JPH07119945B2 - Silver halide photographic light-sensitive material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial application] The present invention relates to a silver halide photographic light-sensitive material, and more specifically, to image quality such as color reproducibility and whiteness, and physical characteristics such as glossiness and pressure resistance increase / decrease. The present invention relates to an improved silver halide photographic light-sensitive material.

BACKGROUND OF THE INVENTION Conventionally, a silver halide color photographic light-sensitive material for printing is imagewise exposed and color-developed to cause a coupling reaction between an oxidant of an aromatic primary amine developing agent and a color-forming agent. , For example, indophenol, indoaniline,
A dye image is formed by producing a dye such as indamine, azomethine, phenoxazine, or phenazine.

In such a photographic system, a color reproduction method by a subtractive color method is usually adopted, and each of the blue-sensitive, green-sensitive and red-sensitive photosensitive silver halide emulsion layers is provided with respective couplers which develop yellow, magenta and cyan. A silver halide color photographic light-sensitive material contained is used.

Examples of the coupler used for forming the yellow dye image include an acylacetanilide type coupler and the like, and examples of the magenta dye image forming coupler include a pyrazolone, a pyrazolobenzimidazole, a pyrazolotriazole or an indazolone type coupler. Further, as the cyan dye image forming coupler, for example, a phenol or naphthol type coupler is generally used.

It is desired that the dye image for printing thus obtained has little fading or discoloration even when exposed to light or stored in a dark place for a long time. Further, it is desired that the uncolored portion (hereinafter referred to as a white background) of the print does not turn yellow even when exposed to light or stored in a dark place for a long time (hereinafter referred to as Y-stain).

In particular, the Y-stain has a great influence on the print quality and has been regarded as important as the discoloration and fading of the dye image. In order to reduce the generation of Y-stain, studies have been conducted on an antioxidant and a magenta coupler.
In particular, it has become clear that further studies on magenta couplers are necessary to prevent the generation of Y-stain.

coming.

Conventionally, pyrazolone-based magenta couplers generally used for color photographic light-sensitive materials for printing, especially 3-
Anilino-1,2-pyrazolo-5-one magenta coupler has good color forming property, and the spectral absorption range of the color forming dye is desirable,
It is known that there is little adverse effect on silver halide such as fog, and it is described, for example, in US Pat. No. 2,343,703 and British Patent 1,059,994.

However, this magenta coupler has a drawback that a large amount of Y-stain is generated on a white background when stored in a dark place for a long time.

As a result of research on various magenta couplers up to the present, magenta couplers having a pyrazolotriazole skeleton described in British Patent 1,047,612, in particular, U.S. Pat.
1-pyrazolo- [3,2-C] -s-
It has been found that the triazole coupler has a very small amount of Y-stain generated on a white background when stored in a dark place for a long time, and has a small side absorption around 430 nm of the formed coloring dye, which is preferable for color reproduction.

However, this pyrazolotriazole-based magenta coupler has a drawback that fog increases during the storage period after the production of the color photographic light-sensitive material until it is used (hereinafter, referred to as increase in raw sample storage fog). . In recent years, small-scale production laboratories called mini laboratories have been increasing as laboratories for color printing.

However, especially in this minilab, the equipment for refrigerating the color photographic light-sensitive material is insufficient and it is used for a long time for a small-scale production. Not suitable for storage. In particular, raw sample storability is an important characteristic for stably obtaining good image quality, and there is an urgent need to ensure the storability of raw samples in a minilab at a constant state.

In recent years, the demand for color photographic light-sensitive materials for printing has grown year by year, and manufacturers are taking steps such as increasing the coating speed in order to secure the production volume and introducing new equipment. The increase in speed is being highlighted. However, due to this increase in coating speed, the amount of charge on the photosensitive material increases, and light emission fog (also called static fog) easily occurs, which is a major obstacle to increase in coating speed. On the other hand, even in the laboratory, it is inevitable to improve productivity in order to meet the demand of customers, and therefore high-speed printers and rapid processing systems are being introduced.

However, the transportability suitable for the printing speed of the photosensitive material in a high-speed printer is an important performance, and it is necessary to improve the slipperiness of the surface of the photosensitive material.

Further, in a rapid processing system, processing time is shortened and processing at a high temperature is performed, so that scratch resistance or glossiness is particularly required to be improved.

That is, a physically tough color photographic light-sensitive material for printing is desired.

Under such circumstances, the technique of incorporating fine particle powder into the protective layer can effectively achieve the above-mentioned problems of antistatic property, slip property, and adhesion property improvement, for example, JP-A-53-70426. , 53-116143, 54-94319, 55-16
1230, 57-14835, 58-66937, 58-153925
No. 58-163936, etc., it is well known in the photographic material manufacturer.

However, it has been found that the technique of incorporating the fine particle powder in the protective layer has a fatal drawback for the photosensitive material for printing, that is, deterioration of gloss over time after printing.

On the other hand, in the photographic layer of a silver halide color photographic light-sensitive material,
Although a hydrophilic colloid such as gelatin is used as a binder, it is resistant to the rapid processing in recent years, and is generally hardened in accordance with the demand from the viewpoint of productivity.

Examples of the hardener used for this hardening treatment include, for example, U.S. Pat. Nos. 3,325,287, 3,645,743 and JP-A-57
-40244 etc., chlorotriazine hardeners, U.S. Pat. No. 3,490,911 and West German Patent (OLS) No. 2,749,260 vinyl sulfone hardeners, other aldehydes, epoxy-based hardeners, etc. Is mentioned.

Among them, chlorotriazine-based hardeners are excellent in rapid hardenability, film gloss and film scratching strength, and are suitable for occupational safety and health.
It has been studied as a hardener which is preferable also from the viewpoint of environmental pollution, and these matters are disclosed in JP-B-47-6151 and JP-A-48-19920.
No. 8, No. 52-128130, No. 52-130326 and No. 56-1043.

In addition, the use of a chlorotriazine-based hardener can effectively reduce the increase in fog during storage of raw samples, which is one of the major drawbacks of the above-mentioned pyrazolotriazole-based magenta couplers.

However, by combining a chlorotriazine-based hardener and a pyrazolotriazole-based magenta coupler, pressure is applied to the silver halide photographic light-sensitive material when it is wet (for example, during processing), so that fog tends to occur remarkably. It was found (hereinafter referred to as wet pressure fog).

This phenomenon has been well known as a photographic pressure effect, and for example, TH James: The Theory of photographic pro.
cess 4th edition, Macmillan Publishers, New York, Item 24 and D. Dautrich, F. Granjer and E. Moiser: J. Photo.Sci,
22, 221 (1973), etc.

The generation of the wet pressure fog significantly lowers the print yield and is a serious problem particularly in high temperature processing or rapid processing.

[Object of the Invention] An object of the present invention is to provide a silver halide photographic light-sensitive material for printing, which is excellent in image storability, image quality and physical properties of a film.

More specifically, the present invention provides a silver halide photographic light-sensitive material for printing, which is less likely to cause yellow stain during storage in a dark place, and is excellent in color reproducibility, white background, slipperiness, adhesiveness, gloss and wet pressure fog resistance. Especially.

[Structure of the Invention] As a result of intensive studies, the present inventors have found that the above-mentioned object of the present invention is to use a specific magenta coupler and a chlorotriazine-based hardener, and further to form a fine particle powder having an average particle diameter of 0.5 to 10 μm in the protective layer. It has been found to be achieved by including it.

That is, the above object of the present invention is to provide a silver halide photographic light-sensitive material having at least one silver halide emulsion layer and a non-photosensitive layer on a reflective support, wherein at least one of the silver halide emulsion layers has the following general formula: [I] containing a magenta coupler, and the non-photosensitive layer at the farthest position on the silver halide emulsion layer side from the support contains fine particle powder having an average particle size of 0.5 to 10 μm. ,
The silver halide emulsion layer containing at least the magenta coupler and the non-photosensitive layer containing the fine grain powder are at least selected from the hardeners represented by the following general formulas [HI] and [H-II]. It is achieved by a silver halide photographic light-sensitive material which is hardened with one hardener.

General formula [I] [In the formula, Z represents a non-metal atom group necessary for forming a nitrogen-containing heterocycle, and the ring formed by Z may have a substituent.

X represents a hydrogen atom or a group which is released by a reaction with an oxidized product of a color developing agent.

R represents a hydrogen atom or a substituent. ] General formula [HI] [Wherein R ₁ is a chlorine atom, a hydroxy group, an alkyl group, an alkoxy group, an alkylthio group, an -OM group (M represents a monovalent metal atom), -NR'R "or -NHCOR (R ',
R ″ and R each represent a hydrogen atom, an alkyl group or an aryl group), and R ₂ has the same meaning as R ₁ excluding a chlorine atom.] General formula [H-II] [Wherein R ₃ and R ₄ represent a chlorine atom, a hydroxy group, an alkyl group, an alkoxy group, or an -OM group (M represents a monovalent metal atom), and -Q- and -Q'- respectively represent Represents an -O-, -S- or -NH- linking group, L represents an alkylene group or an arylene group, and l and m
Represents 0 or 1, respectively. [Specific Structure of the Invention] In the silver halide photographic light-sensitive material of the present invention, at least one of the silver halide emulsion layers contains a magenta coupler represented by the general formula [I] of the present invention and, if necessary, an additive. A fine particle powder having an average particle size of 0.5 to 10 μm is contained in the non-photosensitive layer which is the farthest position on the silver halide emulsion layer side as viewed from the support (hereinafter referred to as the protective layer of the present invention).
Hydrophilic binder and, if necessary, containing additives,
At least the magenta coupler-containing layer and the protective layer are hardened with at least one hardener selected from the hardeners represented by the general formulas [HI] and [H-II].

The magenta coupler of the formula [I] used in at least one of the silver halide emulsion layers of the silver halide photographic light-sensitive material of the present invention is generally used in combination with a green light-sensitive silver halide emulsion.

These magenta couplers can be dispersed in a silver halide emulsion by a solid dispersion method, a latex dispersion method, an oil-in-water type emulsion dispersion method or the like. As the oil-in-water type emulsion dispersion method, a conventionally known method can be applied, and a magenta coupler is usually used.
Dissolve in a high-boiling point organic solvent of 150 ° C or higher with a low-boiling point solvent as required, and stirrer, homogenizer, ultrasonic disperser, etc. using a surfactant in a hydrophilic binder such as an aqueous gelatin solution. To be emulsified and dispersed.

Next, the magenta coupler used in the present invention will be specifically described.

The general formula [I] according to the present invention In the magenta coupler represented by, Z represents a non-metal atom group necessary for forming a nitrogen-containing heterocycle, and the ring formed by Z may have a substituent.

X represents a hydrogen atom or a substituent capable of splitting off upon reaction with an oxidized product of a color developing agent.

R represents a hydrogen atom or a substituent.

Examples of the substituent represented by R include a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a heterocyclic group,
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, amino group, acylamino group, sulfonamide group, imide group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkoxycarbonyl group, aryloxycarbonyl group,
Examples thereof include an alkylthio group, an arylthio group and a heterocyclic thio group.

Examples of the halogen atom include a chlorine atom and a bromine atom, and a chlorine atom is particularly preferable.

The alkyl group represented by R has 1 to 32 carbon atoms, and the alkenyl group and the alkynyl group have 2 to 32 carbon atoms.
As the cycloalkyl group and cycloalkenyl group, those having 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms are preferable, and the alkyl group, alkenyl group and alkynyl group may be linear or branched.

Further, these alkyl group, alkenyl group, alkynyl group, cycloalkyl group, and cycloalkenyl group are substituents [for example, aryl, cyano, halogen atom, heterocycle,
In addition to cycloalkyl, cycloalkenyl, spiro compound residue, bridged hydrocarbon compound residue, those substituted through carbonyl group such as acyl, carboxy, carbamoyl, alkoxycarbonyl, aryloxycarbonyl, and further through hetero atom Substituents (specifically those substituted through an oxygen atom such as hydroxy, alkoxy, aryloxy, heterocyclic oxy, siloxy, acyloxy, carbamoyloxy, nitro, amino (including dialkylamino, etc.), sulfa Substituted through a nitrogen atom such as moylamino, alkoxycarbonylamino, aryloxycarbonylamino, acylamino, sulfonamide, imide and ureido, alkylthio, arylthio, heterocyclic thio, sulfonyl,
Those substituted through a sulfur atom such as sulfinyl and sulfamoyl, those substituted through a phosphorus atom such as phosphonyl, and the like}].

Specifically, for example, methyl group, ethyl group, isopropyl group, t-butyl group, pentadecyl group, heptadecyl group,
1-hexylnonyl group, 1,1′-dipentylnonyl group,
2-chloro-t-butyl group, trifluoromethyl group, 1
-Ethoxytridecyl group, 1-methoxyisopropyl group, methanesulfonylethyl group, 2,4-di-t-amylphenoxymethyl group, anilino group, 1-phenylisopropyl group, 3-m-butanesulfonaminophenoxypropyl group, 3-4 ′-{α- [4 ″ (p-hydroxybenzenesulfonyl) phenoxy] dodecanoylamino}
Phenylpropyl group, 3- {4 '-[α- (2 ", 4"-
Di-t-amylphenoxy) butanamide] phenyl}
-Propyl group, 4- [α- (o-chlorophenoxy) tetradecanamidophenoxy] propyl group, allyl group,
Examples thereof include a cyclopentyl group and a cyclohexyl group.

The aryl group represented by R is preferably a phenyl group and may have a substituent (for example, an alkyl group, an alkoxy group, an acylamino group, etc.).

Specifically, a phenyl group, a 4-t-butylphenyl group,
2,4-di-t-amylphenyl group, 4-tetradecanamidophenyl group, hexadecyloxyphenyl group, 4'-
[Α- (4 ″ -t-butylphenoxy) tetradecanamide] phenyl group and the like.

The heterocyclic group represented by R is preferably a 5- to 7-membered heterocyclic group, which may be substituted or may be condensed.
Specific examples thereof include a 2-furyl group, a 2-thienyl group, a 2-pyrimidinyl group, a 2-benzothiazolyl group.

Examples of the acyl group represented by R include acetyl group, phenylacetyl group, dodecanoyl group, α-2,4-di-t.
Examples thereof include an alkylcarbonyl group such as an amylphenoxybutanoyl group, a benzoyl group, a 3-pentadecyloxybenzoyl group, and an arylcarbonyl group such as a p-chlorobenzoyl group.

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

Examples of the sulfinyl group represented by R include an alkylsulfinyl group such as an ethylsulfinyl group, an octylsulfinyl group and a 3-phenoxybutylsulfinyl group, an arylsulfinyl group such as a phenylsulfinyl group and an m-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, an aryloxyphosphonyl group such as a phenoxyphosphonyl group, and a phenylphosphonyl group. Arylphosphonyl groups such as

The carbamoyl group represented by R may be substituted with an alkyl group, an aryl group (preferably a phenyl group) or the like,
For example, N-methylcarbamoyl group, N, N-dibutylcarbamoyl group, N- (2-pentadecyloctylethyl)
Carbamoyl group, N-ethyl-N-dodecylcarbamoyl group, N- {3- (2,4-di-t-amylphenoxy)
Propyl} carbamoyl group and the like.

The sulfamoyl group represented by R may be substituted with an alkyl group, an aryl group (preferably a phenyl group) or the like,
For example, N-propylsulfamoyl group, N, N-diethylsulfamoyl group, N- (2-pentadecyloxyethyl) sulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, N-phenylsulfamoyl group Groups and the like.

Examples of the spiro compound residue represented by R include spiro [3.3] heptan-1-yl.

Examples of the bridged carbonized compound residue represented by R include bicyclo [2.2.1] heptan-1-yl and tricyclo [3.3.1.1].
^3,7 ] Decan-1-yl, 7,7-dimethyl-bicyclo [2.
2.1] Heptan-1-yl and the like.

The alkoxy group represented by R may be further substituted with the above-mentioned substituents for the alkyl group, for example, a methoxy group, a propoxy group, a 2-ethoxyethoxy group,
Pentadecyloxy group, 2-dodecyloxyethoxy group, phenethyloxyethoxy group and the like can be mentioned.

The aryloxy group represented by R is preferably phenyloxy, and the aryl nucleus may be further substituted with the substituent or the atom described above for the aryl group,
For example, phenoxy group, pt-butylphenoxy group, m
-Pentadecylphenoxy group and the like.

The heterocyclic oxy group represented by R is preferably a 5- to 7-membered heterocyclic ring, and the heterocyclic ring may further have a substituent, for example, 3,4,5,6-tetrahydropyrani Ru-2-oxy group, 1-phenyltetrazole-5
An oxy group.

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

Examples of the acyloxy group represented by R include an alkylcarbonyloxy group, an arylcarbonyloxy group, and the like, which may further have a substituent, and specifically include an acetyloxy group and an α-chloroacetyloxy group. , A benzoyloxy group and the like.

The carbamoyloxy group represented by R may be substituted with an alkyl group, an aryl group or the like, and examples thereof include an N-ethylcarbamoyloxy group, an N, N-diethylcarbamoyloxy group and an N-phenylcarbamoyloxy group. To be

The amino group represented by R may be substituted with an alkyl group, an aryl group (preferably a phenyl group) or the like, and examples thereof include an ethylamino group, anilino group, m-chloroanilino group,
Examples thereof include a 3-pentadecyloxycarbonylanilino group and a 2-chloro-5-hexadecanamide anilino group.

Examples of the acylamino group represented by R include an alkylcarbonylamino group, an arylcarbonylamino group (preferably a phenylcarbonylamino group), and the like, which may further have a substituent, specifically, an acetamide group, α- Ethylpropanamide group, N-phenylacetamide group,
Dodecanamide group, 2,4-di-t-amylphenoxyacetamide group, α-3-t-butyl 4-hydroxyphenoxybutanamide group and the like can be mentioned.

Examples of the sulfonamide group represented by R include an alkylsulfonylamino group and an arylsulfonylamino group, which may further have a substituent. Specifically, a methylsulfonylamino group, a pentadecylsulfonylamino group,
Examples thereof include a benzenesulfonamide group, a p-toluenesulfonamide group and a 2-methoxy-5-t-amylbenzenesulfonamide group.

The imide group represented by R may be an open chain type, a cyclic type, or may have a substituent, and examples thereof include a succinimide group, a 3-heptadecylsuccinimide group, a phthalimide group, and glutar. Examples thereof include an imide group.

The ureido group represented by R may be substituted with an alkyl group, an aryl group (preferably a phenyl group) or the like, and examples thereof include N-ethylureido group, N-methyl-N-decylureido group and N-phenylureido group. , Np-tolylureido group and the like.

The sulfamoylamino group represented by R is an alkyl group,
It may be substituted with an aryl group (preferably a phenyl group) and the like, and examples thereof include an N, N-dibutylsulfamoylamino group, an N-methylsulfamoylamino group and an N-phenylsulfamoylamino group. .

As the alkoxycarbonylamino group represented by R,
It may further have a substituent, for example, a methoxycarbonylamino group, a methoxyethoxycarbonylamino group,
Examples include octadecyloxycarbonylamino group.

The aryloxycarbonylamino group represented by R may have a substituent, and examples thereof include a phenoxycarbonylamino group and a 4-methylphenoxycarbonylamino group.

The alkoxycarbonyl group represented by R may further have a substituent, for example, a methoxycarbonyl group, a butyloxycarbonyl group, a dodecyloxycarbonyl group, an octadecyloxycarbonyl group, an ethoxymethoxycarbonyloxy group, a benzyloxycarbonyl group. Etc.

The aryloxycarbonyl group represented by R may further have a substituent, for example, a phenoxycarbonyl group,
Examples thereof include p-chlorophenoxycarbonyl group and m-pentadecyloxyphenoxycarbonyl group.

The alkylthio group represented by R may further have a substituent, and examples thereof include an ethylthio group, a dodecylthio group, an octadecylthio group, a phenethylthio group and 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,
Examples thereof include p-methoxyphenylthio group, 2-t-octylphenylthio group, 3-octadecylphenylthio group, 2-carboxyphenylthio group and p-acetaminophenylthio group.

The heterocyclic thio group represented by R is preferably a 5- to 7-membered heterocyclic thio group, and may further have a condensed ring or may have a substituent. Examples thereof include a 2-pyridylthio group, a 2-benzothiazolylthio group, and a 2,4-diphenoxy-1,3,5-triazole-6-thio group.

Examples of the substituent which can be removed by the reaction with the oxidized product of the color developing agent represented by X include, for example, halogen atom (chlorine atom, bromine atom, fluorine atom, etc.), carbon atom, oxygen atom, sulfur atom or nitrogen atom. Groups which substitute by

Examples of the group substituting through a carbon atom include a carboxyl group and other general formulas. (R ₁ ′ has the same meaning as R above, Z ′ has the same meaning as Z above, and R ₂ ′ and R ₃ ′ represent a hydrogen atom, an aryl group, an alkyl group or a heterocyclic group). , A hydroxymethyl group, and a triphenylmethyl group.

Examples of the group substituting through an oxygen atom include an alkoxy group, an aryloxy group, a heterocyclic oxy group, an acyloxy group, a sulfonyloxy group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an alkyloxalyloxy group, an alkoxyoxalyloxy group. Is mentioned.

The alkoxy group may further have a substituent, for example,
Examples thereof include an ethoxy group, a 2-phenoxyethoxy group, a 2-cyanoethoxy group, a phenethyloxy group and a p-chlorobenzyloxy group.

The aryloxy group is preferably a phenoxy group, and the aryl group may further have a substituent.
Specifically, phenoxy group, 3-methylphenoxy group, 3
-Dodecylphenoxy group, 4-methanesulfonamidophenoxy group, 4- [α- (3'-pentadecylphenoxy) butanamide] phenoxy group, hexdecylcarbamoylmethoxy group, 4-cyanophenoxy group, 4-methanesulfonylphenoxy group , 1-naphthyloxy group, p
-Methoxyphenoxy group and the like.

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

Examples of the acyloxy group include an acetoxy group, an alkylcarbonyloxy group such as a butanoloxy group, an alkenylcarbonyloxy group such as a cinnamoyloxy group,
An arylcarbonyloxy group such as a benzoyloxy group can be mentioned.

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

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

Examples of the aryloxycarbonyl group include a phenoxycarbonyloxy group and the like.

Examples of the alkyloxalyloxy group include a methyloxalyloxy group.

Examples of the alkoxyoxalyloxy group include an ethoxyoxalyloxy group and the like.

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

Examples of the alkylthio group include a butylthio group, a 2-cyanoethylthio group, a phenethylthio group and a benzylthio group.

Examples of the arylthio group include phenylthio group, 4-methanesulfonamidophenylthio group, 4-dodecylphenethylthio group, 4-nonafluoropentanamidephenethylthio group, 4-carboxyphenylthio group, 2-ethoxy-5-t-butyl. Examples thereof include a phenylthio group.

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

Examples of the alkyloxythiocarbonylthio group include dodecyloxythiocarbonylthio group.

Examples of the group substituting through the nitrogen atom include those represented by the general formula The items shown in are listed. Here, R ₄ ′ and R ₅ ′ 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, an aryloxycarbonyl group, an alkoxycarbonyl group, and R ₄ ′ and R ₅ ′ may combine with each other to form a heterocycle. However, neither R ₄ ′ nor R ₅ ′ is a hydrogen atom.

The alkyl 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,
Alkoxy group, aryloxy group, alkylthio group, arylthio group, alkylamino group, arylamino group,
Acylamino group, sulfonamide group, imino group, acyl group, alkylsulfonyl group, arylsulfonyl group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkyloxycarbonylamino group, aryloxycarbonylamino group, hydroxyl group , A carboxyl group, a cyano group, and a halogen atom. Specific examples of the alkyl group include an ethyl group, an octyl group, a 2-ethylhexyl group, and a 2-chloroethyl group.

The aryl group represented by R ₄ ′ or R ₅ ′ has 6 carbon atoms.
To 32, especially a phenyl group and a naphthyl group are preferable, and the aryl group may have a substituent.
Examples of the substituent for the alkyl group represented by R ₄ ′ or R ₅ ′ and the alkyl group are mentioned. Specific examples of the aryl group include a phenyl group, a 1-naphthyl group, and a 4-methylsulfonylphenyl group.

The heterocyclic group represented by R ₄ ′ or R ₅ ′ is preferably a 5- or 6-membered heterocyclic group, which may be a condensed ring or may have a substituent. Specific examples thereof include 2-furyl group, 2-quinolyl group, 2-pyrimidyl group, 2-benzothiazolyl group, 2
A viridyl group and the like.

The sulfamoyl group represented by R ₄ ′ or R ₅ ′ is N
-Alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-diarylsulfamoyl group and the like can be mentioned, and these alkyl groups and aryl groups are the above-mentioned alkyl groups. And may have a substituent described for the aryl group. Specific examples of the sulfamoyl group include N, N-diethylsulfamoyl group, N-methylsulfamoyl group, N-dodecylsulfamoyl group, and Np-tolylsulfamoyl group.

The carbamoyl group represented by R ₄ ′ or R ₅ ′ is N-
Alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group and the like can be mentioned, and these alkyl groups and aryl groups can have the substituents mentioned above for the alkyl group and aryl group. You may have. Specific examples of the carbamoyl group include, for example, N, N-diethylcarbamoyl group, N-
Methylcarbamoyl group, N-dodecylcarbamoyl group,
Examples thereof include an Np-cyanophenylcarbamoyl group and an Np-tolylcarbamoyl group.

Examples of the acyl group represented by R ₄ ′ or R ₅ ′ include an alkylcarbonyl group, an arylcarbonyl group, and a heterocyclic carbonyl group, the alkyl group, the aryl group,
The heterocyclic group may have a substituent. Specific examples of the acyl group include, for example, a hexafluorobutanoyl group, a 2,3,4,5,6-pentafluorobenzoyl group,
An acetyl group, a benzoyl group, a naphthoyl group, a 2-furylcarbonyl group and the like can be mentioned.

Examples of the sulfonyl group represented by R ₄ ′ or R ₅ ′ include an alkylsulfonyl group, an arylsulfonyl group and a heterocyclic sulfonyl group, which may have a substituent, and specific examples thereof include ethanesulfonyl group. Group, benzenesulfonyl group, octanesulfonyl group, naphthalenesulfonyl group, p-chlorobenzenesulfonyl group and the like.

The aryloxycarbonyl group represented by R ₄ ′ or R ₅ ′ may have the above-mentioned aryl group as a substituent, and specific examples thereof include a phenoxycarbonyl group.

The alkoxycarbonyl group represented by R ₄ ′ or R ₅ ′ may have the substituents described above for the alkyl group, and specific examples include a methoxycarbonyl group, a dodecyloxycarbonyl group, a benzyloxycarbonyl group. Etc.

The heterocycle formed by combining R ₄ ′ and R ₅ ′ is 5 to
A 6-membered one is preferable, and it may be saturated or unsaturated,
Further, it may or may not have aromaticity, and may be a condensed ring. Examples of the heterocycle include N-phthalimide group, N-succinimide group, 4-N-urazolyl group, 1-N-hydantoinyl group, 3-N-2,4-dioxooxazolidinyl group, 2- N-1,1-dioxo-3-
(2H) -oxo-1,2-benzthiazolyl group, 1-pyrrolyl group, 1-pyrrolidinyl group, 1-pyrazolyl group, 1-
Pyrazolidinyl group, 1-piperidinyl group, 1-pyrrolinyl group, 1-imidazolyl group, 1-imidazolinyl group, 1
-Indolyl group, 1-isoindolinyl group, 2-isoindolyl group, 2-isoindolinyl group, 1-benzotriazolyl group, 1-benzimidazolyl 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, 2-1H-pyridone group , A phthalazine group, a 2-oxo-1-piperidinyl group, and the like, and these heterocyclic groups are an alkyl group, an aryl group, an alkyloxy group, an aryloxy group, an acyl group, a sulfonyl group, an alkylamino group, an arylamino group, Substituted with an acylamino group, sulfoneamino group, carbamoyl group, sulfamoyl group, alkylthio group, arylthio group, ureido group, alkoxycarbonyl group, aryloxycarbonyl group, imide group, nitro group, cyano group, carboxyl group, halogen atom, etc. May be.

The nitrogen-containing heterocycle formed by Z or Z'includes a pyrazole ring, an imidazole ring, a triazole ring, a tetrazole ring, and the like, and the substituent which the ring may have is the same as those described above for R. Is mentioned.

In addition, the substituents (for example, R, R _{1 to} R ₈ ) on the heterocycle in the general formula [I] and the general formulas [II] to [VIII] described later are Part (where R ″, X and Z ″ are R in the general formula [I],
Synonymous with X and Z. A), a so-called bis type coupler is formed, which is of course included in the present invention. Also, Z, Z ′,
The ring formed by Z ″ and Z ₁ described later may be condensed with another ring (for example, a 5- to 7-membered cycloalkene). For example, in the general formula [V], R ₅ and R ₆ are In the general formula [VI], R ₇ and R ₈ may combine with each other to form a ring (for example, a 5- to 7-membered cycloalkene or benzene).

What is represented by the general formula [I] is more specifically represented by, for example, the following general formulas [II] to [VII].

General formula (II) General formula (III) General formula (IV) General formula [V] General formula [VI] General formula (VII) In the general formulas [II] to [VII], R _{1 to} R ₈ and X have the same meanings as R and X.

Further, among the general formulas [I], those represented by the following general formula [VIII] are preferable.

General formula [VIII] In the formula, R ₁ , X and Z ₁ have the same meanings as R, X and Z in the formula [I].

Among the magenta couplers represented by the general formulas [II] to [VII], the magenta coupler represented by the general formula [II] is particularly preferable.

Regarding the substituents on the heterocycle in the general formulas [I] to [VIII], R in the general formula [I] and R ₁ in the general formulas [II] to [VIII] are the following condition 1 The following conditions 1 and 2 are more preferable.
The following conditions 1 and 2 are particularly preferable.
And 3 are satisfied.

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

Condition 2 Only one hydrogen atom is bonded to the carbon atom or none is bonded.

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

Most preferable as the substituents R and R ₁ on the heterocycle are those represented by the following general formula [IX].

General formula [IX] In the formula, R ₉ , R ₁₀ and R ₁₁ are each a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an acyl group, a sulfonyl group, a sulfinyl group. , 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, amino group , An acylamino group, a sulfonamide group, an imide group,
Ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group,
It represents an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylthio group, an arylthio group, or a heterocyclic thio group, and at least two of R ₉ , R ₁₀ and R ₁₁ are not hydrogen atoms.

Two of R ₉ , R ₁₀ and R ₁₁ , for example, R ₉ and R ₁₀ may combine to form a saturated or unsaturated ring (eg cycloalkane, cycloalkene, heterocycle), In addition to the ring
R ₁₁ may combine to form a bridged hydrocarbon compound residue.

The group represented by R _{9 to} R ₁₁ may have a substituent, and R ₉
Specific examples of the groups represented by R ₁₁ to R ₁₁ and the substituents that the group may have include the specific examples of the groups represented by R in the aforementioned general formula [I] and the substituents.

Further, for example, specific examples of the ring formed by combining R ₉ and R ₁₀ and the bridged hydrocarbon compound residue formed by R _{9 to} R ₁₁ and the substituent which it may have are as described above. Specific examples of the cycloalkyl, cycloalkenyl, and heterocyclic group-bridged hydrocarbon compound residues represented by R in the formula [I] and the substituents thereof can be given.

Among the general formula [IX], it is preferable that (i) when two of R _{9 to} R ₁₁ are alkyl groups, (ii) one of R _{9 to} R ₁₁ is, for example, R ₁₁ is a hydrogen atom. And when the other two R ₉ and R ₁₀ combine to form a cycloalkyl with the root carbon atom.

Further preferred among (i) is when two of R _{9 to} R ₁₁ are alkyl groups and the other one is a hydrogen atom or an alkyl group.

Here, the alkyl, the cycloalkyl may further have a substituent, and specific examples of the alkyl, the cycloalkyl and the substituent thereof include the alkyl represented by R in the general formula [I], the cycloalkyl and the substituent thereof. Specific examples of the group include:

In addition, the substituent which the ring formed by Z in the general formula [I] and the ring formed by Z ₁ in the general formula [VIII] may have, and R ₂ in the general formulas [II] to [VI] ~
As R ₈ , those represented by the following general formula [X] are preferable.

The general formula (X) -R ¹ -SO ^₂ -R ₂ Formula wherein R ¹ is alkylene, R ² represents alkyl, cycloalkyl or aryl.

The alkylene represented by R ¹ preferably has a straight chain portion having 2 or more carbon atoms, more preferably 3 to 6, and may be straight chain or branched. 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 examples of the substituent which the alkyl group may have are mentioned.

Preferred as the substituent is phenyl.

Preferred specific examples of the alkylene represented by R ¹ are shown below.

The alkyl group represented by R ² may be linear or branched.

Specifically, methyl, ethyl, propyl, iso-propyl, butyl, 2-ethylhexyl, octyl, dodecyl, tetradecyl, hexadecyl, octadacil, 2-
Hexyldecyl and the like can be mentioned.

The cycloalkyl group represented by R ² is preferably a 5- or 6-membered cycloalkyl group, and examples thereof include cyclohexyl.

The alkyl and cycloalkyl represented by R ² may have a substituent, and examples thereof include those exemplified as the substituent for R ¹ described above.

Specific examples of the aryl represented by R ² include phenyl,
Examples include naphthyl. The aryl group may have a substituent. Examples of the substituent include straight-chain or branched alkyl, and those exemplified as the substituent for R ¹ described above.

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 compounds represented by the following general formula [XI] are particularly preferable.

General formula (XI) In the formula, R and X have the same meanings as R and X in the formula [I], and R ¹ and R
² has the same meaning as R ¹ and R ² in the general formula [X].

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

In addition, the coupler is the Journal of the Chemical
Society (Journal of the Chemical Society),
Perkin I (1977), 2047-2052, US Patent
3,725,067, JP-A-59-99437, 58-42045, 59-
No. 162548, No. 59-171956, No. 60-33552, No. 60-43659
Nos. 60-172982 and 60-190779, etc. can be referred to for synthesis.

The coupler of the present invention usually contains 1 × 10 5 mol / mol of silver halide.
It can be used in the range of ^-3 mol to 1 mol, preferably 1 x 10 ^-2 mol to 8 x 10 ^-1 mol.

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

The silver halide photographic light-sensitive material of the present invention has at least one silver halide emulsion layer and a non-light-sensitive layer. In a usual mode, three kinds of light-sensitive materials having different spectral sensitivities are provided on a support. A silver halide emulsion layer and a non-photosensitive layer, each of the silver halide emulsion layers is a diffusion-resistant yellow,
Each of the layers contains three couplers, magenta and cyan.

In such a case, the combination of the light-sensitive silver halide emulsion layer and the coupler is usually a cyan coupler in the red light-sensitive silver halide emulsion layer and at least the main coupler in the green light-sensitive silver halide emulsion layer. The magenta coupler of the invention is further combined with a yellow coupler in the blue-sensitive silver halide emulsion layer.

There is no particular limitation on the order of laminating each emulsion layer, but usually, from the support side, a yellow coupler-containing silver halide emulsion layer, a magenta coupler-containing silver halide emulsion layer, a cyan coupler-containing silver halide emulsion The silver emulsion layers are applied in that order.

As the yellow coupler used in the silver halide emulsion layer of the present invention, a coupler represented by the following general formula [XII] is preferably used.

General formula [XII] In the formula, R ₁ represents an alkyl group or an aryl group, R ₂ represents an aryl group, and X represents a hydrogen atom or a group capable of leaving in the course of a color development reaction. The alkyl group represented by R ₁ is a linear or branched alkyl group, and the aryl group is, for example, a phenyl group. Among the alkyl group and aryl group represented by R ₁ , an alkyl group (particularly t-butyl group) is preferable. The alkyl group and aryl group represented by R ₁ and the aryl group represented by R ₂ include those having a substituent. Further, the aryl group of R ₂ is preferably substituted with a halogen atom, an alkyl group or the like. As X, a group represented by the following general formula [XII-A] or [XII-B] is preferable, and a group represented by [XII-C] in the general formula [XII-A] is particularly preferable.

General formula [XII-A] In the formula, Z ₁ represents a non-metal atom group capable of forming a 4- to 7-membered ring.

In the general formula [XII-B] -O-R 11 formula, but R ₁₁ represents an aryl group, a heterocyclic group or an acyl group, of which an aryl group is preferred.

General formula [XII-C] Where Z ₂ is Represents a non-metal atom group capable of forming a 5- to 6-membered ring together.

In the general formula [XII], the preferable yellow coupler according to the present invention is represented by the following general formula [XII ′].

General formula [XII ′] In the formula, R ₁₄ and R ₁₈ represent a hydrogen atom, a halogen atom, or an alkoxy group. R ₁₄ is preferably a halogen atom and R ₁₈ is preferably a hydrogen atom. R ₁₅ , R ₁₆ and R ₁₇ are each a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an aryl group, a carboxy group, an alkoxycarbonyl group, a carbamyl group, a sulfone group, a sulfamyl group, a sulfonamide group, an acylamide. Base,
Represents a ureido group or an amino group, R ₁₅ and R ₁₆ are each a hydrogen atom, R ₁₇ is an alkoxycarbonyl group,
An acylamido group or an alkylsulfonamide group is preferred. X represents a group having the same meaning as that represented by the above general formula [XII], preferably, among the above general formula [XII-A] or [XII-B], [XII-A], more preferably Examples thereof include groups represented by the above general formula [XII-C].

The layer to which the yellow coupler is added may be any silver halide emulsion layer, but is preferably a blue-sensitive silver halide emulsion layer, and the addition amount thereof is 2 × 10 ^{−3 to} 5 × per mol of silver.
10 ^-1 mol is preferable, and more preferably 1 x 10 ^-2 to 8 x 10
^-1 mol.

The specific examples of the yellow couplers preferably used in the invention are shown below, but the invention is not limited thereto.

Further, as the cyan coupler used in the silver halide emulsion of the present invention, the following general formulas [XIII] and [XIV] are preferable.

General formula [XIII] In the formula, R ₂₁ represents an alkyl group or an aryl group. R ₂₂
Represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group. R ₂₃ represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. R ₂₃ may combine with R ₂₁ to form a ring. Z ₆ represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidized product of an aromatic primary amine type color developing agent.

General formula [XIV] In the formula, R ₂₄ represents a linear or branched alkyl group having 1 to 4 carbon atoms, and R ₂₅ represents a ballast group. Z ₆ is a general formula [XII
I] is synonymous with Z ₆ . R ₂₄ is particularly preferably a linear or branched alkyl group having 2 to 4 carbon atoms.

In the present invention, the alkyl group represented by R ₂₁ in the general formula [XIII] is a linear or branched alkyl group, and for example,
Examples thereof include a methyl group, an ethyl group, an iso-propyl group, a butyl group, a pentyl group, an octyl group, a nonyl group and a tridecyl group, and an aryl group includes, for example, a phenyl group and a naphthyl group. The groups represented by R ₂₁ also include those having a single or a plurality of substituents. For example, as a substituent introduced into a phenyl group, a typical one is a halogen atom (for example, fluorine, chlorine, bromine). Each atom), an alkyl group (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a dodecyl group, etc.), a hydroxyl group, a cyano group,
Nitro group, alkoxy group (eg, methoxy group, ethoxy group), alkyl sulfonamide group (eg, methyl sulfonamide group, octyl sulfonamide group, etc.), aryl sulfonamide group (eg, phenyl sulfonamide group, naphthyl sulfonamide group) Etc.), alkylsulfamoyl group (eg, butylsulfamoyl group), arylsulfamoyl group (eg, phenylsulfamoyl group), alkyloxycarbonyl group (eg, methyloxycarbonyl group), aryl Oxycarbonyl group (eg, phenyloxycarbonyl group), aminosulfonamide group (eg, N, N-dimethylaminosulfonamide group), acylamino group, carbamoyl group, sulfonyl group, sulfinyl group, sulfoxy group,
Examples thereof include a sulfo group, an aryloxy group, an alkoxy group, a carboxyl group, an alkylcarbonyl group and an arylcarbonyl group.

Two or more kinds of these substituents may be introduced into the phenyl group.

The halogen atom represented by R ₂₃ is, for example, each atom of fluorine, chlorine, bromine and the like, the alkyl group is, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a dodecyl group and the like, and an alkoxy group. The group is, for example, a methoxy group,
An ethoxy group, a propyloxy group, a butoxy group and the like.
R ₂₃ may combine with R ₂₁ to form a ring.

In the present invention, the alkyl group represented by R ₂₂ in the general formula [XIII] is, for example, a methyl group, an ethyl group, a butyl group,
Examples thereof include a hexyl group, a tridecyl group, a pentadecyl group, a heptadecyl group, and a so-called polyfluoroalkyl group substituted with a fluorine atom.

The aryl group represented by R ₂₂ is, for example, a phenyl group or a naphthyl group, preferably a phenyl group. The heterocyclic group represented by R ₂₂ is, for example, a pyridyl group or a furan group. The cycloalkyl group represented by R ₂₂ is, for example, a cyclopropyl group, a cyclohexyl group or the like. The group represented by R ₂₂ may have a single or a plurality of substituents. For example, as a substituent introduced into a phenyl group, a typical one is a halogen atom (for example, fluorine or chlorine). , Each atom such as bromine), alkyl group (for example, methyl group, ethyl group, propyl group, butyl group, dodecyl group, etc.), hydroxyl group, cyano group, nitro group, alkoxy group (for example, methoxy group, ethoxy group, etc.), Alkylsulfonamide group (for example, methylsulfonamide group,
Octyl sulfonamide group etc.), aryl sulfonamide group (eg phenyl sulfonamide group, naphthyl sulfonamide group etc.), alkylsulfamoyl group (eg butylsulfamoyl group etc.), arylsulfamoyl group (eg phenyl Sulfamoyl group etc.), alkyloxycarbonyl group (eg methyloxycarbonyl group etc.), aryloxycarbonyl group (eg phenyloxycarbonyl group etc.), aminosulfonamide group, acylamino group, carbamoyl group, sulfonyl group,
Examples thereof include sulfinyl group, sulfooxy group, sulfo group, aryloxy group, alkoxy group, carboxyl group, alkylcarbonyl group and arylcarbonyl group. Two or more kinds of these substituents may be introduced into the phenyl group.

Preferred groups represented by R ₂₂ are a polyfluoroalkyl group, a phenyl group or a halogen atom, an alkyl group, an alkoxy group, an alkylsulfonamido group, an arylsulfonamido group, an alkylsulfamoyl group, an arylsulfamoyl group, an alkyl group. One or two sulfonyl groups, arylsulfonyl groups, alkylcarbonyl groups, arylcarbonyl groups or cyano groups as substituents
It is a phenyl group having three or more.

In the present invention, the cyan coupler represented by the general formula [XIII] is preferably a compound represented by the following general formula [XIII A].

General formula [XIII A] In the general formula [XIII A], R ₂₆ represents a phenyl group. The phenyl group includes those having a single or a plurality of substituents, and typical examples of the introduced substituents include a halogen atom (for example, each atom of fluorine, chlorine, bromine, etc.), an alkyl group (for example, a methyl group). , Ethyl group, propyl group, butyl group, octyl group, dodecyl group, etc.), hydroxyl group, cyano group, nitro group, alkoxy group (eg methoxy group, ethoxy group etc.), alkyl sulfonamide group (eg methyl sulfonamide group, Octyl sulfonamide group etc.), aryl sulfonamide group (eg phenyl sulfonamide group, naphthyl sulfonamide group etc.), alkylsulfamoyl group (eg butylsulfamoyl group etc.), arylsulfamoyl group (eg phenylsulfamoyl group) Moyl group, etc., alkyloxycarbonyl group (eg, methyloxycarbonyl) Boniru group), an aryloxycarbonyl group (e.g., phenyloxycarbonyl group, etc.) and the like. These substituents are 2
One or more species may be substituted with a phenyl group. The preferred group represented by R ₂₆ is a phenyl group, or a halogen atom (preferably each atom of fluorine, chlorine and bromine),
Alkyl sulfonamide group (preferably o-methyl sulfonamide group, p-octyl sulfonamide group, o-dodecyl sulfonamide group), aryl sulfonamide group (preferably phenyl sulfonamide group), alkylsulfamoyl group (preferably Butylsulfamoyl group), arylsulfamoyl group (preferably phenylsulfamoyl group), alkyl group (preferably methyl group, trifluoromethyl group), alkoxy group (preferably methoxy group, ethoxy group) as a substituent Is a phenyl group having one or two or more.

R ₂₇ is an alkyl group or an aryl group. The alkyl group or the aryl group includes those having a single or plural substituents, and typical examples of the substituent include a halogen atom (for example, each atom of fluorine, chlorine, bromine, etc.), a hydroxyl group, a carboxyl group. , An alkyl group (eg, methyl group, ethyl group, propyl group, butyl group, octyl group, dodecyl group, etc.), aralkyl group, cyano group, nitro group, alkoxy group (eg, methoxy group, ethoxy group),
Aryloxy group, alkylsulfonamide group (for example, methylsulfonamide group, octylsulfonamide group, etc.), arylsulfonamide group (for example, phenylsulfonamide group, naphthylsulfonamide group, etc.), alkylsulfamoyl group (for example, butylsulfaamide group) Moyl group etc.), arylsulfamoyl group (eg phenylsulfamoyl group etc.), alkyloxycarbonyl group (eg methyloxycarbonyl group etc.), aryloxycarbonyl group (eg phenyloxycarbonyl group etc.), aminosulfonamide group (Eg, dimethylaminosulfonamide group), alkylsulfonyl group, arylsulfonyl group, alkylcarbonyl group, arylcarbonyl group, aminocarbonylamide group, carbamoyl group, sulfinyl group, etc. Door can be. Two or more kinds of these substituents may be introduced.

Preferred groups represented by R ₂₇ are an alkyl group when n ₁ = 0 and an aryl group when n ₁ = 1 or more. R
_As a more preferable group represented by ₂₇ , n ₁ = 0
In this case, an alkyl group having 1 to 22 carbon atoms (preferably a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group,
Dodecyl group), and when n ₁ = 1 or more, a phenyl group,
Or an alkyl group (preferably t-butyl group, t-amyl group, octyl group), an alkyl sulfonamide group (preferably a butyl sulfonamide group, an octyl sulfonamide group, a dodecyl sulfonamide group), an aryl sulfonamide group (preferably Phenylsulfonamide group), aminosulfonamide group (preferably dimethylaminosulfonamide group), alkyloxycarbonyl group (preferably methyloxycarbonyl group, butyloxycarbonyl group) as a substituent phenyl group having one or more Is.

R ₂₈ represents an alkylene group. It represents a linear or branched alkylene group having 1 to 20 carbon atoms, and further having 1 to 12 carbon atoms.

R ₂₉ represents a hydrogen atom or a halogen atom (each atom such as fluorine, chlorine, bromine or iodine). It is preferably a hydrogen atom.

n ₁ is 0 or a positive integer, preferably 0 or 1.

X is -O -, - CO -, - COO -, - OCO -, - SO 2 NR-,
-NR'SO ₂ NR "-, -S-, -SO- or -SO ₂ -group 2
Represents a valent group. Here, R ′ and R ″ represent an alkyl group, and R ′ and R ″ also include those having a substituent.
X of preferably, -O -, - S -, - SO -, - a group - SO _2.

Z ₆ has the same meaning as Z _{6 in} formula [XIII].

In the present invention, the linear or branched alkyl group having 1 to 4 carbon atoms represented by R ₂₄ of the above general formula [XIV] is, for example, ethyl group, propyl group, butyl group, iso-propyl group, iso- A butyl group, a sec-butyl group, or a tert-butyl group, which may have a substituent. Examples of the substituent include an acylamino group (eg acetylamino group), an alkoxy group (eg methoxy group) and the like.

R ₂₄ is preferably unsubstituted.

The ballast group represented by R ₂₅ is an organic group having a size and shape that provides the coupler molecule with sufficient bulk to prevent the coupler from substantially diffusing the coupler from the layer to which it is applied. .

Representative ballast groups include alkyl or aryl groups having 8 to 32 total carbon atoms.

These alkyl groups or aryl groups may have a substituent. As the substituent of the aryl group, for example, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a carboxy group, an acyl group, an ester group, a hydroxy group, a cyano group, a nitro group, a carbamoyl group, a carbonamido group, an alkylthio group, Arylthio group, sulfonyl group,
Examples thereof include a sulfonamide group, a sulfamoyl group and a halogen atom. Further, examples of the substituent of the alkyl group include the substituents of the aryl group excluding the alkyl group.

Particularly preferred as the ballast group is one represented by the following general formula [XIV A].

General formula [XIV A] R ₂₆ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, Ar represents an aryl group such as a phenyl group, and the aryl group may have a substituent. Examples of the substituent include an alkyl group, a hydroxy group, an alkylsulfonamide group and the like, and the most preferable one is a branched alkyl group such as a t-butyl group.

In the general formulas [XIII] and [XIV], the group capable of splitting off upon reaction with the oxidized product of the aromatic primary amine color developing agent represented by Z ₆ is well known to those skilled in the art, and is a coupler. By modifying the reactivity of the compound or removing it from the coupler to perform functions such as development suppression, bleaching suppression and color correction in the coating layer or other layer containing the coupler in the silver halide color photographic light-sensitive material. It has an advantageous effect. Typical examples include halogen atoms typified by chlorine and fluorine, substituted / unsubstituted alkoxy groups, aryloxy groups, arylthio groups, carbamoyloxy groups, acyloxy groups, sulfonyloxy groups, sulfonamide groups or heteroylthio groups. , A heteroyloxy group and the like. Particularly preferable Z ₆ is a hydrogen atom or a chlorine atom.

More specifically, JP-A-50-10135, 50-120334,
50-130441, 54-48237, 51-146828, 54-1
No. 4736, No. 47-37425, No. 50-123341, No. 58-95346
No. 48-36894, U.S. Patents 3,476,563, 3,73
No. 7,316, and No. 3,227,551.

Typical representative examples of the cyan coupler represented by the general formula [XIII] are shown below, but the invention is not limited thereto.

Next, specific examples of the coupler represented by the general formula [XIV] are shown, but the couplers are not limited to these.

The addition layer of the cyan coupler preferably used in the present invention may be any silver halide emulsion layer, but is preferably a red-sensitive silver halide emulsion layer, and the addition amount thereof is from 0.05 to 1 mol per mol of silver. Is preferred, and more preferably 0.
It is 1 to 0.8 mol.

As a method of adding these couplers to a silver halide photographic light-sensitive material, various methods such as a solid dispersion method, a latex dispersion method, an oil-in-water emulsion dispersion method, etc. can be used in the same manner as a general hydrophobic compound addition method. Can be used and can be appropriately selected depending on the chemical structure of the coupler. In the oil-in-water emulsion dispersion method, the coupler is usually used at a boiling point of about 150 ° C.
In the above high boiling point organic solvent, if necessary, a low boiling point, and / or a water-soluble organic solvent may be used in combination to dissolve, and a stirrer, a homogenizer, a colloid mill using a surfactant in a hydrophilic binder such as an aqueous gelatin solution. The method is to emulsify and disperse using a dispersing means such as a flowgit mixer or an ultrasonic device, and then add to the desired hydrophilic colloid layer. In this dispersion method, a step of removing the low boiling point organic solvent may be added at the same time as the dispersion liquid or the dispersion.

As the high-boiling organic solvent, the boiling point of a phenol derivative, a phthalic acid ester, a phosphoric acid ester, a citric acid ester, a benzoic acid ester, an alkylamide, a fatty acid ester, a trimesic acid ester, etc., which does not react with an oxidized product of a developing agent.
An organic solvent of 150 ° C or higher is used.

In the present invention, the high boiling point organic solvent preferably used for dispersing the yellow, magenta and cyan couplers is a compound having a dielectric constant of less than 6.0, and the lower limit is not particularly limited, but the dielectric constant is preferably 1.9 or more. For example, esters such as phthalic acid ester and phosphoric acid ester having a dielectric constant of less than 6.0, organic acid amides, ketones, hydrocarbon compounds and the like.

Further, in the present invention, it is preferably a high boiling organic solvent having a vapor pressure at 100 ° C. of 0.5 mmHg or less. Further more preferably, phthalic acid esters in the high boiling point organic solvent,
Alternatively, they are phosphoric acid esters. The organic solvent may be a mixture of two or more kinds, and in this case, the mixture may have a dielectric constant of less than 6.0. The dielectric constant indicates the dielectric constant at 30 ° C.

Examples of the phthalic acid ester advantageously used in the present invention include those represented by the following general formula [XV].

General formula [XV] In the formula, R ₂₅ and R ₂₆ each represent an alkyl group, an alkenyl group or an aryl group. However, the total number of carbon atoms of the groups represented by R ₂₅ and R ₂₆ is 9 to 32. Further, the total number of carbon atoms is more preferably 16 to 24.

In the present invention, the alkyl group represented by R ₂₅ and R ₂₆ in the above general formula [XV] is a straight chain or branched group, for example, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group. , Decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group and the like. The aryl group represented by R ₂₅ and R ₂₆ is a phenyl group, a naphthyl group and the like, and the alkenyl group is a hexenyl group, a heptenyl group, an octadecenyl group and the like. These alkyl group, alkenyl group and aryl group may have a single or a plurality of substituents, the substituent of the alkyl group and alkenyl group,
Examples thereof include a halogen atom, an alkoxy group, an aryl group, an aryloxy group, an alkenyl group, and an alkoxycarbonyl group. Examples of the substituent of the aryl group include a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, and an alkenyl group. , And an alkoxycarbonyl group. Two or more of these substituents may be introduced into the alkyl group, alkenyl group or aryl group.

Examples of the phosphoric acid ester advantageously used in the present invention include those represented by the following general formula [XVI].

General formula [XVI] In the formula, R ₂₇ , R _28, and R ₂₉ are each an alkyl group,
Represents an alkenyl group or an aryl group. However, R ₂₇ , R
The total number of carbon atoms represented by ₂₈ and R ₂₉ is 24 to 54.
Is.

Examples of the alkyl group represented by R ₂₇ , R ₂₈ and R ₂₉ in the general formula [XVI] include butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group and tridecyl group. Group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group and the like.

These alkyl group, alkenyl group and aryl group may have a single or a plurality of substituents. Preferably R ₂₇ , R ₂₈ and R ₂₉ are alkyl groups, for example, 2-ethylhexyl group, n-octyl group, 3,5,5-
Trimethylhexyl group, n-nonyl group, n-decyl group,
Examples thereof include sec-decyl group, sec-dodecyl group and t-octyl group.

Specific examples of the organic solvent preferably used in the present invention are shown below.

Exemplified organic solvent These organic solvents are generally used in a proportion of 10 to 150% by weight based on the coupler used in the present invention. It is preferably 20 to 100% by weight based on the coupler.

In the silver halide photographic light-sensitive material of the present invention, it is preferable to further use a color turbidity preventive represented by the following general formula [XVII].

Examples of the color turbidity preventing agent preferably used in the present invention include compounds represented by the following general formula [XVII].

General formula [XVII] In the formula, R ₃₁ , R ₃₂ , R ₃₃ and R ₃₄ are each a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, a cycloalkyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an acyl group, Alkylacylamino group, arylacylamino group, alkylcarbamoyl group, arylcarbamoyl group, alkylsulfonamide group, arylsulfonamide group, alkylsulfamoyl group, arylsulfamoyl group, alkylsulfonyl group, arylsulfonyl group, nitro group , Cyano group,
It represents an alkyloxycarbonyl group, an aryloxycarbonyl group, an alkylacyloxy group or an arylacyloxy group.

In the general formula [XVII], the halogen atom is
For example, each atom of fluorine, chlorine and bromine may be mentioned, and examples of the alkyl group include methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, n-amyl, i-amyl and n-. Examples thereof include octyl, n-dodecyl, and n-octadecyl groups, and an alkyl group having 1 to 32 carbon atoms is particularly preferable.

Examples of the alkenyl group include allyl, octenyl, and oleyl groups, and the alkenyl group having 2 to 32 carbon atoms is particularly preferable.

Examples of the aryl group include phenyl and naphthyl groups.

Examples of the acyl group include acetyl, octanoyl, and lauroyl groups.

Examples of the cycloalkyl group include cyclohexyl and cyclopentyl groups.

Examples of the alkoxy group include methoxy, ethoxy, and dodecyloxy groups, examples of the aryloxy group include a phenoxy group, and examples of the alkylthio group include methylthio, n-butylthio, and n-butylthio.
Examples include dodecylthio groups, examples of arylthio groups include phenylthio groups, examples of alkylacylamino groups include acetylamino groups, and examples of arylacylamino groups include benzoylamino groups. Examples of the alkylcarbamoyl group include a methylcarbamoyl group and the like,
Examples of the arylcarbamoyl group include a phenylcarbamoyl group and the like, and examples of the alkylsulfonamide group include a methylsulfonamide group and the like,
Examples of the arylsulfonamido group include a phenylsulfonamido group and the like, examples of the alkylsulfamoyl group include a methylsulfamoyl group and the like, and examples of the arylsulfamoyl group include a phenylsulfamoyl group. And the like, and the alkylsulfonyl group includes, for example, a methylsulfonyl group,
Examples of the arylsulfonyl group include a phenylsulfonyl group and the like, and examples of the alkyloxycarbonyl group include a methyloxycarbonyl group and the like,
Examples of the aryloxycarbonyl group include a phenyloxycarbonyl group and the like, and examples of the alkylacyloxy group include an acetyloxy group and the like,
Examples of the arylacyloxy group include a benzoyloxy group and the like.

These groups include those having a substituent, and these substituents include an alkyl group, an aryl group, an aryloxy group, an alkylthio group, a cyano group, an acyloxy group, an alkoxycarbonyl group, an acyl group, a sulfamoyl group and a hydroxy group. , A nitro group, an amino group and a heterocyclic group.

Then, at least one group out of R ₃₁ , R ₃₂ , R _33, and R ₃₄ is a group having a total number of carbon atoms of 6 or more including the above-mentioned substituents.

Among the compounds represented by the above general formula [XVII] used in the present invention, the compounds represented by the following general formula [XVII ′] are particularly preferably used in the present invention.

General formula [XVII ′] In the formula, R ₃₅ and R ₃₆ each represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an acyl group, a cycloalkyl group or a heterocyclic group. However, at least one of R ₃₅ and R ₃₆ is a group having a total number of carbon atoms of 6 or more.

In the above general formula [XVII ′], the alkyl group represented by R ₃₅ and R ₃₆ is, for example, methyl, ethyl or n-
Propyl, i-propyl, n-butyl, t-butyl, n
-Amyl, i-amyl, n-octyl, n-dodecyl,
Each group of n-octadecyl and the like are listed, and particularly, the number of carbon atoms is 1 to
32 alkyl groups are preferred.

Examples of the alkenyl group include allyl, octenyl, and oleyl groups, and the alkenyl group having 2 to 32 carbon atoms is particularly preferable.

Examples of the aryl group include phenyl and naphthyl groups.

Examples of the acyl group include acetyl, octanoyl, and lauroyl groups.

Examples of the cycloalkyl group include cyclohexyl and cyclopentyl groups.

Examples of the heterocyclic group include imidazolyl, furyl, pyridyl, triazinyl, and thiazolyl groups.

In the general formula [XVII '], it is preferable that at least one group the sum of the carbon atoms of for R ₃₅ and R ₃₆ is 8 or more, more preferably, the number of carbon atoms R ₃₅ and R ₃₆ are both Is a group of 8 to 18, and most preferably R
_{Both 35} and R ₃₆ are the same alkyl group having 8 to 18 carbon atoms in total.

Specific examples of the compound represented by the above general formula [XVII] used in the present invention are shown below, but of course the present invention is not limited thereto.

These compounds are described, for example, in Research Disclosure, No. 176 (1978), Item 17643, VII I.

The color turbidity-preventing agent represented by the general formula [XVII] used in the present invention can be contained in either the silver halide emulsion layer and / or the non-photosensitive layer, but preferably the magenta coupler of the present invention is used. It is contained in a layer to be contained or a layer adjacent to the layer, and its addition amount varies depending on the type of silver halide emulsion and magenta coupler used and is not particularly limited, but preferably a silver halide emulsion layer and / or The total amount in the non-photosensitive layer is ² to 16 mg / dm ² .

The silver halide photographic light-sensitive material of the present invention may further contain an image stabilizer which prevents deterioration of the dye image.

The image stabilizer preferably used in the present invention is a compound represented by the formula [A] of Japanese Patent Application No. 60-117493, page 101 (specifically, pages 109 to 116). Examples A-1 to A-32), Japanese Patent Application No. 60-117493, page 117, compounds represented by the general formula [B] (specifically, page 123-
Examples B-1 to B-55) shown on page 127, Japanese Patent Application No. 60-
No. 117493, page 128, compounds represented by general formula [C] (specifically, Exemplified C-1 shown on pages 133 to 134 of the same)
To C-17), Japanese Patent Application No. 60-117493, page 128, compounds represented by the general formula [D] (specifically, exemplified D-1 to D shown on pages 135 to 136 of the same). -11), Japanese Patent Application No. 60-117493 No. 137
The compound represented by the general formula [E] (specifically,
Examples E-1 to E-42 shown on pages 3 to 147), Japanese Patent Application No. 60-117493, page 148, compounds represented by the general formula [F] (specifically, page 155). -Exemplary F-1 to F-47 shown on page 159), Japanese Patent Application No. 60-117493, page 160, compounds represented by the general formula [G] (specifically, pages 164 to 164) 1
Examples G-1 to G-45 shown on page 66), Japanese Patent Application No. 60-117
No. 493, page 167 Compounds represented by the general formula [H] (specifically, Exemplified H-1 to H- shown on pages 171 to 174 thereof)
36), Japanese Patent Application No. 60-117493, page 175, compounds represented by the general formula [J] (specifically, exemplified J-1 to J-74 shown on pages 178 to 183 thereof). No. 60-117493, page 188, compounds represented by the general formula [K] (specifically, Exemplified K-1 to K-41 shown on pages 193 to 197), Wish 6
No. 0-117493, page 198, compounds represented by the general formulas [L] and [M] (specifically, examples L-1 to L-20 and Examples M-1 to M-3 shown on page 211, Japanese Patent Application No. 60-117493, page 212, compounds represented by the general formula [N] (specifically, pages 223 to 223)
Examples N-1 to N-107) shown on page 249 are mentioned.

The image stabilizer used in the present invention can be contained in either the light-sensitive layer and / or the non-light-sensitive layer, but is preferably contained in the green light-sensitive silver halide emulsion layer. The addition amount of the image stabilizer of the present invention is not particularly limited in any layer, but preferably ^{2 to} 16 mg / dm ²
Is.

The fine particle powder having an average particle size of 0.5 to 10 μm contained in the protective layer of the present invention is generally referred to as a matting agent in the art, and therefore is hereinafter referred to as a matting agent unless otherwise specified.

As the hydrophilic binder used in the protective layer of the present invention, gelatin, gelatin derivatives (eg acetylated gelatin, phthalated gelatin, etc.), albumin, collodion, etc. are used, and gelatin is preferred.

Examples of the matting agent according to the present invention include crystalline or amorphous silica, titanium dioxide, magnesium oxide, calcium carbonate, barium sulfate, magnesium aluminate silicate, acrylic acid-ethyl acrylate copolymer, acrylic acid-methyl methacrylate. Copolymer, itaconic acid-
Styrene copolymer, maleic acid-methyl methacrylate copolymer, maleic acid-styrene copolymer, acrylic acid-phenyl acrylate copolymer, polymethyl methacrylate, acrylic acid-methacrylic acid-ethyl methacrylate copolymer, polystyrene, starch , Cellulose acetate propionate and the like, and other compounds and the like described in US Pat. Nos. 1,221,980 and 2,992,101 can be used, and these can be used alone or in combination of two or more kinds.

The matting agent may have an average particle diameter of 0.5 to 10 μm, preferably 1 to 5 μm.

The average particle diameter as used herein is the average value of the diameter of spherical particles, and the diameter of a cube or particles of a shape other than spherical when the projected image is converted into a circular image of the same area. When the particle size is ri and the number is ni, it is defined by the following formula.

As a specific measuring method, the method described in JP-A-59-29243 can be used.

The matting agent according to the present invention is dispersed and contained in the protective layer of the present invention, and as a method of dispersing and containing, a nonionic, a cationic or an anionic surfactant is optionally contained in a hydrophilic binder, Add other additives if necessary, high-speed rotating mixer, homogenizer, ultrasonic dispersion,
It can be formed by dispersing with a ball mill or the like by an emulsion dispersion method utilizing shear stress and applying as an outermost layer of a photographic material by any method used in the photographic field.

The coating amount of the matting agent according to the present invention is preferably 0.5 to 50 mg per 1 m ² in the outermost non-photosensitive layer. More preferably, it is contained in an amount of 1 to ²⁰ mg per 1 m ² .

Also, the content of the matting agent is based on the hydrophilic binder.
0.1 to 2% by weight is preferable.

In the silver halide photographic light-sensitive material of the present invention, the non-photosensitivity containing the silver halide emulsion layer containing the magenta coupler of the present invention and the fine particle powder having an average particle diameter of 0.5 to 10 μm is represented by the following general formula [HI]. And at least one hardener selected from [H-II].

General formula [HI] In the formula, R ₁ is a chlorine atom, a hydroxy group, an alkyl group, an alkoxy group, an alkylthio group, —OM group (M represents a monovalent metal atom), —NR′R ″ or —NHCOR (R ′,
R ″ and R each represent a hydrogen atom, an alkyl group or an aryl group), and R ₂ has the same meaning as R ₁ excluding a chlorine atom.

General formula [H-II] In the formula, R ₃ and R ₄ are each a chlorine atom, a hydroxy group,
Represents an alkyl group, an alkoxy group or an -OM group (M represents a monovalent metal atom), -Q- and -Q'- represent a -O-, -S- or -NH- linking group, and L
Represents an alkylene group or an arylene group. l and m
Represents 0 or 1, respectively.

The alkyl group represented by R ₁ and R ₂ of the hardener represented by the general formula [HI] according to the present invention is, for example, a methyl group, an ethyl group, a butyl group or the like, and an alkoxy group represented by them. Is a methoxy group, an ethoxy group, a butoxy group and the like. Also Specific examples of _{-NH 2, -NHCH 3, -NHC 2} H 5 and the like, -NHCO
R As a specific example, -NHCOCH ₃ , Etc. Further, M of the —OM group represented by R ₁ and R ₂ is, for example, a sodium atom or a potassium atom.

Regarding the cyanuric chloride type hardener represented by the above general formula [HI], US Pat. No. 3,645,743, JP-B-47-
6151, 47-33380, 51-9607, JP-A-48-19220
No. 51, No. 51-78788, No. 52-60612, No. 52-128130, No. 5
2-130326 and 56-1043, which can be used according to the above criteria.

Next, the alkyl group represented by R ₃ and R _{4 in} the general formula [H-II] is, for example, a methyl group, an ethyl group, a butyl group or the like, and the alkoxy group is a methoxy group, an ethoxy group, a butoxy group or the like, M of the —OM group is, for example, a sodium atom or a potassium atom.

The alkylene group represented by L is, for example, —CH ₂ —, — (CH
₂ ) ₂₋ , — (CH ₂ ) ₃ — group and the like, and the arylene group is, for example, p-, o- or m-phenylene group.

Regarding the cyanuric chloride type hardener represented by the general formula [H-II], Canadian Patent 895,808, Japanese Patent Publication No. 58-3354.
No. 2, JP-A-57-40244 and the like, and can be selected for use based on the above criteria.

At least one hardener selected from the compounds represented by the above general formulas [HI] and [H-II] according to the present invention is the protective layer of the silver halide photographic light-sensitive material of the present invention and the magenta coupler of the present invention. It may be added to any layer as long as the layer containing is hardened, but it is preferably a protective layer.

The method for adding the hardener used in the present invention is to dissolve the hardener of the present invention in water or alcohol (eg, methyl alcohol, ethyl alcohol, etc.) and apply it to 1 g of coated gelatin.
0.5 to 100 mg, preferably 2 to 50 mg may be added. The addition method may be either a batch method or an in-line method.

The hardener represented by the general formula (H-I) or (H-II) according to the present invention is, for example, U.S. Pat. No. 3,490,911 and West German Patent 2,749,260.
No. 2,950,19, a vinyl sulfone-based hardener described in U.S. Pat.
No. 7, No. 2,804,404, No. 2,983,611, No. 3,271,175,
JP-B-46-40898, aldehyde-based hardeners described in JP-A-50-91315, aziricin-based hardeners, or U.S. Patent 3,047,394, West German Patent 1,085,663, British Patent 1,
It may be used in combination with an epoxy hardener such as those described in No. 033,518 and JP-B-48-35495, and particularly preferably in combination with a vinyl sulfone hardener. The ratio when the hardener of the present invention and the vinyl sulfone-based hardener are combined is 1: 0.2 to 1: 5.0.
(Weight) is preferred.

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

Compound represented by general formula [HI]: Compound represented by general formula [H-II]: In the present invention, the following layer constitutions, which have recently received attention in order to significantly improve the light resistance and the color fading balance of the dye image of the print, are preferable.

That is, two non-photosensitive layers are provided on the opposite side of the silver halide emulsion layer located farthest from the support to the support side, and the ultraviolet absorber is provided in the non-photosensitive layer located on the support side. It is a layer structure formed by containing.

An ultraviolet absorber which can be advantageously used in the protective layer, intermediate layer and silver halide emulsion layer of the light-sensitive material of the present invention is shown by formula [I] in the upper left column of page (4) of JP-A-58-211148. UV absorbers, specifically, specific examples UV-1 to UV-1 shown in the upper left column of the same page (4) to the upper left column of the same page (5)
9 is mentioned.

Examples of the reflective support used in the present invention include plastic films, that is, polyester (for example, polyethylene terephthalate), vinyl alcohol, vinyl chloride,
Homopolymers and copolymers such as fluorinated vinyl and vinyl acetate, cellulose acetate, acrylonitrile, acrylic acid alkyl esters, methacrylic acid alkyl esters, methacrylonitrile, alkyl vinyl esters, alkyl vinyl ethers, polyamides and other homopolymers and copolymers. You can Further, a laminated body of two or more kinds of substrates such as a laminated body of paper or synthetic paper and polyolefin (polyethylene, polypropylene, etc.) and the like are used.

The reflective support according to the present invention may contain a white pigment for imparting reflectivity, or a hydrophilic colloid layer containing a white pigment may be coated on the transparent support.

The white pigment used is an inorganic and / or organic white pigment, preferably an inorganic white pigment,
Examples thereof include sulfates of alkali metals such as barium sulfate, carbonates of alkaline earth metals such as calcium carbonate, finely divided silicic acid, silicas of synthetic silicates, calcium silicate, alumina, hydrated alumina, titanium oxide. , Zinc oxide, talc, clay and the like.

The color light-sensitive material used in the present invention is directly or after (corresponding to the adhesiveness of the support surface, antistatic property, dimensional stability) after subjecting the support surface to corona discharge, ultraviolet irradiation, flame treatment, etc. , To improve abrasion resistance, hardness, antihalation, frictional properties and / or other properties), and may be applied via one or more subbing layers.

The silver halide grains constituting the silver halide emulsion used in combination with the magenta coupler used in the present invention are preferably monodisperse silver halide grains from the viewpoint of further improving wet pressure fog resistance.

The monodispersed silver halide grain in the present invention means that when the emulsion is observed by an electron micrograph, the shape of each silver halide grain looks uniform, the grain size is uniform, and is defined by the following formula. It has a particle size distribution. That is, the value obtained by dividing the standard knitting difference s of the particle size distribution by the average particle size is 0.20 or less, preferably 0.15 or less (also referred to as a particle size distribution of 15% or less).

The average grain size referred to here is the diameter in the case of spherical silver halide grains, and the diameter when the projected image is converted into a circular image of the same area in the case of cubic or non-spherical grains. Is the average value of, and the particle size is ri, and when the number is ni, is defined by the following formula.

The above particle diameter can be measured by various methods generally used in the technical field for the above purpose. A typical method is Loveland's "Particle Size Analysis Table" ASTM Symposium on
Wright Microscopy, 1955, pp. 94-122, or "Theory of Photographic Processes" by Mies and James,
The third edition, published by Macmillan, Inc. (1966), Chapter 2. This particle size can be measured using the projected area of the particle or an approximate diameter. If the particles are of substantially uniform shape, the particle size distribution can be fairly accurately expressed as a diameter or projected area.

The relationship between grain size distributions is described in "The Empirical Relationship Between Sensitometric and Grain Size Distributions in Photographic Emulsions", The Photographic Journal, Volume LXXIX, (1949), pages 330-338, Tribelli and Smith. This can be determined in the manner described.

The monodisperse silver halide grains are used in an amount of at least 50% by weight, preferably 75% by weight or more based on the total silver halide grains.

The silver halide grains constituting the silver halide emulsion used in combination with the magenta coupler used in the present invention are silver halide grains having a silver chloride content of 30 to 70 mol% from the viewpoint of further improving wet pressure fog resistance. Is preferred.

The silver halide grains are used in an amount of at least 50% by weight, preferably 75% by weight or more based on the total silver halide grains.

The silver halide photographic light-sensitive material of the present invention can be, for example, a negative and a positive film of a color negative, a color photographic paper, and the like. In particular, when the color photographic paper used for direct viewing is used, the method of the present invention can be used. The effect of is effectively exhibited.

The silver halide photographic light-sensitive material of the present invention, including this color photographic paper, is usually a silver halide containing magenta, yellow, and cyan couplers as photographic couplers in order to perform color reduction method color reproduction. Although the emulsion layer and the non-photosensitive layer are laminated on the support in an appropriate number of layers and layer order, the number of layers and layer order may be appropriately changed depending on the priority performance and purpose of use.

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

The silver halide grains used in the silver halide emulsion of the present invention may be those obtained by any of the acidic method, the neutral method and the ammonia method. The grains may be grown at one time, or may be grown after forming seed grains. The method of forming seed particles and the method of growing seed particles may be the same or different.

In the silver halide emulsion, halide ions and silver ions may be mixed at the same time, or one of them may be present while the other is mixed. In addition, while considering the critical growth rate of silver halide crystals, the halide ion and silver ion are mixed in the p
It may be generated by sequentially adding H and pAg while controlling them. After the growth, the conversion method may be used to change the halogen composition of the grains.

The grain size, grain shape, grain size distribution and grain growth rate of the silver halide grains can be controlled by using a silver halide solvent, if necessary, during the production of the silver halide emulsion of the present invention.

The silver halide grains used in the silver halide emulsion of the present invention have a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt, a rhodium salt or a complex salt in the step of forming and / or growing the grain. , Iron salt or complex salt,
Can be incorporated into the inside of the particle and / or the surface of the particle by adding a metal ion to the inside of the particle, and by providing an appropriate reducing atmosphere, a reduction sensitizing nucleus is given to the inside of the particle and / or the surface of the particle. I can.

In the silver halide emulsion of the present invention, unnecessary soluble salts may be removed after the growth of silver halide grains is completed, or may be contained therein. The salts can be removed by the method described in Research Disclosure 17643.

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

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

The silver halide grains used in the silver halide emulsion of the present invention may have a regular crystal form, or may have an irregular crystal form such as a sphere or a plate. In these grains, any ratio of {100} plane to {111} plane can be used. Further, it may have a composite form of these crystal forms, and particles of various crystal forms may be mixed.

The silver halide emulsion of the present invention may be used as a mixture of two or more kinds of silver halide emulsions which are separately formed.

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

The silver halide emulsion of the present invention can be optically sensitized to a desired wavelength range by 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. A dye that does not have a spectral sensitizing action by itself with a sensitizing dye, or a compound that does not substantially absorb visible light, and that contains a supersensitizer that enhances the sensitizing action of the sensitizing dye in the emulsion. Is also good.

The silver halide emulsion of the present invention includes a light-sensitive material manufacturing process,
A silver halide emulsion during chemical ripening for the purpose of preventing fog during storage or during photographic processing and / or for maintaining stable photographic performance, and / or at the end of chemical ripening and / or after the end of chemical ripening. By the time of coating, compounds known as antifoggants or stabilizers in the photographic industry can be added.

As the binder (or protective colloid) of the silver halide emulsion of the present invention, it is advantageous to use gelatin,
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 homopolymers or copolymers can also be used.

A plasticizer may 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 using the silver halide emulsion of the present invention.

A photographic emulsion layer or other hydrophilic colloid layer of a light-sensitive material using the silver halide emulsion of the present invention contains a dispersion (latex) of a water-insoluble or sparingly-soluble synthetic polymer for the purpose of improving dimensional stability. Can be done.

In the emulsion layer of the silver halide color photographic light-sensitive material of the present invention, an aromatic primary amine developer (for example, p-phenylenediamine derivative, aminophenol derivative, etc.) is used in the color development process together with the dye-forming coupler. A dye-forming coupler is used which forms a dye by a coupling reaction with the oxidant. The dye-forming couplers are usually selected so that for each emulsion layer a dye is formed which absorbs the light in the light-sensitive spectrum of the emulsion layer.
In the blue light-sensitive emulsion layer, a yellow dye-forming coupler,
Magenta dye-forming coupler in the green light-sensitive emulsion layer,
A cyan dye forming coupler is used in the red light sensitive emulsion layer. However, the silver halide photographic light-sensitive material may be produced by a method different from the above combination depending on the purpose.

The protective layer of the light-sensitive material of the present invention, a hydrophilic colloid layer such as an intermediate layer to prevent fog due to discharge due to the light-sensitive material being charged by friction or the like, and an ultraviolet absorber to prevent deterioration of the image by UV light. It may be included.

The color light-sensitive material using the silver halide emulsion of the present invention may be provided with auxiliary layers such as a filter layer, an antihalation layer and / or an antiirradiation layer, if necessary. In these layers and / or emulsion layers, dyes which may be bleached or bleached from the color light-sensitive material during development processing may be incorporated.

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 antistatic can be added to a light-sensitive material using the silver halide emulsion of the present invention. The antistatic agent may be used in the antistatic layer on the side of the support on which the emulsion is not laminated, and may be used to protect the emulsion layer and / or the emulsion layer on the side of the support other than the emulsion layer. It may be used for the colloid layer.

In the photographic emulsion layer and / or other hydrophilic colloid layer of the light-sensitive material using the silver halide emulsion of the present invention, the coating property is improved,
Various surfactants are used for the purpose of preventing static charge, improving slipperiness, emulsifying and dispersing, preventing adhesion and improving photographic properties (such as acceleration of development, hardening, and sensitization).

When coating a photographic light-sensitive material using the silver halide emulsion of the present invention, a thickener may be used in order to improve coatability. As the coating method, extrusion coating and curtain coating, which can simultaneously coat two or more layers, are particularly useful.

The light-sensitive material of the present invention can be exposed using electromagnetic waves in the spectral region where the emulsion layer constituting the light-sensitive material of the present invention has sensitivity. As a light source, natural light (sunlight), tungsten electric lamp, fluorescent lamp, mercury lamp, xenon arc lamp, carbon arc lamp, xenon flash lamp, cathode ray tube flying spot, various laser light, light emitting diode light, electron beam,
Any known light source such as light emitted from a phosphor excited by X-rays, γ-rays or α-rays can be used.

The exposure time is, of course, from 1 millisecond to 1 second which is usually used in a camera, and it is also possible to use exposure shorter than 1 microsecond, for example, 100 microsecond to 1 microsecond using a cathode ray tube or a xenon flash lamp. However, exposure longer than 1 second is possible. The exposure may be performed continuously or intermittently.

The silver halide photographic light-sensitive material of the present invention can form an image by color development known in the art.

The aromatic primary amine color developing agent used in the color developing solution in the present invention includes known ones widely used in various color photographic processes. These developers include aminophenol-based and p-phenylenediamine-based derivatives. Since these compounds are more stable than the free state, they are generally used in the form of salts, for example, hydrochlorides or sulfates. Also, these compounds are generally used at a concentration of about 0.1 g to about 30 g for color developer 1, preferably at a concentration of about 1 g to about 15 g for color developer 1.

Examples of the aminophenol-based developer include o-aminophenol, p-aminophenol, 5-amino-2-
Oxytoluene, 2-amino-3-oxytoluene, 2
-Oxy-3-amino-1,4-dimethylbenzene and the like are included.

Particularly useful aromatic primary amine color developing agents are N, N'-
A dialkyl-p-phenylenediamine compound,
The alkyl group and phenyl group may be substituted with any substituent. Among them, examples of particularly useful compounds include
N, N'-diethyl-p-phenylenediamine hydrochloride, N
-Methyl-p-phenylenediamine hydrochloride, N, N'-dimethyl-p-phenylenediamine hydrochloride, 2-amino-
5- (N-ethyl-N-dodecylamino) -toluene,
N-ethyl-N-β-methanesulfonamidoethyl-3
-Methyl-4-aminoaniline sulfate, N-ethyl-N
-Β-hydroxyethylaminoaniline, 4-amino-
3-methyl-N, N'-diethylaniline, 4-amino-
Examples thereof include N- (2-methoxyethyl) -N-ethyl-3-methylaniline-p-toluenesulfonate.

The color developing solution used in the processing of the present invention contains various components which are usually added to the color developing solution in addition to the primary aromatic amine color developing agent, such as sodium hydroxide and sodium carbonate. An alkali agent such as potassium carbonate, an alkali metal sulfite salt, an alkali metal bisulfite salt, an alkali metal thiocyanate salt, an alkali metal halide, benzyl alcohol, a water softening agent and a thickening agent can be optionally contained. The pH value of this color developing solution is usually 7 or more, and most commonly about 10 to about
It is 13.

In the present invention, after color development processing, processing is carried out with a processing solution having fixing ability. When the processing solution having fixing ability is a fixing solution, bleaching processing is carried out before that. As the bleaching agent used in the bleaching step, a metal complex salt of an organic acid is used, and the metal complex salt oxidizes the metal silver produced by development to convert it to silver halide, and at the same time, acts to color the uncolored part of the color former. And has a structure in which a metal ion such as iron, cobalt, or copper is coordinated with an aminopolycarboxylic acid or an organic acid such as oxalic acid or citric acid. The most preferable organic acid used for forming such a metal complex salt of an organic acid includes a polycarboxylic acid or an aminopolycarboxylic acid. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts.

The following can be mentioned as specific representative examples of these.

[1] Ethylenediaminetetraacetic acid [2] Nitrilotriacetic acid [3] Iminodiacetic acid [4] Ethylenediaminetetraacetic acid disodium salt [5] Ethylenediaminetetraacetic acid tetra (trimethylammonium) salt [6] Ethylenediaminetetraacetic acid tetrasodium salt [7] Nitrilotritri Sodium acetate salt The bleaching agent used contains the above-mentioned metal complex salt of an organic acid as a bleaching agent and can also contain various additives. As the additive, it is particularly preferable to contain an alkali halide or an ammonium halide, for example, a rehalogenating agent such as potassium bromide, sodium bromide, sodium chloride or ammonium bromide, a metal salt or a chelating agent. In addition, borate, oxalate, acetate, carbonate, phosphate and other pH buffers, alkylamines, polyethylene oxides and the like, which are known to be added to ordinary bleaching solutions, can be appropriately added. .

Further, the fixer and the bleach-fixer are ammonium sulfite,
Sulfites such as potassium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, sodium metabisulfite, boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, carbonic acid A single pH buffer or two or more pH buffers composed of various salts such as potassium, sodium bisulfite, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate and ammonium hydroxide can be contained.

When the processing of the present invention is carried out while replenishing the bleach-fixing solution (bath) with a bleach-fixing replenisher, the bleach-fixing solution (bath) may contain thiosulfate, thiocyanate, sulfite or the like, The bleach-fixing replenisher may contain these salts and be replenished to the processing bath.

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

[Specific effects of the invention] According to the present invention, static fog is less likely to occur in the coating step during the production of a silver halide photographic light-sensitive material, and it has excellent slipperiness during printing in a laboratory, which is excellent in transportability, Wet pressure fog is less likely to occur during processing, and the color reproducibility, white background, and gloss of the resulting print are good, and in addition, little yellow stain is generated even when stored in a dark place for a long time. That is, in order to meet the recent demands for high image quality and high productivity, it is possible to obtain a comprehensively excellent silver halide photographic light-sensitive material for printing.

[Specific Examples of the Invention] The present inventors conducted various experiments in order to confirm the effects of the present invention, and representative examples are shown below.

Example 1 The following first to seventh layers were coated on a reflective support made of polyethylene-coated paper to prepare 20 kinds of samples in total.

First layer: Blue-sensitive silver chlorobromide emulsion layer A silver chlorobromide emulsion containing 5 mol% of silver chloride and the following yellow coupler (Y-1) and 2,5-di- (t) -octylhydroquinone are dioctyl. It was applied using an emulsion dispersion prepared by dissolving it in phthalate.

Second layer ... First intermediate layer Coating was performed using an emulsion dispersion prepared by dissolving 2,5-di- (t) -octylhydroquinone in dioctylphthalate.

Third layer: green light-sensitive silver chlorobromide emulsion layer A silver chlorobromide emulsion containing 30 mol% of silver chloride and having a monodispersity S = 0.12, and a magenta coupler and 2,5-di-diazo shown in Table 2. An emulsion dispersion prepared by dissolving-(t) -octylhydroquinone in dioctyl phthalate and a hardener shown in Table 2 were used for coating.

4th layer ... 2nd intermediate layer The following ultraviolet absorber (UV-1) and 2,5-di- (t) -octylhydroquinone were dissolved in dioctylphthalate and applied using an emulsion dispersion prepared.

Fifth layer: red-sensitive silver chlorobromide emulsion layer A silver chlorobromide emulsion containing 30 mol% of silver chloride and the following cyan coupler (C-1) and 2,5-di- (t) -hydroquinone are dioctyl. It was applied using an emulsion dispersion prepared by dissolving it in phthalate.

6th layer ... 3rd intermediate layer The following ultraviolet absorber (UV-1) and 2,5-di-tertiary-octylhydroquinone were dissolved in dioctylphthalate to form an emulsion dispersion, which was applied.

Seventh layer ... Protective layer Gelatin and a fine particle powder shown in Table-2 were dispersed in water, and a compound shown in Table-2 was used as a hardening agent.

The amounts of the main components (mg amount per 100 cm ² ) of each layer are shown in Table 1.

The performance was evaluated by the method shown below for a total of 20 types of samples (sample numbers 1 to 20) created in this way, and the results are shown in Table-
Summarized in 3.

(1) Fogging resistance against raw sample storage The sample (A) stored for 3 months at 25 ° C and 60% relative humidity and the fresh comparative sample (B) after production were subjected to the following treatments after the end-exposure, and were subjected to fogging. Color densitometer PD
The green density was measured with an A-60 type (manufactured by Konishi Rokusha Kogyo Co., Ltd.).

Raw sample storage fog = Preserved sample fog-Comparative sample fog Standard processing process (processing temperature and processing time) [1] Color development 38 ° C 3 minutes 30 seconds [2] Bleach fixing 33 ° C 1 minute 30 seconds [3] Washing treatment 25 -30 ° C 3 minutes [4] Dry 75-80 ° C Approx. 2 minutes Processing solution composition (color development tank solution) Benzyl alcohol 15ml Ethylene glycol 15ml Potassium sulfite 2.0g Potassium bromide 0.7g Sodium chloride 0.2g Potassium carbonate 30.0g Hydroxyl Amine sulfate 3.0g Polyphosphoric acid (TPPS) 2.5g 3-Methyl-4-amino-N-ethyl-N- (β-methanesulfonamidoethyl) aniline sulfate 5.5g Optical brightener (4,4'-diamino) Stil benz sulfonic acid derivative) 1.0 g Potassium hydroxide 2.0 g Add water to adjust the total volume to 1 and adjust to pH 10.20.

(Bleaching and fixing tank liquid) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% solution) 100ml Ammonium sulfite (40% solution) 27.5ml Adjust to pH 7.1 with potassium carbonate or glacial acetic acid. , And add water to bring the total volume to 1.

(2) Wet pressure fog resistance While developing an unexposed sample with the above color developing solution at 33 ° C., a ball point needle with a ball diameter of 0.3 mm is erected perpendicularly to the sample surface in the color developing solution. 0 to 50 on the ball point needle at the same time while applying parallel coating at a speed of 1 cm / sec.
After the load is continuously changed and the developing process is performed, the load at which magenta fog is generated is recorded to obtain the wet pressure fog resistance. It is evaluated that the larger the value of this load is, the more excellent the wet pressure fog resistance is.

(3) Glossiness Each sample was subjected to the above-mentioned development treatment without being exposed, and then the incident light angle was measured using a gloss meter (produced by Tokyo Denshoku Co., Ltd.)
The glossiness (%) was measured under the condition of 60 ° C. The larger this value is, the better the glossiness is evaluated.

(4) Sliding property (static friction coefficient) After leaving the undeveloped sample for 4 hours at 23 ° C and 80% relative humidity, a load of 5g was applied using a universal testing machine TE-501 (manufactured by Tester Sangyo Co., Ltd.). The coefficient of static friction was measured under the conditions of / cm ² and a moving speed of 50 cm / min to determine the slip property. It is evaluated that the lower this value is, the more excellent the slip property is.

Raw sample storage fog is 0.03 or less, wet pressure fog resistance is 20
If the gloss is not less than g and the glossiness is not more than 90%, there is a visual problem after printing, and the image quality is greatly impaired.

The slip property is preferably 0.15 or less, and when it is 0.3 or more, it is a practical problem.

Only the samples of the present invention (Sample Nos. 9 to 11 and 13 to 20) satisfy all of the above performances in view of the above criteria, and the performances are not affected by the layer distribution of the hardener. I also understand that.

It was also confirmed that the sample of the present invention is excellent in the generation of yellow stain on a white background when stored in a dark place for a long time.

Example-2 In Example-1, the cyan coupler in the red-sensitive silver chlorobromide emulsion layer was replaced with C-1 in the following C-2 and Example 1.
2 mg / dm ² of each of C-1 used in Example 1 was added, and silver chlorobromide, a magenta coupler and a hardener in the green-sensitive silver chlorobromide emulsion layer, and a matting agent and a hardener in the protective layer. Was changed as shown in Table 4 to prepare 16 kinds of samples in total.

The above 16 kinds of samples (Sample Nos. 21 to 36) were used in Example 1.
The results are summarized in Table-5.

Samples of the present invention (Sample Nos. 22 to 36) were prepared in the same manner as in Example 1.
It was possible to confirm that the sample was suitable for the purpose of the present invention, because all the performances of raw sample storage fog, wet pressure fog resistance, glossiness and slipperiness were satisfied.

Comparative Example The hardeners of the third layer and the seventh layer of Sample No. 10 of Example 1 are shown in the table.
Samples 40 and 41 modified as in Example 3 were prepared.

This sample was treated in the same manner as in Example 1 and the performance of the sample was evaluated. The results are shown in Table-4. From the results in Table 4, it is understood that the samples of the present invention are superior to the comparative samples 40 and 41 in terms of raw sample storage fog, wet pressure fog resistance, gloss and slipperiness.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication G03C 7/38

Claims (4)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer and a non-photosensitive layer on a reflective support, wherein at least one of the silver halide emulsion layers is represented by the following general formula [I]. An average grain size of 0.5 is contained in the non-photosensitive layer which contains the indicated magenta coupler and is farthest from the support on the silver halide emulsion layer side.
A silver halide emulsion layer containing at least the magenta coupler and a non-photosensitive layer containing the fine particle powder have the following general formulas [HI] and [H-II]. ] A silver halide photographic light-sensitive material characterized by being hardened with at least one hardener selected from the group consisting of General formula [I] [In the formula, Z represents a non-metal atom group necessary for forming a nitrogen-containing heterocycle, and the ring formed by Z may have a substituent. X represents a hydrogen atom or a group which is released by a reaction with an oxidized product of a color developing agent. R represents a hydrogen atom or a substituent. ] General formula [HI] [Wherein R ₁ is a chlorine atom, a hydroxy group, an alkyl group, an alkoxy group, an alkylthio group, an -OM group (M represents a monovalent metal atom), -NR'R "or -NHCOR (R ',
R ″ and R each represent a hydrogen atom, an alkyl group or an aryl group), and R ₂ has the same meaning as R ₁ excluding a chlorine atom.] General formula [H-II] [In the formula, R ₃ and R ₄ represent a chlorine atom, a hydroxy group, an alkyl group, an alkoxy group, and an -OM group (M represents a monovalent metal atom), and -Q- and -Q'- are each- O
Represents a-, -S- or -NH- linking group, L represents an alkylene group or an aryl group, and l and m each represent 0 or 1. ] 2. The silver halide emulsion layer containing a magenta coupler represented by the general formula [I] contains a monodisperse silver halide emulsion, as set forth in claim (1). Silver halide photographic light-sensitive material. 3. A silver halide emulsion layer containing a magenta coupler represented by the general formula [I] has a silver chloride content of
The silver halide photographic light-sensitive material according to claim (1) or (2), which contains substantially 30 to 70 mol% of silver chlorobromide grains. 4. At least one hardener selected from the hardeners represented by the general formulas [H-1] and [H-2] is an aldehyde-based, aziridine-based, epoxy-based or vinylsulfone-based hardener. Claims (1), (2) or (3), characterized by being used in combination with
A silver halide photographic light-sensitive material as described in the above item.