-1. As is clear from the results in Margin Table 1 below, the coupler of the present invention can be used simply.
For sample No. 1 used by Germany, the general formula (b
) Sample No. using the compound alone. 2 improves the softening of the leg part, but the light fastness deteriorates and the M scale
Ting is not improved. However, using comparative coupler-1
Using the compound of general formula (b) for sample No. 17,
Sample No. 18 has improved leg softening and light fastness.
It has no effect on sexuality. In addition, tests using the compound of general formula (a) of the present invention alone
Sample No. 0.3 is sample No. using comparative compound (A);
Although the light fastness and M stain are improved compared to 4.
Nono's leg softening is not improved. In contrast to these, the present invention
Samples No. 015 to 13 of
Soft legs without sacrificing robustness and M-stin improvements
has been improved. Roughly speaking, samples N005 to N0.13 of the present invention are comparative couplers.
Compared to sample No. 17.18 using -1, moisture resistance
There is little increase in Y stain, and it has a negative impact on color reproducibility.
It can be seen that there is little side absorption. <Example-2> The samples shown in Table-2 were prepared in the same manner as in Example-1, and
A similar test was conducted on a sample obtained by the same treatment.
Ta. The binding is shown in Table-2. As is clear from the results in Margin Table-2 below, the test of the present invention in Example-1
Compound of general formula (a), general formula
Even if the compound (b) is changed, it is carried out in the same manner as in Example-1.
Compared to comparative sample No. 1 to 4.17.18 of Example-1
Improved light fastness, M stain and leg softening.
Ru. <Example 3> Coating liquids for each layer were prepared to have the composition shown in Tables 3 and 4.
Multi-layer silver halide color is coated sequentially from the support side.
-Produced a photographic material. After exposing the thus prepared sample to light according to the test,
The treatment was carried out according to the treatment steps, and the following tests were conducted. Gradation of magenta dye image> Evaluation was made using γ1 and γ2 in the same manner as in Example 1. <Three-layer gradation balance> Both edges of the gray coloring pigment are blue (B), green (G), and red (
R) Measured with light, respectively γ1B, γ2B, γ + G% γ2G
, γ1 R1 γ2R, centered around γ1G and γ2G
The balance was evaluated as described below. γ) Balance γ+B/G=(γ+B/γ+G)X100γ+R/
G=(γ+ R/γ+G)X100γ2 Balance γ2B/G=(γ2 B/γ2G)X100γ2 R/
G = (γ2R/γ2G)X100 print image
When awarding vA, γ1[3/G”, 100 72 B/Gζ 10
0γ+R'/G Saitama 110 γ2R/G No. 105
is preferred. Evaluation was carried out in the same manner as in Example-1. <Lightfastness> Using an underglass outdoor exposure table for magenta coloring dye images
and irradiated with sunlight for 20 days.
Rated 11IIi. <11iiiIY stain resistance> Evaluation was made in the same manner as in Example-1. Spectral Absorption Characteristics> Evaluated as 11, the same as in Example-1. Table-3 ai Structure 7th layer Gelatin (1, OQ/i') (protective layer) 6th layer Gelatin (1, OL'm') (3rd intermediate
layer) UV absorber LJV-1 (0,2CI/71')tJV-2(0
, I Q/v') HQ-6((1,02(1/f> High boiling point solvent dinonyl phthalate (0,2a/f) 5th layer Gelatin (1,2Q/v') (red sensitive layer)
Silver chlorobromide emulsion [containing 70-E/1z% AQ 3r] (Silver nail 0.25
Q/f) Cyan coupler [C-29/C-47] (silver halide
0.4 tl per mole) HQ-6 (0.01a/V
) High boiling point solvent dioctyl phthalate (0,2Q/i') 4th layer Gelatin (1=5 (1/,') (2nd layer
Intermediate layer) T: External radiation absorber LJV-1 (0,5Q/v2) LJV-2 (0,20/m2>1-I Q-6(0,03o/II2>high boiling point solvent di
Nonyl phthalate (0-3Q/v2) 3rd layer Gelatin (1,5Q/12) (green-sensitive layer)
Silver chlorobromide emulsion [containing 707% of AIJBr] Ta coupler containing silver [Table 4] (0,4(+/112) General formula (a) compound (0,2Q/1') General formula (1) ) compound (0,02(1/n') high boiling point solvent dioquidyl phthalate (0,25g/i) 2nd layer gelatin (1,0g/x2) (1st intermediate layer
) HQ-6 (0,07(1/n') high boiling point solvent di
Isodecyl phthalate (0, o4a/v) 1st layer Gelatin (2, OMf) (blue sensitive layer) Silver chlorobromide emulsion (silver fp 0.3/m'
) Yellow coupler Y-5 (0,80/i') HQ-6 (0,02Q/f) High boiling point solvent dinonyl phthalate (3 a/vr) Support Polyethylene coated paper (inside) coating amount or Represents the addition port. Comparison of margins below Magenta coupler 2 Ultraviolet absorber (UV-1) As is clear from the results in Ultraviolet absorber Table 4, this phenomenon occurred in the multilayer sample.
For sample N0032 using a bright coupler alone,
Sample No. using the compound of general formula (b) of the present invention alone
, 33 has improved leg softness, but the γ2 balance is not good.
However, the light fastness deteriorated, and the M stain was improved.
Not done. However, sample No. using comparative coupler-2,
Sample No. 53 using the compound of general formula (b).
54 has improved leg softness, γ1 balance, γ2 balance
It also has good stability and does not affect light fastness. Furthermore, when the compound of general formula (a) of the present invention is used alone,
Sample No. 0.34 is sample No. using the comparative compound (A>,
Lightfastness and M stain are improved compared to 35.
Softening of the legs of things and γ1 balance, γ2 balance
is not improved. In contrast, sample No. 3 of the present invention
6 to 52 have better light fastness and better light fastness than comparative sample No.34.
leg softness and
γ1 balance and γ2 balance have been improved. Further, trials of the present invention No. 36 to No. 521. Ratio 1
Compared to sample No. 53.54 using coupler-2.
There is little increase in moisture resistance Y stain, and there is no negative impact on color reproducibility.
It can be seen that there is little sub-absorption giving . <Example-4> Higher than the configuration conditions of sample No. 36 in Table-4 of Example-3.
Prepare samples by changing the boiling point solvent and image stabilizer as shown in Table 5.
The same test as in Example 3 was conducted, and the results are shown in Table 5.
Indicated. However, the thickness of the lightfastness test for magenta dye images is
The sunlight irradiation time was 30 days. Also apply image stabilizer
5 was set to 0.2<1/l'. From the results in Margin Table 5 below, it is clear that the present invention is effective as stated in the specification.
The use of high boiling point solvents with a dielectric constant of 6°θ or less and the image quality are
The combination of a fixing agent improves the gradation of the edges and improves the magenta dye image.
It can be seen that the effect is shown by improving the light fastness of .

Claims (2)

[Claims] (1) In a silver halide photographic material having at least one silver halide emulsion layer on a support, at least one of the silver halide emulsion layers has the following general formula [
Magenta coupler represented by I], the following general formula [a]
A silver halide photographic material containing a compound represented by the following general formula [b]. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. It's okay. X represents a hydrogen atom or a substituent that can be separated by reaction with an oxidized product of a color developing agent. Further, R represents a hydrogen atom or a substituent. ] General formula [a
] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1 and R_2 each represent an alkyl group. R_3 is an alkyl group, -NR'R'' group, -SR
' group (R' represents a monovalent organic group), or -CO
OR'' group (R'' represents a hydrogen atom or a monovalent organic group). m represents an integer from 0 to 3. ] General formula [b] ▲Mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_2_1 and R_2_2 are hydrogen atoms, alkyl groups, alkenyl groups, aryl groups, acyl groups,
Represents a cycloalkyl group or a heterocyclic group, R_2_3
, R_2_4, R_2_5 and R_2_6 are each a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, a cycloalkyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an acyl group,
Alkylacylamino group, arylacylamino group, alkylcarbamoyl group, arylcarbamoyl group, alkylsulfonamide group, arylsulfonamide group, alkylsulfamoyl group, arylsulfamoyl group,
It represents an alkylsulfonyl group, an arylsulfonyl group, a nitro group, a cyano group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an alkylacyloxy group, or an arylacyloxy group. However, R_2_3, R_
When 2_4, R_2_5 and R_2_6 are hydrogen atoms at the same time, R_2_1 and R_2_2 are never hydrogen atoms at the same time. ] (2) The compound represented by the general formula [a] and the compound represented by the general formula [b] are added to the silver halide emulsion layer using a high boiling point organic solvent with a dielectric constant of 6.0 or less. The silver halide photographic material according to claim 1, which is characterized in that: