JPS6313040A - Silver halide photographic sensitive material having improved stability of dye image - Google Patents

Abstract

PURPOSE:To improve the fastness of a magenta dye image by incorporating a magenta coupler expressed by specific constitutional formula and a magenta dye image stabilizer expressed by specific constitutional formula into the titled material. CONSTITUTION:This silver halide photographic sensitive material is constituted by incorporating at least one of the magenta coupler expressed by general formula I and at least one of the magenta dye image stabilizer expressed by general formula II therein. In formula I, Z denotes a nonmetallic atomic group necessary for forming a nitrogenous heterocycle and the ring to be formed by said Z may have a substituent. X denotes a substituent which can be eliminated by reaction with the oxidant of a color developing agent. R denotes a hydrogen atom or substituent. In formula II, R<3> and R<4> respectively denote a hydrogen atom, alkyl group, alkenyl group, cycloalkyl group, aryl group, heterocyclic group, acyl group, etc. The discoloration and color fading by light are thereby suppressed and the generation of Y-stains in the undeveloped color part by the effect of light, heat and humidity is prevented according to such color photographic material.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a silver halide photographic material, and in detail,
This invention relates to a silver halide color photographic light-sensitive material in which a dye image is stable against heat and light, and staining is prevented.

[Conventional technology]

Conventionally, a silver halide color photographic light-sensitive material is imagewise exposed and color developed to perform a coupling reaction with an oxidized product of an aromatic primary amine color developing agent and a color former. It is well known that , indoaniline, ingmin, azomethine, fenoxanone, 7enazine, and pigments similar to these are produced and a color 1Aiii image is formed. In such photographic systems, a subtractive color reproduction method is usually adopted, and the blue-sensitive, green-sensitive, and red-sensitive light-sensitive silver halide emulsion layers each have an extra color I3! A silver halide color photographic light-sensitive material containing a color forming agent in category J, that is, a coupler that develops yellow, magenta, and cyan colors, is used.

Examples of couplers used to form the yellow dye image include acylacetanilide couplers, and examples of couplers used to form magenta dye images include pyrazolone, pyrazolobenzimidazole, pyrazolotriazole, and ingzolone couplers. Furthermore, as a coupler for forming a cyan dye image, for example, a 7-er or 7-tole coupler is generally used.

It is desired that the dye 11ii image obtained in this way does not change color or fade even if it is exposed for a long time or is stored under high temperature and high humidity. Also, uncolored areas of silver halide color photographic materials (hereinafter referred to as color photographic materials) turn yellow when exposed to light or moist heat! (hereinafter referred to as Y-stin) is desired.

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

The broad couplers used to form the magenta dye are 5-pyrazolones. The dye formed from this 5-pyrazolone magenta coupler is
In addition to the main absorption near 430n+a, a major problem is that it has a sub-absorption near 430n+a, and various studies have been conducted to solve this problem.

Magenta couplers having an anilino group at the 3-position of 5-pyrazolones have small side absorption and are particularly useful for obtaining color images for printing. These techniques are described in, for example, US Pat. No. 2,343.703 and British Patent No. 1,059,994.

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

Another means for reducing the Paris absorption near 430 nm of the magenta coupler is the British patent Pt5l.

047.612, ingzolones described in U.S. Pat. No. 3,770.447, U.S. Pat. No. 3,725.067, British Patent No. I H-pyrazolo[5,1-cl-1,2,4-
) Riazole coupler, JP-A-359-171956
No., Research Disclosure No. 2453
IH-pyrazoty [1,5-bl-1] described in 1.

2.4-) Liazole type coupler, I H-pyrazolo[1,5-cl-1,2,3-) lyazole type coupler described in Research Disclosure No. 24626, VF 182548/1987 , Research Disclosure No. 24531, IH-imidazo[1,2-bl pyrazole coupler, JP-A-1986-
No. 43659, Research-Disclosure No. 2
IH-virazo a (1,5-b7 bizole type coupler, JP-A-60-3:1552, Research Disclosure No. 4230).

II-pyrazolo[1,5-d
Magenta couplers such as l-tetrazole type couplers have been proposed. Among these, IH-pyrazolo[5,1-c
l-1,2,4-) lyazole coupler, IH-pyrazolo[1,5-bl-1,2,4-)lyazole coupler, 1H-pyrazoo[1,5-cl-1,2,3 −
) lyazole coupler, IH-imidazo[1,2-b
J pyrazole type sicaplar I H-pyrazolo[1,5-
bl pyrazole-type couplers and I H-pyrazoel [
The dye formed from the 1,5-dl tetrazole type coupler has significantly smaller H11 absorption near 430 nm than the dye formed from the 5-pyrazolones having an anilino group at the 3-position, and has color reproduction. This is preferable, and furthermore, it has the advantage that the occurrence of Y-stain in uncolored areas is extremely small when exposed to light, heat, and humidity.

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

Mata, JP-A-59-125732 Niha, IH-pyrazo.

IH-pyrazolo[5,1-cl-1,2, 4-) A technique has been proposed for improving the light fastness of magenta dye images obtained from lyazole-type magenta couplers. However, it has been recognized that even the above techniques are still not sufficient to prevent the magenta dye image from fading due to light, and moreover, it is almost impossible to prevent discoloration due to light.

[Important of the invention]

The present invention has been made in view of the above problems, and a first object of the present invention is to provide a color photographic material with excellent color reproducibility and significantly improved light fastness of magenta dye images. There is a particular thing.

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

A third object of the present invention is to provide a color photographic material in which the occurrence of Y-stain in uncolored areas is prevented from occurring due to light, heat, and humidity.

[Structure of the invention]

The above-mentioned object of the present invention is to provide an i! will be accomplished.

General formula [l].

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

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

Moreover, R represents a hydrogen atom or a substituent.

General formula (Xl[] In the reverse formula, R3 and R4 are each a hydrogen atom, an alkyl group,
Represents an alkenyl group, an alkynyl group, a dichlorofurkyl group, a cycloalkenyl group, an aryl group, a heterocyclic group, a 7-syl group, a sulfonyl group, a phosphonyl group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, or a 7-aryloxycarbonyl group.

Hereinafter, unless otherwise specified, the general formula according to the present invention [
The compound represented by [2] is called a magenta dye image stabilizing compound.

Next, the present invention will be specifically explained.

In the magenta coupler represented by the general formula [I] according to the present invention, Z represents a nonmetallic atomic group necessary to form a nitrogen-containing double ring, and 1 is formed by JZ. The ring may have a substituent.

X represents a hydrogen atom or a substituent that can be converted to R by reaction with an oxidized product of a color developing agent.

Also, (■) represents a hydrogen atom or a substituent.

Examples of the substituents represented by [ku] include halogen atoms,
Alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkynyl group, aryl group, heterocyclic store, acyl group, sulfonyl group, sulfinyl group, phosphonyl group, carbamoyl group, sulf77moyl group, sia7 group,
Spiro compound residue, bridged hydrocarbon compound residue, alkoxy group, aryloxy group, heterocyclic oxy group, siloxy group, 7-syloxy group, carbamoyloxy group, amine 7 group, acylamino group, sulfonamide group, imide group, Examples include ureido group, sulfamoyl 7mino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkoxycarbonyl group, aryloxycarbonyl group, alkylthio group, arylthio group, and heterocyclic thio group.

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

The furkyl group represented by R includes those with carbon WL1 to 32, and the alkenyl group and alkynyl group include those with carbon WL1 to 32.
32, dichlorofurkyl group, and cycloalkenyl group preferably have 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms,
The alkyl group, alkenyl group, and alkynyl group may be linear or branched.

In addition, these furkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, and cycloalkenyl groups are substituents [e.g., aryl, cyano, halogen atoms, heterocycles, cycloalkyl, cycloalkenyl, spiro compound residues, bridged hydrocarbon compounds] In addition to residues, those substituted via a carbonyl group such as 7-syl, carboxy, carbamoyl, alkoxycarbonyl, and aryloxycarbonyl, and those substituted via a heteroatom (specifically, hydroxy, alkoxy, and aryl) Oxy, heterocyclic oxy, siloxy, 7-syloxy, those substituted through an oxygen atom such as carbamoyl oxine, nitro, amino (including dialkylamino, etc.), sulfamoylamino, flukoxyluponylamino, aryloxycarbonyl 7
Mi7.7Syl7mino, sulfonamide, imide, ureido etc. substituted via nitrogen atom, furkylthio,
arylthio, heterocyclic thio, sulfonyl, sulfinyl, sulfamoyl, etc., which are substituted via a sulfur atom, and phosphonyl, which is substituted via a phosphorus atom, etc.).

Specifically, for example, methyl group, ethyl group, isopropyl group, t-butyl group, pentadecyl group, heptadecyl group, 1
-hexylnonyl group, 1.1'-nopentylnonyl group,
2-chloro-butyl group, trifluoromethyl group, 1
-Ethoxytridecyl group, 1-nodoquinisopropyl group, methanesulfonylethyl group, 2.4-not-7 milphenoxymethyl group, 7297 group, 1-phenylisopropyl group, 3-1-butanesulfone 7 mino7e/xipavir group, 3-4'-10-(4''(p-hydroxybenzenesulfonyl)phenoquine)dodecanoyl7mi/
) phenylpropyl group, 3-(4'-[a-(2'',
4''-di-t-7milphenoxy)butane7mido]7enyl)-propyl group, 4-[α-(0-chlorophenoxy)tetradecane7midophenoxy]propyl group, allyl group, cyclopentyl group, cyclohexyl group, etc. can be mentioned.

[The 7-aryl group represented by t' is preferably a phenyl group, and may have a substituent (for example, an alkyl group, an alkoxy group, a 7-syl amino group, etc.).

Specifically, phenyl group, 4-t-butyl 7-enyl group,
2.4-not-7 milphenyl group, 4-tetradecane 7-midophenyl group, hexadecyloxy 7-enyl group, 4'
-[α-(4″-t-butyl 7eth/xy)tetradecane 7midophenyl group and the like.

The heterocyclic group represented by R is preferably one with 5 to 7 shells, and may be substituted or fused.
Specific examples include 2-furyl group, 2-chenyl group, 2-pyrimidinyl group, and 2-benzothiazolyl group.

Examples of the acyl group represented by R″t′ include acetyl group, phenylacetyl group, dodecanoyl group, a-2,4-
Examples include a furkylcarbonyl group of not-t-amylphenoxybutanoyl M+''!P, a 7-aryl carbonyl group such as a benzoyl group, a 3-pentadecyloxybenzoyl group, and a p-chlorobenzoyl group.

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

The sulfinyl group represented by R''Ch includes an alkylsulfinyl group such as an ethylsulfinyl group, an octylsulfinyl group, a 3-72/xybutylsulfinyl group,
Examples include 7ylsulfinyl groups such as 7enylsulfinyl group and -pentadecylphenylsulfinyl group.

The phosphonyl group represented by R includes an alkylphosphonyl group such as a butyloctylphosphonyl group, an alkoxyphosphonyl group such as an octyloxyphosphonyl group, a 7-aryloxyphosphonyl 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 or an aryl group (preferably a phenyl group), such as N-methylcarbamoyl group, N,N-butylcarbamoyl group, N-(2 -pentadecyloctylethyl)carbamoyl group, N-ethyl-N-dodecylcarbamoyl group, N-13-(2,4-sheet-t-7-milphenoxy)propyl)carbamoyl group, and the like.

The sulfamoyl group represented by R may be substituted with an alkyl group, a 7-aryl group (preferably a phenyl group), etc.
For example, N-propylsul77moyl group, N,N-butylcarbamoyl group, N-(,2-pentadecyloxyethyl)sul77moyl group, N-ethyl-N-dodecylsulfamoyl group, N-7znylsulf Examples include a 77 moyl group.

Examples of the pyro compound residue represented by It' include spiro[3,3]heptan-1-yl and the like.

The Ia carbonized compound residues represented by R include, for example, bicyclo[2,2,11butan-1-yl, tricyclo[
Examples include 3,3,1,1''1decane-1-yl, 7゜7-dimethyl-bicyclo[2,2,11hebutan-1-yl, and the like.

The alkoxy group represented by R't' may be further substituted with the substituents listed above for the alkyl group (e.g., methoxy group, propoxy group, 2-ethoxyethoxy group, pentadecyloxy group, Examples include 2-dodecyloxyethoxy group and 7enethyloxyethoxy group.

The 7-aryloxy group represented by R″r is preferably phenyloxy, 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, ρ-1-butylphenoxy group,
Examples include iso-pentadecyl 7-enoxy group.

The heterocyclic oxy group represented by R preferably has 5 to 7 heterocycles, and the heterocycle may further have a substituent, for example, 3゜4.5.6-tetrahydro. Examples include pyranyl-2-oxy group and 1-7enyltetrazole-5-oxy group.

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

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

The carbamoyloxy group represented by R″c is a furkyl group,
It may be substituted with a 7-aryl group, and examples thereof include an N-ethylcarbamoyloxy group, an N,N-noethylcarbamoyloxy group, and an N-7xylcarbamoyloxy group.

The amine 7 group to be R″c-& is an alkyl group, an aryl group (
(preferably phenyl group), etc., such as ethylamino group, anilino group,
group, 3-bentadecyloxycarbonyl 7nily7 group,
7 groups of 2-chloro-5-hexadecaneamide aniline and the like are listed.

Examples of the 7-sylamine 7 group represented by R include alkylcarbonyl 7 groups, 7-aryl carbonyl 7-groups (preferably 7-enylcarbonyl 7 groups), and may further have a substituent. Specifically, acetamido group, a-ethylpropanamide group, N-phenylacetamido group,
Examples include dodecanamide group, 2,4-sheet t-7milphenoquinacetamide 1/i, (7-3-L-butyl 4-hydroxyphenoxybutane 7mido group), and the like.

Examples of the sulfonamide group represented by R''C include an alkylsulfonyl 7mino group, a .7lylsulfonyl amine 7 group, and may further have a substituent.

Specifically, methylsulfonyl 7mi7 group, bentadenrus J lehonylamino group, benzenesulfone 7mido group, 9-
) Luensulfone 7mid-! , 2-z) Kin-5 (-7
Examples include milbenzenesulfonamide group.

The imide group represented by R″C may be open-chain or cyclic, and may have a substituent, for example, a succinimide group, a 3-heptadecylphuccinimide group,
Examples include talimide group and glutarimide group.

The ureido group represented by R″t′ may be substituted with an alkyl group, a 7-aryl group (preferably a phenyl group), etc., such as an N-ethylureido group, an N-methyl-N-
Decylureido group, N-7! Nilureido group, N-p-
) a lylureido group, etc.

The 7 sulfoylamine groups represented by R are an alkyl group,
It may be substituted with a 7-aryl group (preferably a phenyl group), etc., such as N,N-dibutylsulf γmoyl 7 group, N-methylsulf 77 moyl amine/u, N-phenylsulf 7 amoyl 7mino group, etc. .

The alfkhidicarbonylamide 7 group represented by R is,
It may further have a substituent, for example, methoxycarbonyl 7 groups, methoxyethoxycarbonyl amine 7 groups,
Octadecyloxycarbonyl 7-7 groups etc. can be accelerated.

The 7-aryloxycarbonylamine group represented by R may have a substituent, and examples thereof include phenoxycarbonylamine group and 4-methylphenoxycarbonyl group.

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

The aryloxycarbonyl group represented by R''Ch may further have a substituent, such as a phenoxycarbonyl group, a p-chlorophenoquinecarbonyl group, a -pentadecyloxyphenoxycarbonyl group, and the like.

The alkylthio group represented by R may further have a substituent (for example, an ethylthio group, a dodecylthio group, an octadecylthio group, a 7enethylthio group, a 3-phenoxypropylthio group).

The arylthio group represented by R is preferably a phenylthio group and may further have a substituent, for example, a phenylthio group,
p-)) xy7enylthio group, 2-t-octylphenylthio group, 3-octadecylphenylthio group, 2-carboxyphenylthio group, p-77F7minophenylthio group, etc. are early C).

The heterocyclic thio group represented by R is preferably a 5- to 7-shell heterocyclic thio group, which may further have a condensed ring (or may have a substituent. For example, 2 -pyrinorthio group, 2-benzothiazolylthio group, and 2,4-diphenoxy-1,3,5-)lyazole-6-thio group.

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

Examples of the group substituted via a carbon atom include a carboxyl group and, for example, a group of the general formula (R5' is the same as R in iη, Z' is the same as the above Z, R2' and R3' are hydrogen atoms, aryl group, a group represented by > representing a group, an alkyl group, or a heterocyclic group, a hydroxymethyl group, and a triphenylmethyl group.

Examples of groups substituting via an oxygen atom include alkoxy groups, aryloxy groups, heterocyclic oxy groups, 7-syloxy groups, sulfonyloxy groups, alkoxycarbonyloxy groups, aryloxy-alponyloquine groups, furkyloxalyloxy groups, and alkoxyoxalyl groups. An example is an oxy group.

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

The 7-aryloxy group is preferably a phenoxy group, and the aryl group may further have a substituent, specifically a 7-ethyloxy group, a 3-methylphenoxy group, a 3-
Dodecylphenoxy group, 4-methanesulfonamidophenoxy group, 4-((?-(3'-pentadecylphenoxy)butanamido)phenoxy group, hexidecylrubamoylnotoxy group, 4-cyanophenoxy group, 4-methanesulfonylphenoxy group group, 1-naphthyloquine group, p
-7 toxyphenoxy group and the like.

The heterocyclic oxy group is preferably a 5- to 7-shell heterocyclic oxy group, which may be a fused ring (or may have a substituent, specifically, 1-phenyltetra Examples include zolyloxy group and 2-benzothiazolyloxy group.

Examples of the 7-syloxy group include acetoxy group, fulkylcarbonyloxy group such as butatsuroxy group, fluorenylcarbonyloxy group such as cinnamoyloxy group,
Examples include arylcarbonyloxy groups such as benzoyloxy groups.

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

Examples of the alkoxycarbonyloxy group include an ethoxycarbonyloxy group and a benyloxycarbonyloxy group.

Examples of the aryloxycarbonyl group include a 7ethyloxycarponyloquine group and the like.

Examples of the fulkyloxalyloxy group include a methyloxalyloxy group.

Examples of the alkoxyoxalyloxy group include an ethoxyoxalyloxy group.

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

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

The arylthio group includes phenylthio group, 4-notanesulfone 7midophenylthio group, 4-dodecyl 7enethylthio group, 4-7sufluoropentanamide 7enethylthio group, 4-carboxyphenylthio group, 2-ethoxy-5-t- Examples include butyl 7enylthio group.

Examples of the heterocyclic thio group include 1-phenyl-1,
Examples include 2,3,4-tetrazolyl-5-thio group and 2-benzothiazolylthio group.

Examples of the alkyloxythiocarbonylthio group include a dodenyloxythiocarbonylthio group and the like.

Examples of the group substituting via the nitrogen atom include those represented by the general formula -N.
' Ru, 1' here? , J and R3' represent a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a sulfamoyl group, a carbamoyl group, an acyl group, a sulfonyl group, a 7-aryloxycarbonyl group, an alkoxycarbonyl group, and R4
' and R51 may be combined to form a heterocycle, provided that R, 7 and R1' are not both hydrogen atoms.

The furkyl group may be straight chain or branched and is preferably of ml to 22 carbons. Further, the alkyl group may have a substituent, and examples of the substituent include an aryl group, an alkoxy group, an aryloxy group, an alkylthio group,
Arylthio group, alkyl 7mi 7 group, arylami 7 group, acyl 7mi 7 group, sulfone 7mido group, imino group, acyl group, alkylsulfonyl group, arylsulfonyl group,
Carbamoyl group, sulfamoyl group, alkyloxycarbonyl group, aryloxycarbonyl group, alkyloxycarbonyl 7 group, 7lyloxycarbonyl amine 7
group, hydroxyl group, carboxyl group, Schiff/group, and halogen atom.

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

The 7-aryl group represented by R1' or R1' is preferably a carbon WL6 to 32, particularly a phenyl group or a naphthyl group, and the aryl group may have a substituent such as the above R1' or Examples of the substituent for the furkyl group represented by R3/ include those listed above and an alkyl group. Specific examples of the aryl group include 1r phenyl group, 1-su7tyl group, and 4-methylsulfonylphenyl group.

The heterocyclic group represented by R1' or R5' is 5 to 6
Shellfish are preferred, and may be fused rings or have substituents. Specific examples include 2-furyl group, 2-quinolyl group, 2-pyriminol group, 2-benzothiazolyl group, 2- Bilinol MW is mentioned.

The sulfamoyl group represented by R4' or R7' includes N-furkylsulfamoyl group, N,N-dialkylsulfamoyl group, N-7lylsul77moyl group, N-7lylsulfamoyl group,
, N-noaryl 7-aryl group, etc., and these furkyl groups and 7-aryl groups may have the substituents listed above for the alkyl group and aryl group. Specific examples of the sul 77-moyl group include, for example: N, N-diethylsulfamoyl group, N-methylsulfamoyl i, N
-1'decylsul77 moyl group, N-p-)lylsul7
A 7 moyl group is mentioned.

As the carbamoyl group represented by R, 1 or R5',
Examples include N-furkylcarbamoyl group, N,N-dialkylcarbamoyl group, N-arylcarbamoyl group, N,N-noarylcarbamoyl group, etc., and these alkyl groups and aryl groups are the same as those mentioned above for the alkyl group and aryl group. Specific examples of the carbamoyl group which may have a substituent include N,N-noethyl carbamoyl group, N-methyl carbamoyl group, N-dodecylcarbamoyl group, N-p-cyanophenylcarbamoyl group, N-
-p-)lylcarbamoyl group.

Examples of the acyl group represented by R47 or R5' include an alkylcarbonyl group, an arylcarbonyl group, and a heterocyclic carbonyl group. Good too. Specific examples of the acyl group include hexafluorobutanoyl group, 2゜3.4.5.6-pentafluorobenzoyl group, acetyl group, benzoyl group, naphthonyl group, 2-furylcarbonyl group, etc. .

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

The 7-aryloxycarbonyl group represented by , ' or R5' may have any of the substituents listed above for the aryl group, and specific examples thereof include phenoxycarbonyl group and the like.

The alkoxycarbonyl group represented by R, 1 or R, 7 may have the substituents listed for the furkyl group, and specific examples include methoxycarbonyl group, dodecyloxycarbonyl group, pennoloxycarbonyl group. Examples include groups.

The heterocycle formed by combining I, ' and R5' is preferably 5 to 6 rings, and may be saturated or unsaturated, and may or may not have aromaticity. Examples of the heterocycle, which may be a fused ring, include an N-7 thalimide group, an N-succinimide group, a 4-N-urazolyl group, a 1-N-hydantoinyl group, and a 3-N-2,4- Dioxooxazolidinyl group, 2-N-1,1-nooxo-3-(2H)-oxo-1°2-benzthiazolyl group, 1-pyrrolyl group, 1-pyrrolinonyl group, 1-pyrazolyl group, 1-pyrazolidinyl group group, 1-piperinonyl group, 1
-pyrrolinyl group, 1-imidazolyl group, 1-imidazolinyl group, 1-indolyl group, 1-isoindolinyl group,
2-isoindolyl group, 2-isoindolinyl group, 1-
Benzotriazolyl group, 1-pencyimigzolyl group, 1
-(1,2,4-triazolyl) group, 1-(1,2,3
-triazolyl) group, 1-(1,2,3,4-tetrazolyl) group, N-morpholinyl group, 1.2.3.4-tetrahydroquinolyl group, 2-oxo-1-pyrrolidinyl group, 2-IH -pyridone group, 7tala7one group, 2-oxo-1-piperinonyl group, etc., and these heterocyclic groups include alkyl groups, aryl groups, alkyloxy groups, aryloxy groups, acyl groups, sulfonyl groups, and alkylamino groups. 7
group, 7 arylamide groups, 7 acylamide groups, 7 sulfonamide groups, carbamoyl group, sulfamoyl group, alkylthio group, 7lylthio group, ureido group, flukoxyluponyl group, aryloxycarbonyl group, imido group, nitro group, cyano group, carboxyl It may be substituted with a group, a halogen atom, etc.

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

In addition, substituents on the heterocycle (for example, R9[(, ~l(,
) has a moiety (herein, R'', x and Z II have the same meanings as R, .

Further, the ring formed by z, z', z" and ZI described below may be further fused with another ring (for example, a cycloalkene with 5 to 7 shells). For example, in the general formula (V), R
1 and R6, in the general formula [■], Rt and R,
are bonded to each other to form a ring (e.g. 5-7 shell cycloalkenes,
benzene).

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

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

Also, among the general formula (1), the following general formula [
■].

General formula [■] N-N., -.' In the formula, X and Zl have the same meanings as RlX and Z in general formula (1).

Among the magenta couplers represented by the general formulas [■] to [■], particularly preferred is the magenta coupler represented by the general formula (111).

Regarding the substituents on the heterocycle in general formulas (1) to [■], R in general formula (1) and R1 in general formulas (II) to [■] satisfy the following condition 1. It is preferable that the following conditions 1 and 2 are satisfied, and more preferable.
The following conditions 1 and 1 are particularly preferred.
This is a case where 15Q is added to 2 and 3.

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

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

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

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

General formula [Iy] R- R,, -C- In the formula, R,, R,, and c/R,, are each a hydrogen atom, /
A-lodene atom, alkyl group, cycloalkyl group, fulkenyl group, cycloalkyl group, furkynyl group, aryl group, heterocyclic group, acyl group, sulfonyl group, sulfinyl group, phosphonyl group, carbamoyl group, sulfamoyl group, cyano group, spiro Compound residue, bridged hydrocarbon compound residue, alkoxy group, aryloxy group, heterocyclic oxy group, siloxy group, acyloxy group, carbamoyloxy group, amine 7 group, acylami 7 group, sulfonamide group, imide group, thureid group, 7 sul7amoylamino groups, 7 alkoxycarbonyl7 groups, 7 aryloxycarbonylami groups, an alkoxycarbonyl group, an aryloxycarbonyl group, a furkylthio group, an arylthio group, a heterocyclic thio group, R9゜R8゜and R11 at least 2 of
One is not a hydrogen atom Jukus Il Also, the above R,,R,. and two of R11, for example R9
3. may be bonded to form a saturated or unsaturated ring (e.g., cycloalkane, cycloalkene, heterocycle), and R1 may be bonded to the ring to form a bridged hydrocarbon compound residue. good.

R9-[<1. The group represented by may have a substituent, and specific examples of the group represented by R9-R1 and the substituent that the layer may have include Specific examples of the represented groups and substituents are listed.

Also, for example, a ring formed by combining R9 and RIO and R,
Specific examples of the bridged hydrocarbon compound residue formed by ~R11 and its optional substituents include cycloalkyl, cycloalkyl, cycloalkyl, and hetero-mMti carbonized which R in the above-mentioned general formula (1) represents. Specific examples of hydrogen compound residues and their rf1 substituents are listed.

Among the general formula [IX], (+)l? s~
If two of RIl are alkyl groups, (ii) R=~
When one of R1, for example R11, is a hydrogen atom and the other two, R5 and R11+, combine to form a cycloalkyl together with the root carbon atom, the following is true.

Furthermore, in (i), two of the widths of R1 to R11 are alkyl groups, and the other width is a hydrogen atom or an alkyl group.

Here, the furkyl and the dichlorofurkyl may further have a substituent, and specific examples of the alkyl, the cycloalkyl, and the substituent thereof include the alkyl, cycloalkyl, and the substituent thereof represented by R in the general formula (1). Specific examples include:

In addition, substituents that the ring formed by Z in general formula [I] and the ring formed by Zl in general formula [■] may have, and R in general formulas [■] to (Vl)
As 2 to R, those represented by the following general formula [X] are preferable.

General formula [X] -R'-8Q2-R2 In the formula, 1 (1 represents alkylene, R2 represents alkyl, dichlorofurkyl or 7-lyl).

The alkylene represented by R1 is preferably straight! The number of carbon atoms in the 1′1 portion is 2 or more, more preferably 3 to 6,
It does not matter whether it is a straight chain or 9 branches. Further, this alkylene may have a substituent.

Examples of the substituent include R in the above general formula [I]
When is an alkyl group, the substituents that the furkyl group may have include those shown. A preferred substituent is phenyl.

Preferred specific examples of fullkylene represented by R1 are shown below.

-C112C112CH-, -C11□CI! 2C11
,C11□-1-C! hCII2CH2CII-9R2
The furkyl group represented by is a straight chain with a length of about 1 minute. can be mentioned.

The dichlorofurkyl group represented by R2 is preferably one having 5 to 6 shells, such as cyclohexyl.

Furkyl and cycloalkyl represented by R2 may have a substituent, and examples thereof include those exemplified as the substituent for R1 in 1.

Specific examples of the 7-aryl represented by 7 include phenyl and naphthyl. The aryl group may have a substituent. Examples of the substituent include linear or branched furkyl, Examples of the r!1 substituent to R' mentioned above may be mentioned.

Moreover, when there are two or more substituents, those substituents may be the same or different.

Among the compounds represented by the general formula [I], the following general formula [X! ].

General formula (XI) N-N-LI-8'-:) + to U2- In the formula, R and X are synonymous with R and X in general formula [I] l) R' and R2 are the general formula (X) lnio i+le R'
.

It has the same meaning as R2.

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

However, the numbers in the table represent the following groups.

-F-CI-B rl
1 12 13CH3CF 3
C! HsC3Ht (!
)C3Ht -(t)04 Hsshikei ρσ r〃 Shiyamashi1M+tL'ノ(CH2)sOc+tHzs rσ し4t'1・(t) C1h ■ CH=CH2CHSO2C1tH2% - Cy H+ s CHxCH2CH2SO2CH*CHzSO2 C1zH
2sCH+1CHtCH2CH3O2CaH+tC@H
+ 3 C4H* CHCHICHtSOzC+*H3) CH3 CHCHzCH2SO2C+sH3? Hot CH.

CCHtCH2S02C+sH33 words CH.

CH.

t N HC()CtH+s a NHCOCFs NHCOCaF 7
NHCO(CF2)sHdo- OCHz CON HCHz CH20CHs
OC2H5S Ca H self
S C+ s H
S? - S O2C+ a H3t Also, the coupler is glossy op-the-chemical.
Society 4 (Journal of the C
bimical 5ociety), Birkin (Pe
rkin) I (1977)-2047~205
2. US patent! l1m No. 3,725,067, JP-A-59-99437, JP-A No. 58-42045, JP-A No. 59-
No. 162548, No. 59-171956, No. 60-3
No. 3552, No. 60-43659, No. 60-1729
It can be synthesized by referring to No. 82 and No. 60-190779.

The couplers of the invention usually contain 1) I per mole of silver halide.
It can be used in a range of X10-3 mol to 1 mol, preferably 1X10-2 mol to 8X10-' mol.

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

The magenta dye image stabilizer represented by the general formula (XHI) used in conjunction with the magenta coupler of the present invention not only has an IL effect of preventing fading of the magenta dye image due to light, but also has an effect of preventing discoloration due to light. He is also a conductor of the Kalikantin course.

General formula [■] In the R general formula [■], an alkyl group, alkenyl group, alkynyl group, dichlorofurkyl group, cycloalkenyl group, aryl group, heterocyclic group, acyl group, sulfonyl group represented by R″ or R″ group, phosphonyl group, carbamoyl group,
Specific examples of the sulfamoyl group, alkoxycarbonyl group and aryloxycarbonyl group include the general formula [I
] In R, the groups described in detail can be mentioned.

Preferably, both R3 and R4 are an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group, an acyl group, a sulfonyl group, a carbamoyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group.

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

Next, a typical synthesis example of the magenta dye image stabilizer according to the present invention will be shown.

Synthesis Example 1 (Synthesis of Exemplary Compound A-7) Calicantin 35. manufactured by Fuldrich. and pyrinone 20aZ were dissolved in 150% ethyl acetate, and 62 g of 2,5-not-7 milphenoxyacetic acid chloride was added to give 30 molecules.To the refluxed reaction solution was added 200 mN of water, and the mixture was shaken well with a separatory funnel. I set it to W#. The ethyl acetate layer was separated, dried over anhydrous sodium sulfate, and then ethyl acetate was distilled off under reduced pressure. 60 mN of 1-hexane was added to the residue, cooled with water, and the precipitated crystals were extracted to obtain 52 g of a white powder product. The structure was confirmed by nuclear magnetic resonance spectroscopy and mass spectroscopy.

Synthesis Example 2 (Synthesis of Exemplified Compound A-12) 35 g of caricantin and 49 g of dodecyl bromide were mixed with 2 ml of ethyl alcohol.
The reaction mixture was dissolved in 0.00ml1', further added with 15g of potassium hydroxide, and boiled and refluxed for 3 hours. The reaction solution was poured into ice water 11, and the precipitated crystals were collected and recrystallized from methyl alcohol to obtain a white powder product 41. I got it. Both nuclear magnetic resonance spectra and mass spectra supported the structure of the target compound.

The amount of the magenta dye image stabilizer represented by the general formula (XI[) of the present invention to be used is preferably 5 to 400 mol% relative to the magenta coupler represented by the general formula [■] of the present invention. More preferably, it is 10 to 300 mol%.

Although the magenta coupler of the present invention and the magenta dye image stabilizer of the present invention are preferably used in the same layer, the stabilizing layer may be used in a layer adjacent to the scrap in which the coupler is present. .

In the silver halide photographic light-sensitive material of the present invention, in addition to the magenta dye image stabilizer according to the present invention, another magenta dye image stabilizer represented by the following general formula (Xn[), that is, a phenolic compound and A phenyl ether compound can also be used in combination.

General formula (XI[I) K1 1%In the formula, R% is a hydrogen atom, a furkyl group, an alkenyl group, 7
Represents a ryl group or a heterocyclic group, R'IR'lR''t
R'' each represents a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group, an alkenyl group, a 7-aryl group, an alkoxy group, or an acylamino group, and R6 represents an alkyl group, a hydroxy group, a 7-aryl group, or an alkoxy group. and R6 may be ring-closed with each other to form a 5-shell or 6-shell ring, in which case R8 represents a hydroxy group or an alkoxy group, and %R' and R' may be ring-closed to form a methylene oxy ring. Furthermore, R? and R may be ring-closed to form a five-shell hydrocarbon ring, in which case R5 represents an alkyl group, an aryl group, or a heterocyclic group, provided that R5 is hydrogen Except when R- is an atom and is a hydroxy group.

In the general formula (XI), R5 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group, and examples of the furkyl group include a methyl group, an ethyl group, a propyl group, an octyl group, and a t- Straight chain or branched alkyl groups such as octyl group, benyl group, and hexadecyl group can be mentioned.

Further, this furkyl group may have a substituent, and examples of the alkenyl group represented by R5 include allyl, hexanyl, and octenyl groups.

Further, examples of the 7-aryl group of Rs include phenyl and naphthyl groups.

This 7-aryl group can have a substituent, and specific examples include a methoxyphenyl group and a chlorphenyl group. Furthermore, as the heterocyclic group represented by R5,
Specific examples include a tetrahydropyranyl group and a biriminol group.

General formula (Xnl)l:t;i? ”, R@, R1, R@ and 1/R10 are hydrogen atoms, halogen atoms, hydroxy groups,
It represents an alkyl group, an alkenyl group, an aryl group, an alkoxy group, or a 7-syl group. Among these, the furkyl group, alkenyl group, and aryl group are the same as the alkyl group, alkenyl group, and aryl group mentioned above regarding R%. The same ones can be mentioned. Further, the halogen atom is
Examples include atoms such as fluorine, chlorine, and bromine. Furthermore, specific examples of the alkoxy group include a methoxy group, an ethoxy group, a benoloxy group, and the like. Further, the 7-sylamine 7 group is represented by R'NlIC0-, where R' is an alkyl group (e.g. methyl,
ethyl, propyl, butyl, octyl, -octyl,
benzyl, etc.), alkenyl groups (e.g. allyl, octenyl, oleyl, etc.), aryl groups (e.g. 7
(enyl, methoxyphenyl, naphthyl, etc.) or a heterocyclic group (eg, birinol, pyrimidyl, etc.).

In addition, in the general formula (Xlll), R' represents a furkyl group, a hydroxy group, an aryl group, or an alkoxy group, and among these, the alkyl group and aryl group are the same as the alkyl group and aryl group shown in R% above. The following can be specifically mentioned. As for the alkoxy group of R1, the same alkoxy groups as mentioned above for R'fR', It@ and Rlo can be mentioned.

A phenolic compound or phenyl ether represented by the general formula (XI[I) used in combination with the magenta coupler represented by the general formula ([) of the present invention and the compound represented by the general formula [■]] Among the thread compounds, particularly preferred are tetraalkoxyvining compounds, which can be represented by the following general formula (Xff).

General formula (XfV) In the formula, R is a furkyl group (e.g. methyl, ethyl, propyl, octyl, t-octyl, benol, hexadecyl), an alkenyl group (e.g. 7lyl, octenyl, oleyl), an aryl group (e.g. phenyl, Naphthyl) or a heterocyclic group (e.g., tetrahydropyranyl, pyrimidyl). methyl, ethyl, butyl, benzyl), alkenyl groups (e.g. allyl, hexenyl, octenyl)
or represents an alkoxy group (e.g. methoxy, nidoxy, benoloxy), where R'2 is a hydrogen atom, an alkyl group (e.g. methyl, ethyl, butyl, benol), an alkenyl group (e.g. 2-propenyl, hexenyl, octenyl)
, or represents an aryl group (eg phenyl, methoxyphenyl, chlor7enyl, naphthyl).

The compound represented by the general formula (XIII) is disclosed in U.S. Pat. No. 3,935.016, U.S. Pat. No. 145530, British Patent Publication No. 2,077.45
No. 5, No. 2,062,888, U.S. Patent No. 3.764
, No. 337, No. 3,432,300, No. 3,574.
No. 827, No. 3,573,050, JP-A-52-15
No. 2225, No. 53-20327, No. 53-1772
No. 9, No. 55-6321, British Patent No. 1,347=5
No. 56, Opening Y42,066.975, Special Publication No. 1973-
No. 12337, No. 48-31625, U.S. Patent No. 3,
It also includes compounds described in No. 700.455 and the like.

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

P H-1 H-2 P H-3 C) I3 H-4 H-5 P) (-6 H-7 H-8 H-9 P H-10 P H-11 H-12 H-13 P H -14 H-15 L;113 L;Ill PH-16 PH-17 H3 H-18 H-19 L:H3(:H3 H-20 H-21 H-22 H-23 H-24 H-25 H- 28 H-27 H-28 H-29 H-30 H-31 CH11111 P II -32 The phenolic compound or phenyl ether compound represented by the general formula (XI [ (2) is preferably 200 mol% or less, more preferably 140 mol% or less based on the magenta dye image stabilizer represented by
It can be used in amounts up to mol%.

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

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

Generally, the magenta dye image obtained from the magenta coupler not only shows a slight fading when exposed to light, but also undergoes discoloration due to light, and the color tone of the dye image changes from magenta to yellowish. The magenta dye image stabilizer represented by the general formula [■] of the present invention can prevent the magenta dye image obtained from the magenta coupler from fading and discoloration due to light, and is different from the conventional 7-Nol compound. It also has effects that cannot be achieved with magenta dye image stabilizers made of phenyl ether compounds.

Therefore, the conventional phenolic compound and 7-enyl compound
When the magenta dye image stabilizer of the tel-based compound is mixed and used in combination with the magenta dye image stabilizer represented by the general formula [■] of the present invention, the above-mentioned conventional The amount of the magenta dye image stabilizer of the 7-ethanol compound and the V-phenyl ether compound must be selected.

An appropriate amount of the conventional magenta dye image stabilizer of the general formula (XI[[)] is added to the magenta dye image stabilizer of the present invention represented by the general formula [■] When used in combination with drugs, a synergistic effect may be observed due to the combination.

The color photographic light-sensitive material of the present invention can be, for example, color black and white film, and color photographic paper, but in particular, when a color photographic paper intended for direct viewing is used, the method of the present invention can be used. The effect is effectively demonstrated.

The silver halide photographic light-sensitive materials of the present invention, including this color photographic paper, may be for single color or multicolor.In the case of multicolor silver halide photographic materials, subtractive color reproduction is possible. In order to carry out this process, silver halide emulsion layers containing magenta, yellow couplers and cyan couplers as photographic couplers and non-light sensitive layers are usually laminated on a support in an appropriate number and order. Although it has a road, the corresponding MW
L and the layer order may be changed as appropriate depending on the important performance and purpose of use.

The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention includes conventional halides such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride. Any used in silver emulsions can be used.

The silver halide grains C1 used in the silver halide emulsion are:
A method for producing IA particles, which may be obtained by any of the acid method, neutral method, or ammonia method, and the particles may be grown all at once, or may be grown after producing seed particles. The methods of growing may be the same or different.

In the silver halide emulsion, halide ions and silver ions may be mixed simultaneously, or one may be mixed while the other is present.Also, taking into consideration the critical growth rate of silver halide crystals, p in the pot mixing halide ions and silver ions
Growth may be carried out by sequentially or simultaneously adding H*pAg in a controlled manner. After growth, a conversion method may be used to change the silver halide composition of the grains.

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

The silver halide grains used in silver halide emulsions are produced in the process of forming and/or growing grains, such as cadmium salts, nitric acid salts, lead salts, thallium salts, iridium salts or complex salts, rhodium salts or complex salts, iron Metal ions can be added to the inside of the particles and/or on the surface of the particles using salts or complex salts, and reduction-sensitized nuclei can be formed inside the particles and/or on the surface of the particles by placing them in an appropriate reducing atmosphere. can be granted.

After the growth of silver halide grains is completed, unnecessary soluble salts may be removed from the silver halide emulsion, or unnecessary soluble salts may be left in the silver halide emulsion. It can be done based on the method.

The silver halide grains may have a uniform M h layer inside and on the surface, or may be composed of different layers.

The silver hemodenide grains may be such that a latent image is mainly formed on the surface, or may be such that a latent image is mainly formed inside the grain.

The silver halide grains may have a regular crystal shape or may have an irregular crystal shape such as a spherical shape or a plate shape.

Any ratio between the 11001 plane and the 1llll1 plane can be used. Further, the particles may have a composite form of these crystal forms, or particles of various crystal forms may be mixed.

The silver halide emulsion may be a mixture of two or more silver halide emulsions that have been separately formed.

The silver halide emulsion is chemically sensitized by conventional methods. Namely, sulfur-containing compounds that can react with silver ions, sulfur sensitization using active gelatin, selenium sensitization using selenium compounds, reduction sensitization using reducing substances, and noble metals using gold and other metal compounds. Sensitization methods and the like can be used alone or in combination.

Silver halide emulsions are produced in the photographic industry by using dyes known as sensitizing dyes to produce optical rays in a desired wavelength range.
This can be sensitized. Sensitizing dyes may be used alone, but 21
A dye that does not itself have a spectral sensitizing effect together with a sensitizing dye, or a compound that does not substantially absorb visible light, which may be used in combination of one or more of them, and a strong color that enhances the sensitizing effect of the sensitizing dye. A sensitizer may also be included in the emulsion.

Silver halide emulsions are used during the manufacturing process of photosensitive materials, during storage,
Alternatively, for the purpose of preventing capri during photographic processing and/or maintaining stable photographic performance, chemical ripening and/or at the end of chemical ripening, and/or after the end of chemical ripening, silver halide emulsion. Compounds known in the photographic industry as anti-capri agents or stabilizers can be added prior to coating.

Binder (or protective colloid) for silver halide emulsions
It is advantageous to use gelatin, but other synthetic hydrophilic polymers such as gelatin derivatives, graft polymers of gelatin and polymers, proteins, sugar derivatives, cellulose 44, single or copolymers, etc. Hydrophilic colloids such as molecular substances can also be used.

The photographic emulsion layer and other wood-loving colloid layers of the light-sensitive material of the present invention are hardened by using alone or in combination with a hardening agent that crosslinks binder (or protective colloid) molecules and increases film strength. . It is desirable to add the hardening agent in an amount that can harden the photosensitive material to the extent that it is not necessary to add the hardening agent to the processing solution, but it is also possible to add the hardening agent to the processing solution.

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

A dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer can be included in the photographic emulsion layer or other hydrophilic colloid layer of a light-sensitive material for the purpose of improving dimensional stability.

In the emulsion layer of the color photographic material of the present invention, aromatic primary amine developers (for example, 9-phenylenediamine derivatives, aminophenol derivatives, etc.) are used in color development processing.
performs a coupling reaction with the oxidized form of to form a pigment,
Dye-forming couplers are used. The dye-forming coupler is of the form r! A yellow dye-forming coupler is typically selected for the blue light-sensitive emulsion layer, a magenta dye-forming coupler for the green light-sensitive emulsion layer, and a magenta dye-forming coupler for the red light-sensitive emulsion layer. A cyan dye-forming coupler is used. However, depending on the purpose, the silver halide color photographic material may be used in a manner different from the above combination.

Yellow dye-forming couplers include acyl-7-ceto-7-mido couplers (e.g., benzoylacetate (anilides),
In addition to the couplers of the present invention, there are other magenta dye-forming couplers such as 5-pyrazolone couplers, pyrazolobenzimidazole couplers, pyrazolotri7zole couplers, and 1-chain acylacetrinitole couplers, which form cyan dyes. Couplers include 7-tall couplers and phenol couplers.

It is desirable that these dye-synthesizing couplers have a group called a ballast group in the molecule, which makes the coupler non-diffusive and has 8 or more carbon atoms. It may be either 4-equivalence, in which 100 silver ions need to be reduced, or 2-equivalence, in which only 2 molecules of silver ions need to be reduced.

For hydrophobic compounds such as dye-forming couplers that do not need to be adsorbed onto the silver halide crystal surface, various methods such as solid dispersion, latex dispersion, and oil-in-water emulsion dispersion can be used. can be appropriately selected depending on the chemical structure of the hydrophobic compound, etc. The oil-in-water emulsion dispersion method can be applied using conventionally known methods for dispersing hydrophobic additives such as couplers, and is usually mixed with a high boiling point organic solvent having a boiling point of about 150°C or higher, and if necessary, a low boiling point and/or a high boiling point organic solvent. Alternatively, it can be dissolved using a water-soluble organic solvent and mixed with a surfactant in a hydrophilic binder such as an aqueous gelatin solution using a stirrer or homo7.
After emulsifying and dispersing using a dispersion means such as a colloid mill, a 70-jet mixer, or an ultrasonic device, it can be added to the desired hydrophilic colloid layer. A step of removing the organic solvent may also be included.

Examples of high boiling point oils include phenol derivatives that do not react with the oxidized form of the developing agent, 7-talic acid ester, phosphoric acid ester, citric acid ester, benzoic acid ester, furkyl 7-mid,
Boiling point of fatty acid ester, trimesic acid ester, etc. 150
An organic solvent having a temperature of ℃ or higher is used.

7-Nionic surfactants, nonionic surfactants, cations are used as dispersion aids when dissolving a hydrophobic compound in a low boiling point solvent alone or in combination with a high boiling point solvent and dispersing it in water using a machine or ultrasound. A surfactant can be used.

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

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

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

The color photographic material of the invention can be provided with auxiliary layers such as a filter layer, an anti-halesian layer and/or an anti-irraqueditan layer. These layers and/or the emulsion layer may contain dyes that flow out of the color light-sensitive material or are bleached during development.

A matting agent may be added to the silver halide emulsion layer and/or other hydrophilic colloid layer of the photosensitive material for the purpose of reducing the gloss of the photosensitive material, increasing the ease of writing, and preventing mutual (pecking) of the photosensitive materials. A lubricant can be added to reduce the sliding friction of the photosensitive material.

An antistatic agent for the purpose of preventing static electricity can be added to the photosensitive material of the present invention. Antistatic agents are sometimes used in the antistatic layer on the side of the support on which the emulsion is not laminated, or they are used to protect the emulsion layer and/or the side other than the emulsion layer on which the emulsion layer is laminated with respect to the support. It may also be used as coid waste.

The photographic emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material has the following properties: improvement of coating properties, antistatic properties, improvement of slipperiness, emulsification dispersion, prevention of adhesion, and photographic properties (such as development acceleration, contrast enhancement, and sensitization). Various surfactants are used for the purpose of improvement.

The photographic emulsion layer and other layers of the light-sensitive material are baryta layers or a
- A flexible reflective support such as paper or synthetic paper laminated with olefin polymer, etc., consisting of semi-synthetic or synthetic polymers such as cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate F, polyamide, etc. It can be applied to films and rigid bodies such as glass, metal, and ceramics.

The photosensitive material may be exposed to corona discharge, ultraviolet irradiation, or flame path P [! etc., the adhesion directly or on the support surface, antistatic property, dimensional stability, abrasion resistance, hardness, anti-halesian property, J1! It may be applied through one or more subbing layers to improve rub properties and/or other properties.

When coating photosensitive materials, a thickener may be used to improve coating properties. Extract coating and curtain coating, which can simultaneously coat 2F1 or more scraps, are particularly useful coating methods. .

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

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

Images can be formed using the photosensitive material of the present invention by color development as known in the art.

The aromatic primary amine color developing agents used in the color developing solution of the present invention include known ones that are widely used in various color photographic processes. These developers include aminophenol and 9-phenylenediamine derivatives. Since these compounds are more stable than the R-phase state, they are generally used in the form of a salt, such as a hydrochloride or a sulfate. Additionally, these compounds are generally present in a concentration of about 0.1 g to about 30 g per color developer 11, preferably about 1.0 g per color developer all. Use at a concentration of ~1.5 g.

For example, as a 7 minophenol developer, 0-7 min/
Phenol, p-7 minophenol, 5-7 minnow 2-
These include hydroxytoluene, 2-7minor-3-hydroxytoluene, 2-human axy-3-7min/-1°4-dinothylbenzene, and the like.

Particularly useful primary aromatic amino color developers are N, N'
-Difurkyl-p-phenylenenoamine type compound, the furkyl group and the phenyl group may be substituted with any substituent.Among them, a particularly useful example is N,N'-diethyl-p-phenylenediamine hydrochloride. salt,
N-methyl-1)-7! Nylennoamine [flt salt, N
, N'-tumethyl-p-phenylenediamine hydrochloride, 2
-7minnow5-(N-ethyl-N-dodecyl7mino)-
Toluene, N-ethyl-N-β-19sulfonamidoethyl-3-methyl-4-7mino7-diphosphorus sulfate, N-
Ethyl-N-β-hydroxyethylamino 7niline, 4
-7 minnow 3-methyl-N,N'-noethylaniline,
Examples include 4-amino-N-(2-nodoxyethyl)-N-ethyl-3-methyl 7niline-p-)luenesulfonate.

In addition to the above-mentioned primary aromatic amine color developer, the color developer used in the processing of the color photographic material of the present invention further contains various components normally added to color developer (2a), such as water. Optionally contains alkaline agents such as sodium oxide, sodium carbonate, potassium carbonate, alkali metal sulfites, alkali metal bisulfites, alkali metal thiocyanates, alkali metal halides, benzyl alcohol, water softeners and thickeners, etc. You can also force it.

The color developer usually has an II value of 7 or more, most commonly about 10 to about 13.

In the present invention, after color development processing, processing is performed with a processing liquid having a fixing ability, but if the processing liquid having a fixing ability is a fixing liquid, a bleaching treatment is performed before that. A metal complex salt of an organic acid is used as a bleaching agent in the bleaching process, and the metal complex salt has the effect of oxidizing the metallic silver produced during development and converting it into silver halide, and at the same time coloring the uncolored areas of the coloring agent. Therefore, its composition is one in which metal ions such as iron, cobalt, copper, etc. are coordinated with amide/polycarboxylic acid or organic acids such as oxalic acid and citric acid. R used in C1 to form such a metal complex salt of an organic acid
Among these, preferable fi acids include polycarboxylic acids and aminopolycarboxylic acids. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts.

Specific representative examples of these include the following.

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

Also, the pH of borates, oxalates, acetates, carbonates, phosphates, etc.
l Impact, alkylamines, polyethylene oxide M
Those known to be added to ordinary bleaching solutions, such as bleaching agents, can be added as appropriate.

Furthermore, the fixer and bleaching constant "X1a" may contain sulfites such as ammonium sulfite, potassium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, sodium metabisulfite, boric acid, Borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bisulfite, sodium bicarbonate, potassium bicarbonate, acetic acid,
A pH buffer consisting of various salts such as sodium acetate and ammonium hydroxide may be used alone or may contain 2F1 or more.

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

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

〔Effect of the invention〕

According to the color photographic material containing the magenta coupler represented by the general formula [I] of the present invention and the magenta dye image stabilizer represented by the general formula [■], heretofore, in particular,
The fastness of magenta dye images, which have low fastness to heat and humidity, is improved, and specifically, discoloration and fading are significantly suppressed, and the occurrence of Y-stin in uncolored areas against light and heat is reduced. This can be effectively prevented.

Furthermore, by using a dye image stabilizer represented by the general formula (Xllll) in combination, the light resistance of the magenta dye image is further improved.

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

Example 1 On a paper support laminated on both sides with polyethylene, gelatin (12,0II [I/100c+*2), the following comparative magenta coupler m (4,5 mg/100c)
m2) to 2.5-di to one-octylhydroquinone (
After dissolving and emulsifying and dispersing trioctylphos 7 x -) (4,0mg7100100e) with
Sample 1 was obtained by mixing with coating silver mold 3.8 tag/100 c 2), coating, and drying.

A sample 2 was obtained by adding the above-mentioned 1-1:l as a magenta dye image stabilizer to the above sample 1 in a mole twice that of the magenta coupler.

Samples 3 and 7.11 were obtained in the same manner except that the magenta coupler in Sample 1 was replaced with magenta couplers 1.44 and 130 of the present invention, respectively.

In each of the above samples 3 and 7.11, twice the mole of the magenta dye image stabilizer pH-13 as the coupler was added to obtain sample 4.8.12, and further the pH-13
Instead, magenta dye image stabilizer A-2 of the present invention was added in twice the mole of the coupler, and samples 5.9 and 13 were prepared.
I got it. In addition, in the sample 3, 7.11, the gate l-
13 and A-2 in a ratio of 1 = 5 to form the coupler 2
Two times the molar amount was added to prepare samples 6°10 and 14, respectively.

Comparative magenta coupler a rσ I The sample obtained above was exposed to light using a conventional method. After exposure through a wedge,
The treatment was carried out in the following steps.

[Processing process] Processing temperature Processing time Color development
33℃ No. 3 Bleach fixing for 30 seconds
Wash with water at 33℃ for 1 minute and 30 seconds
Dry for 3 minutes at 33℃
50-80°C for 2 minutes The components of each treatment solution are as follows.

[Color developer]

Benzyl 7 Lefurun Ethylene Glycol 1Ol 111 Potassium Carbonate 25g Bromide Tori City
0.6g anhydrous sodium sulfite
2,0.

Hydroxylamine sulfate 2.58N-ethyl-N-βnotanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 4.5g Add water to make 11, and adjust pH to 2 with sodium hydroxide. 1
! ! Adjustment.

[i-vote self-fixer]

Ammonium thiosulfate 120877m
Sodium sulfite 15g Anhydrous sodium sulfite 3g EDTA ferric ammonium salt 65g Add water to make 11, and adjust 11 to 6.7 to 6.8.

The concentrations of Samples 1 to 14 treated above were measured using a Density 8F (Konishi Roku Photo Industry Co., Ltd. 11K (1-7R type)) under the following conditions.

Each of the above-mentioned processed samples was exposed to a xenon fade meter for 15 days to examine the light fastness of the dye image and the Y-stin (y-s) of the uncolored area. The dye image was left in a high humidity atmosphere for 140 hours, and the moisture resistance of the dye image and the Y-stain of the uncolored area were examined. obtained f
The results are shown in Table 1.

However, the evaluation of each item of light fastness and moisture fastness of the dye image is as follows.

〔Survival rate〕

Percentage of dye remaining after 1 light, moisture resistance test for initial density 1.0.

[Y-Stin]

The value obtained by subtracting the Y-stin density on the 1-light, humidity-resistant test surface from the Y-stin density after the 1-light, humidity-resistant test.

[Degree of discoloration]

(Yellow density) after light fastness test at initial density 1.0/
(magenta density) to yellow density before the light emission test)/
(magenta density), and the larger this value is, the easier it is to change the color tone from magenta to yellowish. 1° As is clear from Table 1, Sample 3.7. made using the coupler of the present invention.
11 is 1 mo, compared to sample 1 prepared using a conventional 4-equivalent type 3-7 nilino-5-pyrazolone coupler.
It can be seen that Y-stain is extremely difficult to generate in the moisture resistance test, but it can be seen from the residual rate and degree of discoloration of the dye image area in the light test that it is easily discolored and faded by light.Samples 4 and 8 .12 is conventionally well known for the coupler of the present inventionC)
This sample was prepared in combination with the magenta dye image stabilizer Pl+-13, which has been published in 2007. Although this certainly significantly improves the fading of the dye image due to light, it cannot improve the discoloration.

On the other hand, in Sample 5.9.13 prepared using the coupler of the present invention and the dye image stabilizer of the present invention, the color change and fading of the dye image were small in the resistance test against heat and humidity, and no color was developed. It can be seen that almost no Y-stin occurs. This could not be achieved with the conventional combination of a 4-equivalent type 3-7 nilino-5-pyrazolone type coupler and the dye image stabilizer Pl+-13 (Sample 2).

In addition, in addition to the coupler and magenta dye image stabilizer of the present invention, Samples 6, 10 and 14, in which a conventional magenta dye image stabilizer was added, further improved the dye residual rate in the 1-light test. Recognize.

Example 2 Samples 15 to 30 were prepared by applying couplers and magenta dye image stabilizers in combinations shown in the Pt52 table in exactly the same manner as in Example 1. Samples 15-3o were processed as described in Example 1. Furthermore, these samples were prepared in Example 1.
A light resistance test and a moisture resistance test were conducted in the same manner as above, and the results shown in Table 2 were obtained.

The comparative magenta coupler in the table has the following structure.

As is clear from Table 2 of the comparative magenta couplers, the conventionally used magenta couplers are
When the magenta dye image stabilizer of the present invention is used in combination with a 4-equivalent type 3-aniso15-pyrazolone type coupler (Sample 15.16) and the magenta dye image stabilizer conventionally commonly used in the coupler of the present invention (Samples 19, 20, 21.22), it was not possible to improve all of the discoloration, fading, Y-stin in the uncolored area in the light test, and Y-stin in the moisture resistance test, and this was not possible. It can be seen that all of the above-mentioned improvements can only be achieved by using the coupler of the invention in combination with the magenta dye image stabilizer of the invention.

Example 3 On a paper support laminated on both sides with polyethylene, the following layers were sequentially coated from the support side to prepare a multicolor silver denide photographic material, and Sample 31 was obtained.

1st layer: blue-sensitive silver halide emulsion layer a-pipalyl-α-(2°4
-dioxo-1-bennolimigzolinon-3-yl)
6.8 mg of -2-chloro-5-[γ-(2t4-cut-7milphenoxy)butyl7mido]aceto7nilide
/100cI112, blue-sensitive silver chlorobromide emulsion (silver bromide 85
(mol% content) converted to silver is 3.2g/100c theory 2
, 3.5 mg/100 cm of diptyl 7-thaletate,
And gelatin was coated in an amount of 13.5 mg/7100 cm''.

2nd layer: middle layer 2.5-not-t-octylhydroquinone 0.5g
/100C Export 2, Diptyl 7 Talate 0.5mg/
100cm+2 and gelatin 9.0-g7100cm
” It was painted so that it looked like this.

Third waste: green-sensitive silver halide emulsion layer containing the magenta coupler 18 at 4.0 g/100 c 2
, green-sensitive silver chlorobromide emulsion (containing 80 mol% silver bromide) in terms of silver is 2.5 g/100c+*2, butyl 7-thalet is 3, OwB/100 cm2, and gelatin is 14. O+H/100c ring 2 was painted.

4th M: 5. Add 2-(2-hydroxy-3-5ee-butyl-5-t-butylphenyl)benzotriazole as an intermediate layer UV absorber. Oieg/10100e, Norbutyl 7 Talate at 4.0 tag/100cv'', 2,5-Not-octylhydroquinone at 0.5 mg/100 cm2, and gelatin at 12.0 mg/100 cm2 were coated.

5th layer: Red-sensitive silver halide emulsion layer 2-(ff-(2,4-di-t-
4.2-g/100c+
2. Red-sensitive silver chlorobromide emulsion (containing 80 mol% silver bromide) converted into silver. 3. OB/100c paper 2, tricresyl phos 7ate was coated at 3.5 g/100 cm'' and gelatin was coated at 11.5 mg at 7100 cm2.

vJll: Protective layer gelatin 8. The coating was applied so that the thickness was 100 cm.

In the above sample 31, the magenta dye image stabilizer of the present invention was added to the third layer in the proportions shown in Table 3 to prepare multilayer samples 32 to 40, which were exposed and processed in the same manner as in Example 1. After that, a light emission test (a xenon fade meter was irradiated for 15 days) was conducted. The results are also shown in Table 3.

7-Table 3 From this result, the magenta dye image stabilizer of the present invention:
The magenta coupler of the present invention is effective in stabilizing dye images, and the effect becomes greater as the amount added increases. *Compared to sample 31, samples 32 to 40 showed extremely small discoloration of the dye image in the mold light test. Furthermore, in the samples of the present invention, discoloration and fading of the magenta dye were extremely small, and as a whole color photographic material after the one-light test, the color balance with the yellow and cyan couplers was good, and the color reproducibility remained extremely good. Ta.

Claims (1)

[Scope of Claims] A silver halide photograph characterized by containing at least one magenta coupler represented by the following general formula [I] and at least one compound represented by the following general formula [XII] Photosensitive material. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. You may. X represents a hydrogen atom or a substituent that can be separated by reaction with an oxidized product of a color developing agent. Moreover, R represents a hydrogen atom or a substituent. ] General formula [XII] ▲ Numerical formulas, chemical formulas, tables etc. Represents an aryl group, a heterocyclic group, an acyl group, a sulfonyl group, a phosphonyl group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group. ]