JPS62186263A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the titled material having an improved yellow stain due to a humidity and a heat while storing it by incorporating a magenta coupler and a specific compd. to at least one layer of silver halide emulsion layers. CONSTITUTION:The titled material contains the magenta coupler and the compd. shown by the formula in at least one layer of the silver halide emulsion layers. The compounding method of adding the coupler and the compd. to the titled material is for example, an oil-in-water type emulsion dispersing method. The oil-in-water type emulsion dispersing method lies in dissolving the compd. shown by the formula with the magenta coupler, and then emulsifying the obtd. solution in a hydrophilic binder such as a gelatin aqueous solution, using a surface active agent by means of the dispersing apparatus such as an agitator, a homogenizer, a colloidal mill, a flow jet mixer and a supersonic wave means, etc., then incorporate it to the silver halide emulsion layer. In the formula, R1, R2 and R3 are each an aliphatic or an aryl group.

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material with improved yellowing due to humidity. [Background of the Invention] Silver halide color photographic materials are Q)! After being exposed to light, the image is developed using an aromatic primary amine color developing agent, and a dye image is formed by the reaction between the oxidized product of the color developing agent and the coupler. In this method, an acylacetamide or benzoylmethane yellow coupler, a pyrazolone, cyanoacetyl, indacylon or pyrazolotriazole magenta coupler, and a phenol or naphthol cyan coupler are usually used to form yellow, magenta and cyan dye images, respectively. used. The resulting dye image consists of an azomethine or indoaniline dye formed by the reaction of an oxidized color developing agent with a coupler. Color photographic images obtained in this way are usually stored for long periods as records or exhibited, but the non-colored parts of these dye images, that is, the white background, are not necessarily stable against light, heat, and humidity. Exposure to light for long periods of time or storage in high temperature and humidity may cause discoloration of the white background and deterioration of image quality. If the resulting color photographic image is exposed to light for a long time, or stored or displayed in high temperature and humidity, the white background will turn yellow (
Hereinafter referred to as Yellowstin. ) phenomenon is well known. This phenomenon is said to be mainly due to the decomposition of the magenta coupler contained in silver halide photographic materials, and is also reported in the Journal of American Photographic Science (J.A.P.S.') 5,200 (1979), R.J. Tu
(ite) reported that yellow stain is produced using a magenta coupler as a starting material. As specific methods for preventing yellow stain, studies have been conducted to develop magenta couplers that are resistant to decomposition under light and high temperature and humidity, and to search for compounds that prevent yellow stain on white backgrounds. Examples of compounds conventionally known as compounds that prevent yellow stain include antioxidants, such as 2.
5-Ji-

Hydroquinone derivatives including [-butylhydroquinone, 2.6-di-t-butyl-p-cresol, 4.4'-methylenebis(2,6-di-t-butylphenol), 2.2'-methylenebis(4- These include phenol derivatives such as ethyl-6-[-butylphenol), 4,4'-isopropylidene diphenol, and compounds such as tocopherol. These compounds such as hydroquinone derivatives, phenol derivatives, and tocopherols were substantially ineffective in preventing yellow stain caused by humidity and heat during storage. On the other hand, a metal complex is used in the magenta coupler-containing layer for the purpose of improving light resistance, but although the use of a metal complex improves light resistance, it has the drawback of increasing yellow stain. Therefore, a silver halide photographic material that does not generate yellow stain due to humidity and heat during storage has been desired. [Object of the Invention] An object of the present invention is to provide a silver-genide photographic material in which roasting due to humidity and heat during storage is improved. [Structure of the Invention] An 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 contains a magenta coupler and the following general This was achieved using a silver halide photographic material containing the compound represented by formula (1). General formula (1) In the formula, R1, R2 and R3 each represent an aliphatic group or an aryl group. [Specific Configuration of the Invention] The magenta coupler used in the present invention will be explained. Examples of magenta couplers used in the present invention include 5-pyrazolone type, cyanoacetophenone type, indashilon type, pyrazolinobenzimidazole type, and pyrazolotriazole type couplers. These magenta couplers are described, for example, in U.S. Pat.
No. 600,788, No. 3,062,653, No. 3
, No. 684.514, No. 1,183,515, Belgian Patent No. 1.130,287, Special Publication No. 1973-265
No. 89, No. 45-20036, No. 45-41473
No. 49-111631, and JP-A-49-111631. Preferred magenta couplers used in the present invention are those represented by the following general formulas [XI] and [il, and particularly preferred are magenta couplers represented by the general formula [I]. General formula [XI [] In the above general formula [XI [], groups, etc.), alkoxy groups (e.g., methoxy groups, ethoxy groups, etc.), aryloxy groups (e.g., phenoxy groups, etc.)
, amide group (e.g., acetylamide group, etc.), hydroxy group, amino group, or nitro group, and Y+, Y2, and Y3 each represent a hydrogen atom, a halogen atom, (e.g., a chlorine atom, etc.), an alkyl group (e.g., a medyl group, ethyl group, etc.), alkoxy M (e.g., methoxy group, ethoxy group, etc.), carboxy group, alkoxycarbonyl group (e.g., ethoxycarbonyl group, etc.), nitro group, aryloxy)! (e.g., phenyloxy), cyano group or acylamino group (e.g., acetylamino group, etc.),
Wl represents a hydrogen atom, a halogen atom (V/lI, chlorine atom, etc.) or an organic group. z2 represents an atom or group that is removed by fIi upon coupling. A represents -NH-1-NHCO-1-CONH- or -NHCONH-. Examples of monovalent groups represented by Wl include a nitro group, an alkyl group including those each having a substituent, an alkoxy group, an acylamimide sulfonamide group, an alkylcarbamoyl group, an arylcarbamoyl group, and an alkylsulfamoyl group. , an arylsulfamoyl group, an alkylsuccinimide group, an alkoxycarboxamide group, an aracoxycarboalkylamino group, an aralkoxycarboalkylamino group, an arylaminocarboalkylamino group, and the like. be. Examples of magenta couplers represented by the general formula [XI[] are listed below. The following are examples of magenta couplers in the margins. Represents a group of nonmetallic atoms necessary for forming 2, 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 the coloring agent Q. Further, R represents a hydrogen atom or a substituent. Examples of the substituent represented by R include a halogen atom,
Alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkynyl group, aryl group, heterocyclic group, anthyl group, sulfonyl group, sulfamole group, phosphonyl group, carbamoyl group, sulfamoyl group, cyano group, spiro compound residue, Bridged hydrocarbon compound residue, alkoxy group, aryloxy group, peterocyclic oxy group, siloxy group, acyloxy group, carbamoyloxy group, amine 7
group, 7 acyl amide groups, sulfonamide group, imide group, ureido group, 7 sulfonyl amide groups, 7 alkoxycarbonyl amine groups, 7 lyloxycarbonyl 7 groups, alkoxycarbonyl group, aryloxycarbonyl group,
Examples include a furkylthio 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. R? Examples of the furkyl group represented include those having 1 to 32 carbon atoms, alkenyl groups, and alkynyl groups having 2 to 3 carbon atoms.
2, cycloalkyl groups and cycloalkenyl groups preferably have 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms, and the alkyl groups, alkenyl groups and alkynyl groups may be linear or branched. , these furkyl groups, alkenyl groups, alkynyl groups, dichlorofurkyl groups, and cycloalkenyl groups are substituents [
For example, aryl, cyano, -)lodene atom, heterocycle,
In addition to cycloalkyl, cycloalkenyl, spiro compound residues, and endogenous hydrocarbon compound residues, acyl, carboxy,
Those substituted through a carbonyl group such as carbamoyl, flukoxycarbonyl, and aryloquinecarbonyl;
Furthermore, those substituted through a hetero atom 114: those substituted through an oxygen atom such as hydroxy, alkoxy, aryloxy, heterocyclic oxygen, siloxy, °acyloxy, carbamoyloxy, nitro, and /
(including rifurkyl 7mi7, etc.), sulfamoyl fumino, alkoxycarbonyl amide/, 7lyluoquine carbonyl 7mino, acylamino, sulfonamide, imide,
Substitution via a nitrogen atom such as ureido, substitution via a sulfur atom such as alkylthio, arylthio, heterocyclic thio, sulfonyl, sulfinyl, sulfamoyl, substitution via a phosphorus atom such as phosphonyl, etc.) It may have. Specifically, for example, a methyl group, an ethyl group, an isopropyl group, a butyl group, a pentadecyl group, a heptadecyl group, 1
-hexylnonyl group, i, i'-dichlorofurkyl group, 2
-chloro-t-butyl group, tri7fluoromethyl group, 1-
Ethoxytridenyl group, 1-methoxyisopropyl group,
Methanesulfonylethyl group, 2,4-not-7 milphenoxymethyl group, anilino group, 1-7enylisopropyl a, 3-wr-butanesulfonamino 7e/xypropyl group, 3-4'-1ff- (4”(p-hydroxybenzenesulfonyl)phenoquine]dodecanoylamine/
17z2-p-a-sy group, 3-14'-[ff-(2"
, 4”-sheet t-7milphenoxy)butanamide] phenyl l-propyl group, 4-(ff-(.-chlorophenoxy)tetradecanamidophenoxy)
Examples include propyl group, allyl group, cyclopentyl group, and cycloalkyl group. The aryl group represented by R is preferably a phenyl group, which may have a substituent (eg, an alkyl group, an alkokene group, a 7-syl amino group, etc.). Specifically, phenyl group, 4-t-butyl 7-enyl group,
2,4-di-t-7mylphenyl group, 4-tetradecane7midophenyl group, hexadecylquinphenyl group, 41
(, a-(477t-butyl heptanoxy)tetradecanamide] phenyl group, etc. The heterocyclic group represented by R″Ch preferably has 5 to 7 members, and may be substituted, or IA: physical 1, which may be fused, is a 2-7yl group, a 2-chenyl group,
Examples include 2-pyrimidinyl group and 2-benzothiazolyl group. R′? Examples of the acyl group represented include acetyl group,
Phenylacetyl group, dodeca/yl group, α-2,4-'
Examples thereof include a furkylcarbonyl group such as a not-7mil7e/xybuta/yl group, a 7-arylcarbonyl group such as a benzoyl group, a 3-pentadecyloxybenzoyl group, and a p-chlorobenzoyl group. Examples of the sulfonyl group represented by R''ch include methylsulfonyl group, alkylsulfonyl group such as dodecylsulfonyl group, benzenesulfonyl group, and arylsulfonyl group such as p-)luenesulfonyl group. Sulfinyl group represented by R Examples include alkylsulfinyl i, 7z such as ethylsulfinyl group, octylsulfinyl g, 3-phenoxybutylsulfinyl group
Examples include 7-arylsulfinyl groups such as nylsulfinyl iN m-pentadecylphenylsulfinyl group. The phosphonyl group represented by R includes an alkoxyphosphonyl group such as a butyloctylphosphonyl group, an alkoxyphosphonyl group such as an octyloxyphosphonyl group, an aryloquinephosphonyl group such as a phenoxyphosphonyl group, and a phenylphosphonyl group. Examples include arylphosphonyl groups such as. The carbamoyl group represented by R may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc.
For example, N-methylcarbamoyl group, N,N-noptylcarbamoyl group, N-(2-pene, tadenluoctylethyl)7>lupamoyl group, N-ethyl-N-dodecylcarbamoyl! , N-13-(2,4-not-amylphenoxy)propyl)carbamoyl group, and the like. The sul77moyl group represented by the margin R below may be substituted with a furkyl group, an aryl group (preferably a phenyl group), etc.
For example, N-propylsulfamoyl group, N,N-noethylsulfamoyl group, N-(2-pentadecyl oquinethyl)sulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, N-phenylsulfamoyl group. Examples include groups. Examples of the spiro compound residue represented by R''Ch include spiro[3,3]hebutan-1-yl. Examples of the bridged carbonized compound residue represented by R include bicyclo[2,2, 1] Heptan-1-yl, tricyclo[3
, 3,1,1''71decane-1-yl, 7,7-tumethyl-bicyclo[2,2,1]hebutan-1-yl, and the like. The alkyl group may be substituted with the substituents listed above, such as a methoxy group, a propoxy group, a 2-ethoxyethoxy group,
Examples thereof include a pentadecyloxy group, a 2-dodecyloxyethoxy group, and a fewinteryloxyethoxy group. R1? The aryloxy group represented is preferably 7enyloxy, and the aryl nucleus may be further substituted with any of the substituents or atoms listed above for the aryl group (
, for example phenoxy group, p--butylphenoxy group,
---bentadenulfenoxy group and the like. The heterocyclic oxy group represented by R preferably has 5 to 7 heterocyclic rings, and the heterocyclic ring may further have a substituent (for example, 3°, 4.5.6- Examples include tetrahydrobilanyl-2-oxy group and 1-phenyltetrazol-5-oxy group. The siloxy group represented by R may be further substituted with an alkyl group, etc. ,
Examples include triethylsiloxy group and trimethylbutylsiloxy group. Examples of the acyloxy group represented by R'''Ck include an alkylcarbonyloxy group, a 7-arylcarbonyloxy group, etc., and may further have a substituent, specifically an acetyloxy group, a-chloro Acetyloxy group, benzoyloxy group, etc. are accelerated.Carbamoyloxy group represented by R is a furkyl group, 7
It may be substituted with a lyl group, and examples thereof include N-ethylcarbamoyl oxine group, N,Nyethylcarbamoyloxyi, N-phenylcarbamoyloxy group, and the like. 7mi/-M represented by R may be substituted with an alkyl group, a 7lyl group (preferably a phenyl group), etc. (e.g., an ethyl group), an anilino group, a tsuru-chlor7nily7 group. , 3-pentadecyloxyluponyl 7nylino group, 2-
Examples include chloro-5-hexadecane 7mide 7nily7 groups. Examples of the acylamine 7 groups represented by R include alkylcarbonyl amide 7 groups, 7lyl carbonyl amine 7 groups (preferably phenylcarbonyl 7 groups), etc., and may further have a substituent. is 7set7mir group, a-ethylpropanamide group, N-phenylacetamide group,
Examples include a dodecane 7-mido group, a 2.4-y-t-7 milphenoxyacetamide group, and an α-3-L-butyl 4-hydroxyphenoxybutanamide group. Examples of the sulfone 7 mido group represented by R include an alkylsulfonylamino group, an arylsulfonylamino group, and may further have a substituent. Specifically, 7 methylsulfonylamide groups, 7 pentadecylsulfonylamide groups, 7 benzenesulfone mido groups, p-)
Examples include a luenesulfone 7mido group, a 2-7toxy 5-t-7 milbenzenesulfonamide group, and the like. The imide group represented by R may be open-chain or cyclic, and may have a substituent, such as a succinimide group, a 3-hebutadecylcoheriimide group, a 7-talimide group, a do group, etc. , glutarimide group, and the like. R'? The ureido group represented may be substituted with an alkyl group, an aryl group (6F phenyl group), etc., such as an N-ethylureido group, N-methyl-N-
Decylureido group, N-7z nylureido group, N-p-
) norureido group, etc. The sul77moyl7mino group represented by R is a furkyl group,
It may be substituted with an aryl group (preferably a phenyl group), and examples thereof include N, N-diptylsul7amoyl7m7M, N-methylsulf7amoyl7m7 group, N-phenylsulfTmoylamy7 group, etc. . The alkoxycarbonylamide 7 group represented by R is,
It may further have a substituent, for example, 7 methoxycarbonylamide groups, 7 methoxyethoxycarbonylamide groups,
Examples include 7 octadecyloxycarbonylamide groups. The aryloxycarbonyl amine 7 group represented by R may have a substituent, and examples thereof include phenoxycarbonyl amine 7 group and 4-methyl 7e/xycarbonyl amine 7 group. The alkoxycarbonyl group represented by R may further have a substituent (for example, methoxycarbonyl 8-butylenecarzenyl Tatsumi I#daS nornaxycarbonyl group, octadecyloxycarbonyl group, ethoxyno)oxy Examples include carbonyloxy group, benyloxycarbonyl group, and the like. The aryloxycarbonyl group represented by R"C'!! may further have a substituent (for example, phenoxycarbonyl group, p-chlorophenoxycarbonyl group, -1pentadecyloxyphenoxycarbonyl group, etc.) 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 7-yonethylthio group, and a 3-phenoxypropylthio group.R' The arylthio group represented by ? is preferably a phenylthio group and may further have a substituent, such as 7-ethyl, nylthio group, p-nodoxyphenylthio group, 2-t-octylphenylthio group, 3-octadecyl phenylthio group,
Examples thereof include 2-carboquinphenylthio group and p-7doaminophenylthio group. The heterocyclic thio group represented by R″Q is preferably a 5- to 7-shell heterocyclic thio group, and may further have a fused ring,
Examples of the substituent which may be substituted include a 2-pyridylthio group, a 2-benzothiazolylthio group, and a 2,4-nophenoxy(1.3.5-)7zole-6-thio group. Due to the reaction with the oxidized product of the color developing agent represented by X! ) ra#g that can leave! Examples of the group include a group that performs W1 substitution via a laxative atom of a halogen atom (chlorine atom, bromine atom, heptasteon atom, etc.), an oxygen atom, a sulfur atom, or a nitrogen atom. In addition to the carboxyl group, examples of the group substituted via a carbon atom include the general formula (R,' is the same as the above R, Z' is the same as the above Z, R2', r, I'R3' are a hydrogen atom, a 7-aryl group, an alkyl group or a heterocyclic group),
Examples include a hydroxymethyl group and a tri72dylmethyl group. Examples of groups substituted via an oxygen atom include phenoxy group, aryloxy group, heterocyclic oxy group, 7-syloxy group, sulfonyloxy group, flukoxyluponyloxy group, 7-aryloxycarponyloxy group, alkyloxalyloxy group, and flukoxy group. An example is an oxadyloxy group. The phenoxy group further has r! It may have one substituent (for example, an ethoxy group, a 2-phenoxyethoxy group, a 2-cyanoethoxy group, a 7-ethyloxy group, a p-alpencyloxy group, etc.).The aryloxy group is preferably a 7-ethyl/oxy group, and the 7-aryl group may further have a substituent, specifically a phenoxy group, 3-methylphenoxy group, 3-
Bidet. Silphenoxy group, 4-notanesulfone 7midophenoxy S, 4-Ca-(3'-pentadecylphenoxy)butanamide]7e/oxy group, hexydecylcarbamoylmethoxy group, 4-cyanophenoxy group, 4-methanesulfonyl phenoxy group, 1-s7tyloxy group,
Examples include p-methoxy72/xy 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, specifically, 1-phenyltetrazoli and 2-benzothiazolyloxy group. The 7-syloxy group includes, for example, an acetoxy group, a flukylcarbonyloxy group such as a butazuroxy group, a flukylcarbonyloxy 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 flukoxylponyloxy group include an ethoxycarbonyloxy group and a benzyloxycarbonyloxy group. Examples of the aryloxycarbonyl group include a 7-enoxycarponyloxy group. Examples of the alkyloxalyloxy group include a methyloxalyloxy group. Examples of the flukoxyoxadyloxy group include an ethoxyoxalyloxy group. Examples of groups substituted via a sulfur atom include alkylthio groups, arylthio groups, heterocyclic thio groups, and flukyloxythiocarbonylthio groups. Examples of the furkylthio group include a butylthio group, a 2-cyanoethylthio group, a 7ethylthio group, a bencurthio group, and the like. The arylthio group includes phenylthio group, 4-7thanesulfone7midophenylthio group, 4-dodecyl7enethylthio group, 4-nonafluoropentanamide7enethylthio group, 4-carboxyphenylthio group, 2-ethoxy;, -5-t -butylphenylthio group and the like. Examples of the heterocyclic thio group include 1-722-1.
2.3.4-tetrazolyl-5-thio group, 2-benzothiazolylthio group, and the like. Examples of the fulkyloxythiocarbonylthio group include dodecyloxythiocarbonylthio group. For example, those represented by the general formula -N represent an aryl group, a heterocyclic group, a sulfamoyl group, a carbamoyl group, an acyl group, a sulfonyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, and R, / and R5' are a bond. to form a heterocycle, provided that R4' and Rs
' cannot both be hydrogen atoms. The furkyl group may be linear or branched, and preferably has 1 to 22 carbon atoms. Further, the furkyl group may have a substituent, and examples of the substituent include an aryl group, an alkoxy group, a 7-aryloxy group, a furkylthio group,
Arylthio group, alkyl 7-mi 7 group, arylami 7-group, 7-silami 7 group, sulfonamide group, imino group, acyl group, alkylsulfonyl group, arylsulfonyl group,
Carbamoyl group, 7-moyl group, alkoxycarbonyl group, 7-aryloxycarbonyl group, alkyloxycarbonylamino group, aryloquinyl 7-moyl group
group, hydroxyl group, carboxyl group, cyano group, and 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 Ri' preferably has 6 to 32 carbon atoms, particularly a phenyl group or a naphthyl group,
The 7-aryl group may have a substituent, and examples of the substituent include those listed above as a substituent for the alkyl group represented by R4' or R1' and an alkyl group. Specific examples of the 7-aryl group include a 7-ethyl group, a 1-su7tyl group, and a 1,4-methylsulfonylphenyl group. The heterocyclic group represented by R4' or R1' is 5 to 6
The true one is insectophilic, may be a fused ring, and may have a substituent, specific examples include 2-7lyl group, 2-quinolyl group, 2-pyrimidyl group, 2-benzothiazolyl group, Examples include 2-bilinol group. The sulfamoyl group represented by R4' or R1' includes N-furkylsulfamoyl group, N,N-noalkylsul7Tmoyl group, N-7lylsul7Tmoyl i, N
, N-noarylsul, 7-amoyl group, etc., and these alkyl groups and aryl groups may have the substituents listed for the furkyl group and aryl group,
Specific examples of the sulf77moyl group include N,N-diethylsulfamoyl group, N-methylsulfamoyl group,
N-dodecylsul77 moyl group, N-p-)dilsul7
T-moyl group is mentioned. The carbamoyl group represented by R4' or R,7 is,
N-furkylcarbamoyl group, N,N-noalkyllupamoyl group, N-7lylcarbamoyl group, N,N-nor-17-rucarbamoyl group, etc., and these alkyl groups and aryl groups correspond to the above-mentioned alkyl groups and aryl groups. Specific examples of the carbamoyl group which may have the substituents mentioned above include N,N-noethylcarpamoyl group, N-methylcarbamoyl group, N-dodenlecar Imoyl a, N-p-cyanophenyl Examples include carbamoyl group and N-p-)zylcarpamoyl group. Examples of the acyl group represented by R4' or Rs' include an alkylcarbonyl group, an arylcarbonyl group, and a heterocyclic carbonyl group, and the alkyl group, the 7-aryl group, and the heterocyclic group have a substituent. Specific examples of the acyl group that may be used include hexafluorobutanoyl group, 2゜3.4.5.6-pentafluorobenzoyl group, acetyl group, benzoyl group, naphthonyl group, etc.
, 2-7lylcarbonyl group, and the like. Examples of the sulfonyl group represented by R4' or Rs' include an alkylsulfonyl group, an arylcarbonyl group, and a heterocyclic sulfonyl group, which may have a substituent, and specific examples include an ethanesulfonyl group. , a benzenesulfonyl group, an octanesulfonyl group, a naphthalenesulfonyl group, a p-chlorobenzenesulfonyl group, and the like. The aryloxycarbonyl group represented by 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 R1' or R5' may have the substituents listed above for the alkyl group, and specific examples include a methoxycarbonyl group, a dodecyloxycarbonyl group, and a benzyloxycarbonyl group. etc. The heteroc2 ring formed by the bonding of R4' and vRs' preferably has 5 to 6 rings, and may be saturated or unsaturated, and may or may not have aromaticity. , and may be a condensed ring, such as N-7 talimide group, N-succinimide group, 4-N-urazolyl group, 1-N-hydantoinyl group, 3-N-2,4-no Oxooxazolicinyl group, 2-N-1,1-dioxo-3-(2H)-oxo-1,2-benzthiazolyl group, 1-pyrrolyl group, 1-pyrrolidinyl group, 1-pyrazolyl group, 1-pyrazolidinyl group , 1-piperidinyl group, 1
-pyrrolinyl group, 1-imidazolyl group, 1-imigzolinyl group, 1-indolyl group, 1-isoindolinyl group,
2-isoindolyl group, 2-ineindolinyl group, 1-
Benzotriazolyl group, 1-pencyimigzolyl group, 1
-(1,2,4-)riazolyl) group, 1-(1,2,3
-)riazolyl) group, 1-(1,2,3,4-tetrazolyl) group, N-morpholinyl group, 1,2,3.4-tetrahydroquinolyl group, 2-oxo-1-pyrrolidinyl group, 2- IH-pyridone group, 7-thalassion group, 2-oxo-1-piperidinyl group, etc., and these heterocyclic groups include furkyl group, 7-aryl group, alkyloxy group, aryloxy group, anru group, sulfonyl group, alkyl group, etc. Amino group, acylamino group, acylamino group, sulfone 7mino group, carbamoyl group, sulfone moyl group, furkylthio group, arylthio group, ureido group, flukoxyluponyl group, 7lyloxycarbonyl group, imido group, nitro group, cyano group It may be substituted with a group, a carboxyl group, a halogen atom, etc. Examples of the nitrogen-containing heterocycle formed by Z or ZI include a pyrazole ring, imidazole ring, triazole ring, or tetrazole ring, and the substituents that the ring may have include those described for R above. Can be mentioned. In addition, in general formula (T) and general formulas (II) to [■] described later, the substituents on the bicyclic ring (for example, R9R3 to Ra) are moieties (herein, R'', X and Z 77 are general formula (synonymous with R, For example, in the general formula (V), R
1 and R6, and in general formula (Vl), R2 and R, may be bonded to each other to form a complete ring (for example, a 5- to 7-membered cycloalkene, benzene). What is represented by the general formula (1) below is more specifically represented by, for example, the following general formulas (I[) to [■]. General formula [“] General formula (I [I) N -N -N General formula (ff) N -N -NH General formula [v] General formula [■] General formula [■] Said general formula [■] ~ [ (2)], R1-R and
■]. General formula [■] In the formula, RI-X and Zl have the same meanings as R1X and VZ in the general formula (1). Among the magenta couplers represented by the general formulas (n) to [■], particularly preferred is the magenta coupler represented by the general formula (II). Regarding the substituents on the heterocycle in general formulas (1) to [■], R in general formula CI) and R1 in general formulas (II) to [■] satisfy the following condition 1. The following conditions 1 and 2 are more preferable and more preferable.
The following condition 1. is particularly preferable.
2 and 3. This is the case when the following is satisfied. Condition 1: The Miyc atom directly connected to the heterocycle is a carbon atom. Condition 2: Only one hydrogen atom is bonded to the carbon atom, or all (no) hydrogen atoms are bonded. Condition 3: All the bonds between the carbon atom and adjacent atoms are single bonds. The most preferable substituents R and R+ are those represented by the general formula (IX) below. , halogen atom, furkyl group, dichlorofurkyl group, alkenyl group, cycloalkenyl group, alkynyl group, aryl group, heterocyclic group, heptadyl group, sulfonyl group, sulfinyl group,
Phosphonyl group, carbamoyl group, sulfur moyl group, cyano group, spiro compound residue, bridged hydrocarbon compound residue,
Flucoquine group, aryloxy group, heterocyclic oquine group,
Simixy group, acyloxy group, carbamoyloxy group,
Ami 7 group, acyl amide 7 group, sulfone 7 mido group, imido group, ureido group, sulfone 7 amoylamino group, alkoxycarbonyl 7 group, 7 aryloquine carpoelamino group, alkoxycarbonyl group, aryloxycarbonyl group, furkylthio represents a group, an arylthio group, a heterocycle, a thio group, and at least two of Rst/R16 and R's are not hydrogen atoms. Also, the above R,,R,. and V R+ +, for example, R, and R1° may be combined to form a saturated or unsaturated ring (e.g. dichloroflucan, cycloalkene, heterocycle), and RII is further bonded to the ring. may constitute a bridged hydrocarbon compound residue. The group represented by R1 to R11 may have a substituent, and specific examples of the group represented by R9-R1 and the substituent that the iron group may have include the aforementioned general formula (1). Specific examples of the group represented by R and substituents are listed. Also, for example, a ring formed by combining R1 and R+O, and R1
−1 formed by R11! Specific examples of li hydrocarbon compound residues and substituents thereof include specific examples of dichlorofurkyl, cycloalkyl, and heterocyclic group-containing bridged hydrocarbon compound residues represented by R in the general formula (1) mentioned above; The substituents include. Among the general formulas (ff), preferred are >RS~R0
If two of them are alkyl groups, (ii) one of R, to R8, for example R11, is a hydrogen atom, and the other two R
When 1 and R16 combine to form a cycloalkyl together with the root carbon atom, then Furthermore, preferred among (i) is the case where two of R1-R1 are furkyl groups and the other one is a hydrogen atom or a furkyl group. Here, the alkyl and the cycloalkyl may further have a substituent (specific examples of the alkyl, the dichlorofurkyl, and the substituent thereof include R in the general formula (1) above).
Specific examples of alkyl, cycloalkyl and their substituents are listed. In addition, substituents that the ring formed by Z in general formula (1) and Z in general formula [■] may have, and R2 in general formulas (II) to (VI) As Rs, those represented by the following general formula (X) are preferred. General formula (X) -R'-8Q, -R'' In the formula, R1 represents alkylene and R'' represents alkyl, cycloalkyl or aryl. The alkylene represented by R1 is preferably t1-silo whose straight chain moiety has 2 or more carbon atoms, more preferably 3 carbon atoms, and it does not matter whether the straight chain has 1 or more carbon atoms, and this alkylene may have a substituent. Examples of the substituent include R in the general formula CI) described above.
When is an alkyl group, the substituents that the alkyl group may have include those shown below. Preferred substituents include phenyl. Preferred specific examples of fullkylene represented by R+ are shown below. The alkyl group represented by R2 is a straight chain or unbranched.
. Specific examples include methyl, ethyl, propyl, 1so-propyl, butyl, 2-ethylhexyl, octyl, dodecyl, tetradecyl, hexadecyl, octadacil, and 2-hexyldecyl. The cycloalkyl group represented by R2 is preferably a cycloalkyl group having 5 to 6 shells, such as cyclohexyl. The alkyl and dichlorofurkyl 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 7-aryl group may have a substituent, and examples of the substituent include linear or branched furkyl and those exemplified as the substituent for R1 described above. In addition, if there are two or more substituents, those substituents are
They may be the same or different. Among the compounds represented by the general formula (1), particularly preferred are those represented by the following general formula (XI). General formula (XI) In the formula, R and X have the same meanings as R and X in the general formula [■], and RI and R2 have the same meanings as RIGR2 in the general formula (X). Specific examples of compounds used in the present invention are shown below. Below margin CH3 ■ CH3 CH. CH2 ■ CH3 Below margin Cl2H2N C4H. CH3 CH. C1H□ Js cn. Hs blasphemy, 62 Cfu HIs L CaH+3 rt1 Kaoru CHI OCR, C0NIICI1. C1,0C11゜0CH2
Ct12SO2CBg C,H. CJs ru,. L shiwitg! O5 O6 5llti II3 I3 Bs 12fu3G H3 U 7uts H,CCH3 14fu0(CH2)2υji12t12! 5G N -N -N 1 flow 17F N -N
, Birkin (
Perkin) 1 (1977), 2047~
2052, U.S. Patent No. 3,725,067, JP-A-59
-99437, 5B-42045, 59-1
No. 62548, No. 59-171956, No. 60-33
No. 552, No. 60-43659, No. 60-17298
It can be synthesized with reference to No. 2 and No. 6G-190779. The couplers of the invention are typically 91X1 per mole of silver halide.
G-Comole 1 mole, preferably 1X10” mole to 8X
It can be used in a range of 10-1 mol. 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 (1) will be explained. In the general formula (1), R1, R2 and R
3 may be the same or different, and each represents an aliphatic group or an aryl group. Examples of the aliphatic groups represented by R1, R2 and R3 include alkyl groups and alkenyl groups. The alkyl group may be linear or branched, and includes, for example, a butyl group, a pentyl group, a hexyl group, a hebble group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, Examples of the alkenyl group include hexadecyl group, heptadecyl group, octadecyl group, and the like, and examples of the alkenyl group include hexenyl group, heptenyl group, and octadecenyl group. Also R1, R
Examples of the aryl group represented by 2 and R3 include phenyl group and naphthyl group. These alkyl groups, alkenyl groups, and aryl groups each include those having substituents, and examples of the substituents on the alkyl groups include halogen atoms, alkenyl groups, alkoxy groups, aryl groups, and aryloxy groups.
Examples of the substituent for the alkenyl group include the same substituents for the alkyl group as described above except for the alkenyl group, and an alkyl group.Also, for the aryl group, Examples of substituted bases include those similar to the substituents for the alkyl group described above except for aryl groups, and alkyl groups. Preferred as R+, R2 and R3' are aliphatic groups, and particularly preferred are alkyl groups. In general formula (1), the total number of carbon atoms of the groups represented by R1, R2 and R3 including substituents is preferably 18 to 55, particularly preferably 24 to 40. Typical specific examples of the compound represented by the general formula (1) are shown below, but the invention is not limited to these. The ratio of 0.25 to 2!ifi is preferable, and the ratio of 0.5 to 1.5ffiffi is more preferable.In the silver halide photographic material of the present invention, at least one of the silver halide emulsion layers contains the magenta coupler and The compound represented by the general formula (1) is added to the silver halide photographic material, for example, by an oil-in-water emulsion dispersion method.Oil-in-water emulsion dispersion method The method involves dissolving a magenta coupler in the compound represented by the above general formula (1)C, stirring it in a hydrophilic binder such as an aqueous gelatin solution using a surfactant, using a vessel, a homogenizer, a colloid mill, or a flow jet. After emulsifying and dispersing using a dispersion means such as a mixer or an ultrasonic device, it may be added to the target silver halide emulsion layer.In the present invention, when dispersing the magenta coupler, the general formula (1) The compound represented by the following general formula (2) can be used in combination with the compound represented by the following general formula (2). Next, the compound represented by the general formula (2) will be explained. General formula (2) % formula % In the formula, R4 and R5 are hydrogen atom, aliphatic ° respectively
or aryl group. Further, R4 and R5 may be combined to form a cycloaliphatic group. R6 represents an aliphatic a group or an aryl group, and oR7 represents a hydrogen atom, an aliphatic group, an aryl group, or +J2 hinoki-COOR
a (Ra represents 1g of fat or an aryl group.)
represents. Jl and J2 each represent a divalent linking group. l and n represent O or 1, respectively. In the general formula (2), R+ and R5 may be the same or different, and each represents a hydrogen atom, an aliphatic group, or an aryl group. R4 and R5
Examples of the aliphatic group represented by include an alkyl group and an alkenyl group. The alkyl group may be straight chain or branched, such as butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, Examples of the alkenyl group include a hexadecyl group, a heptadecyl group, and an octadecyl group, and examples of the alkenyl group include a hexenyl group, a heptenyl group, and an octadecenyl group. Examples of the aryl group represented by R4 and R5 include phenyl group and naphthyl group. These alkyl groups,
Alkenyl groups and aryl groups each include those having substituents, and examples of substituents for alkyl groups include!
ψ Represents a rogen atom, an alkenyl group, an alkylene group, an aryl group, an aryloxy group, an alkenyl group, an alkoxycarbonyl group, or an aryl group. ) etc. Examples of the substituent for the alkenyl group include the same substituents as for the alkyl group except for the alkenyl group, and an alkyl group. Examples of substituents for the aryl group include those similar to the substituents for the alkyl group described above except for the aryl group, and alkyl groups. Further, R4 and R5 may be combined to form a cycloaliphatic M (for example, a cycloalkenyl group). Preferred R4 and R5 are each a hydrogen atom. R6 represents an aliphatic group (for example, an alkyl group, an alkenyl group, etc.) or an aryl group. Specific examples of these alkyl groups, alkenyl groups, aryl groups, etc. are the above-mentioned R,)
and those similar to R5. Further, each of these groups includes those having a W1 substituent, and specific examples of the substituent include those mentioned above for R4 and R5. Preferred as R6 are aliphatic groups, particularly preferred are alkyl groups. R7 is a hydrogen atom, an aliphatic group, an aryl group, or + J
2-COORa (Ra represents a fatty xi or an aryl group); specific examples of the aliphatic group and aryl group represented by R7 and 'Ra include those similar to R4 and R5 above. Further, each of these groups includes those having a substituent, and specific examples of the substituent include the same as those for R4 and R5 above. Preferred as R7 is +J2 Hinoki-COORa,
Particularly preferred is the case where R8 is an aliphatic group, especially an alkyl group. Jl and J2 each represent a divalent linking group, but 2
Preferred as the valent linking group are alkylene groups (eg, methylene group, ethylene group, etc.). In general formula (2), R6 and R7 including substituents
The total number of zero carbon atoms in the group represented by is preferably 8 to 30, particularly preferably 12 to 20. Typical specific examples of the compound represented by the general formula (2) are shown below, but the invention is not limited thereto. M-I HC-COOCzHsll HC-COOC,H. M-28C-COOC,H% HC-COOC,H. M-3HC-COOC,H,. HC-COOCaHIt M-4HC-COOC,H. H*C40C400C -CHHC=COOCsH+t M-9CH2=CH-C00CHICH20-P→OC
1Hs) aM-13CH2=CH-CH2-COOC1
zHts or less margin When using the compound represented by general formula (2) and the compound represented by general formula (1) together, the amount of the compound represented by general formula (2) to be used is It is preferably used in a range of 10 to 200 m2%, particularly preferably 50 to 100 m2%, based on the compound. In the present invention, in addition to the compound represented by the general formula (2), the high boiling point organic solvent that can be used in combination with the compound represented by the general formula (1) has a dielectric constant of 13.0 or less. Compounds are preferred, for example, with a dielectric constant of 6.
Examples include esters such as 0 or less 7-talic acid esters and phosphoric acid esters, organic acid amides, ketones, and hydrocarbon compounds. Preferably, the dielectric constant is 6.0 or less and 1.9 or more, and the vapor pressure at 100°C is 0.5111118! It
The following high boiling point organic solvents are used. Even more preferred are heptatarates or phosphoric acid esters in the high-boiling organic solvent. Furthermore, the high boiling point solvent may be a mixture of two or more. Note that the dielectric constant in the present invention refers to the dielectric constant at 30°C. Examples of phthalic acid esters advantageously used in the present invention include those represented by the following general formula [a]. General formula [a] In the formula, %R1 and 11 R2 each represent an alkyl group, an alkenyl group or an aryl group. However, the total number of carbon atoms in the groups represented by R1 and R2 is 8 to 32.
It is. More preferably, the total number of carbon atoms is 16
It is 24 to 24. In the present invention, R1 and R2 of the general formula [a]
The alkyl group represented by may be linear or branched, such as butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tri, decyl group, These include a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, and the like. The aryl group represented by R1 and R2 is, for example, a phenyl group, a naphthyl group, etc., and the alkenyl group is, for example, a hexenyl group, a heptenyl group, an octadecenyl group, etc. These alkyl groups, alkenyl groups, and aryl groups may have a single or multiple a-substituents, and examples of substituents for the alkyl groups and alkenyl groups include halogen atoms, alkyl groups, koxy groups,
Examples include an aryl group, an aryloxy group, an alkenyl group, an alkoxycarbonyl group, and a! 11
Examples of the group include a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an alkenyl group, and an alkoxycarbonyl group. Phosphate esters advantageously used in the present invention include those represented by the following general formula [>b]. General formula [b]kC4 In the formula, R3, R4 and R5 are each an alkyl group,
Represents an alkenyl group or an aryl group. However, the total number of carbon atoms represented by Ra, R4 and R5 is 24 to 54. The alkyl groups represented by R3, R4 and R5 in the general formula [b] are, for example, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group. group, pentadecyl group, hexadecyl group, heptadecyl group,
Examples of the aryl group include a phenyl group and a naphthyl group, and examples of the alkenyl group include a hexenyl group, a heptenyl group, and an octadecenyl group. These alkyl groups, alkenyl groups and aryl groups may have single or multiple substituents. Preferably Rs, R4 and R5 are alkyl groups, such as 2-ethylhexyl group, n-octyl group, 3.5
．． Examples thereof include 5-trimethylhexyl group, n-nonyl group, n-decyl group, 5OC-decyl group, 5ec-dodecyl group, and [-octyl group. Below are the materials used in the present invention! Typical specific examples of solvents are shown below, but the present invention is not limited thereto. Below are examples of organic solvents in the margin C2H舊S-13 S-14 υ-CI* kiz I(El) -2O These high boiling point organic solvents with a dielectric constant of 6.0 or less and the compound represented by the general formula (1) When used in combination, the use of high boiling point organic solvents with an index R of 6.0 or less is based on general formula (1).
10 to 2001 ffi% for the compound represented by
It is preferable to use it in the range of 50 to 100ffiff
It is particularly preferable to use it in a range of 1%. Various metal complexes can be used in the magenta coupler-containing layer of the silver halide photographic material of the present invention for the purpose of improving light resistance. The metal complex used in the present invention has the following general formula [L-1
1 to [L-Vl are preferred. General formula [L-II Space below General formula CL-I[] ↓ General formula [L-I[[] [General formula [L-II, General formula [L-II and General formula []
L-III], M represents a metal atom. xl and x2 each represent an oxygen atom, a sulfur atom, or -NR'- (R' represents a hydrogen atom, an alkyl group, an aryl group, or a hydroxyl group). x3 represents a hydroxyl group or a mercapto group. Y represents an oxygen atom or a sulfur atom. R3, R4, R51!
5 and R6 each represent a hydrogen atom, a halogen atom, a cyano group, or an alkyl group, aryl group, cycloalkyl group, or heterocyclic group bonded to a carbon atom directly or via a divalent linking group. Also R3, R4 and R5
At least one of the combinations of and R6 may form a 5m- or 6-membered ring together with the carbon atoms that are bonded to each other. zo represents a compound capable of coordinating with M or a residue thereof. ] General formula [L-IV]

[In the formula, R21s R22, R23 and H2 are each
Hydrogen atom, halogen atom, hydroxy group, cyano group or
directly or indirectly through a divalent linking group
Alkyl groups, aryl groups, and cylindrical groups bonded to carbon atoms on the ring.
Represents a chloroalkyl group or a heterocyclic group. Also R2+
and R22, R22 and R23, or R23 and R24 are interchangeable.
may be bonded to form a 6-membered ring. R25 represents a hydrogen atom, an alkyl group or an aryl group.
Was. A is a hydrogen atom, an alkyl group, an aryl group, or a human
Represents 0xy group. M represents a gold R atom. 1 The above general formula [L-II, general formula [L-1[] and general formula
[L-1 [X1 and ×2 of [ ] are the same or different
may contain oxygen atoms, sulfur atoms, or
-NR? -(R' is a hydrogen atom, an alkyl group (e.g. metal)
thyl group, ethyl group, n-propyl group, 1-propyl group,
n-butyl 1, t-butyl group, i-butyl group, benzyl
groups), aryl groups (e.g. phenyl groups, tolyl groups,
(phthyl group, etc.) or hydroxyl group. ) represents
, preferably an oxygen atom or a sulfur atom, and further
Preferably it is an oxygen atom. X3 in the general formula [L-Iff] is a hydroxyl group or
represents a mercapto group, preferably a hydroxyl group
be. General formula [L-II, general formula [L-ml and general formula [L
-II has two Ys (there are two in the general formula [L-III])
Y present may be the same or different from each other>m element
a sulfur atom, preferably a sulfur atom
It is. General formula [L-II, general formula [L-I[]j5 and general formula
[R3, R4, R5 and R6 of L-II are the same
hydrogen atoms, halogen atoms,
child (fluorine, chlorine, bromine, iodine) cyano group, directly or
Divalent linking group [e.g. -0-1-S-1-N R7'-
1 [R7' is a hydrogen atom, a hydroxyl group, an alkyl group (
For example, butyl group, ethyl group, n-propyl group, 1-propyl group,
Lopyl group, n-butyl group, t-butyl group, i-butyl group
etc.), aryl groups (e.g. phenyl group, tolyl group, naphthyl group)
Represents a monovalent group such as a chill group, etc. ), -0CO-5-
CO-1-NHCO-1-CONH-1-COO-1-
3O2NH-1-NH8O2-1-802- etc.]
an alkyl group (e.g. methyl group, ethyl group) bonded to a carbon atom
Tyl group, propyl group, butyl group, hexyl group, octyl group
group, dodecyl group, hexadecyl group, etc.
The alkyl group can be a straight chain alkyl group or a branched alkyl group.
good. ), aryl groups (e.g. phenyl, naphbul)
groups), cycloalkyl groups (e.g. cyclopentyl groups, etc.), cycloalkyl groups (e.g. cyclopentyl groups,
cyclohexyl group) or heterocyclic group (e.g. pyridyl group)
group, imidazolyl group, furyl group, chenyl group, pyrrolyl group
layer, pyrrolidinyl group, quinolyl group, morpholinyl group, etc.)
represents. Among these, carbon atoms are connected via divalent linking groups.
Alkyl group, aryl group, cycloalkyl group bonded to child
A group formed by a group or a heterocyclic group together with the divalent linking group
For example, an alkoxy group (e.g. methoxy group, ethoxy group)
Toxy group, rope tyloxy group, octyloxy group, etc.
straight chain or branched alkyloxy group), alkoxyl
Bonyl group (e.g. methoxycarbonyl group, ethoxycarbonyl group)
Direct carbonyl group, n-hexyloxycarbonyl group, etc.
chain or branched alkyloxycarbonyl group), alkyl
carbonyl group (e.g. acetyl group, valeryl group, stereocarbonyl group)
Straight chain or branched alkylcarbonyl groups such as aroyl groups
), arylcarbonyl group (e.g. benzoyl group, etc.),
alkylamino group (e.g. N-n-butylamino group,
N,N-di-n-butylamino group, N,N-di-n-o
Straight chain or branched alkylamino groups such as cutylamino groups
), arylcarbamo groups (e.g.
Straight chain or branched bamoyl n-dodecylcarbamoyl group, etc.
alkyl carbamoyl group), alkyl sulfamoyl group)
group (e.g. n-butylsulfamoyl group, n-dodecyl group)
Straight-chain or branched alkyl sulfur groups such as sulfamoyl group
famoyl group), alkylacyl amino group (e.g. ali
straight chain or branched amino group, valmitoylamino group, etc.
branch alkylcarbonylamino group), aryloxy group
(e.g. phenoxy group, naphthoxy group, etc.), aryl group
xycarbonyl M (e.g. phenoxycarbonyl, na
phthoxycarbonyl group, etc.), arylamino group (e.g.
N-phenylamino group, N-phenyl-N-methylamino group
(e.g. phenyl group), arylcarbamone group (e.g. phenyl
carbamoyl group, etc.), alkylsulfamoyl group (e.g.
phenylsulfamoyl group, etc.), arylacylamide
(e.g., benzoylamino group, etc.)
I can do it. In addition, general formula [L-I], general formula [L-I] and general formula
R3, R4, RS and R6 of formula [L-III] are
, a small number of combinations of R3 and R4 and R5 and R6 (both 1
5-membered or
A 6-membered ring may also be formed. In this case, the number of combinations U of R3 and R4 and R5 and R6 is small.
with at least one carbon atom connected and bonded to each other
The 5- or 6-membered ring to be formed is, for example, cyclope
tenthene ring, cyclohexene ring, benzene ring (however, this
Benzene rings include fused benzene rings, i.e. naphthalene rings.
ring, anthracene ring), etc.
Hydrocarbon rings, heterocycles with unsaturated f-bonds (e.g. nitrogen-containing
5Fl or 6-membered 'heterocycle). this
When the 5- or 6-membered ring has a W1 substituent, this
As the r1 substituent, for example, a halogen atom (fluorine, chlorine
, bromine, iodine), cyano groups, alkyl groups (e.g. methyl
group, ethyl group, n-propyl group, n-butyl M, n-o
Carbons such as ctyl group, t-octyl group, n-hexadecyl group, etc.
linear or branched alkyl group having 1 to 20 elementary atoms),
Aryl group (e.g. phenyl group, naphthyl group, etc.),
Koxy group (e.g. methoxy group, n-butoxy group, t-butoxy group)
I ~ straight chain or branched alkyloxy group such as xy group),
Aryloxy group (e.g. phenoxy group etc.), alkoxy group
Cycarbonyl group (e.g. n-pentyloxycarbonyl
group, t-pentyloxycarbonyl group, n-octyloxycarbonyl group,
oxycarbonyl group, t-octyloxycarbonyl M, etc.
linear or branched alkyloxycarbonylcarbonyl group (e.g. phenoxycarbonyl group, etc.), acyl
group (e.g. straight chain or acetyl group, stearoyl group, etc.)
is a branched alkylcarbonyl group, etc.), acylamino group (
Straight-chain or branched alkyl, e.g. ace1-amide group
Aryl such as carbonylamino group, benzoylamino group, etc.
carbonylamino group), arylamino group (e.g. N-
phenylamino group, etc.), alkylamino group (e.g. N-
n-butylylamino group, N,'h-diedylamino group, etc.
straight-chain or branched alkylamino group), carbamoyl M
(direct or branched, such as rope tylcarbamoyl groups)
alkylcarbamoyl group, etc.), sulfamoyl group (e.g.
For example, N, N-Gi-N-Pudilsulf? Moyle? 4, N-
Straight chain or branched atom such as n-dodecylsulfamoyl group
), sulfonamide groups (e.g.
Straight chain or branched alkali such as methylsulfonylamino group
Kylsulfonylamino group, phenylsulfonylamino group
arylsulfonylamino groups), sulfonyl groups (e.g.
Straight chain or branched alkylsulfonyl such as mesyl group
group, arylsulfonyl group such as tosyl group), cycloal
List of kill groups (e.g. cyclohexyl group, etc.)
I can do it. General formula [L-I], general formula [L-Ill and general formula [
L-IIll is preferably R3, R4, R5 and R
The alkyl group, aryl group, or R3 and R4 represented by 6
and at least one of the combinations of R5 and R6 are connected to each other
form a 5- or 6-membered ring
More preferably, it is selected from the following:
The combinations of R3 and R4 and R5 and R6 are mutually
6-membered rings with linked carbon atoms, particularly preferred
[This is the case when a yubenzene ring is formed. Also, general formula [L-I], general formula [L-Ill and general formula
M in formula [L-1111 represents a metal atom, preferably
is a transition metal atom, more preferably a nickel atom,
Copper atom, iron atom, cobalt atom, palladium atom, platinum
atom, most preferably a nickel atom. Arranged at M represented by Zo in the general formula [L-III]
Compounds capable of positioning are preferably linear or branched argyl
Alkylamine having a group, particularly preferably an alkylamine having an alkyl group.
The total number of carbon atoms in the kill group is 2 to 36, more preferably 3 to 2
dialkylamine, trialkylamine, which has 4
Specific examples of these include punalamine and octylamine.
(e.g. t-octylamine), dodecylamine (e.g. t-octylamine), dodecylamine (
For example, n-dodecylamine), hexadecylamine,
Monoalkylamines such as kutatoolamine, diethyl amines
Min, dibutylamine, dioctylamine, didodecyl
amine, jetanolamine, jetanolamine, etc.
Dialkylamine, and triethylamine, tributylamine
triamine, trioctylamine, triethanolamine
, tributanolamine, trioctaturamine, etc.
Trialkylamines and the like can be mentioned. General formula [1-I], general formula [L-Ill and general formula [
Gold f! according to the present invention, denoted by L-11[]! More of a complex
Preferred ones are the following general formula [L-Ia] and the general formula [L-Ia].
L-ffa ] and general formula [L-111a 1
It is a total bending complex. Below are the blanks General formula [L-Ia] General formula 1-1 [a] Z. ↓ General formula [L-111a] General formula [L-Ia], General formula [L-IIal and General
In the formula [L-1[[a], M, XI, X2, X
3, Y and zo each have the same meaning as above.
. General formula [L-Ia], general formula [L-I[a] and -
General formula [L-1[[ale, RHL[+2, R13
, RM is an alkyl group (e.g. methyl group, ethyl group)
group, n-propyl group, n-butyl group, n-octyl group,
[-1 carbon atom such as octyl group, n-hexadecyl group, etc.
~20 linear or branched alkyl groups), aryl groups
(e.g. phenyl group, naphthyl group, etc.), alkoxy group (
For example, methoxy group, n-butoxy group, t-butoxy group, etc.
linear or branched alkyloxy groups), aryloxy
cy group (e.g. phenoxy group, etc.), alkoxycarbonyl
groups (e.g. n-pentyloxycarbonyl group, [-pen
tyloxycarbonylcutyloxycarbonyl group, [-octyloxycarbo
Straight chain or branched alkyloxycarbonyl such as nyl group
group), aryloxycarbonyl U (e.g. phenoxy
carbonyl group, etc.), acyl group (e.g. acetyl group,
Straight chain or branched alkylcarbonyl groups such as aroyl groups
etc.), acylamino groups (e.g., straight chain such as acetamide groups)
or branched alkylcarbonylamino group, benzoyl
Aryl carbonylamino group such as amino group), aryl
Mitsubishi (e.g. N-phenylamino group, etc.), alkyl
Amino group (e.g. N-n-butylamino group, N.N-di
Straight chain or branched alkylamino groups such as ethylamino groups
), carbamoyl fi! (e.g. n-butylcarbamoy
linear or branched alkylcarbamoyl groups, etc.)
, sulfamoyl. groups (e.g. N,N-di-n-butylsulfamoyl M,
Straight chain or branched N-n-dodecylsulfamoyl group, etc.
alkylsulfamoyl group, etc.), sulfonamide N (
For example, a straight chain or branched chain such as a methylsulfonylamino group
Alkylsulfonylamino base, phenylsulfonylamino group
Arylsulfonyl amines such as 1, sulfonyl groups (
Straight chain or branched alkyl sulfonyl group such as mesyl group
arylsulfonyl group such as tosyl group, tosyl group) or
Represents a loalkyl group (eg, cyclohexyl group, etc.). m and n each represent an integer of 0 to 4. General formula [L-Ia], [L-1[a], [L-1[
A more preferable compound among [al] has the general formula [L-1[
This is a compound represented by al. General formula [L-1[al]
The most preferred compound among the compounds shown is the general formula [L
-Ib]. General formula [L-1] iI@R I S N + R+ t In general formula [L-IIb], M, XI, X2, Y
, R'', R'2,m, and n are the same as above, and R1
5, R16 and R17 are hydrogen atoms, alkyl groups (e.g.
(for example, butyl group, octyl group, stearyl group) or
represents an aryl group (e.g. phenyl group, naphthyl group, etc.)
Was. However, at least among R+5, RlB, and R17
Two represent an alkyl group or an aryl group. The following margin is the general formula [L-Wl, %R21R21tR
The halogen atom represented by z and R24 is a fluorine atom
, chlorine atom, bromine atom, and iodine atom. R2rs Rg2t R2x and R'24
The furkyl group is preferably an alkyl group having 1 to 19 carbon atoms.
I-chain alkyl group, I-chain alkyl group, branched alkyl group.
It may be any one of the above, and also includes those having substituents. Rats Rt2* 7 represented by R23 and R34
1) The -l group is preferably a 7-l group having 6 to 14 carbon atoms.
It is also a group having a substituent. Roll Ftzzs i3 and R14
The elementary ring group is preferably 5Rm or 6jtJJ! It is
, including those having substituents. R21f R2□Cyclo represented by R23 and VR24
The alkyl group is preferably a 5-membered ring group or a 6-membered ring group.
It also includes those with substituents. The 6 embodiments formed by combining R21 and R=2 are
, for example. R22 and R23 or R2 and R14 are bonded to each other
The six-shell ring formed is preferably a benzene ring.
, this benzene ring includes those having substituents, and
It may be a combination. Rats Rtx: Rtx represented by R23 and Rt4
Examples of the alkyl group include methyl group, ethyl group, and propylene group.
Pyl group, butyl group, t-butyl group, hexyl group, octyl group
group, decyl group, dodecyl group, tesiladecyl group, hexyl group, decyl group, dodecyl group, tesiladecyl group,
This ends with a list of sadecyl and octadecyl groups. Ant represented by R2nd R, , R, and I'tt4
Examples of the metal group include phenyl group and naphthyl group.
can be given. R1l5 Rats R22 and R24
Barocyclic groups preferably have as few heteroatoms in the ring.
Both contain one nitrogen atom, oxygen atom or sulfur atom.
A 5- to 6-membered heterocyclic group such as %7lyl group,
Hydro7lyl group, chenyl group, pyrazolyl group, pyrrolidi
ru group, bi, lysyl group, imidazolyl group, pyrazolyl group,
Quinolyl group, indolyl group, oxacylyl group, thiazolyl group
and the like. Rzlt Rats Rzs and R2,4
As a cycloalkyl group, for example, a cyclopentyl group
, cyclohexyl group, Schiff ahequinyl group, cyclohexyl group
This concludes by listing the sagenyl group, etc. R2cy R2** FCzs and VRi4 are connected to each other.
Examples of the 6-membered ring formed by combining include a benzene ring,
naphthalene ring, inbenzothiophene ring, isobenzof
Examples include a run ring and an inton ring. RatsR2□R22 and R24 above
alkyl group, cycloalkyl group, aryol group or heterocycle
The group is a divalent linking group, for example, an oxy group (-o-), a thio group.
group (-s-), amine 7 group;
Bonyl group, carbamoyl group, sulf77moyl group, carbo
Nylami 7 group, sulfonylamino group, sulfonyl group or
is a carbon on the benzene ring via a carbonyloxy group, etc.
May be bonded to an atom and has a preferred group within it
There is also. Rats Rats Rzko and a symbol represented by R24
The alkyl group is attached to the benzene ring via the above 2[1 linking group.
An example of a flukoxy group (
For example, methoxy, ethoxy, butoxy, propoxy
xy group, 2-ethylhexyloxy group, ■-decyloxy group
cy group, n-dodecyloxy group, or n-hexadecyl
(oxy group, etc.), alkoxycarbonyl group (e.g., methoxy group),
Cycarbonyl group, ethoxycarbonyl group, butoxycarboxylic group
Bonyl group, n-decyloxycarbonyl group or n-h
xadecyloxycarbonyl group, etc.), acyl group (e.g.
, acetyl group, ... relyl group, stearyl group,
benzoyl group or toluoyl group), acyloxy group
(e.g. acetoquine group or hexadecylcarbonyl group)
xy group, etc.), alkylamino7 group (e.g.
Mi7 group, N, N-ethylamine/group or N, N-kude
silami7 group, etc.), alkylcarbamoyl group (e.g.,
Butyl carbamoyl group, N,N-noethyl carbamoyl group
group, or n-dodecylcarbamoyl group, etc.), alkyl
sulfamoyl group (e.g., butylsulfamoyl i,
N, N-noethylsul 77 moyl group or n-dotecyl
sulfonyl 7-amino group, etc.), sulfonyl 7-mino group (for example,
Methylsulfonyl 7-group, or butylsulfonyl group
(e.g., mesyl group, etc.), sulfonyl group (e.g., mesyl group, or
ethanesulfonyl group, etc.), or 7-sylami7 group (e.g.
For example, 7 acetylamides, 7 valerylamides, valmitoy
7 groups of benzoylamides or 7 groups of toluoyl.
), etc.). Rz++ R22* The series represented by R22 and R24
The chloroalkyl group connects to the carbon on the ring via the above divalent linking group.
An example of bonding to an elementary atom is cyclohexyloxy
cy group, cyclohexylcarbonyl group, cyclohexyl group
xycarbonyl group, cyclohexylamine 7 groups, cyclohexyl group
Xenylcarbonyl group or cyclohexyloxy group, etc.
can be mentioned. R, , , R, □ Array represented by R23 and R3,
The group is linked to a carbon atom on the ring via the above divalent linking group.
Examples of combinations include aryloxy groups (e.g.
phenoxy group or captoxy group), 717-ruoxy
carbonyl group (e.g. phenoxycarbonyl group or
7-toxycarbonyl group, etc.), acyl group (e.g., benzyl group),
zoyl group or 7toyl group), anilino group (e.g.
Phenylami7 group, N-methyl7nylino group or N-7
cetylanili/it, etc.), acyloxy groups (e.g.,
benzoyloxy group or toluoyloxy group), a
lylcarbamoyl group (e.g. phenylcarbamoyl group)
etc.), arylsul77 moyl group (e.g. phenylsul
77 moyl group 1), arylsulfonyl amine 7 group (e.g.
For example, phenylsulfonyl amine 7 groups, p-tolylsulfony
7 groups), arylsulfonyl groups (e.g. benzyl sulfonyl groups),
(zenesulfonyl group, tosyl group, etc.), or acylamide 7
groups (e.g. benzoylamino/groups etc.)
reactor. Roll R22* Represented by R2co and R24 above
Furkyl group, aryl group, heterocyclic group, dichlorofurkyl group
Ro group or R21 and R22, Ro and R1 or R=3
and R2, are combined with each other to form a six-shell ring, which is a halo
Gen atoms (e.g. chlorine atom, bromine atom or fluorine atom, etc.)
), sia7 group, alkyl group (e.g. methyl group, ethyl group)
group, i-propyl group, butyl group, hexyl group, octyl group
group, decyl group, dodecyl group, tetradecyl group, hexa
Decyl group, heptadecyl group, octa;decyl group, or
methoxyethoxyethyl group, etc.), aryl group (e.g.
Phenyl/14%) + fluor group, naphthi, ru group, chloro7e
Dyl group, /toxyphenyl group or acetyl 7-enyl group
etc.), phenoxy group (e.g. nodoxy group, ethoxy group)
, butoxy group, propoxy group or methoxyethoxy group
etc.), aryloxy groups (1 e.g. 7eth/oxy groups, tri-
Roxy group, naphthoxy-i or methoxyphenoxy group
etc.), alkoxy groups (e.g., methoxycarbonyl groups),
carbonyl group, butoxycarbonyl group or phenoxyno
doxycarbonyl group, etc.), aryloxycarbonyl group (
For example, phenoxycarbonyl group, trilo, xycarboxylic
(nyl group or nodoxyphenoxycarbonyl group, etc.), 7
Syl group (e.g. formyl group, acetyl group, valeryl group)
, stearoyl group, benzoyl group, toluoyl group, naph
toyl group or p-nodoxybenzoyl group), acyl
Oxy groups (e.g. acetoxy or acyloxy groups)
etc.), 7 sylami 7 groups (e.g., acetamide group, ben
zamide group, methoxyacetamide group, etc.),
Rhino group (e.g., phenylamide 7 group, N-methylanili group)
7 groups, N-phenyl 7 groups, or N-7 cetyl 7 groups
-butylamino groups, etc.), alkylamino groups (e.g. -butylamino groups),
No group, N, N-quetyl 7 group, 4-methoxy-n-
butylamide 7 groups, etc.), carbamoyl groups [e.g.
Tylcarbamoyl group, N,Nyethylcarbamoyl group
, n-phthylsul7γmoyl group, N,N-noethyls
7-amoyl group, n-dodecylsulfamoyl group, and
is N-(4-methoxy-n-butyl)sulfamoyl group
1. Sulfonylamino/groups (e.g. methylsulfonylamino)
mino group, phenylsulfonylamino group, or methoxy group
methylsulfonylamino group, etc.), or sulfonyl group
(e.g. nosyl, tosyl or methoxymethane)
sulfonyl group, etc.). The alkyl group represented by Rzs and A has a substituent
It can be straight-chained or branched.
These alkyl groups, excluding the carbon atoms in the substituent part,
, preferably a furkyl group having 1 to 20 carbon atoms,
For example, methyl group, ethyl group, propyl group, butyl group,
hexyl group, octyl group, decyl group, dodecyl group, tetyl group
radecyl group, hexadecyl group, heptadecyl group or
Examples include tadecyl group. The aryl group represented by Rzs and A″Ch has a substituent
including those having a preferable
Preferably, it is a 7-reel group of Li2 with 6 carbon atoms, for example
l11 Phenyl group, silyl group, 7-tyl group, etc.
can be mentioned. Also, through A, two ligands are connected to 2
! ! It may be tied. In the formula, λi represents a metal atom, preferably a transition metal atom
It is. More preferably Cus COx N + *
P d* Fe or Pt, particularly preferably N
It is i. A preferred group for A is a hydroxy group. In addition, a complex represented by the above general formula (L-mV)
Among these, those in which R1 is an oxy group are preferably used.
, thio group, carbonyl group, alkyl group, diclof
alkyl group, aryl group or heterocyclic group, hydroxy group or
or seven elements'), expressed as 1zsR23 or R24.
At least one of the groups is a hydrogen atom, a hydroxy group,
It is an alkyl group or an alkoxy group. Among them even more
Preferably, R2% is a hydrogen atom,
R21*Rzzt Rls or Rffi4
A complex in which the total number of carbon atoms in the groups is at least 4 or more.
Ru. Specific examples of the metal complexes according to the present invention are shown below.
The invention is not limited to these compounds. Exemplary metal complex H C8H1 quotient λ (3) (4) N R2C8Hly
(S■ H NHzCs Hl7(t) ↓ N&CeHty ↓ NH2C12Hzs ↓ (B) NHzCts~ ↓ (10) NH2CJIH17(
S↓ (S(:6 HllooCC00CsHtt(LJ(1
4) N(C4HsOH)i↓ 0- Ni -0 (15) NHzCtzHzs↓ (17) NH(C4H11)2↓ ↓ -Ni-O CsHtdli C11H17(su0- Nf -0 C5Htdt) CaHxdt)HHC500C
COOCsHH QC1, a H2 coυCt12 to tl(L;ztlsJL;4tb(52)
C2H5 (5) CONHCJiy (iso) (67 (132) General formula [L-V] with blank space below) In the formula, R9 and Rlt are an alkyl group, a cyclo
Represents an alkyl group or an aryl group. Squirrel. As the alkyl group represented by R9 and I'ht,
Specifically, methyl group, edyl group, t-butyl group, [-oc
thyl group, 2-ethylhexyl group, n・-nonyl group, n-
Decyl group, n-dodecyl M, n-tadecyl group, n-
Examples include octadecyl group. Table with R9 and Rlt
Examples of the cycloalkyl group include cyclopene
Examples thereof include ethyl group, cyclohexyl group, and the like. R9 and
The aryl group represented by
Examples include phenyl group and naphthyl group. Also R9, R1
1 may be the same or different. The above alkyl groups, cycloalkyl groups and aryl groups
also include those each having a substituent. Alkyl group
Examples of substituents include halogen atoms, cyano groups, and cyano groups.
Examples include chloroalkyl group, aryl group or heterocyclic group.
It will be done. As a substituent for the cycloalkyl group, cycloalkyl
Substituents similar to alkyl groups except for kyl groups, and
Examples include alkyl groups. As a substituent for an aryl group,
, similar substituents for alkyl groups except for aryl groups,
and alkyl groups. In addition, the above R9 and R
Alkyl group, cycloalkyl group and alkyl group represented by h
The lyl group is a divalent linking group R' [specifically 10-1-S-1-N-1 (R' is a hydrogen atom)
child, hydroxyl group, alkyl group (e.g. methyl group,
Ethyl group, n-propyl group, 1-propyl group, n-butyl group
(tyl group, t-butyl group, i-butyl group, etc.), aryl group
(e.g. phenyl group, tolyl group, naphthyl group, etc.)
(represents a valent group), -COO-1-OCO-1-CO-
1-NHCO-1-CONH-1-8O2NH-1-N
H3O2-1-8O2- etc. through J to alkyl group,
Loalkyl group or aryl group may be substituted
. Specifically, the halogen atom as a substituent is a fluorine atom,
Examples include chlorine atom, bromine atom, iodine atom, etc., and alkyl
Specifically, the groups include methyl group, ethyl group, propyl group, and butylene group.
cycloal group, hexyl group, octyl group, etc.
Specific examples of the alkyl group include a cyclohexyl group, etc.
, the aryl group specifically includes a phenyl group, a naphthyl group, etc.
Examples of heterocyclic groups include pyridyl groups, indyl groups, etc.
dazodyl group, furyl group, chenyl group, pyrrolyl group, pyro
Examples include lysyl group, quinolyl group, and morphonyl group. Rho is an alkyl group, a cycloalkyl group, or an aryl group.
and may be different, but hydrogen atoms and alkyl atoms, respectively,
represents a group or an aryl group. ) or -NHCOR
+Gin (R14 is a hydrogen atom, alkyl is represented by Rlo)
Alkyl groups, cycloalkyl groups and aryl groups
Specific examples of groups and substitutions when they have substituents
Specific examples of groups include those similar to the above RB and Rtt.
can be mentioned. Cylamino group, t-octylamino group, anilino group, 2
．． 4-di-t-amyl-anilino group, etc., -NHCORn
Specific examples include [-octylcarbonamide group, n-
Dodecylcarbonamide group, phenylcarbonamide group
, t-octylaminocarbonamide, phenylamino
Examples include carbonamide group. Here R+2, R+
Alkyl group and aryl represented by 3 and R14
Groups include those with substituents, and specific examples of the substituents are shown below.
Examples include those similar to the above-mentioned R9%R11. Preferred as R9 is an aryl group, and Rlo and
and Ru are each preferably an alkyl group. In addition, carbon atoms including substituents of R9, R10 and R11
The total number of atoms is preferably 16 or more, and further
More preferably, it is 24 or more and 42 or less. In the general formula [L-Vl, M represents a metal atom]
is preferably a transition metal atom, more preferably
Fe, Ni, Go, Cu, pd. P[atom, particularly preferably N1 atom. The gold rag body represented by the general formula [L-Vl is bidentate
However, two ligands can be interesting even if they are the same.
It may be. Examples of the metal complex represented by the general formula [L-Vl] are as follows.
Although examples are shown, the present invention is not limited to these.
. The following margins are 1モヰヰ　1% １ぢq し１■ノ1&7 16r 1&9 1'71 +qz In the present invention, the general formula [L-11, [L-], [L
−1 [[], [L-IV] and [L-V]
Of the gold fiA#i bodies, -the quenching rate of the heavy element is preferably
Is the degree constant 3X10? M-1・SeC-1 or higher metal tin body
Yes, more preferably lX108-1・Sec” or more
It is. In addition, in the present invention, expressed by these general formulas:
The quenching rate constant of doublet oxygen is 3.
X10'M'Sec'' or more gold [one body is preferably used
and more than lX10'M"-8ec-1
It can be used more preferably than those within the range. Above - The quenching rate constant of doublet oxygen is
Dical Chemistry
ical Chemistry) 83. 591 (
Measurement of ye fading of luprene as described in (1979) et al.
Determined by the method. That is, a chloroform solution of luprene and a
Equal energy to the chloroform solution mixed with the compound to be measured
irradiate with light. The initial concentration of rubrene at this time is [R], and the compound to be measured is
The concentration of the substance is [Q], and the rubrene solution after the test is
Let the concentration of Blen be [R]: and try WAtu's Le Ble
[R]
S, then the quenching rate constant (kq) of -uta term oxygen is calculated as follows. Represented by the general formula [L-1,;l~[L-1[[]
The metal complexes described in British Patent No. 858,890 and German Patent No.
The method described in Application Publication No. 2.042.652 etc.
It can be synthesized by The gold rIA complex represented by the general formula [L-IV] is
E.G. Cox, L.F. Double Pinkard, D.
Bull Wardlow and K.C. Webster, The
Journal of Chemical Society (E, G,
Cox, F.W., Pinkard, W. WardlaW and K, C, Webster
, J., Chew. Soc,, ) 1935. Listed in 459
It can be synthesized by a method. Gold v represented by the general formulas [L-I] to [L-TV]
4. The introduction depends on the type of metal complex used and the capacitor used.
It varies depending on the type of coupler, but for coupler 1'Ele
It is preferably used in a range of 0.1 mol to 2 mol.
Furthermore, it is used in the range of 0.5 mol to 1 mol.
preferable. The gold a complex represented by the general formula [L-Vl] is
Similar to the method described in 58-216244 Tan Publication
It is synthesized by the following method. The general formula [L-Vl is the use of gold g4 釦xiu m,
Used in a ratio of 0.01 to 1 mol per 1 mol of coupler.
preferably used in an amount of 0.05 to 0.5 mol.
Ru. The silver halide photographic light-sensitive material of the present invention can be used, for example, in color.
negative and positive films, and color photographic paper.
can be used for direct am use.
The effects of the present invention are effectively produced when color photographic paper is used.
Kudzu is displayed. Silver halide of the present invention including this color photographic paper
Photographic materials can be single-color or multi-color.
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 structure of 81 layers with appropriate calendar numbers and layer order,
The number and order of layers may be changed as appropriate depending on the important performance and purpose of use.
You may do so. 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 oxide, silver chlorobromide, and silver 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 emulsions simultaneously contain halide ions and silver ions.
Even if mixed, if one exists, the other is mixed.
You may. In addition, the critical growth rate of silver halide crystals is
While taking into account the p
Sequential and simultaneous addition while controlling H and pAa
It may be generated by Conversion method after growth
may be used to change the halogen composition of the particles. 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 octhalide 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
Mu salt or complex salt, rhodium salt 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 surface and in a suitable reducing atmosphere.
By leaving the particle inside and/or on the particle surface, reduction sensitization can be achieved.
Can give a nucleus. The silver halide emulsion of the present invention has a composition of silver halide grains.
You can remove unnecessary soluble salts after the
Rui may be left as it is. When removing the salts
is described in Research Disclosure No. 17643.
It can be done based on the method. 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 is a particle whose latent image is mainly formed on the surface.
J:U 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 (100) planes to (111) planes is arbitrary.
Dangerous items can be used. 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 method using other noble metal compounds can 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
A combination of 28 or more may be used. 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 capri 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, I! derivative, cellulose
Synthetic highly hydrophilic polymers such as base derivatives, single or copolymers
Hydrophilic colloids of molecular substances can also be used. The photographic emulsion of the silver halide photographic light-sensitive material of the present invention;
The other hydrophilic colloid layer is a binder (or protective colloid).
d) A hardening agent used alone or used to cross-link molecules and increase film strength.
When used together, it hardens. The hardening agent is added to the processing solution.
The photosensitive material can be hardened to such an extent that it is not necessary to add a hardening agent.
It is desirable to add a hardening agent to the processing solution.
It is also possible to 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-unspecified 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 TR9, aminophenol
A coupling reaction is performed with an oxidized form of a derivative (such as a derivative) to produce a dye.
A dye-forming coupler that forms is used. The pigment forming force
The puller determines the sensitivity spectrum of each emulsion layer for each emulsion layer.
is selected so that a pigment that absorbs light is formed.
Normal, yellow dye formation in blue light sensitive emulsion layer
The coupler forms a magenta dye in the green light-sensitive emulsion layer.
A coupler is present in the red light-sensitive emulsion layer.
A puller is used. However, depending on the purpose,
Silver halide color photographic effect when used in different ways than mixing
You can also make optical materials. The cyan dye-forming couplers used in the present invention include:
Phenol type, naphthol type 4 or 2 mm
Type cyan dye-forming couplers are typical, and specific examples are
No. 2,423,730, U.S. Pat. No. 2,474,
No. 293, No. 3,227,554 and No. 3, 48
8. No. 193 for winter [1:IJ, and JP-A-1989-1
No. 0135, No. 5G-25228, No. 50-1304
No. 41, No. 51-37647, No. 51-108841
No., Special Publication No. 45-6993, etc.
There is. Furthermore, the cyan dye type used in the silver halide emulsion of the present invention
As the coupler, the following general formula [CC-1] is preferable.
stomach. General formula [CC-1] In the formula, R1 represents an alkyl group or an aryl group 11
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
Reaction with Il compound of aromatic primary amine color developing agent
represents a group that can be separated by In the present invention, R1 of the general formula rcc-1j is
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, phenyl, sodium, etc.
Such as phthyl group. These groups represented by R1 may have a single or multiple substituents.
It also includes those with substituents, such as those introduced into phenyl groups.
Typical substituents include halogen atoms (e.g.
fluorine, chlorine, bromine, etc.), alkyl groups (e.g.
For example, methyl group, ethyl group, propyl group, butyl group,
decyl ink, etc.), hydroxyl group, cyano group, nitro group,
Alkoxy group (e.g. methoxy group, ethoxy group),
alkylsulfonamide group (e.g. methylsulfonamide group)
group, octyl sulfonamide group, etc.), aryl sulfonamide group, etc.
amide II (e.g., phenylsulfonamide group,
phthylsulfonamide group, etc.), alkylsulfamoyl
groups (e.g., butylsulfamoyl group, etc.), aryls
rufamoyl group (e.g., phenylsulfamoyl group, etc.)
), alkyloxycarbonyl groups (e.g. methyloxycarbonyl groups),
cycarbonyl group, etc.), aryloxycarbonyl group (e.g.
(e.g., phenyloxycarbonyl group, etc.), aminosulfonyl group, etc.
Namido J! ! (For example, N,N-dimethylaminosulfur
(honamido group, etc.), acylamino group, carbamoyl group,
Sulfonyl group, sulfinyl group, sulfoxy group, sulfonyl group
ho group, aryloxy group, alkoxy group, carboxyl
group, alkylcarbonyl is formed. These H ways are 2w! The above is introduced into the phenyl group
It's okay to stay. 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,
They are ethoxy group, propyloxy group, and butoxy it. R3 may combine with R1 to form a ring. In the present invention, the general formula [represented by R2 of CG-11]
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 or a furan 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 single or multiple substituents.
It also includes those with a phenyl group, for example, a phenyl group.
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, cyam L nide 0 group, alco
Oxy group (e.g. methoxy group, ethoxy group, etc.), alkyl
Sulfonamide groups (e.g. methylsulfonamide groups,
(cutylsulfonamide group, etc.), arylsulfonamide
groups (e.g. phenylsulfonamide group, naphthylsulfonamide group)
honamide group, etc.), alkylsulfamoyl M (e.g.
butylsulfamoyl group, etc.), arylsulfamoyl
group (e.g., phenylsulfamoyl group, etc.), alkyl
Oxycarbonyl group (e.g. methyloxycarbonyl
group), aryloxycarbonyl group (e.g. phenyl group), aryloxycarbonyl group (e.g.
oxycarbonyl group, etc.), aminosulfonamide group,
Acylamino group, carbamoyl sulfinyl group, sulfoxy group, sulfo group, aryl group
Oxy group, alkoxy group, carboxylalkylcarbony group
Examples include carbonyl groups, arylcarbonyl groups, etc.
. One of these! ! The substituents are 2 f1 or more leading to 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, arylcarbonyl group, arylcarbo
One or two nyl or cyano groups as substituents
It is a phenyl group having the above. In the present invention, shear represented by the general formula [CC-1.1]
The dye-forming coupler preferably has the following general formula [CG-
This is a compound represented by 21. General formula [CG-2] In general formula [CC-2], R6 represents a phenyl group.
vinegar. This phenyl group carries single or multiple ff2 substituents.
Typical substituents to be introduced include those with
halogen atoms (e.g. fluorine, chlorine, bromine, etc.)
atoms), alkyl groups (e.g. methyl, ethyl,
robyl group, butyl group, octyl group, dodecyl group, etc.), hydrogen
droxyl group, cyam L nitro group, alkoxy group (e.g.
alkyl sulfonate, ethoxy group, etc.),
Mido group (e.g. methylsulfonamide group, octylsulfonamide group)
honamide group, etc.), arylsulfonamide group (e.g.
Phenylsulfonamide group, naphthylsulfonamide group
etc.), alkylsulfamoyl groups (e.g. butylsulfamoyl groups),
), arylsulfamoyl group (such as fluorocarbon),
phenylsulfamoyl group, etc.), alkyloxycarbonyl
group (e.g. methyloxycarbonyl group, etc.), aryl group
Oxycarbonyl group (e.g. phenyloxycarbonyl
etc.). These substituents are 2
11 or more may be converted into phenyl groups. R6
Preferred groups represented by include phenyl group, or
Halogen atoms (preferably fluorine, chlorine, and bromine atoms)
), alkylsulfonamide group (preferably O-methyl
Sulfonamide group, p-octylsulfonamide group, 0
-dodecylsulfonamide group), arylsulfonamide group
do group (preferably phenylsulfonamide group), alkyl
Rusulfamoyl group (preferably butylsulfamoyl)
), arylsulfamoyl group (preferably phenyl
sulfamoyl group), alkyl group (preferably butyl group)
, trifluoromethyl group), alkoxy group (preferably
One or two substituents (methoxy group, ethoxy group)
It is a phenyl group having one or more. R7 is an alkyl group or an aryl group. Alkyl group
or the aryl group has single or multiple substituents
Typical examples of this substituent include halo.
Gen atoms (e.g. fluorine, chlorine, bromine, etc.),
droxyl group, carboxyl group, alkyl group (e.g.
Tyl group, ethyl group, propyl group, butyl group, octyl group
, dodecyl group, etc.), aralkyl group, cyano group, nitro group
, alkoxy group (e.g. methoxy group, ethoxy group),
lyloxy group, alkylsulfone 7mido group (e.g.
(tylsulfonamide group, octylsulfonamide group, etc.)
, arylsulfonamide groups (e.g. phenylsulfone
amide group, naphthylsulfonamide group, etc.), alkyl group
Rufamoyl group (PA such as butylsulfamoyl group, etc.)
, arylsulfamoyl group (e.g. phenylsulfamoyl)
moyl group (99), alkyloxycarbonyl group (e.g.
methyloxycarbonyl group, etc.), aryloxycarboxyl group, etc.)
Bonyl group (e.g. phenyloxycarbonyl group, etc.),
Minosulfonamide kudzu (e.g. dimethylaminosulfone)
(amide group, etc.), alkylsulfonyl group, arylsulfonyl group,
Nyl group, alkylcarbonyl group, arylcarbonyl group
, aminocarbonylamide group, carbamoyl, etc. Two or more of these substituents
May be introduced. Preferred groups represented by R7 include l11xO and
is an alkyl group, and when nl-1 or more is an aryl group.
Ru. More preferable groups represented by R7 include:
When nl-0, an alkyl group having 1 to 22 carbon atoms (preferably
or methyl group, ethyl group, propyl group, butyl group,
(cutyl group, dodecyl group), and on r++=11X
is a phenyl group or an alkyl group (preferably t-butyl group).
tyl group, t-amyl group, octyl group), alkyl sulfonate
amide group (preferably butylsulfonamide group,
tylsulfonamide group, dodecylsulfonamide group),
Arylsulfonamide group (preferably phenylsulfonamide)
aminosulfonamide group), aminosulfonamide group (preferably di-amide group), aminosulfonamide group (preferably
methylaminosulfonamide group), alkyloxycal
Bonyl group (preferably methyloxycarbonyl group, butyl group)
1 or 2 substituents
It is a phenyl group having the above. R8 represents an alkylene group. i! Iffi or branch
1 to 20 carbon atoms, further 1 to 12 carbon atoms
represents an alkylene 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. nl is 0 or a positive integer, preferably O or 1
It is. X is 10-, -CO-, -COO-, -OCO-, -SO2NR-, -NR'802NR''
-, -S-, -SO-t. divalent group of bar 3Q2 -u
represents. Here, R' and R'' represent an alkyl group.
, R', and R'' each include those having substituents.X
Preferably -0-, -S-, -SO-, -SO2
-m and Z>. In general formulas [CC-1] and [CC-21, it is
Aromatic primary amine color developer and crude drug, each represented by Z
Groups capable of leaving by reaction with oxidants of are well known to those skilled in the art.
to modify the reactivity of the coupler or
silver halide in color photographic light-sensitive materials.
In the coating layer or other layer containing the coupler,
Performs functions such as color correction, bleaching control, color correction, etc.
This works more advantageously. A typical example is
, for example, halogen atoms such as chlorine and fluorine, substitution
・Unsubstituted alkoxy group, aryloxy group, aryl
Thio group, carbamoyloxy group, acyloxy group, sulfur
Honyloxy group, sulfonamide group or heteroyl group
o group, heteroyloxy group, etc. 2 especially
Preferred is a hydrogen atom or a chlorine atom. More specifically, JP-A-Sho-10135, JP-A No. 50-
No. 120334, No. 50-130441, No. 54-4
No. 8237, No. 51-146828, No. 54-147
No. 36, @J47-37425, same 5゜123341
@, No. 58-95346, Special public candy No. 48-36894
, National Patent No. 3,476.563, National Patent No. 3.737.31
No. 6 and No. 3.22.551. Below in the margin, cyan turnip 9- expressed by the general formula (cc-1)
Typical specific examples are shown below;
Cxs&s 5OzNH COOCxaHssCn) CzzHxs(b) CL 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 In the formula, R11 is alkyl! (e.g. methyl group, ethyl group
, propyl group, butyl group, etc.) or aryl I (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, Rn, R+s, and R+s 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
Koxycarbonyl group, carbamyl group, sulfone group,
7-mil group, sulfonamide group, acylamide group,
Represents a ureido group or an amino group, and yt has the above meaning.
has. These include, for example, US Pat. No. 2.778.65 (No. 1,
Same No. 2,875,057, Same No. 2.908.573
, No. 3,227.155, No. 3.227.550
No. 3.253.924, No. 3.265.50
No. 6, No. 3,277.155, No. 3.341,
331, 3.369.895, 3.384
．． 657, 3.408.194, 3.41
5.652, 3,447.928, 3.5
No. 51.155, No. 3,582,322, No. 3,
125,072, 3,894,875, etc.
I Mountain, German Patent Publication No. 1,547,868, German Patent Publication No. 2
, No. 057,941, No. 2.1 (No. i2,899, No.
No. 2,163,812, No. 2,213,461,
Same No. 2,219,917, Same No. 2,261,361 @
, No. 2,263,875, Special Publication No. 49-13576
@, JP-A-48-29432, JP-A No. 4g-66834
, 49-10736, 49-122335, 49-122335, 49-10736, 49-122335,
No. 5o-28834, and No. 50-132926 Danko
It is stated in the report etc. 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. The following margin is Y-3 ] h The following margin is between the emulsion layers of the silver halide photographic light-sensitive material of the present invention (
color-sensitive interlayers and/or different color-sensitive layers), developing agent
The oxidant or electron transfer agent may migrate and cause color turbidity,
To prevent deterioration of sharpness and noticeable graininess, color
Anti-bleeding agents are used. The color antifoggant may be used in the emulsion layer itself or in the middle.
An interlayer may be provided between adjacent emulsion layers and used as the intermediate layer.
. Color photosensitive materials using the silver halide emulsion of the present invention
use an image stabilizer to prevent deterioration of the dye image.
I can do it. As an image stabilizer preferably used in the present invention
The following general formulas [A] to [H] and [J], [K] are listed.
can be given. Below is the blank general formula [A1, where R1 is a hydrogen atom, a furkyl group, an alkenyl group, an atom
Represents a lyl group or a heterocyclic group, R6, Rco1. R,,
R, is a hydrogen atom, a halogen atom, a hydroxy group, respectively
, furkyl group, alkenyl group, aryl group, alkoxy
group or 7 silami 7 group, R1 is an alkyl group
, represents a hydroxy group, a 7-aryl group or an alkoxy group. Also, R and R2 close each other to form a 5-shell or 6-shell ring.
In this case, R1 may be a doroxy group or an alkyl group.
When the xy group is added, R3 and R4 are ring-closed, and 5-shell carbon
A hydrogenated ring may be formed, and R+ in the gloss is alkyl.
group, aryl group, or heterocyclic group, provided that R
Except when 2 is a hydrogen atom and R1 is a hydroxy group
Ku. In the general formula [AI, R1 is a hydrogen atom, an alkyl
group, alkenyl group, aryl group or heterocyclic group.
However, among these, as an alkyl group, for example, a methyl group
, ethyl group, propyl group, n-octyl group, tert-
Direct M or branched atom such as octyl group, hexadecyl group, etc.
Mention may be made of the alkyl group. Hail again in R1
Examples of alkenyl groups include allyl, hexenyl,
Examples include octenyl group. In addition, 7 Lee of %R1
Examples of the group include phenyl and naphthyl groups.
. Furthermore, as the heterocyclic group represented by R1, tetrahydro
Specific examples include robilanyl group and pyriminol group.
Ru. Each of these groups can have a substituent, for example,
Benzyl group, ethoxymethane group as an alkyl group having a substituent
As an aryl group having a thyl group or a substituent,
Toxy 7enyl group, chlorphenyl group, 4-hydroxy
Examples include -3,5-butylphenyl group. In the general formula [AI, R2, R3, R1 and R6 are
Hydrogen atom, halogen atom, hydroxy group, alkyl group,
alkenyl group, aryl group, alkoxy group or 7-syl group
Among these, alkyl groups and alkylene groups
Regarding the nyl group and aryl group, as described above for R1.
Same as alkyl group, alkenyl group, aryl group
Can be mentioned. Further, as the halogen atom, for example,
Examples include fluorine, 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
7 groups are denoted by R'CONH-, where R#
is an alkyl group (e.g. methyl, ethyl, n-propyl,
n-butyl, n-octyl, tert-octyl, ben
syl groups), alkenyl groups (e.g. allyl, octyl groups),
thenyl, oleyl, etc.), aryl groups (e.g.
each group such as phenyl, methoxyphenyl, naphthyl),
or heterocyclic groups (e.g. pyridyl, pyrimidyl groups)
). In addition, in the general formula [AI, R4 is an alkyl group,
Represents a droxy group, aryl group or alkoxy group,
Among these, for alkyl groups and aryl groups, the above R,
Specifically, the same furkyl group and aryl group as shown in
It is possible to mention the following. Also, regarding the alkenyl group of R1
I mentioned R2, R1, R1 and VR6 above.
The same groups as alkoxy groups can be mentioned. R3 and R2 close each other to form a benzene ring
As a ring, for example, chroman, coumaran, methylene diode
Examples include xybenzene. Also, R1 and R1 are ring-closed to form a benzene ring.
An example of the ring is indane. these
The ring may contain substituents (e.g. alkyl, alkoxy, aryl).
). Also, R1 and R2 or R1 and R4 are formed by ring closure.
A spiro compound is formed by using the atom in the ring as a spiro atom.
Good 1. Using R2, R4, etc. as a linking group, the bis body is
may be formed. A phenolic compound represented by the general formula [A]r, or
Among the phenyl ether compounds, preferred are R
O- group (R is an alkyl group, alkenyl group, aryl group,
or represents a heterocyclic group,
and is particularly preferably a compound represented by the following general formula [A-
1]. General formula [A-1] In the formula, R is a furkyl group (e.g. methyl, ethyl, propyl
, n-octyl, tert-octyl, benzyl, hexyl
sadecyl), alkenyl groups (e.g. allyl, octenyl),
oleyl, oleyl), aryl groups (e.g. phenyl, naphyl),
) or heterocyclic groups (e.g., tetrahydropyrani)
Represented by le, pyrimizole)! aRI and R3゜ are each a hydrogen atom,
Halogen atoms (e.g. fluorine, chlorine, bromine), alkaline
Kyl groups (e.g. methyl, ethyl, n-butyl, benzyl
), alkoxy groups (e.g. allyl, hexenyl, octene)
), or alkoxy groups (e.g. methoxy, ethoxy)
cy, benzyloxy), and R11 is a hydrogen atom, an alkyl
Kill groups (e.g. methyl, ethyl, n-butyl, benol)
), flukenyl 1t (flJ, 2-propenyl,
xenyl, octenyl), or aryl groups (e.g.
phenyl, methoxyphenyl, chlorphenyl, naphthyl
) at. The compound represented by the general formula [A] is disclosed in U.S. Patent No. 3,
No. 935,016, No. 3,982,944, No. 4
．． No. 254,216, JP-A No. 55-21004, No. 5
No. 4-145530, British Patent Publication rM2, 0.77.4
No. 55, No. 2,062, No. 888, U.S. Patent No. 3,7
64,3:l (7, same No. 3.432300, same No. 3,
No. 574,627, tA3,573,050, Unexamined Patent Publication
No. 52-152225, No. 53-20327, No. 5
No. 3-17729, No. 55-6321, British Patent No. 1
, No. 347,556, Publication No. 2.066.975, Special
Publication No. 54-12337, Publication No. 4B-31625, United States
Also includes compounds described in Patent No. 3,700,455 etc.
nothing. The amount of the compound represented by the general formula [A] is mazen.
It is preferably 5 to 300 mol% based on Tacoupler, and more
Preferably it is 10 to 200 mol%. Typical examples of the compound represented by the general formula [A] are shown below.
Give an example. Type (1) R1 8 type (2) Type (3) Type (4) Type (5) Type (6) Type (7) Type (2) Below margin type (4) Below margin type・ (5) Below margin type (6) Below margin A-7 Below margin general formula tB] (In the formula, R and R4 are hydrogen atoms and halogen atoms, respectively.
child, alkyl group, alkenyl group, alkoxy group, alke
Nyloxy group, hydroxy group, 71J-l group, 7yl
Oxy group, 7 syl group, 7 sylami 7 group, 7 syloxy group
, sulfonamide group, cycloalkyl or alkoxy
carbonyl group, Rt is hydrogen atom, furkyl
group, alkenyl group, aryl group, 7syl group, cycloal
a kill group or a heterocyclic group, R3 is a hydrogen atom,
Halogen atom, alkyl group, alkenyl group, 717-ru
group, 7-aryloki2/group, acyl group, acyloxy group,
Sulfone 7mido group, cycloalkyl group or furufukidi group
Hail carbonyl group. Each of the groups listed above may be substituted with other substituents.
For example, furkyl group, alkenyl group, alkoxy group,
Aryl group, 7-aryloxy group, hydroxy group, alco
oxycarbonyl group, aryloxycarbonyl group, 7-carbonyl group
7 groups, acyloxy group, carbamoyl group, sulfo group
Examples thereof include a 7-mido group, a sul-77 moyl group, and the like. Also, R2 and R5 close each other to form a 5-shell or 6-shell ring.
may be formed, I R2 and R5 are ring-closed and co-exist with the benzene ring.
Examples of rings formed in
The xybenzene ring is accelerated. Y is necessary to form a chroman or coumaran ring
Hail atomic groups. Chroman or coumaran ring is a halogen atom, furkyl
group, cycloalkyl group, alkoxy group, alkenyl group,
Alkenyloxy group, hydroxy group, aryl group, 71
May be substituted with J-ruoxy group or heterocycle
, may further form a spiro ring. 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
-31, [B -4], [B -51]
included in General formula [B-17 to' General formula [B-2] General formula [B-3] General formula [B-43 General formula [B-51 81 General formula [B-1], [B-2], [B-3], [B
-41 and R3, R2, R3 and [B-5]
and R4 have the same meanings as in the general formula [B] above.
, R3, Rε, 'R1, R1 and R3° are hydrogen atoms.
child, halogen atom, alkyl group, alkoxy group, hydro
xy group, alkenyl group, fulkenyloxy group, aryl
group, aryloxy group or heterocyclic group. Furthermore, R6 and R,, R8 and R1, R and R6, R, and R
1 and R9 and R1° are cyclized with each other to form a carbocycle
Furthermore, the carbocycle may be substituted with an alkyl group.
Good too. The general formula [B-1], [B-2], [B-3], [
In B-41 and [B-5], R1 and R4 are
Hydrogen atom, furkyl group, alkoxy group, hydroxy group or
or dichlorofurkyl group, R1, R,, R7, Re, Re
and R1 is a hydrogen atom, an alkyl group, or a cycloatom
Particularly useful are compounds that are alkyl groups. The compound represented by the general formula [B] is tetrahedron (Te
trahedron), 1970. vo126,474
pp. 3-4751, Journal of the Chemical Society of Japan, 1972 = NolO*
pp. 0987-1990, Chemical (chew, Lett.
), 1972 (4)? pp. 115-318, Japanese Patent Application Publication No. 1977.
Represents the compound described in No. 5-139383, and includes
and synthesize according to the methods described in these
be able to. The 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. Typical specific examples of these compounds are shown below. The following is a blank general formula [C] RI R'' General formula [D] [1! In the formula, R1 and R2 are hydrogen atoms, ) 10 dene atoms, alkaline
Kyl group, alkenyl group, alkoxy group, alkenyloxy
cy group, hydroxy group, 7-aryl group, aryloxy group,
7-syl group, acylami/group, 7-syloxy group, sulfone
Contains an amide group or an alkoxycarbonyl group. Each of the groups listed above may be substituted with other substituents.
For example, halogen atom, alkyl group, alkenyl group,
Alkoxy group, aryloxy group, hydroxy group, alkoxy group, aryloxy group, hydroxy group,
Koxycarbonyl group, aryloxycarbonyl group,
Silami 7 groups, carbamoyl group, sulfonamide group, sulphate
Examples include rufamoyl group. Y is a benzene ring and a dichroman or nocoumaran ring
Hail the groups of atoms necessary to form . Chroman or coumaran ring is a halogen atom, furkyl
group, cycloalkyl group, alkoxy group, artenyl group,
Alkenyloxy group, hydroxy group, aryl group, 7-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 [C] and [D], this
Compounds useful for the invention have general formulas [C-1] and [C-2
], [D-11 and [D-2]
included in General formula [C-1] General formula [C-2] 1 General formula [D-1] General formula [D-2] General formula [C-1], [C-2], [D-1] and 2D
-2], R1 and R2 are represented by the general formula [C] or
and have the same meaning as in [D], Ryu, R1,
R1, R6, R1 and R8 are hydrogen atoms, halogen atoms
, alkyl group, alkoxy group, hydroxy group, alkenyl group
group, alkenyloxy group, 7-aryl group, aryloyl group
cy group or heterocyclic group, and R3 and R4
, R1 and R1 and R1 and R7 and VB2 and R1 and
may be cyclized with each other to form a carbon ring, and furthermore, the carbon
*The ring may be substituted with a furkyl group. The general formula (c-i), [C-2], [D-11 and
[D = 2], R6 and R3 are hydrogen atoms,
Furkyl group, alkoxy group, hydroxy group or cyclo
Alkyl and R. is a hydrogen atom, an alkyl group, or a cycloalkyl group
Particularly useful are compounds in which the radical is a radical. Expressed by the general formula [CI, [DI]. The compound to be used is Nihon Kagaku.
Journal (J.CheIl.Soc, part C) 1
988. (14)t pp. 1937-18, Organic Synthetic Chemistry
Journal of the Association 1970% 28 (1), pp. 60-65, Tetra
Hedron (Tetrahedron Letters)
1973, (29), 2707-2710.
Contains the compounds listed in the list and those listed therein.
It can be synthesized according to the law. The usage 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 to 200 mol%
%. Specific representative examples of these compounds are shown below. Below is a blank space below: General formula [E] In the formula, R' is a hydrogen atom, a furkyl group, an alkenyl group, a 7-ring
group, acyl group, cycloalkyl group or heterocycle
R' is hydrogen atom, halogen atom, alkyl
group, alkenyl group, aryl group, aryloxy group, a
Syl group, 7 acylamide groups, acyloxy group, sulfona group
Mido group, dichlorofurkyl group or alkoxycarbonyl group
represents a group. R2 and R4 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,
Alkoxycarbonyl group, 7lyloxycarbonyl group
, 7-syl amino group, carbamoyl group, sulfonamide group
, sul77 moyl group, and the like. In addition, R' and R2 close each other to form a 5- or 6-membered ring.
may be formed. At that time, R3 and R4 are hydrogen atoms, halogen atoms, and hydrogen atoms.
Kyl group, alkenyl group, alkoxy group, alkenyloxy
cy group, hydroxy group, aryl group, aryloxy group,
Acyl group, 7 sylami 7 groups, 7 syloxy group, sulfone
Represents an amide group or an alkoxycarbonyl group. Y is necessary to form a chroman or coumaran ring
Represents a group of atoms. Chroman or coumaran ring is a halogen atom, alkyl
group, cycloalkyl group, alkoxy group, alkenyl 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 (E),
The compound used is general formula (E-1). (E-2), (E-3), (E-4) and (E-5
) is included in the compounds shown. General formula (E-13 OR+ General formula (E-2) OR+ General formula (E-3) General formula (E-4) $i1 General formula (E-5) General formula (E-1) to (E-5 ) in R 1% R2,
R3 and R4 have the same meaning as the throat in the above general formula (E).
Have a taste, R', R', R? , R', R-Original R'' is
Hydrogen atom, halodene atom, alkyl group, alkoxy group
, hydroxy group, fulkenyl group, alkenyloxy group,
Represents an aryl group, aryloquine group or heterocyclic group.
Wash, more Rs and R6, 8 prefectures and Rfu, Rfu and Rs, R
s, R1 and f/R" and R" are cyclized with each other to form a carbocyclic ring.
may be formed, and the R ring is further substituted with an alkyl group.
may be done. In the general formulas (E-1) to (E-5), Rl,
Rz, Rs and R4 are hydrogen atoms, alkyl groups,
or a cycloalkyl group, the general formula (E-53)
So, R3 and R4 are hydrogen atoms, furkyl groups, alkoxy groups.
cy group, hydroxy group or cycloalkyl group, before i et al.
In the general formulas (E-1) to (E-5), Ri, R
s, R7, R'', R't (from which n'' is a hydrogen atom,
Compounds that are alkyl, * or cycloalkyl groups are particularly
Useful. The compound represented by the general formula [E] is tetrahedron (
Tetrahedron Letters) 1965
．． (8) *pp.457-460 Chemical Society of Japan Fiit (J
, Chew, Soc, part C) 1966
゜(22), pp. 2013-2016, (Zh, Or
G, Khim) 1970. (6). 1230-1237,
and be synthesized according to the methods described therein.
I can do it. The usage amount of the compound represented by the general formula [E-1] is as follows.
5 to 300 moles for the magenta coupler according to the present invention.
preferably 10 to 200 mol%, more preferably 10 to 200 mol%.
be. Specific representative examples of these compounds are shown below. Below is the general formula (F) in which R5 is a hydrogen atom, an alkyl group, an alkenyl group, an ali
group, acyl group, cycloalkyl group or heterocycle
represents a group, R2 is a hydrogen atom, a halogen atom, an alkyl group
, alkenyl group, aryl group, aryloxy group, acyl
7yl group, 7yl7mi7 group, acyloxy group, = sulfona group
Mido group, cycloalkyl group, or alkoxycarboxylic group
Hail nil group. R1 is a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group
group, aryl, group, acyl group, acylamino group, sulfur
Honamido group, cycloalkyl group or alkoxy group
Hail the rubonyl group. R4 is a hydrogen atom, a halogen atom, a furkyl group, an alkenyl group
group, alkoxy group, alkenyloxy group, hydroxy
group, aryl group, 71J-ruoxy group, acyl group, acyl group,
Ruami/group, 7-syloxy group, sulfonamide group, if
or an alkoxycarbonyl group. Each of the groups listed above may be substituted with other substituents.
For example, an alkyl group, an alkenyl group, an alkoxy group,
Aryl group, 7-aryloxy group, hydroxy group, alco
oxycarbonyl group, 7lyloxycarbonyl group, acyloxycarbonyl group,
lamino group, carbamoyl group, sulfonamide group, sulfonamide group,
Examples include famoyl group. Also, R and R2 close each other to form a 5-shell or 6-membered ring.
In that case, R2 and R1 are hydrogen atoms, halogen atoms.
atom, alkyl group, alkenyl group, alkoxy group,
lekenyloxy group, hydroquine group, aryl group, aryl group
oxy group, acyl group, 7 sylami 7 groups, acyloxy
group, sulfonamide group, or alkoxycarbonyl
Hail to the foundation. Y is necessary to form a chroman or coumaran ring
Hail atomic groups. Chroman or coumaran ring is a halogen atom, alkyl
group, dichlorofurkyl group, alkoxy group, alkenyl group,
Alkenyloxy group, hydroxy group, aryl group, aryl group
may be substituted with an oxy group or a heterocyclic group.
Furthermore, a spear ring may be formed. Among the metal compounds represented by the general formula [F],
Compounds of general formula [F-11, [F-2], [F-
3], [F -4]tf (denoted by /[F -51
It is included in the compounds. Below are blank spaces General formula [F-1] General formula (F-23 General formula (F-3) General formula (F-4) General formula CF-5) R1% in General formulas [F-1] and [F-51 R2
, R1 and R4 are the same as in the above general formula [F]
R5, R2, R1, R1, R1 and R1
゜ is hydrogen atom, 710 dene atom, alkylalkoxy group
, hydroxy group, alkenyl group, alkenyloxy group,
Aryl group, aryloxy group or heterocyclic group
It will be. Furthermore, R6 and R, R6 and R2, R1 and R,, R8 and R
3 and R, and R+o are cyclized with each other to form a carbocycle
Furthermore, the carbocycle may be substituted with an alkyl group.
Good too. Also [F-3], [F-4] and (/[F-51 smell)
The two R1-R1゜ are the same or different.
Good too. The general formula [F-11, [F-21, [F-31, [F
-4] R11Rx in the upstream [F-5], and
R, can hydrogen atom, furkyl group, dichlorofurkyl group, R
4 is hydrogen atom, alkyl group, alkoxy group, hydroxy
group or cycloalkyl group, further R1, R, R,, R
1, R1 and R1° are hydrogen atoms, alkyl groups, or
Particularly useful are compounds that are cycloalkyl groups. The compound represented by the general formula [F] is tetrahedron (
Tetrahedron Letters) 19F O
, Vol 26.4743-4751, Chemical Society of Japan
Magazine 1972. No. 10 = pages 1987-1990,
Synthesis 1975. V
ol L392-393, (Bul Soc, Ch
ime Ileg) 1975. Vo184 (7
), including the compounds described on pages 747-759.
, and can be synthesized according to the methods described therein.
I can do it. The amount of the compound of the general formula [Fl″C reduced is as follows:
5 to 300 mol for the magenta coupler according to the present invention
%, more preferably 10 to 200 mol%.
Ru. Specific representative examples of compounds represented by general formula [F] are shown below.
show. The following is a general formula (G) R in which R' and R1 are a hydrogen atom and a halogen atom, respectively.
, alkyl group, artenyl group, alkoxy group, hydroxy group
cy group, 7 aryl group, aryloxy group, 7 syl group, 7 syl group
Ruami 7 group, 7 syloxy group, sulfonamide group,
Represents a loalkyl group or an alkoxycarbonyl group. R2 is a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group.
group, hydroxy group, 7-aryl group, acyl group, 7-syl group
Mi7 group, acyloxy group, sulfonamide group, cycloa
represents an alkyl group or an alkoxycarbonyl group. Each of the groups listed above may be substituted with other substituents.
Examples of substituents include alkyl groups, alkenyl groups,
Alkoxy group, aryl group, acyloxy group, hydroxy group
cy group, alkoxycarbonyl group, 7lyloxycarbo
Nyl group, 7syl 7mi7 group, carbamoyl group, sulfone 7
Examples include mido group and sulf7moyl group. In addition, R2 and R3 are ring-closed with each other, and carbonization of 5 or 6 shells occurs.
This 5-shell or 6-true hydrocarbon may form a hydrogen ring.
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 ring is a halogen atom, a furkyl group, an alkenyl group,
Alkoxy group, cycloalkyl group, hydroxy group, ali
Substituted with aryl group, aryloxy group, or heterocyclic group, etc.
or may further form a spiro ring. Among the compounds represented by general formula (G), most useful for the present invention
Compounds represented by the general formula (G-13 to (G-33)
included in the compound. The following margins are general formula (G-1) K+ general formula (G-2) general formula (G-3) R1 in general formulas (G-1) to (G-3). R2 and
R3 has the same meaning as in general formula CG), R',
R', R', R', R" and (/R"li, tsuretsure hydrogen
atom, halogen atom, furkyl group, alkoxy group, alkyl
Kenyl group, hydroxy group, aryl group, 7-aryloxy
group or heterocyclic group, R4 and R5, R' and R',
R' and R', R' and R'' and t/R'' and R1 are mutually closed rings.
to form a hydrocarbon ring, furthermore, the hydrocarbon ring may be
It may be substituted with a furkyl group. In the general formulas (G-1) to (G-3), R1 and (
/R' is a hydrogen atom, an alkyl group, an alkoxy group, a hydro
xy group or cycloalkyl group, R2 is hydrogen atom, alkyl group,
Kyl group, hydroxy group or dichlorofurkyl group, R',
RS, R@, R), R1 and R@ are hydrogen atoms, a
Compounds that are alkyl or cycloalkyl groups are particularly
Useful. The amount of the compound represented by the general formula [G]
It is preferably 5 to 300 mol% based on the zenta coupler,
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) R3 where R1 and R2 are a hydrogen atom and a halogen atom, respectively.
, alkyl group, alkenyl group, aryl group, 7-syl group,
Acylamino group, acyloxy group, sulfonamide group,
Represents a cycloalkyl group or an alkoxycarbonyl group
. R3 is a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group
aryl group, alkoxy group, hydroxy group, aryl group, 7
lyloxy group, acyl group, acylami 7 group, acyloxy group, acyl group
xy group, sulfonamide group, cycloalkyl group or a
Represents a lucoxycarbonyl group. Each of the groups listed above may be substituted with other radicals.
For example, an alkyl group, an alkenyl group, an alkoxy group,
Aryl group, aryloxy group, hydroxy group, alco
oxycarbonyl group, aryloxycarbonyl group, acyloxycarbonyl group,
lamino group, carbamoyl group, sulfonamide group, sulfonamide group,
Examples include famoyl group. In addition, R1 and R2 and R2 and R3 are ring-closed with each other, and five shells or
or a six-shell hydrocarbon ring, and the hydrocarbon ring
is a halogen atom, an alkyl group, a cycloalkyl group, an alkyl group,
Koxy group, alkenyl group, hydroxy group, aryl group,
May be substituted with aryloxy group, hetero Ilk group, etc.
stomach. Y represents an atomic group necessary to form a kidney bean ring, and
The indane ring can replace the above hydrocarbon ring I! ! replacement group
They may be interchanged or may further form a spiro ring. Among the compounds represented by general formula (H), particularly useful for the present invention
Compounds represented by general formulas (H-1) to (H-2) are
included in the compound. General formula [H-23 General formula (H-3) General formula (H-1) -('R' in H-33, R2 and
and R3 have the same meanings as in general formula (H), and R'
, R', R', R', R" and (/R" are that ('shimizu)
Elementary atoms, halogen atoms, alkyl groups, flukoxy groups,
droxy group, alkenyl group, 7-aryl group, arylox
represents a cy group or a heterocyclic group, and R' and Rs, R5 and
R', R' and R', R' and R' and t/R8 and R9 are mutually
may be ring-closed to form a hydrocarbon ring, and further the hydrocarbon
Bare rings may be substituted with alkyl groups. In the general formulas (H-1) to (H-3), R' and
R2 is a hydrogen atom, an alkyl group or a cycloalkyl group, respectively
Kyl group %R'' is a hydrogen atom, an alkyl group, a flukoxy group,
Hydroxy group or cyclo7kafk group, R', R',
R', R', R'' and t/R' are each a hydrogen atom, a
Compounds that are alkyl or cycloalkyl groups are particularly
It is for use. The method for synthesizing the compound reduced by the general formula [H] is known.
There, US Patent No. 3, No. 057929, Chetm. Ber, 1972.95(5)t 1673-16
74 pages, Che+m1st-ry Le Letters,
1980, pp. 739-742. The compound magenta coupler represented by the general formula [H]
It is preferably 5 to 300 mol%, more preferably 1
Pickled at 0 to 200 mol%. Specific representative examples expressed by the general formula [Hlt%] are shown below. The following margin general formula (J), +-. The 717-l group is reduced, and Y together with the nitrogen atom is 5-7
Represents a group of nonmetallic atoms necessary to form a heterocyclic ring,
However, in the nonmetallic atoms containing nitrogen atoms forming the heterocycle,
, if there are two or more heteroatoms, at least two heteroatoms
Teroatoms are heteroatoms that are not adjacent to each other. ] The aliphatic group represented by Rt' may have a substituent.
unsaturated alkyl groups, and unsaturated groups that may have substituents
A furkyl group is mentioned. Examples of Q-furkyl groups include
For example, methyl group, ethyl group, butyl group, octyl group,
Decyl group, tetradecyl group, hexadecyl group, etc.
Examples of the unsaturated furkyl group include ethynyl group,
Examples include propenyl group. The dichlorofurkyl group represented by R' has a substituent.
For example, 5 to 7 cycloalkyl groups may be used.
Examples include a lopentyl group and a cyclohexyl group. As the 7-aryl group represented by R1, each substituent is
Represents an optional phenyl group or naphthyl group. Aliphatic group, cycloalkyl group, aryl represented by R1
Substituents for groups include alkyl groups, aryl groups, and alkyl groups.
xy group, carbonyl group, carbamoyl group, acylami 7
group, sulf77 moyl method, sulfonamide group, carbonyl
Oxy group, alkylsulfonyl group, arylsulfonyl group
group, human mixi group, heterocyclic group, alkylthio group,
These substituents can be further substituted.
It may have a group. In the general formula (J), Y together with the nitrogen atom is 5 to 7
Represents a group of nonmetallic atoms necessary to form a shell ring.
is a group of nonmetallic atoms containing nitrogen atoms forming the heterocycle.
(Both two must be heteroatoms, and
This small (both two hete a/F, children are FiJ each other)
Of the compound represented by the general formula [J] that must not be in contact with each other!
If all the heteroatoms are adjacent to each other in the I-ring
In this case, it exhibits fi ability as a magenta dye image stabilizer.
I don't like it because I can't do it. The 5 to 7 shell rings of the compound represented by the general formula (J)
The heterocycle may have a substituent, and the substituent includes
Kyl group, aryl group, 7-syl group, carbamoyl group, alkyl group,
Koxycarbonyl group, sulfonyl group, sulfonyl group
etc., and the rf1 substituent may be added, and the 5
~7 The complex ring of shell rings may be saturated, but the complex ring of saturated
A ring is preferable, and a benzene ring etc. is fused to 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 represented by the general formula (1) of the present invention
- is preferably 5 to 300 mol%, more preferably
is 10 to 200 mol%. Typical specific examples represented by general formula (J) are shown below. J-63 J-64 J-69 J-70 ■C戊H2s Among the compounds represented by the general formula (J), piperazine
type compounds and homoviperacun type compounds are highly preferred;
More preferably, the following general formula (J-1) or (J-
This is a compound represented by 23. General formula (J-1) General formula (J-2) In the formula, % R1 and 1/R' are a hydrogen atom and an alkyl atom, respectively.
represents a group or an aryl group, provided that R2 and R″ are the same
m R' to R13 are each
Represents a hydrogen atom, an alkyl group, or an aryl group. In the general formulas (J-1) and (J-23), R2 and
R2 is a hydrogen atom, an alkyl group, or an aryl group, respectively.
represents a group, but as an alkyl group represented by R2 or R3
For example, methyl group, ethyl group, butyl group, octyl group, etc.
group, dodecyl group, tetradecyl group, hexadecyl group,
Examples include octadecyl group. Decayed by R2* or R3
Examples of the aryl group include phenyl group, etc.
The alkyl group and 7-aryl group represented by R2 or R3 are
It may have a substituent (as a substituent, a halogen atom,
Alkyl group, aryl group, alkoxy group, arylox
Examples include a cy group, a heterocyclic group, and the like. The total number of carbon atoms of R2 and R2 (including substituents) is 6 to
40 is preferred. In the general formula (J-13 or (J-2)), R
4 to R'' are each a hydrogen atom, an alkyl group, or an ali
represents an alkyl group represented by R4 to R'3.
Examples of the group include a methyl group and an ethyl group. Aryl groups represented by R4 to R'' include phenyl groups, etc.
can be mentioned. The compound represented by the general formula (, J-13 or (J-2))
Specific examples of the compounds include the exemplified piperazine compounds (J
-1)-(J-30) and exemplary homobi, racine compounds
As described in @(J-51)-(J-62)
Ru. Next, a representative example of the present invention represented by the above general formula [J,]
An example of synthesis of a magenta dye image stabilizer is shown. Synthesis N-1 (gold of compound J-2!!1.) Piperazine 9
．． 0. and 10 in which 55 g of myristyl bromide was dissolved.
Add 15 g of anhydrous potassium carbonate to 77 tons of 0 mQ.
The mixture was boiled and refluxed for 10 hours to react. After the reaction, pour the solution into 50011IQ water and add acetic acid.
Ethyl 500! All were extracted. Sulfurize the ethyl acetate layer
After drying with magnesium chloride and distilling off the ethyl acetate, a white
The desired product was obtained as colored crystals. Reunited with 7 Seton 3001d
Crystallized to obtain 34 g of white flaky crystals (yield 70%).
Ta. Melting 1ss-ss℃ Synthesis Example-2 (Synthesis of Compound *J-34) 18g of 4-morpholinoaniline was added to 100□□ of ethyl acetate.
After dissolving the mixture, while stirring and keeping the reaction solution at 20°C,
Acetic anhydride 12i1Q was added little by little. After adding acetic anhydride
After cooling with water and filtering out the precipitated crystals, filtrate again with ethyl acetate.
Crystallized to obtain 16.5 g of white powder crystals (yield 75%).
Ta. Melting point: 207-210°C General formula (K) In the formula, R1 is an aliphatic group, a dichlorofurkyl group, or an aryl group.
Y represents a heterocyclic ring with 5 to 7 shell rings together with a nitrogen atom.
Mere bond or divalent hydrocarbon required to form
R2tR3, R41R', R~R? teeth,
Hydrogen atom, aliphatic group, cycloalkyl group or 1, respectively
y represents an aryl group, provided that R2 and R4 and R3 and R6
are bonded to each other to form a simple bond and form a nitrogen atom, Y
May form a monounsaturated 5-7 shell bicyclic ring with
, and when Y is just a bond, R% and R7 are mutually exclusive.
to form a simple bond, and together with the nitrogen atom and Y
May form an unsaturated five-shell bicyclic ring, and Y
When it is not just a bond, %R' and Y%R7 and Y or
forms an unsaturated bond with Y itself, forming a nitrogen atom and an unsaturated bond with Y.
A saturated hexashell or 7R biplane ring may be formed. 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. @As an alkyl group, for example,
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. The cycloalkyl group represented by R' has a substituent.
5 to 7 cycloalkyl groups, for example, Schif
Examples include pentyl group and cyclohexyl group. As the aryl group represented by R1, even if it has a substituent,
Represents a good phenyl group or naphthyl group. Aliphatic group, cycloalkyl group, aryl represented by R1
Substituents for groups include alkyl groups, aryl groups, and alkyl groups.
xy group, carbonyl group, carbamoyl group, acylamino
group, sulfamoyl group, sulfonamide group, carbonyl group
Oxy group, alkylsulfonyl group, arylsulfonyl group
group, hydroxy group, heterocyclic group, alkylthio group, ali
These substituents further include ra
It may 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, R5 and R7 combine with each other to form a simple bond.
to form an unsaturated 5R-ring heterocycle.
When Y is a divalent monovalent hydrogen group, that is, when it is a methylene group,
In this case, Rs and Y or R7 and Y form an unsaturated bond.
However, it may form an unsaturated hexacyclic heterocycle, and
In the case of tyrene group, % R' and Y, R' and Y or Y itself
The body forms an unsaturated bond, forming an unsaturated heptad-ring heterocycle.
The divalent hydrocarbon group further represented by Y may be
It may have a substituent, and this substituent includes an alkyl group,
Carbamoyl group, alkyloxycarbonyl group, acyl
Ami7 group, sulfonamide group, sulfamoyl group, ali
Examples include a ring group, a heterocyclic group, and the like. In the general formula (K), R21R3fR'tR5°
R& and tlR7 are a hydrogen atom, an aliphatic group, and a dichloromethane group, respectively.
It represents a lofurkyl group or an aryl group, and R2-R7
The aliphatic group represented is a saturated group that may have a substituent.
Alkyl group and unsaturated alkyl group that may have substituents
is mentioned. Examples of saturated alkyl groups include methyl
group, ethyl group, butyl group, octyl group, dodecyl group,
Examples include tetradecyl group, hexadecyl group, etc., and unsaturated
Examples of alkyl groups include ethynyl group, propenyl group,
Examples include groups. The cycloalkyl group represented by R2-R7 is
! l! Dichlorofurkyl with 5 to 7 shells optionally having i group
A group, for example, a cyclopentyl group, a cyclohexyl group, etc.
can be mentioned. The aryl group represented by R2-R7 has a substituent.
Examples include a phenyl group, a naphthyl group, and the like. Aliphatic group represented by R2 to R7 above, cycloalkyl
As substituents for groups and aryl groups, furkyl groups, aryl groups, etc.
group, flukoxy group, carbonyl group, carbamoyl group,
Acylamide 7 groups, sulfamoyl group, sulfonamide group
, carbonyloxy group, furkylsulfonyl group, aryl
rusulfonyl group, hydroxy group, heterocyclic group, t-ruki
Examples include ruthio group. The compound represented by the general formula (K) has 5 to 7 shell rings.
It is preferable to have a bicyclic ring than to be unsaturated.
stomach. The amount of the compound represented by the general formula (K) below is as follows:
Magenta coupler represented by the general formula (1) of the present invention
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 -38 to -39 to -40 to -41 Next, vicarious synthesis of the compound decayed by the above general formula (K)
Give an example. Synthesis M-1 (synthesis of compound -14) Add 9.0 g of piperazine and 28 g of myristyl bromide.
In 77 tons of dissolved 80 mQ, anhydrous potassium carbonate a
-or was added, and the mixture was boiled and refluxed for 20 hours to react. After the reaction, the reaction solution was poured into 300-g water, and then acetic acid ethyl chloride was added.
Extracted with Chill 300.9. ethyl acetate layer with sulfuric acid mag
After drying with nesium, the ethyl acetate layer was distilled off to give white crystals.
The target object was obtained. 7 Seton 100 Tll! in re
After crystallization, 12 g of white tuna flake-shaped crystals (yield 43%) were obtained.
Ta. ! 1175-180°C Storage layer, intermediate layer, etc. of the silver halide photographic material of the present invention
The hydrophilic colloid layer of the photosensitive material becomes charged due to friction, etc.
Preventing fogging caused by electrical discharge, and preventing image degradation caused by UV light.
It may also contain an ultraviolet absorber to prevent it from becoming oxidized. The silver halide photographic light-sensitive material of the present invention includes a filter layer.
, anti-halation layer, and/or anti-irradiation layer.
An auxiliary layer such as a stop layer can be provided. These residences and
/or in the emulsion layer, from the color photosensitive 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 sensitive materials from sticking to each other to reduce gloss and increase ease of writing
A matting agent can be added with the aim of achieving a 2nd grade finish. The sliding friction of the silver halide photographic light-sensitive material of the present invention is reduced.
A lubricant can be added to make it smoother. 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
Emulsion? Can be used as an antistatic layer on the non-alW side
In some cases, the emulsion layer is stacked on the emulsion layer and/or the support.
It is not used for the protective colloid layer other than the emulsion layer on the layered side.
It's okay to be The photographic emulsion layer and/or the silver halide photographic light-sensitive material of the present invention
or other hydrophilic colloid layers to improve coating properties and prevent static electricity.
, improved slipperiness, emulsification and dispersion, prevention of adhesion, and (promotion of development)
, high contrast, sensitization, 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
Cellulose acid, cellulose nitrate, borisdylene, polysalt
Vinyl chloride, polyethylene terephthalate-1-, polycarbonate
Made of semi-synthetic or synthetic polymers such as nates, polyamides, etc.
Can be applied to films, glass, metals, ceramics, and other rigid objects.
come. The silver halide photographic light-sensitive material of the present invention can be used as a support as needed.
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 primer openings). 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 possible to apply more than 2+ff1 at the same time.
Ex-dollion coating and curtain coating
This is particularly useful. The silver halide photographic light-sensitive material of the present invention is composed of
'F in the spectral region to which the emulsion layer is sensitive
Can be exposed using i-magnetic waves. Natural light (sunlight) is the light source.
light), tungsten electric lamp, fluorescent lamp, mercury lamp, xenon
Arc lamp, carbon arc lamp, xenon flash lamp, overpass
Wire tube flying spot, various laser lights, light emitting diodes
excited by code light, electron beams, X-rays, gamma rays, alpha 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 using a pole, wire tube or xenon flash lamp
Exposures of 1 microsecond can be used, or exposures of 1 second or more can be used.
Longer exposures are also possible. The fog light is carried out continuously.
However, it may be performed intermittently. ' The silver halide photographic material of the present invention is a silver halide photographic material known in the art.
An image can be formed by performing color development.
Ru. Aromatic primary atom used in color developing solution in the present invention
Min-based coloring agents are suitable for various color photographic processes.
This includes well-known and widely used methods. These developers are aminophenolic and p-phenylene
Contains diamine derivatives. These compounds
It is generally in the form of 3g because it is more stable than the state.
is used in the form of sulfur salt. Also, these compounds are
In general, color development IL! ! 11. about 0.10 to about 3
0 (l concentration, preferably approximately for color developer 111)
Use at a concentration of 1g to about 15o. Aminophenol type agents include, for example, 0-
Aminophenol, p-aminophenol, 5-amino
-2-oxytoluene, 2-amino-3-oxytoluene
2-oxy-3-amino-1,4-dimethylbenze
This includes things such as Particularly useful primary aromatic amine color developers are N, N4
-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 Pd
a 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-hydroxyethylaminoaniline, 4
-amino-3-methyl-N. N'-diethylaniline, 4-amino-N-(2-meth
xyedyl)-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
In addition to primary aromatic amine color developer, color developer a
Various ingredients commonly added to liquids, such as hydrochloric acid
Alkali such as thorium carbonate, thorium carbonate, and potassium carbonate
agent, alkali synthetic sulfite, alkali gold ff) J sulfite
salt, alkali metal thiocyanate, alkali synthetic halogen
compound, benzyl alcohol, water softener and v:J thickening
It is also possible to optionally contain agents and the like. This color development
The pH value of the image solution is usually 7 or higher, most commonly about
10 to about 13. In the present invention, after color development processing,
However, if the processing liquid with the fixing ability is
If it is wetted with liquid, a bleaching process is performed beforehand. 55
As the bleaching agent used in the whitening process, metal complex salts from Yun Yoshi are used.
However, in order to collude with this, Mizuki Shio used the metallic silver produced by development.
Oxidizes and converts to silver halide, and at the same time, the coloring agent does not develop color.
It has the effect of coloring the skin, and its 4R composition is based on amino acids.
Iron can be removed with organic acids such as nopolycarboxylic acid, a-acid, and citric acid.
Coordinated with metal ions such as , cobalt, and copper. used to form metal complexes of such organic acids.
The most preferred timing 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. [1] Ethylenediaminetetraacetic acid [2] Nitrilotriacetic acid [3] IminodirIF acid [4] Ethylenediaminetetraacetic acid disodium salt [5] Ethylenediaminetetraacetic acid tetra(trimethyl
Ammonium) salt [6] Ethylenediaminetetraacetic acid tetrasodium salt [71 Nitrilotriacetic acid sodium salt] The bleaching agent used is a total complex salt of fjnH as mentioned above.
In addition to containing it as a bleaching agent, it also contains various additives.
I can do it. As an additive, especially Arno J Rehalide or
or ammonium halides, such as potassium bromide, bromide
Recycling of sodium, sodium chloride, ammonium bromide, etc.
Contains halogenating agent, gold salt, and chelating agent
is desirable. Also, if salt, oxalate, vinegar wi salt, charcoal wi salt, phosphorus salt
l) H buffering agents, alkylamines, polyethylene, etc.
It is known to be added to ordinary bleaching solutions such as oxinides.
It is possible to add as appropriate. Furthermore, the fixer and bleach-fixer contain ammonium sulfite,
Potassium sulfite, ammonium bisulfite, TEA
Potassium R, VA sodium sodium metabisulfite
monium, potassium metakawa sulfite, sodium metachlorite sulfite
um, etc., sulfurous @ salt and (In!, ■ sand, sodium hydroxide
, potassium hydroxide, carbonate, potassium carbonate,
Sodium bisulfite, sodium bicarbonate, potassium bicarbonate
ammonium hydroxide, acetic acid, 1-lium acetate, ammonium hydroxide, etc.
Contains one or more pH buffers consisting of various salts
be able to. 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 salt, diocyanate, sulfite, 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
Acid salts, persulfates, etc. may be added as appropriate. The following margin [Effect of the invention]
Magenta coupler of the invention and represented by the general formula (1)
By containing a compound that reduces humidity during storage,
It was possible to improve the yellow stain caused by moisture. [Example] The present invention will be explained in more detail by showing specific examples below.
However, the embodiments of the present invention are not limited by these.
do not have. Example 1 Illustrated magenta on a support made of polyethylene coated paper
4 m of puller MC-1 (1/df, green-sensitive silver chlorobromide emulsion)
4meJ/df by replacing it with silver, dibutyl phthalate
411 J/dm2 and 16 mg/dr of gelatin
The area with the coating was painted in a way that made it look like it was being painted. Furthermore, apply 9mg/dllt of gelatin on the top layer.
It was painted so that it would become appendix 4. The sample thus prepared is referred to as sample 1. Next, the above sample 1
in the coupler-containing layer of the coupler and organic solvent.
Trial F1 except that the combinations were changed as shown in Table 1.
Samples 2 to 6, which were the same as Sample 1, were prepared. However, sample 7 and
The silver coating openings of No. 8 and No. 8 were set at 2 InlJ/df. Also the sample
The sweetness of the organic solvent used in 3 and 4 is 4rAQ/
df. These samples were measured using a sensitometer (KS-7 model manufactured by Konishiroku Photo Industry ■).
) to perform a wedge exposure of green light, and then perform the following processing.
I did it. Standard treatment process (between treatment concentration and treatment 118) [1] Color development
Hold 38℃ 3 minutes 30 seconds [2] 1! white fixation
33℃ 1 minute 30 seconds [3] ゛Water washing treatment 25~
30℃ 3 minutes [4] Drying 75-80℃ approximately 2 minutes
[Color developer] Benzyl alcohol 151e ethyle
nglycol 151Q potassium sulfite
2.0g sodium bromide
0.7a sodium chloride
0.2g potassium carbonate 3
0.0 Q hydroxylamine sulfate salt 3.
0Q polyphosphoric acid (TPPS) 2.5 (
+3-Methyl-4-amino-N- (β-methanesulfonamidoethyl) -Aniline sulfurized Jn 5.50 Fireflies
Optical brightener (4,4'-diaminosdilbenzsulfone aia form) 1.0g hydroxy acid
Add 2.0g of water
The total m is 1 ft, and the pi is adjusted to 110,20. [Bleach-fix solution] Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60g ethylene
Diaminetetra vinegar M3 (+-f-1rt
aKi! 27 ammonium (70% solution) 1001
12 Sulfite ammonium (40% solution) 27.5
．． Adjust to DH7.1 with 42 potassium carbonate or glacial acetic acid.
Add water to bring the total to 12. The yellow stain of each sample obtained after treatment was treated as follows.
I did it. [Measurement of yellow stain] Store each sample in a constant temperature bath at 70°C and 80% relative humidity for 7 days.
The difference between the initial blue C degree and the blue density after storage is calculated as yellow color.
It was tinged. The results are shown in Table-1. Margin Table-1 Below As is clear from Table-1, in the sample of the present invention, neither
Yellow stain reduction effect also on magenta couplers.
You can see that the fruit is large. Example 2 The following layers were deposited on a support made of polyethylene-coated paper.
Coating is applied sequentially from the support side, and silver halide photographic exposure for multicolors is applied.
The material was prepared. 1st W! U = blue-sensitive silver halide emulsion layer yellow coupler
α-pivalyl-α-(1-benzyl-2,4-
dioxy-imidaridin-3-yl)-2-chloro-5
-[γ-(2゜4-di-t-amylphenoxy)butyl
Amide]-7cetanilide at 8 mg/dt”, blue
Sensitive silver chlorobromide emulsion converted into silver: 3 mQ/df, 2.
4-G monobutylphenol-3', 5'-G [
-3m of amyl-4'-hydroxybenzoate! 7/
d, 2, dioctyl phthalate with 3AQ/df and zeolite
Apply 16 m of latin (J/di')
Painted. 2nd layer: Apply gelatin in the middle with a coating of 4111 g/df.
did. 3rd layer: Green-sensitive silver chlorobromide emulsion layer The above-mentioned exemplary magenta coupler (MC-1) was added at 4 m1J/d.
1', green-sensitive silver chlorobromide emulsion was converted to silver and 41I1g/
di', dibutyl phthalate 4mQ/dv'oyohi
Add geladin to 16111 (1/df).
It was painted on. 4th layer: Intermediate layer UV absorber 2-hydroxy-3',5'-di-t
-amylphenyl)-benzotriazole to 3ffl(
1/df, 2-(2'-hydroxy-3'.5'-di-t-amylphenyl)-benzotriazole
3 m<1/di', 4 m of dioctyl phthalate
Q/di' J3 and gelatin 14100/dl
The coating was applied so that the coating amount was 2. Fifth Tang: 2,4-dichloro-3-Mejilu as cyan coupler in red-sensitive silver chlorobromide emulsion layer
6-[α-(2,4-di-t-amylphenoxy)buty
1111 g/df, 2-(
2,3,4,5,6-pentafluorophenyl)acyl
Amino-4-chloro-5-[α-(2,4-diter
t-amylphenoxy)pentylamide] at 3 mg/
dl12, dioctyl phthalate 2mg/d, t or
and red-sensitive silver chlorobromide emulsion converted to silver: 3+1111
The coating was applied at a coating amount of 1/d and 2. 6th layer: 2-(2'-hydroxy-3'
, 5'-di[-amylphenyl)-benzotriazo
2ml/dr of alcohol, 2-(2'-hydroxy
C-3',5'-di-t-butylphenyl)-benzo
Triazole 2111Mdf, dioctyl phthalate
Apply 2rAQ/df and gelatin at 6mg/df.
It was painted to serve as an opening. 7th layer: Protective layer gelatin 911 (1/dl)
Painted. The sample thus prepared is designated as sample 9. Next, the magenta coupler and metal complex were added to the third layer of Sample 9.
, an organic solvent and an image stabilizer as shown in Table 2.
Samples 10 to 34 were prepared which were the same as sample 9 except that
did. However, for samples 13 to 34, the 3rd W! Application of 4
Ginryo was set as 2no/di'. The thus prepared sample was subjected to the same exposure and treatment as in Example 1.
I did the right thing. Examples for each sample obtained after treatment
1. In the same way, add yellow stain as follows.
The light resistance was measured. The results are shown in Table-2. [Light resistance test] Each sample was tested for 30 days using an underglass outdoor exposure table.
Measure the green light density before and after fading when exposed to sunlight.
Ta. The degree of color fading due to light (1ffl color rate) is set as follows.
I asked. Fadeki-tei = (Do-D)/Do x 100 (%) [)
0-Light! l! Oumae c1 Good D=Less than the degree of strength after photobleaching.The metal complex is 1 mol per 1 mol of the coupler, and has a high boiling point when used in combination.
The solvent is the same fQ as the compound represented by the general formula (1) above.
(no/df), and the image stabilizer is added to 1 mole of coupler.
1 mol was added to each. As is clear from Table 2, the samples of the present invention are for comparison. It was found that the yellow stain was improved compared to the sample.
Karu. In particular, when comparing test 114.16, it is found that in the general formula [I]
When a metal complex is used in combination with the magenta coupler shown
, compared to the comparative sample, the sample of the present invention has poor light resistance.
It was found that yellow stain was significantly reduced.
Ru. In addition, in the present invention, a compound represented by general formula (1)
Sample 3 using a high boiling point organic solvent with a dielectric constant of 6.0 or less
0-32 and 34, yellow stain is further reduced.
You can see that there is a little bit.

Claims (3)

[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 contains a magenta coupler and a compound represented by the following general formula (1). A silver halide photographic material characterized by containing. General formula (1) ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, R_1, R_2 and R_3 each represent an aliphatic group or an aryl group. ] (2) Claim (1) characterized in that the silver halide emulsion layer containing the magenta coupler and the compound represented by general formula (1) further contains a metal complex. silver halide photographic material. (3) The silver halide photographic material according to claim (2), wherein the magenta coupler is a magenta coupler represented by the following general formula [I]. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. Including things. 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. ] (4) A patent characterized in that the magenta coupler is added to the silver halide emulsion layer using a compound represented by the general formula (1) and a compound represented by the following general formula (2). A silver halide photographic material according to claim (1). General formula (2) ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, R_4 and R_5 each represent a hydrogen atom, an aliphatic group, or an aryl group. Also R_4 and R_5
may be combined to form a cycloaliphatic group. R_6 represents an aliphatic group or an aryl group. R_7 represents a hydrogen atom, an aliphatic group, an aryl group, or -(J_2)-_nCOOR_8 (R_8 represents an aliphatic group or an aryl group). J_1 and J
_2 each represents a divalent linking group. m and n each represent 0 or 1. ]