JPS61158334A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a colored photographic material having an improved fastness against light of a Magenta colored image and an excellent color reproducibility by incorporating at least one of specific couplers contg. a nitrogen atom and at least one of specific stabilizers for a colored image contg. an oxygen atom. CONSTITUTION:The titled material contains at least one of couplers shown by formula (I) and at least one of specific stabilizers for a colored image contg. an oxygen atom. In the Magenta coupler shown by formula (I), R is a hydrogen atom or a substituent. The substituent of R is a halogen atom or a heterocyclic thio group. Said halogen atom comprises a chlorine or a bromine atoms, preferably a chlorine atom. The Magenta colored image stabilizer joint-used with a magenta coupler has an anti-decoloring effect of the Magenta colored image against a light and also an anti-discoloring effect of the Magenta colored image against a light and is a chroman or a chraman compds. shown by formula (XI). The compounding amount of the Magenta colored image stabilizer is 5-300mol%, preferably 10-200mol% on the basis of the Magenta coupler.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application 1] The present invention relates to a silver halide photographic material.
This invention relates to a silver halide color photographic light-sensitive material in which a dye image is stable against heat and light, and staining is prevented.

[Prior Art 1] Conventionally, a silver halide color photographic light-sensitive material is imagewise exposed and color developed to cause a coupling reaction between an oxidized product of an aromatic primary amine color developing agent and a color former. For example, it is well known that indoenol, indoaniline, ingumin, azomethine, 7e/xanone, 7enanone, and pigments similar to these are produced and color images are formed. In such photographic systems, a subtractive color reproduction method is usually adopted, and color forming agents having additional colors, namely yellow and magenta, are added to blue-sensitive, green-sensitive, and red-sensitive light-sensitive silver halide emulsion layers, respectively. A silver halide color photographic light-sensitive material containing Kabu2-, which develops a cyan color, is used.

Couplers used to form the above-mentioned yellow-a color image include, for example, acylaceto-7 dilide couplers, and couplers for forming magenta color images include, for example, pyrazolone, virazolobenzimigzole, and pyraproto-1. Fufusol or ingzolone couplers are known, and as couplers for forming cyan images, for example, phenol or 7tol couplers are generally used.

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

However, in the case of magenta couplers, Y-staining due to moist heat in uncolored areas and fading due to light in dye image areas are extremely large compared to yellow couplers and cyan couplers, and often pose a problem.

Couplers commonly used to form magenta dyes are 1,2-pyrazolo-5-ones. This one
, 2-pyrazolo-5-one magenta couplers have a main absorption near 550 n +s.
Having sub-absorption near 430 nm is a major problem, and various studies have been conducted to solve this problem.

A magenta coupler having a 7-nylino group at the 3-position of a 1.2-pyrazolo-5-one has a small side absorption and is particularly useful for obtaining a color image for printing. Regarding these techniques, see, for example, U.S. Patent No. 2,343,703;
It is described in British Characteristic No. 1,059,994, etc.

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

As another means to reduce the 114 absorption near 430n of the above magenta coupler, the British feature 1.047
, 3,770,447, Ingzon a as described in US Patent No. 3,770,447, and US Pat. No. 3,725,067, UK FFt.
No. 252゜418, I described in No. 1,334,515
H-pyrazolo[5,1-c)-1,2,4-triazole type coupler, Research Disclaw Tsuya No. 24
IH-pyrazolo(1,5-b)-1 as described in , 531,
2,4-) lyazole type coupler, IH-pyrazolo(
1,5-c)-1,2,3-) lyazole coupler,
IH-imidazo (
1,2-b)-pyrazole type Kab 2-, IH-pyrazo I described in Research Disclosure No. 24,230
Magenta couplers such as ff(1,5-b) pyrazole couplers and IH-virazo O(1,5-d) tetrazole couplers described in Research Disclosure No. 24,220 have been proposed. Among these, IH-pyrazolo(5,1-c) 1,2,4-)7zole coupler, IH-pyrazolo(1,5-b)-1,2,4
-triazole coupler, IH-pyrazolo I: 1.5
-c) -1,2,3-triazole coupler, I 1
1-imidazo[1,2-b) pyrazole coupler, ]
The dye formed from the H-pyrazolo(1,5-d) pyrazole coupler and the l/I H-pyrazolo(1,5-d) tetrazole coupler has a subabsorption at around 430 nm at the 3-position above. It is significantly smaller than dyes formed from 1,2-pyrazol-5-ones having a nilino group, which is preferable in terms of color reproduction, and furthermore, the occurrence of Y-stin in uncolored areas when exposed to light, heat, and humidity is also extremely small, which is preferable. It has advantages.

However, the fastness of the 7-dimethine 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.

Furthermore, in JP-A No. 59-125732, a 7 ether compound or a phenyl ether compound is added to an IH-pyrazolo(5,1-e)-1,2,4) lyazole type magenta coupler. A technique has been proposed for improving the light fastness of a magenta dye image obtained from a 1 H-pyrazolo(5,1-c) 1.2.4-) lyazole type magenta coupler by using them together. However, it has been recognized that even the above techniques are still not sufficient to prevent the magenta dye image from fading due to light, and moreover, it is almost impossible to prevent discoloration due to light.

[Object of the Invention] The present invention has been made in view of the above problems, and the object of the rjSl of the present invention is to provide a color photograph with excellent color reproducibility and markedly improved light fastness of magenta dye images. The purpose is to provide materials.

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

The third object of the present invention is to reduce Y in uncolored areas against light and moist heat.
- Color photography in which generation of styrene is prevented [Structure of the Invention] The object of the present invention is to provide at least one coupler represented by the following general formula (1) t' and a compound represented by the following general formula (XI). This is achieved by a silver halide photographic material characterized by containing at least one of the following.

General formula (1) In the formula, Z represents a group of nonmetallic atoms necessary to form a nitrogen-containing heterocycle, and the ring formed by Z may have a substituent.

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

General formula (XI'] R2R) In the formula, R' represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an acyl group, a cycloalkyl group, or a heterocyclic group, and R2 represents a hydrogen atom, a) rodene atom, or an alkyl group. represents a group, an alkenyl group, an aryl group, an aryloxy group, an acyl group, an acylamide group, an acyloxy group, a sulfonamide group, a cycloalkyl group, or an alkoxycarbonyl group.

R″ represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, an acyl group, an acylamino group, a sulfonamide group, a cycloalkyl group, or an alkoxycarbonyl group.

R→ represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkenyloxy group, a hydroxy group, an aryl group, an aryloxy group, an acyl group, an acylamine group, an acyloxy group, a sulfonamide group, or an alkoxycarbonyl group. represent.

Further, R1 and R2 may be ring-closed with each other to form a 5-shell or 6-shell ring.

At that time, R) and [/R' are a hydrogen atom, a halogen atom, a furkyl group, an alkenyl group, an alkoxy group, an alkenyloxy group, a hydroxy group, an aryl group, a 7-aryloxy group, an acyl group, an acylamine 7 group, an acyloxy group, Represents a sulfone 7-mido group or an alfkhidicarbonyl group.

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

Next, the present invention will be specifically explained.

Examples of the substituent represented by the general formula [■] General formula CI) according to the present invention include a halogen atom, a furkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a heterocyclic group, and an acyl group. , sulfonyl group, sulfinyl group, phosphonyl group, carbamoyl group, sulfamoyl group, sia7 group, spiro compound residue, bridged hydrocarbon compound residue, alkoxy group, aryloxy group, heterocyclicoxy group, siloxy group, acyloxy group , carbamoyloxy group, amine 7 group, acylamino group, sulfonamide group, imide group, ureido group, sulfonyl amine 7 group, alkoxycarbonyl amine 7 group, aryloxycarbonyl amine/group, alkoxycarbonyl group, aryloxycarbonyl group, Examples include an alkylthio group, an arylthio group, and a heterocyclic group.

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

The alkyl group represented by R'1' has 1 to 32 carbon atoms.
The alkenyl group and alkynyl group preferably have R1k number of 2 to 32, and the dichlorofurkyl group and cycloalkenyl group preferably have 3 to 12 carbon atoms, especially 5 to 7 carbon atoms, and the furkyl group, alkenyl group, and alkynyl group may be linear or branched.

In addition, these alkyl groups, alkenyl groups, alkynyl groups, dichlorofurkyl groups, and cycloalkenyl groups include substituents (e.g., 7-aryl and Schiff), halogen atoms, heterocycles, cycloalkyl, cycloalkenyl, spiro compound residues, and bridged hydrocarbons. In addition to compound residues, those substituted via a carbonyl group such as acyl, carboxy, carbamoyl, alkoxycarbonyl, and aryloxycarbonyl, and those substituted via a hetero atom, specifically hydroxy, alkoxy, and aryl. Oxy, heterocyclic oxy,
a2 such as siloxy, acyloxy, carbamoyloxy, etc.
Substituents via elementary atoms, nitro, ami/(including noalkyl amide/etc.) sulfamoyl amide/, flukoxyl amine/, aryloxycarbonyl amine, acyl amide:, sulfonamide, imide, thureide, etc. nitrogen those substituted via an atom, those substituted via a sulfur atom such as alkylthio, arylthio, heterocyclic thio, sulfonyl, sulfinyl, sulf7moyl, and those substituted via a phosphorus atom such as phosphonyl). You can leave it there.

Specifically, for example, methyl group, ethyl group, isopropyl group, [-butyl group, pentadecyl group, heptadecyl group, 1
-hexyl/nyl group, 1.1'-nopentylnonyl group,
2-chloro-1-butyl group, tri7fluoromethyl group, 1
-Ethoxytridecyl group, 1-methoxyisopropyl group, methanesulfonylethyl group, 2,4-not-7mil7ethyl/oxymethyl group, anilino group, 1-phenylisopropyl group, 3-methoxybutanesulfone7ethyl/phenoxy Propyl group, 3-4'-1α-(4”(p-hydroxybenzenesulfonyl)71/xy]dodeca/yl7mino)
7enylpropyl i 3-i4'-[α-(2”, 4
"-not-7mil7eth7xy)butanamide]phenyl I-7'robyl group, 4-(α-(0-chlor7eth/quin)tetofudecanamide7ethy/xy)propyl group, allyl group, Examples include cyclopentyl group and cyclohexyl group.

The 7-aryl group represented by R''C is preferably a 7-enyl group, which may have a substituent (for example, a furkyl group, a flukoxy group, an acylami 7 group, etc.).

Specifically, phenyl group, 4-t-butylphenyl group,
2,4-not-7mil7enyl group, 4-tetradecanamidophenyl group, hexadecyloxyphenyl group, 4'
-[α-(4″-t-butyl 7eth/xy)tetradecane 7mido]phenyl group, etc. are mentioned.

The heterocyclic group represented by R''C is preferably a 5- to 7-membered one, which may be substituted or fused, specifically a 2-7lyl group, a 2-chenyl group, Examples include 2-pyrimidinyl group and 2-pensothi7zolyl group.

Examples of the 7-syl group to be Rri include an acetyl group, a phenyl 7-cetyl group, a dodecamyl group, a fulkylcarbonyl group such as an α-2,4-not-t-amylphenoxybuta/yl group, a benzoyl group, and a 3-pentadecyl group. Examples include 7-arylcarbonyl groups such as oxybenzoyl group and p-arylbenzoyl group.

Examples of the sulfonyl group represented by R'1' include a methylsulfonyl group, an alkylsulfonyl group such as a dodecylsulfonyl group, and an arylsulfonyl group such as a benzenesulfonyl i, p-)luenesulfonyl group.

The sulfinyl group represented by R''Ch includes an alkylsulfinyl group such as an ethylsulfinyl group, an octylsulfinyl group, a 3-7e/xybutylsulfinyl group,
Phenylsulfinyl i% Examples include arylsulfinyl groups such as m-pentadecylphenylsulfinyl group.

Examples include phenylphosphonyl groups such as phenoxyphosphonyl groups, aryloxyphosphonyl groups such as phenoxyphosphonyl groups, and arylphosphonyl groups such as phenylphosphonyl groups.

The carbamoyl group represented by R may be substituted with an alkyl group, a 7-aryl group (preferably a phenyl group), etc.
For example, N-methylcarbamoyl group, N,N-butylcarbamoyl group, N-(2-pentadecyloctylethyl)carbamoyl group, N-ethyl-N-dodecylcarbamoyl group, N-13-(2,4-di- The sulfamoyl group represented by (t-7mil7eth/xy)propyl) R may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as N-propylsulfamoyl M,
N, N-noethylsul7amoyl group, N-(2-pentadecyloxyethyl)sulfamoyl group, N-ethyl-
N-dodecylsulfamoyl group, N-phenylsul77
Examples include moyl group.

Examples of the spiro compound residue represented by R″C′ include spiro[3,3]hebutan-1-yl.

Examples of the carbonized compound residue represented by R1' include bicyclo[2,2,1]hebutan-1-yl, tricyclo[
3,3,1,1'']decan-1-yl, 7,7-nomethyl-bicyclo[2,2,1]hebutan-1-yl, and the like.

The alkoxy group represented by R"C'! may be further substituted with the substituents listed above for the alkyl group, such as methoxy group, propoxy group, 2-ethoxyethoxy group, pentadecyloxy group, -dodecyloxyethoxy group, 7enethyloxyethoxy group, etc.

The aryloxy group represented by R''C is preferably 7enyloxy, and the aryl nucleus may be further substituted with any of the substituents or atoms listed above for the aryl group, such as a 7eth/oxy group, Examples include p-t--ythyl 7eth/oxy group, -1pentadecyl 7ethyl/oxy group, and the like.

The heterocyclic oxy group represented by R'11% preferably has a 5- to 7-membered heterocycle, and the heterocycle may further have a substituent, for example, 3°4.5.6 -tetrahydrobilanyl-2-oxy group and 1-phenylnato2zole-5-oxy group.

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

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

The carbamoyloxy group represented by R may be substituted with an alkyl group, an aryl group, etc., such as an N-ethylcarbamoyloxy group, an N,N-noethylcarbamoyloxy-3,N-phenylcarbamoyl oxine group, etc. can be mentioned.

The amine 7 group represented by R may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as an ethylamino group, an anilino group, a m-chloroanilino group,
Examples include 3-pentadecyloxytriponyl 7 groups, 2-chloro-5-hexadecaneamide 7 groups, and the like.

Examples of the acylamine 7 group represented by R include alkylcarbonyl amine 7 groups, arylcarbonyl amine 7 groups (preferably phenylcarbonyl amine 7 groups), and may further have a substituent. Acetamide group, α-ethylpropane 7-mido group, N-phenylacetamide group,
Examples include a dodecane 7-mido group, a 2,4-not-t-7 milphenoxyacetamide group, and an α-3-t-butyl 4-hydroxyphenoxybutanamide group.

Examples of the sulfone 7 mido group represented by R''c include an alkylsulfonyl amine/group, an arylsulfonyl 7 amide group, and may further have a substituent.

Specifically, 7 methylsulfonylamide groups, 7 pentadecylsulfonylamide groups, benzenesulfonamide group, p-)
Luenesulfonamide group, 2-/)xy-s t
Examples include 7-methylbenzenesulfonamide group.

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

The ureido group represented by R''C may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as an N-ethylureido group, an N-methyl-N-decylureido group, an N-phenylureido group. , N-p) ryclide group, and the like.

The sul7amoylami/group represented by R''C may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as N, N-butylsul7amoylamy7 group, N-methylsul7amoylamy7 group, !=, N-phenylsul7amoyl7mi7 groups, and the like.

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 octatecyloxycarbonylamide groups.

The aryloxycarbonylamide 7 groups represented by R may have a substituent, and examples include 7-enoxycarbonylamide 7 groups and 4-methylphenoxycarbonylamide 7 groups.

The alkoxycarbonyl group represented by R′C may further have a substituent, such as a methoxycarbonyl group, a butyloxycarbonyl group, a dodecyloxycarbonyl group,
Examples include octadecyloxycarbonyl group, ethoxymethoxycarbonyloxy group, benoloxycarbonyl group, and the like.

The aryloxycarbonyl group represented by R may further have a substituent, for example, a 7-ethyloxycarbonyl group,
Examples include p-chloro7e/oxycarbonyl group, --pentadecyloxyphenoquine carbonyl group, and the like.

The alkylthio group represented by R'''C may further have a substituent (e.g., ethylthio group, dodecylthio group, octadecylthio group, 7enethylthio group, 3-7 dinoquinprobylthio group). .

The arylthio group represented by Rr is preferably a phenylthio group and may further have a substituent, for example, a phenylthio group,
Examples include p-methquinphenylthio group, 2-octylphenylthio group, 3-octadecylphenylthio group, 2-carboxyphenylthio group, and p-7cetaminophenylthio group.

The heterocyclic thio group represented by R'1' is preferably a 5- to 7-shell heterocyclic thio group, which may further have a condensed ring or a substituent, e.g. 2-bilinorthio group, 2-benzothiazolylthio group, 2,4-)7e7
xy-1.3.5-) lyazole-6-thio group.

r!, which can be released by reaction with the oxidized product of the color developing agent represented by X! The l substituent includes, for example, a group that substitutes a norodene atom (salt i atom, bromine atom, fan atom, etc.) via a laxative atom, 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' and R3' are hydrogen atoms, aryl group, a group represented by ) representing an alkyl group or a heterocyclic group, a hydroxymethyl group, and a triphenylmethyl group.

Examples of the group substituting via an oxygen atom include an alkoxy group, an aryloxy group, a heterocyclic oxy group, a 7-syloxy group, a sulfonyloxy group, and an alkoxyoxalyloxy group.

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

The 7-aryloquine group is preferably a phenoxy group, and the aryl group may further have a substituent, specifically a phenoxy group, a 3-methyl 7e/oxy group, a 3°-dodecylphenoxy group. , 4-methanesulfonamidophenoxy! , 4-(ff-(3'-bentadenru 7 engineering/
xy)butanamide]7eth/oxy group, hexidecylcarbamoylmethoxy group, 4-cyanophenoxy group, 4-methanesulfonylphenoxy group, 1-su7tyloxy group,
Examples include ρ-methoxyphenoxy group.

The heterocyclic oxy group is preferably a 5- to 7-shell heterocyclic oxy group, which may be a condensed ring or may have a substituent, specifically, 1-phenyltetrazoli and 2-benzothiazolyloxy group.

Examples of the 7-yloxy group include acetoxy group, a fulkylcarbonyloxy group such as a butanoloxy group, an alkenylcarbonyloxy group such as a cinnamoyloxy group,
Examples include arylcarbonyloxy groups such as penzoyluoquine.

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

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

Examples of the 7-aryloxycarbonyl group include a phenoxycarbonyloxy group.

Examples of the fulkyloxalyloxy group include a methyloxalyloxy group.

Examples of the alkoxyoxalyloxy group include an ethoxyoxalyloxy group.

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

As the furkylthio group, butylthio group, 2-thia/
Examples include ethylthio group, 7ethylthio group, and benzylthio group.

The arylthio group includes phenylthio group, 4-methanesulfonamidophenylthio group, 4-dodecyl7enethylthio group, 4-nonafluoropentanamido7enethylthio group, 4-carboxyphenylthio group, 2-ethoxy-5-t-butyl Examples include phenylthio group.

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

The fulkyloxythiocarbonylthio group is used as the fulkyloxythiocarbonylthio group.

Examples include those represented by the general formula -N, which represent an aryl group, a heterocyclic group, a sulfamoyl group, a carbamoyl group, an acyl group, a sulfonyl group, a 7-aryloxycarbonyl group, and an alkoxycarbonyl group, R, t and Rs' may be combined to form a hetero-a ring, 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 alkyl group may have a substituent, and examples of the substituent include an aryl group, a flukoxy group, a 7-aryloxy group, an alkylthio group,
Arylthio group, alkyl7mi7 group, aryl7mi7 group, acyl7mi7 group, sulfonamide group, imino group, acyl group, alkylsulfonyl group, 7lylsulfonyl group,
Carbamoyl group, sulfamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkyloxycarbonyl group, aryloxycarbonylamine 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 R, I is preferably a carbon &6-32 group, a phenyl group or a naphthyl group,
The aryl group may have a substituent, and examples of the substituent include those listed as substituents for the alkyl group represented by R4', R, and I above, and an alkyl group. Specific examples of the aryl group include a phenyl group, a 1-su7tyl group, and a 4-methylsulfonylphenyl group.

Hete117 represented by R,/or Rs'! ! The group preferably has 5 to 6 shells, may be a fused ring, and may have a substituent, specific examples include 2-furyl group,
Examples include 2-quinolyl group, 2-biriminol group, 2-benzothiazolyl group, and 2-bilinol group.

R,/or R, /-'c as a sulfamoyl group, 1"fi, N-furkylsulfamoyl group, N,N-noarylcarbamoyl group, N-7lylsul7amoyl group, N,N-nor Specific examples of the sulfamoyl group include N, N-
Examples thereof include a noethylsulfamoyl group, an N-methylsulfamoyl group, an N-dodecylsulfamoyl group, and an N-p-)lylsul7T moyl group.

The carbamoyl group represented by R4' or R, t,
Examples include N-furkylcarbamoyl group, N,N-noarylcarbamoyl group, N-7lylcarbamoyl group, N,N-noarylcarbamoyl group, etc., and these alkyl groups and aryl groups are similar to the above-mentioned alkyl and aryl groups. Specific examples of carbamoyl groups which may have the above-mentioned substituents include N,N-noethylcarbamoyl group, N-methylcarbamoyl group, N-dodecylcarbamoyl group, N-p-cya/phenylcarbamoyl group. , N
-p-)lylcarbamoyl group.

Examples of the acyl group represented by R4' or R5' include a furkylcarbonyl group, a 7-aryl carbonyl group, and a heterocyclic carbonyl group. Specific examples of the 7-syl group that may be present include, for example, hexafluorobuta/yl group, 2゜3.4.5.6-pentafluorobenzoyl group, acetyl group, benzoyl group, naphthonyl group. , 2-7lyl carbonyl group, and the like.

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

The aryloxycarbonyl group represented by R1' or RS/ may have any of the substituents listed above for the aryl group, and specific examples include a 7-enoxycarbonyl group.

The alfkidicarbonyl group represented by R or Rs' may have the substituents listed for the alkyl group, and specific examples include a methoxycarbonyl group, a dodecyloxycarbonyl group, and a benzyloxycarbonyl group. etc.

The heterocycle formed by combining R, I and R, / is preferably 5 to 6 rings, and may be saturated or unsaturated, and may or may not have aromaticity. Well, again,
Examples of the heterocycle, which may be a condensed ring, include N-7 talimide group, N-fluorinyl imide group, 4-N-urazolyl group, 1-N-hyguntoynyl group, 3-N-2,4-dioxo Oxacylinonyl group, 2-N-1,1-dioxo-3-(2H)-i'/-1,2-benzthiazolyl group, 1-pyrrolyl group, 1-pyrrolinonyl group, 1-pyrazolyl group, 1- Pyrazolinonyl group, 1-piperinonyl group,
1-pyrrolinyl group, 1-imidazolyl group, 1-indolyl group, 1-indolyl group, 1-isoindolinyl group, 2
-isoindolyl group, 2-isoindolinyl group, 1-benzotri7zolyl group, 1-pencyimigzolyl group, 1-
(1,2,4-tri7zolyl) 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, 7thalathion group, 2-oxo-
These heterocyclic groups include furkyl group, aryl group, alkyloxy group, aryloxy group, acyl group, sulfonyl group, alkyl7mino group, arylami7 group, acylami7 group, sulfonami7 group, etc.
group, carbamoyl group, sulfamoyl group, alkylthio group, 7-arylthio group, ureido group, alphkidicarbonyl group, aryloxycarbonyl group, imido group, nitro group, sia/group, carboxyl group, halogen atom, etc. good.

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, in general formula (1) and general formulas (II) to [■] described later, substituents on the heterocycle (for example, R1R6 to R,) are partial, where R'', X and Z II are general (synonymous with R, X, and Z in formula [!]) forms a so-called screw-type coupler, which is of course included in the present invention.

In addition, the ring formed by z, z', z" and Z 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), is R
5 and R1, in the general formula [■], R2 and R,
are bonded to each other to form a ring (e.g. 5-7 cycloalkenes,
benzene) and 'C is also acceptable.

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

General formula (II) General formula (I) N -N -N General formula (fV) N -8-88 General formula (V) General formula (VI) General formula [■] Said general formula [■] to [■] In R3 to R8 and XI
i: Synonymous with tJ RAvX.

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

General formula [■] In the formula, R1X and Zl are R in the general formula CI).

It is synonymous with X and Z.

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

Regarding the substituents on the heterocycle in the general formula (+) ~ [ ~ 1], R in the general formula (1) and R in the general formula (II) ~ [■] 1, R1 meets the following condition 1
It is preferable that the following condition 1 is satisfied, and more preferable is the case where the following condition 1 is satisfied.
and 2, and most preferred is the case where conditions 1, 2, and 3 below are satisfied.

Condition l vl The root atom directly connected to the elementary ring is a carbon atom.

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

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

The most preferred substituents R and R6 on the heterocycle are those represented by the following general formula (ff).

General formula (IX) R1 R1゜-〇- In the formula, R'l+RIO and RII are each a hydrogen atom,
Norodene atom, alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, furkynyl group, aryl group, heterocyclic group, anlu group, sulfonyl group, sulfinyl group, phosphonyl group, carbamoyl group, sulfamoyl group, sia7 group, spiro Compound residue, endowed hydrocarbon compound residue, alkoxy group, aryloxy group, heterocyclic oxy group, siloxy group, acyloxy group, carbamoyloxy group, ami7 group, acyl7mi7 group, sulfone7mido group, imido group , represents a ureido group, 7 sul7amoylamino groups, 7 alkoxycarbonylamino groups, 7 aryloxycarbonylamino groups, an alkoxycarbonyl group, a 7lyloxycarbonyl group, an alkylthio group, an arylthio group, a heterocyclic group, and RltRl. At least two of and 1/R, , are hydrogen atoms.

Furthermore, two of the above RI I Rl O and RII, for example, R1 and Rlo, may be combined to form a saturated or unsaturated ring (e.g., cycloalkane, cycloalkene, heterocycle), and furthermore, a chain ring may be formed. R11 may be bonded to form an endowed hydrocarbon compound residue.

The group represented by R9-R1 may have a substituent,
Specific examples of the groups represented by R1 to R11 and substituents that the groups may have include specific examples and substituents of the group represented by R fIt in the aforementioned general formula (1).

Also, for example, a ring formed by combining R9 and R10 and R,
Specific examples of the endowed hydrocarbon compound residue formed by ~R1 and the substituents it may have include specific examples of the cycloalkyl, cycloalkenyl, and heterocyclic groups represented by R in the above general formula [1]; The substituents include.

Among the general formula CIIM), (Rs~R
When two of 11 are alkyl groups, (ii) R=~R
For example, when one of 11, RIl, is a hydrogen atom, and the other two, R9 and R1G, combine to form a cycloalkyl with the root carbon atom, the following is true.

Furthermore, it is preferable among (i) that two of R1 to R11 are alkyl groups and the other one is a hydrogen atom or an alkyl group.

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

CHl H3 2H5 Cl2H25 C4H.

C1l.

I CI+.

C) 1° OCR,C0NI(CH2C)+2QC)I.

0CII□IJI2So□CH3 C2H.

C21+5 shi4t19 csl(ti so2c.

H3 H3 QC, I+.

CH! 82 CtHtsH
iCCHx N -N -N N -N -NH W C=Hs +14 N -N -N tl The synthesis of the above coupler is
theChe+5ical 5ociety v P
erkin I (1977) +2047~20
52, U.S. Feature No. 3,725,067, Special [@59-9
The synthesis was carried out with reference to No. 9437 and Japanese Patent Application Laid-open No. 58-4Z045.

The couplers of the present invention typically contain 1 per mole of halogenated fli.
Xl0-'mol to 5X10-mol, preferably 1X1
It can be used in a range of 0-2 mol to 5 x 10-' mol.

Moreover, the coupler of the present invention can be used in other ways! It can also be used in combination with a Class 11 magenta coupler.

Furthermore, when the silver halide photographic material according to the present invention is used as a multicolor photographic material, in addition to the coupler of the present invention, yellow couplers and cyan couplers commonly used in this industry are used in the usual manner. be able to. Furthermore, if necessary, colored couplers having a color correction effect may be used. Two or more types of the above couplers may be used together in the same layer in order to satisfy the characteristics required for a photosensitive material, or the same coupler may be used in combination. It is also possible to add compounds with different ratios of 2/I or higher.

The maze/red dye image stabilizer used in conjunction with the magenta coupler of the present invention not only has the effect of preventing fading of the magenta dye image but also has the effect of preventing discoloration due to the following general formula: Chroman, expressed in degrees Celsius, is a coumaran-based compound.

In the general formula (XI) R2R, R' represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an acyl group, a cycloalkyl group, or a heterocyclic group, and R2 represents a hydrogen atom, a halogen atom, an alkyl group, or an alkenyl group. , aryl group, aryloxy group,
It represents an acyl group, an acylamide group, an acyloxy group, a sulfonamide group, a cycloalkyl group, or an alkoxycarbonyl group.

R3 represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, a 7-syl group, an acylamino group, a sulfonamide group, a cycloalkyl group, or an alkoxycarbonyl group.

R+ represents a hydrogen atom, a halogen atom, a furkyl group, an alkenyl group, an alkoxy group, an alkenyloxy group, a hydroxy group, a 7-aryl group, an aryloxy group, an acyl group, an acylamino group, an acyloxy group, a sulfonamide group, or an alphkidicarbonyl group. represent.

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

Further, R' and R2 may be ring-closed with each other to form a 5-shell or 6-shell ring, in which case R3 and R4 are hydrogen atoms,
Halogen atom, furkyl group, alkenyl group, alkoxy group, alkenyloxy group, hydroxy group, aryl group,
It represents an aryloxy group, an acyl group, a 7-syl amino group, an acyloxy group, a sulfonamido moiety, or a flufucidicarbonyl group.

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

The chroman or coumaran ring is a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkenyl group,
It may be substituted with an alkenyloxy group, a hydroxy group, an aryl group, an aryloxy group, or a heterocyclic group, and may further form a pyrocyclic ring.

Among the compounds represented by the general formula (XI), the compounds particularly useful in the present invention are the general formulas [XI), , (X'I)b, [1
1) Included in the compounds represented by c, (IT)d and (XT)e.

General formula (Xlla General formula (XI) b General formula [XI] C General formula [XI) d General formula [XI) e General formula [XI) a , (XI) b , (XI) c, (X
R1, R2, R3 in I) d and CXI) e
and tlR4 have the same meanings as in the general formula (XI), R5, R6, R7, R-1R9 and Rto
is hydrogen atom, herodene atom, alkyl group, alkoxy group, hydroxy group, fulkenyl group, alkenyloxy group,
R5 and R6, R6 and R7, R7 and R6, R
8 and R and R' and R10 may be cyclized with each other to form a carbocycle, and the carbocycle may be further substituted with an alkyl group.

General formula (XI)a, [XI)b, (XI)e, (X
In I)d and (XI)e, R1, R2 and R
3 is a hydrogen atom, an alkyl group, a cycloalkyl group, R4 is a hydrogen atom, an alkyl group, an alkoxy group, a hydroxy group or a cycloalkyl group, R5, R6, R7, R6, Rg
Compounds in which VR+6 and VR+6 are a hydrogen atom, an alkyl group, or a cycloalkyl group are particularly useful.6 Typical specific examples of these compounds are shown below, but the compounds used in the present invention are limited thereby. It's not a thing.

B-13B-2) B-3) B-4) B-
5) B-6) B-7)
B-8)B-9)
B-10) B-11)
B-12)B-13)
B-14)B-15)
B-16)B-17)
B-181B-19)
B-20) B-23
)B-24)B
-25) B -26)
B-27) B-28) B-:(O) B-34) ○H OH ○H C,2H,,0 H B-42) B-4
3)B-44)B-
45) B -46) B
-47) The magenta dye image stabilizer according to the present invention is
Tetrahedron, 1970, Vol.
26, pp. 4743-4751, Journal of the Chemical Society of Japan, 197
2, No. 10, pp. 1987-1990, S
synthesis 1975, Vol 6 + 3
pp. 92-393, Bull Socy Chi
my Be'lH1975, Vol 84(7),
747-759 N, and can be synthesized according to the methods described therein.

In the color photographic material of the present invention, the amount of the magenta dye image stabilizer represented by the general formula (Xll"C") of the present invention is preferably 5 to 300 mol% relative to the magenta coupler of the present invention. , the magenta dye ii!ii image stabilizer according to the present invention is further compounded by the following general formula [X■]
It is also possible to use other magenta dye side <1 stabilizers shown in the following, ie, 7 ether compounds and V7 enyl ether compounds.

General formula [X■1 In the formula, RII is a hydrogen atom, an alkyl group, an alkenyl group,
Represents an aryl group or a heterocyclic group, R12, R13,
RIs and R1' are each a hydrogen atom, )10 dene atom,
Represents a hydroxy group, a furkyl group, an alkenyl group, an aryl group, an alkoxy group or an acylamide group, and R14
represents an alkyl group, a hydroxy group, an aryl group, or an alkoxy group, or RII and R'2 may be ring-closed with each other to form a 5-shell or 6-shell ring, in which case R14
represents a hydroxy group or an alkoxy group, and R
1 and R'' may be ring-closed to form a /tyreneoxy ring.

Furthermore, 1<13 and R11 may form an Ill ring to form a five-shell hydrocarbon ring, in which R11 represents a furkyl group, an aryl group, or a heterocyclic group. However, R1
Except when 1 is a hydrogen atom and R11 is a hydroxy group.

In the general formula [X1], R11 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group, and examples of the alkyl group include, for example, a methyl group, a methyl group, a propyl group, and an n-octyl group. , Lert-octyl group, benol group, hexadecyl group, etc. can be mentioned.In addition, this alkyl group may have a substituent, and R
Examples of the alkenyl group represented by II include allyl, hexenyl, and octenyl groups. Furthermore, examples of the 7-aryl group of RII include phenyl and naphthyl groups. This aryl group may have a substituent, and specific examples include a methoxyphenyl group and a chlorphenyl group.

Further, specific examples of the heterocyclic group represented by R'' include a tetrahydropyranyl group and a liminol group.

General formula [X■ In 1, R12, R1, R'' and R
IG 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 acylami/group. Examples include the same alkyl groups, alkenyl groups, and aryl groups as mentioned above.

Further, examples of the halogen atoms include fluorine, chlorine,
Examples include bromine. Further, specific examples of the alkoxy group include a methoxy group, an ethoxy group, a benoloxy group, and the like. Further, said acylami/group is represented by R'NHCO-, where R'
is an alkyl group (e.g. methyl, ethyl, n-propyl,
n-butyl, n-octyl, lert-octyl, benol, etc.), alkenyl groups (e.g. allyl, octenyl, oleyl, etc.), aryl groups (e.g. phenyl, methoxyphenyl, naphthyl, etc.), or It can represent a heterocyclic group (eg, birinol, biriminol groups).

In addition, in the general formula [X■], R'' is an alkyl group,
It represents a hydroxy group, an aryl group, or an alkoxy group, and among these, for an alkyl group or an aryl group, the above R
Specific examples include the same alkyl groups and aryl groups as shown in the figure. As for the alkenyl group of R14, the same alkoxy groups mentioned above for R12, R'', R'' and VR'' can be mentioned.

Among the phenolic compounds or phenyl ether compounds represented by the general formula [X It can be expressed by the formula [X■].

General formula [X~l] i:l(.

In the formula, 826 is an alkyl group (e.g. methyl, ethyl, propyl, n-octyl, Lert-octyl, benol,
hexadecyl), alkenyl groups (e.g. allyl, octenyl, oleyl), aryl groups (e.g. phenyl,
naphthyl) or a heterocyclic group (e.g., tetrahydrobirani, biriminorun). , ethyl, n-butyl, benol), an alkenyl group (e.g. allyl, hexenyl, octenyl) or an alkoxy group (e.g. methoxy, nidoxy, benzyloxy);
9 is a hydrogen atom, an alkyl group (e.g. methyl, ethyl, n
-butyl, benol), alkenyl Jls ((M et! 2-]a benyl, hexenyl, octenyl), or aryl J, 9 (ffll eIf phenyl, /
(toxyphenyl, chlorphenyl, naphthyl).

n? Compounds represented by the general formula No. 145530, British Characteristics Publication 2.077.45
No. 5, No. 2,062,888, U.S. Feature No. 3,764,
No. 337, No. 3,432,300, No. 3,574,6
No. 27, No. 3, No. 573, No. 050, JP-A-52-1
No. 52225, No. 53-20327, No. 53-177
No. 29, No. 55-6321, British Features 1,347,5
No. 56, Publication No. 2.066.975, Special Publication No. 1974-1
No. 2337, No. 48-31625, US Feature 3,70
It also includes compounds described in No. 0,455 and the like.

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

P II-1 H-2 H-3 CH.

H-4 H-5 H-6 PI-1-10 P　H-11 P H-12 H-13 CH3CH.

Pll-14 CI+3 H-15 H-16 H-17 II3 H-18 H-19 H-20 H-21 CH3C113 H-22 H-23 H-24 H-25 1'H-26 PH-28 H-29 CH,C)l.

1) H-30 H-31 H-32 Correction The 71-nol compound or phenyl ether compound represented by the general formula [X■] is the magenta compound represented by the general formula [XI] of the present invention. It can be used in an amount of preferably 200 mol % or less, more preferably 140 mol % or less, based on the dye image stabilizer.

The 7-functional compound and the 7-2-functional compound have the effect of preventing fading of the magenta dye image obtained from the magenta coupler of the present invention, but have almost no effect of preventing discoloration. .

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

In general, the magenta dye image obtained from the magenta coupler not only shows noticeable fading when exposed to light, but also shows noticeable discoloration due to light, and the color tone of the color image changes from magenta to yellowish. nsf of the invention The magenta dye represented by the general formula (XI) [i] The image stabilizer is the phenolic compound of the conventional example in that it can prevent fading and discoloration of the magenta dye image obtained from the magenta coupler due to light. It also has effects that cannot be achieved with magenta dye image stabilizers made of phenyl ether compounds.

The magenta coupler according to the invention and the magenta dye image stabilizer according to the invention are preferably used in the same layer, but the stabilizer may be used in a layer adjacent to the layer in which the coupler is present. .

The silver halide photographic light-sensitive material of the present invention can be, for example, a color negative or Bott film, or a 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 effects of this will be 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 do this, it usually has a structure in which a silver halide emulsion layer containing magenta, yellow and cyan couplers as photographic couplers and a non-light sensitive layer are laminated on a support in an appropriate number and order of layers. However, the number and order of layers may be changed as appropriate depending on the important performance and purpose of use.

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

The silver halide grains used in the silver halide emulsion of the present invention may be obtained by any of the acid method, neutral method, and ammonia method. The method for creating seed particles and the method for growing them may be the same or different.

Silver halide emulsions can be prepared by mixing halide ions and silver ions at the same time, or by mixing one in the presence of the other. ions and silver ions in a mixing pot
The grains may be grown by sequentially and simultaneously adding HypAg in a controlled manner, or the silver halide composition of the grains may be changed using the Comperblanc method after growth.

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

The silver halide grains used in the silver halide emulsion of the present invention are prepared in the process of grain formation and/or grain growth using cadmium salts, zinc salts, miba salts, thallium salts, irinotum salts or complex salts, rhodium salts or complex salts. , iron salts or complex salts,
Metal ions can be added and incorporated into the particles and/or on the particle surfaces, and by placing them in an appropriate reducing atmosphere, reduction sensitizing nuclei can be provided inside the particles and/or on the particle surfaces.

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

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

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

The silver halide grains used in the silver halide emulsion of the present invention may have a regular crystal shape or may have an irregular crystal shape such as a spherical shape or a plate shape. Any ratio of the [100] plane to the (111) plane can be used.

Further, the particles may have a composite form of these crystal forms, or particles of various crystal forms may be mixed.

The silver halide emulsion of the present invention may include a mixture of two or more silver halide crystal agents formed separately.

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

The silver halide emulsion of the present invention can be optically sensitized to a desired wavelength range using a dye known as a sensitizing dye in the photographic industry. The sensitizing dyes may be used alone or in combination of two or more, and together with the sensitizing dyes, dyes that do not themselves have a spectral sensitizing effect, or 1
A supersensitizer, which is a compound that does not naturally absorb visible light and enhances the sensitizing action of the sensitizing dye, may be included in the emulsion.

The silver halide emulsion of the present invention includes steps for producing light-sensitive materials,
During chemical ripening, and/or at the end of chemical ripening, and/or after the end of chemical ripening, silver halide is used to prevent capri during storage or photographic processing, and/or to maintain stable photographic performance. 7 Compounds known in the photographic industry as antifoggants or stabilizers can be added prior to applying the coating.

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

The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material using the silver halide emulsion of the present invention may be formed using a hardening agent that cross-links the baingu (or colloid) and increases the film strength, either alone or in combination. It is hardened by this. As for the hardening agent, it is desirable to add the photosensitive material in an amount equal to the hardening film so that there is no need to add the hardening agent to the processing solution, but it is also possible to add a hardening agent to the processing solution. It is.

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

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

In the emulsion layer of the silver halide color photographic light-sensitive material of the present invention, an aromatic primary amine developer (
For example, a dye-forming coupler is used that forms a dye by performing a coupling reaction with an oxidized product of (l)-phenylenediamine derivative, aminophenol derivative, etc.). The dye-forming couplers are typically selected for each 7L emulsion layer to form a dye that absorbs light in the emulsion layer's light-sensitive spectrum, and for the blue light-sensitive emulsion layer to form a yellow dye-forming dye. A magenta dye-forming coupler is used in the green light-sensitive emulsion layer, and a cyan dye-forming coupler is used in the red light-sensitive emulsion layer. However, depending on the purpose, silver halide color photographic materials may be produced using different combinations from the above.

Examples of yellow dye-forming couplers include acylacetamide couplers (e.g., benzoylaceto 7nilides, pivaloylacetanilides), and magenta dye-forming couplers include, in addition to the couplers of the present invention, 5-pyrazolone couplers and virazolobenlimigsol. There are couplers such as pyrazolotriazole and open-chain acylacetamide couplers, and examples of cyan dye-forming couplers include 7-toll couplers and 7-toll 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. Either the 4-equivalence type, in which the plate ion of the molecule needs to be reduced, or the 2-equivalence type, in which only two molecular silver ions need to be reduced, may be used.

Hydrophobic compounds such as dye-forming couplers that do not need to be attached to the surface of silver herodenide crystals can be treated using various methods such as solid dispersion, latex dispersion, and oil-in-water emulsion dispersion. It can be appropriately selected depending on the chemical structure of the hydrophobic compound such as the coupler. The oil-in-water emulsion dispersion method can be applied to conventionally known methods for dispersing hydrophobic additives such as couplers, and is usually used in a high-boiling organic solvent with a boiling point of about 150°C or higher, and if necessary, a low-boiling point and Or, if water-soluble, dissolve it in combination with a solvent, and use a surfactant in a hydrophilic binder such as an aqueous gelatin solution using a 4'l' machine, homogenizer, colloid mill, 70-noe 7 mixer, ultrasonic device, etc. After emulsifying and dispersing using a dispersion means,
A step of removing the low-boiling organic solvent simultaneously with the dispersion or dispersion may be added to the desired hydrophilic colloid layer.

Examples of high boiling point oils include heptanols N4, heptalic acid esters, phosphoric acid esters, citric acid esters, benzoic acid esters, alkylamides, fatty acid esters, trinosic acid esters, etc. with a boiling point of 15, which do not react with the oxidized form of the developing agent.
An organic solvent having a temperature of 0° C. or higher is used.

Anionic surfactants, nonionic surfactants, and cationic surfactants are used as dispersion aids when hydrophobic compounds are dissolved in a low boiling point solvent alone or in combination with a high boiling point solvent and dispersed in water using machines or ultrasound. Surfactants can be used.

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

The antifoggant may be used in the emulsion layer itself, or an intermediate layer may be provided between adjacent emulsion layers to form an intermediate layer.

In the color light-sensitive material using the halogenated JLT 7L ablation layer of the present invention, an image stabilizer can be used to prevent deterioration of the dye image.

In order to prevent fogging due to discharge caused by the photosensitive material being charged by rubbing, etc. on the hydrophilic colloid layers such as the protective layer and intermediate layer of the photosensitive material of the present invention, and to prevent the deterioration of the image due to U light, ultraviolet rays are used. It may also contain an absorbent.

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

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

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

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

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

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

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

The photographic emulsion layer of the light-sensitive material using the silver halide emulsion of the present invention, the other layers are a baryta layer or an α-olefin polymer, etc., a flexible reflective support such as paper laminated with paper, synthetic paper, cellulose acetate, nitric acid, etc. cellulose, polystyrene,
It can be applied to films made of semi-synthetic or synthetic polymers such as polyvinyl chloride, polyethylene tere-7-thalerate, polycarbonate, and polyamide, as well as rigid bodies such as glass, metal, and ceramics.

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

When coating a photographic light-sensitive material using the silver halide emulsion of the present invention, a thickener may be used to improve coating properties. Rootskin coatings and curtain coatings are particularly useful.

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

As for the exposure time, not only the exposure time of 1 millisecond to 1 second, which is normally used in a camera, but also the exposure time shorter than 1 microsecond, for example, the exposure time of 100 microseconds to 1 microsecond using a cathode #lA tube or xenon flash lamp. It is also possible to make exposures longer than 1 second. The exposure may be performed continuously or intermittently.

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

The aromatic primary amine color developing agents used in the color developing solution of the present invention include known ones that are widely used in various color photographic processes. These developers include ami/7er/-el and p-phenylenenoamine derivatives. These compounds are generally used in the form of salts, such as hydrochlorides or sulfates, since they are more stable than in the free state. These compounds also generally have a concentration of about 0.1 g to about 30 g per Ω of color developer, preferably about 11 r to about 1.58 g per Ω of color developer IQ.
Use at a concentration of

As an aminophenol developer, for example, 0-7 μ/
7e/-, p-7mi/phenol, 5-amino-2-
Oxytoluene, 2-7 minnow 3-oxytoluene, 2
-Oxy-3-7/-1°4-tmethylbenzene and the like are included.

Particularly useful 1a aromatic amino color developers are N, N'
-Dialkyl-9-phenylenenoamine type compound, and the alkyl group and V-phenyl group may be substituted with any substituent.Among them, a particularly useful compound example is N,N'-diethyl-p- phenylenediamine hydrochloride,
N-methyl-p-7 22 diamine salt, N, N'
-Tmethyl-9-phenylene7mine salt 1'! ! salt, 2
-7 minnow 5-(N-ethyl-N-dodecylamine/)-
Toluene, N-ethyl-N-β-7thanesulfone 7midoethyl-3-methyl-4-aminoaniline sulfate, N-
Ethyl-N-β-hydroxyethylaminoaniline, 4
-7mi7-3-methyl-N,N'-noethylaniline,
Examples include 4-ami/-N-(2-7F xyethyl)-N-ethyl-3-methylaniline-p-toluenesulfonate.

The color developing solution used in the process of the present invention contains, in addition to the 1st m aromatic amine color developing agent, various components that are normally added to color developing solutions, such as sodium hydroxide, sodium carbonate, and carbonic acid. Alkaline agents such as potassium, alkali metal sulfites, alkali metal bisulfites,
Alkali metal thiocyanates, alkali metal halides, bennorfurfur, water softeners, thickeners, and the like may optionally be included. This color developer p
The H value is usually 7 or higher, most commonly about 10 to about 13.

In the present invention, after color development, 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. As the bleaching agent used in the bleaching step, a metal complex salt of Iff acid is used, and the metal complex salt is a metal complex salt of gold R produced by development.
It has the effect of oxidizing silver and converting it into silver helodenide, and at the same time coloring the uncolored parts of the coloring agent. Its composition is amide/polycarboxylic acid or organic acids such as oxalic acid and citric acid, and iron, cobalt, It is coordinated with metal ions such as copper. The most preferred organic acids used to form such organic acid metal complexes include polycarboxylic acids or 7-minobolycarboxylic acids. These polycarboxylic acids or ami/polycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts.

In the present invention, after color development processing, processing is performed with a processing liquid having fixing ability, but if the processing liquid having fixing ability is fixing O, "C, bleaching processing is performed before that. The bleaching step A metal complex salt of an organic acid is used as a bleaching agent, 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 part of the coloring agent. And that emotion is Ami/
Polycarboxylic acid or organic acids such as oxalic acid and citric acid to remove iron,
Coordinated with metal ions such as cobalt and copper. The most preferred organic acids used to form such a metal complex salt of a Wi acid include polycarboxylic acids and aminopolycarboxylic acids. These polycarboxylic 1, 2 or 7 minoboricarboxylic acids may be alkali metal salts, -ammonium salts or water-soluble amine salts.

Specific representative examples of these include the following.

[1] Ethylenedi7minetetraacetic acid [2] Nitrilotriacetic acid [3] Imi7noacetic acid [4] Ethylenedi7minetetraacetic acid cinatritum salt [5] Ethylenedi7minetetraacetic acid tetra(trimethylammonium) salt [6] Ethylenenoaminetitraacetic acid Tetrasodium acetate salt (7) di) Sodium lylotriacetate The whitening agent (7) used contains the above-mentioned metal complex salt of an acetic acid as a bleaching agent, and may also contain various additives. As the additive agent, it is particularly desirable to include a rehalogenating agent such as an alkali halide or an ammonium halide, such as potassium bromide, sodium bromide, sodium chloride, or ammonium bromide, a metal salt, or a metal salt.

pH 1f of borate, oxalate, acetate, carbonic acid support, phosphate, etc.! Agents II, alkylamines, polyethylene oxides, and other substances known to be commonly added to bleaching solutions can be added as appropriate.

Further, the constant II solution and the V bleach-fix solution contain 7 ammonium sulfite, potassium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, meta-m sulfite, etc. pH 411 consisting of various salts such as sulfite, boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bisulfite, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, heptadmonium hydroxide, etc. A single type of buffering agent or two or more types of buffering agents may be included.

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

In the present invention, in order to increase the activity of the bleach-fix solution, air or oxygen may be blown into the bleach-fix bath and the bleach-fix replenisher storage tank, if desired, or a suitable oxidizing agent, For example, hydrogen peroxide, bromate, persulfate, etc. can be used as appropriate. According to color photographic materials containing magenta dye image stabilizers, conventionally,
In particular, the fastness of magenta dye images, which have low fastness to light, heat, and humidity, is particularly important.
This effectively prevents Y-stain from occurring in uncolored areas due to humidity.

Furthermore, the light fastness of the dye image is greatly improved by the combined use of a dye image stabilizer represented by the general formula [X■].

〔Example〕

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

Example 1 On a paper support double-sided laminated with polyethylene, gelatin (15,0 mH/100 cm2), the following comparative magenta coupler A (6,0-g/100,100e) was mixed with 2,5-tert-oct/l/hydrochloric acid. /
7 (0.8 kg/100 cm2) in tricresyl 7t and emulsified and dispersed.
Sample 1 was obtained by mixing with 100 cm2), coating and drying.

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

Samples 3, 7 and 11 were obtained in the same manner except that the magenta coupler in sample 1 was replaced with magenta couplers 2, 7 and 115 according to the present invention, respectively.

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

Comparative magenta coupler A O ll After exposing the sample obtained above through an optical wedge according to a conventional method,
The treatment was carried out in the following steps.

[Processing process] Processing temperature Color development during processing
Bleach fixing at 33℃ for 3 minutes and 30 seconds
Wash with water at 33°C for 1 minute and 30 seconds 33°C
Dry for 3 minutes 50-80
℃ 2 minutes The components of each treatment solution are as follows.

[Color developer]

Bennol alcohol 12ml Ethylene glycol 10+eQ Potassium carbonate 25g Sodium bromide
0.6g anhydrous sodium sulfite
2.0g hydroxylamine sulfate
2.5g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 4.5g water was added to make IQ, and the pH was adjusted to 10.2 with NaOH.

[Bleach-fix solution]

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

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

Each of the above-mentioned processed samples was irradiated with a xenon 7-ade meter for 10 days to examine the light fastness of the dye image and the Y-stin of the uncolored area, while each sample was exposed to a high temperature and high humidity atmosphere of 60°C and 80% RH. The dye image was left to stand for 14 days, and the moisture resistance of the dye image and the Y-stain of the uncolored area were examined. The results obtained are shown in Table 1.

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

〔Survival rate〕

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

(ys) Value obtained by subtracting the concentration of Y-stin before the light and moisture resistance test from the concentration of Y-stin after the light and humidity resistance test.

[Degree of discoloration]

(Yellow density) after light emission test at initial density 1.0/
(magenta density) to (yellow density) before light test /
(magenta density), and the larger this value is, the easier it is to change the color tone from magenta to yellowish.

ff1l Table 1 As is clear from Table 1, sample 3.7.11 prepared using the coupler of the present invention is different from the conventional 4-equivalent type 3
-7 Nilino 1,2-pyrazolo-5-one type coupler compared to sample 1, the light and moisture resistance tests showed Y
It can be seen that S is extremely generated, 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 exposed to light and discolors and fades. Sample 4, 8.12 is
This sample was prepared by using the coupler of the present invention in combination with the well-known magenta dye image stabilizer PH-13, and although it is true that this greatly improves the fading of the dye image due to light, there is no discoloration. cannot be improved.

On the other hand, in Samples 5 and 9.13 prepared using the coupler and dye image stabilizer of the present invention, the color change and fading of the dye image were small in the resistance test against light, heat, and humidity, and the Y - It turns out that Stin also doesn't occur.

This was not possible with the conventional combination of a 4-equivalent type 3-anisoy 1t2-pyrazolo-5-one type coupler and a dye image stabilizer (Sample 2).

In addition to the coupler and magenta dye image stabilizer according to the present invention, sample 6 further contained a conventional magenta dye image stabilizer. It can be seen that for 1O and 14, the residual rate of the dye in the light test was further improved significantly.

Example 2 The coupler and magenta dye image stabilizer combinations shown in Table 2 were coated exactly as in Example 1, and sample 1
5 to 30 were generated. Samples 15-30 were processed as described in Example 1. Further, these samples were subjected to a light resistance test and a moisture resistance FJ test in the same manner as in Example 1, and the results shown in Table 2 were obtained.

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

Table 2 As is clear from Table 2, the conventionally used
4 When the conventional 3-anili/-1,2-pyrazolo-5-one type coupler was used in combination with the magenta dye image stabilizer of the present invention (Samples-15 and 16), and when the conventional coupler of the present invention was used, 11 magenta dyes used! When an image stabilizer was used in combination (sample = 19.20, 21.22), the resistance to U, discoloration in the test, fading, YS and Vit of the uncolored area
It can be seen that it is not possible to improve all of the YS in the wet test, and that all of the aforementioned improvements can only be achieved by using the coupler of the present invention in combination with the magenta dye image stabilizer of the present invention.

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

1st/PI: Blue-sensitive silver halide emulsion layer Yellow 17
α-pivaloyl-α-(2,4-dioxo-1-bennolimidazolinon-3-yl)-2-chloro-5-[γ-(2,4-not-7mil) 72/Kishi)
6.8 mg/100
e■2, blue-sensitive silver chlorobromide emulsion (containing 85 mol% i bromide)
The coating amount was 3.2a+g/100cTs'' in terms of silver, 3.5mg/100cTs'' of di-butyl 7tate, and 13.5ur/100c+a'' of gelatin.

2nd layer: Middle layer 2.5-octylhydroquinone 0.5mg
/100cm”, Nobutyl 7 Talate 0.5B/
100 cffi2 and gelatin 9.0g/1010
It was coated so that it was 0c.

Third layer: Green-sensitive silver halide emulsion layer The magenta coupler 36 is 3.5B/100c++*
2. Blue-sensitive silver chlorobromide emulsion (containing 80 mol% silver bromide) in terms of silver: 2.5+g/100cm", di-butyl 7
Tallate was coated at 3.0 mg/100 cm" and gelatin was coated at H,0+B/100 cm2.

4th layer: Intermediate layer UV absorber 2-(2-hydroxy-3-5ee-phthyl-5-t-14-ruphenyl)benztriazole 7.0mg/100c2, nobutyl 7 tallate 6.0ng/100cm ", 2,5-no, 1 octylhydroquinone 0.5mg/100es2 and gelatin 12.OmH/100cm"! This was painted.

5th layer: Red-sensitive silver halide milk-closed layer cyan coupler containing 4.2-[α-(2,4-not-bentyl-7/xy)butanamide]-4,6-nochloro-5-ethyl-7enol. 2-g/to.

cI112 tricrenoraos 7ate”-511g
/ 100c@” and gelatin at 11.5-g/101
It was painted so that it became 00e.

PIS6N = Protective layer gelatin 8. It was coated so that it was Omg/100es2.

In the above sample 31, the dye image stabilizer of the present invention was added to the third layer in the proportions shown in Table 3, and multilayer sample 32
40 was prepared, exposed and processed in the same manner as in Example 1, and then subjected to a light emission test (irradiated to a xenon 7 ademeter for 15 days). The results are also shown in the rjS3 table.

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

Claims (1)

[Claims] At least one coupler represented by the following general formula [I]
and at least one compound represented by the following general formula [X I ]. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. It's okay. X represents a hydrogen atom or a substituent that can be separated by reaction with an oxidized product of a color developing agent. Moreover, R represents a hydrogen atom or a substituent. ] General formula [X I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R^1 is a hydrogen atom, an alkyl group, an alkenyl group,
Represents an aryl group, acyl group, cycloalkyl group or heterocyclic group, R^2 is a hydrogen atom, halogen atom, alkyl group, alkenyl group, aryl group, aryloxy group, acyl group, acylamino group, acyloxy group, sulfonamide group, cycloalkyl group or alkoxycarbonyl group. R^3 represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, an acyl group, an acylamino group, a sulfonamide group, a cycloalkyl group, or an alkoxycarbonyl group. R^4 is a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkenyloxy group, a hydroxy group, an aryl group, an aryloxy group, an acyl group, an acylamino group, an acyloxy group, a sulfonamide group, or an alkoxycarbonyl group. represent. Further, R^1 and R^2 may be ring-closed with each other to form a 5- or 6-membered ring. At that time, R^3 and R^4 are hydrogen atoms, halogen atoms,
It represents an alkyl group, an alkenyl group, an alkoxy group, an alkenyloxy group, a hydroxy group, an aryl group, an aryloxy group, an acyl group, an acylamino group, an acyloxy group, a sulfonamido group, or an alkoxycarbonyl group. Y represents an atomic group necessary to form a chroman or coumaran ring. ]