EP0422595A1

EP0422595A1 - A silver halide color photographic light-sensitive material

Info

Publication number: EP0422595A1
Application number: EP90119366A
Authority: EP
Inventors: Katsumasa Yamazaki; Shigeto Hirabayashi
Original assignee: Konica Minolta Inc
Current assignee: Konica Minolta Inc
Priority date: 1989-10-12
Filing date: 1990-10-09
Publication date: 1991-04-17
Also published as: JPH03126031A

Abstract

There is disclosed a silver halide light-sensitive photographic material having improved graininess and processing stability. The light-sensitive material has on a support at least one green-sensitive layer containing a magenta coupler represented by Formula M-I and a compound represented by Formula A-I:

wherein Z represents the group of non-metallic atoms for forming a nitrogen containing heterocyclic ring; X represents a hydrogen atom or a substituent capable of splitting off by a reaction with an oxidation product of a developer; and R represents a hydrogen atom or a substituent;
Formula A-I
H O (̵J)̵ C O O Y
wherein J represents a divalent organic group; Y represents an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an alkynyl group, a cycloalkenyl group and a heterocycilc group.

Description

FIELD OF THE INVENTION

The present invention relates to a silver halide color photographic light-sensitive material having an excellent processing stability and improved graininess.

BACKGROUND OF THE INVENTION

In recent years, there have been studying light-sensitive materials having higher image quality, in particular, more excellent color reproducibility, graininess and sharpness.
U.S. Patent No. 3,725,067, Japanese Patent Open to Public Inspection (hereinafter referred to as Japanese Patent O.P.I. Publication) Nos. 42045/1983, 171956/1984, 43659/1985 and 190779/1985 each disclose the methods of improving color reproducibility by use of magenta couplers which form dyes having no secondary absorptions.
The pyrazoloazole magenta couplers significantly improve the reproducibility of red color while there exists such a problem that a density of a dye image is liable to vary by change of processing conditions, in particular, pH change of a developer.
In the invention, it has been found that the preceding problem can be solved by use of the pyrazoloazole magenta couplers in combination with a compound having a hydroxyl group and an ester group.

SUMMARY OF THE INVENTION

The primary object of the invention is to provide a silver halide color photographic light-sensitive material having an improved processing stability and graininess.
The secondary object of the invention is to provide a light-sensitive material capable of providing a dye image having a stable color density against change of processing conditions, in particular, pH change of a developer.
The above objects can be attained by a silver halide color photographic light-sensitive material comprising a support and provided thereon plural light-sensitive layers including at least one green-sensitive layer, wherein the at least one green-sensitive layer contains a magenta coupler represented by Formula M-I and a compound represented by Formula A-I:
wherein Z represents a group of non-metal atoms necessary to form a nitrogen-containing heterocycle which may have a substituent; X represents a hydrogen atom or a group which can be released by a reaction with an oxidation product of a color developing agent; and R represents a hydrogen atom or a substituent;
Formura A-I
H O (̵J)̵ C O O Y
wherein J represents a divalent organic group; and Y represents an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an alkynyl group, a cycloalkenyl group and a heterocyclic group.

DETAILED DESCRIPTION OF THE INVENTION

In Formula M-1, the examples of the substituent represented by R are an alkyl group, an aryl group, an anilino group, an acylamino group, a sulfonamide group, an alkylthio group, an arylthio group, an alkenyl group, a cycloalkyl group, a halogen atom, a cycloalkenyl group, an alkynyl group, a heterocyclic group, a sulfonyl group, a sulfinyl group, a phosphonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a cyano group, an alkoxy group, an aryloxy group, a heterocyclicoxy group, a siloxy group, an acyloxy group, a carbamoyloxy group, an amino group, an alkylamino group, an imido group, an ureido group, a sulfamoylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclicthio group, a spiro compound residue and a bridged hydrocarbon residue.
The respective groups represented by R are as follows: the alkyl group has preferably 1 to 32 carbon atoms and may be linear or branched; the aryl group is preferably phenyl; the examples of the acylamino group are alkylcarbonylamino and arylcarbonylamino; the examples of the sulfonamide group are alkylsufonylamino and arylsulfonylamino; the alkyl and aryl components in the alkylthio and arylthio groups may be the same as the above alkyl and aryl groups; the alkenyl group has preferably 2 to 32 carbon atoms and may be linear or branched; the cycloalkyl and cycloalkenyl groups each have preferably 3 to 12, more preferably 5 to 7 carbon atoms; the examples of the sulfonyl group are alkylsulfonyl and arylsulfonyl; the examples of the sulfinyl group are alkylsulfinyl and arylsulfinyl; the examples of the phosphonyl group are alkylphosphonyl, alkoxyphosphonyl, aryloxyphosphonyl and arylphosphonyl; the examples of the acyl group are alkylcarbonyl and arylcarbonyl; the examples of the carbamoyl group are alkylcarbamoyl and arylcarbamoyl; the examples of the sulfamoyl group are alkylsulfamoyl and arylsulfamoyl; the examples of the acyloxy group are alkylcarbonyloxy and arylcarbonyloxy; the examples of the carbamoyloxy are alkylcarbamoyloxy and arylcarbamoyloxy; the examples of the ureido group are alkylureido and arylureido; the examples of the sulfamoylamino group are alkylsulfamoylamino and arylsufamoylamino; the heterocyclic group is preferably a 5 to 7-membered ring such as 2-furyl, 2-thienyl, 2-pyrimidyl and 2-benzothiazolyl; the heterocyclicoxy group is preferably a 5 to 7-membered ring such as 3,4,5,6-tetrahydropyranyl-2-oxy and 1-phenyltetrazole-5-oxy; the heterocyclicthio group is preferably a 5 to 7-membered ring such as 2-pyridylthio, 2-benzothiazolylthio and 2,4-diphenoxy-1,3,5-triazole-6-thio; the examples of the siloxy group are trimethylsiloxy, triethylsiloxy and dimethylbutylsiloxy; the examples of the imido group are succinic imido, 3-heptadecyl succinic imido, phthalimido and glutarimido; the spiro compound residue includes a spiro [3.3] heptane-1-yl; the examples of the bridged hydrocarbon compound residue are bicyclo [2.2.1] heptane-1-yl, tricyclo [3.3.1.1 ³,⁷] decane-1-yl and 7,7-dimethyl-bicyclo [2.2.1] heptane-1-yl.
The examples of the group represented by X are a halogen atom, an alkoxy group, an aryloxy group, a heterocyclicoxy group, an acyloxy group, a sulfonyloxy group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an alkyloxalyloxy group, an alkoxyoxalyoxy group, an alkylthio group, an arylthio group, a heterocyclicthio group, an alkoxythiocarbonylthio group, an acylamino group, a sulfonamide group, a nitrogen-containing heterocycle having a bonding site at the nitrogen atom, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a carboxyl group,
wherein R₁′ and Z′ are the same groups as those defined for R and Z in Formula M-I, respectively, and R₂′ and R₃′ each represent a hydrogen atom, an aryl group, an alkyl group and a heterocyclic group. Of them, a halogen atom, in particular chlorine is preferable.
The nitrogen-containing heterocycles formed by Z and Z′ are a pyrazole ring, an imidazole ring, a triazole ring and a tetrazole ring, and may have the same substituents as those defined for R.
The magenta coupler represented by M-I are represented by the following Formulae M-II to M-VII:
wherein R₁ to R₈ and X represent the same groups as those defined for R and X in Formula M-I, respectively.
The magenta coupler represented by Formula M-I is represented preferably by the following Formula M-VIII:
wherein R₁, X and Z₁ represent the same groups as those defined for R, X and Z in Formula M-I, respectively.
Of the magenta couplers represented by Formulae M-II to M-VII, preferable are those represented by Formula M-II.
The substituents for the rings formed by Z in Formula M-I and Z₁ in Formula M-VIII and the groups represented by R₂ to R₆ in Formula M-II to M-VI are represented preferably by the following Formula M-IX:
Formura M-IX
- R¹ - SO₂ - R₂
wherein R₁ represents an alkylene group and R₂ represents an alkyl group, a cycloalkyl group or an aryl group. R₁ or R₂ has preferably at least one acid group. This acid group is preferably a carboxylic group or a sulfonic group, more preferably a carboxylic group or a salt thereof.
The alkylene group represented by R₁ is a linear or branched alkylene group which has preferably 2 or more, more preferably 3 to 6 carbon atoms in its linear structure. The cycloalkyl group represented by R₂ is preferably 5 to 6-membered.
When the light-sensitive material is used for forming a positive image, R and R₁ are preferably the groups represented by Formula M-X:
wherein R₉, R₁₀ and R₁₁ each represent the same groups as those defined for R, provided that two of R₉, R₁₀ and R₁₁ may combine to form a saturated or unsaturated ring such as cycloalkane, cycloalkene and heterocycle and that R₉ or R₁₁ may combine with this ring to form a bridged hydrocarbon residue.
Of the substituents represented by Formula M-X, preferable is (i) the one in which at least two of R₉ to R₁₁ are alkyl groups, or (ii) the one in which at least one of R₉ to R₁₁ is a hydrogen atom and the remaining two combine to form a cycloalkyl group.
In the case of (i), further preferable is the one in which two of R₉ to R₁₁ are alkyl groups and the remaining one is either a hydrogen atom or an alkyl group.
When the light-sensitive material is used for forming a negative image, R and R₁ are preferably those represented by Formula M-XI:
Formura M-XI
R₁₂ - CH₂ -
wherein R₁₂ is the same group as that defined for R.
R₁₂ is preferably a hydrogen atom or an alkyl group.
The examples of the above magenta couplers are given below:
The other examples of the magenta couplers usable in the invention are described in Japanese Patent Application No. 9791/1986.
The preceding magenta couplers can be synthesized by the methods described in Journal of the Chemical Society, Perkin I (1977), pp. 2047 to 2052, U.S. Patent No. 3,725,067, Japanese Patent O.P.I. Publication No. 99437/1984, 42045/1983, 162548/1984, 171956/1984, 33552/1985, 43659/1985, 172982/1985 and 190779/1985.
The preceding magenta couplers are added normally in an amount of 1 x 10⁻³ to 1 mol, preferably 1 x 10⁻² to 8 x 10⁻¹ mol per mol of silver halide, and may be used in combination with other couplers.
Next, the compound represented by Formula A-I is explained below.
The examples of the divalent organic group represented by J are an alkylene group, an alkenylene group, a cycloalkylene group, a carbonyl group, a carbonyloxy group, an allylene group and a heterocyclic group, each of which may have a substituent. Of them, the above group is preferably an arylene group, more preferably a phenylene group.
The alkyl, cycloalkyl, aryl, alkenyl, alkynyl and cycloalkenyl groups represented by Y each have preferably 1 to 32 carbon atoms and may have a substituent. The alkyl, alkenyl and alkynyl groups may be either linear or branched.
The heterocyclic group represented by Y is preferably a nitrogen-containing heterocyclic group such as pyrrolyl, pyrazolyl, imidazolyl, pyridyl, pyrrolinyl, imidazolidinyl, imidazolinyl, piperadinyl and piperidinyl, each of which may have a substituent.
The examples of the compound represented by Formula A-I are given below:
In the invention, the magenta coupler represented by Formula M-I (hereinafter referred to as Magenta coupler M-I) and the compound represented by Formula A-I (hereinafter referred to as Compound A-I) are incorporated into at least one of the green-sensitive layers.
Magenta coupler M-I and Compound A-I can be added by a known method; Magenta coupler M-I and Compound A-I are dissolved singly or in combination in a mixed solvent of a high boiling solvent such as dibutyl phthalate and tricresyl phosphate and a low boiling solvent such as butyl acetate and propionic acid; the solution is dispersed in a gelatin solution containing a surfactant with a high-speed rotary mixer, a colloid mill or an ultrasonic apparatus; and the dispersion is added to an emulsion, or the gelatinized dispersion is cut into pieces, rinsed and then added to an emulsion.
In the invention, Magenta coupler M-I and Compound A-I are added to a silver halide emulsion after dispersing them separately by the above dispersion method, and the dispersion containing both compounds is added to an emulsion.
The amount of Compound A-I is preferably 0.01 to 10 g, more preferably 0.1 to 3.0 g per gram of Magenta coupler M-I. Compound A-I may be employed either alone or in combination.
The silver halide emulsions used in the invention may be conventional ones.
The silver halide emulsions can be chemically sensitized by conventional methods, and can be spectrally sensitized to a prescribed wavelength region with a sensitizing dye,
The silver halide emulsion may contain such an additive as antifoggant and a stabilizer. Gelatin is preferably used as a binder.
The emulsion layers and other hydrophilic colloidal layers may be hardened and contain a plasticizer an a latex.
Also usable are a colored coupler, a competitive coupler and a compound which releases by a coupling reaction with an oxidation product of a development agent such photographically significant fragments as a development accelerator, a bleaching accelerator, a developing agent, a silver halide solvent, a toning agent, a hardener, a fogging agent, an antifoggant, a chemical sensitizer, a spectral sensitizer and a desensitizer.
There may be provided auxiliary layers such as a filter layer, an anti-hallation layer and an anti-irradiation layer. These layers and/or the emulsion layers may contain a dye which can be removed from the light-sensitive material or bleached during development.
The light-sensitive material may contain a formalin scavenger, a fluorescent bleaching agent, a matting agent, a lubricant, an image stabilizer, a surfactant, an anti-fogging agent, a development accelerator, a development retarder and a bleaching accelerator.
The examples of the support are polyethylene-laminated paper, a polyethylene terephthalate film, baryta paper and a cellulose triacetate film.
A dye image can be obtained by processing an exposed light-sensitive material by conventional methods.

EXAMPLES

The present invention will be described in more detail with reference to the following Examples.
In the examples, the amounts of ingredients are given by g/m² unless otherwise indicated. The amounts of silver halide and colloidal silver are converted to the amounts of silver,

Example 1

A multilayer color photographic light-sensitive material (Sample No. 1) was prepared by providing on a cellulose triacetate film support the layers of the following constitutions in sequence from the support.

1st Layer: Anti-halation layer (HC-1)
Black colloidal silver	0.20
UV absorber (UV-1)	0.20
Colored coupler (CC-1)	0.05
Colored coupler (CM-1)	0.05
High boiling solvent (Oiℓ-1)	0.20
Gelatin	1.5

2nd Layer: Intermediate layer (IL-1)
UV absorber (UV-1)	0.01
High boiling solvent (Oiℓ-1)	0.01
Gelatin	1.5

3rd Layer: Low-speed red-sensitive emulsion layer (RL)
Silver iodobromide emulsion (Em-1)	0.8
Silver iodobromide emulsion (Em-2)	0.8
Sensitizing dye (SD-1) 2.5 x 10⁻⁴ (mol per mol silver)
Sensitizing dye (SD-2) 2.5 x 10⁻⁴ (mol per mol silver)
Sensitizing dye (SD-3) 0.5 x 10⁻⁴ (mol per mol silver)
Cyan coupler (C-1)	1.0
Colored cyan coupler (CC-1)	0.05
DIR compound (D-1)	0.002
High boiling solvent (Oiℓ-1)	0.5
Gelatin	1.5

4th Layer: high-speed red-sensitive emulsion layer(RH)
Silver iodobromide emulsion (Em-3)	2.0
Sensitizing dye (SD-1) 2.0 x 10⁻⁴ (mol per mol silver)
Sensitizing dye (SD-2) 2.0 x 10⁻⁴ (mol per mol silver)
Sensitizing dye (SD-3) 0.1 x 10⁻⁴ (mol per mol silver)
Cyan coupler (C-1)	0.25
Cyan coupler (C-2)	0.05
Colored cyan coupler (CC-1)	0.015
DIR compound (D-1)	0.05
High boiling solvent (Oiℓ-1)	0.2
Gelatin	1.5

5th Layer: Intermediate layer (IL-2)
Gelatin	0.5

6th Layer: low-speed green-sensitive emulsion layer (GL)
Silver iodobromide emulsion (Em-1)	1.0
Sensitizing dye (SD-4) 5 x 10⁻⁴ (mol per mol silver)
Sensitizing dye (SD-5) 1 x 10⁻⁴ (mol per mol silver)
Magenta coupler (M-A)	0.1
Magenta coupler (M-B)	0.2
Colored magenta coupler (CM-1)	0.01
DIR compound (D-3)	0.02
DIR compound (D-4)	0.02
High boiling solvent (Oiℓ-2)	0.3
Gelatin	1.0

7th Layer: high-speed green-sensitive emulsion layer (GH)
Silver iodobromide emulsion (Em-3)	1.3
Sensitizing dye (SD-6) 1.5 x 10⁻⁴ (mol per mol silver)
Sensitizing dye (SD-7) 2.5 x 10⁻⁴ (mol per mol silver)
Sensitizing dye (SD-8) 0.5 x 10⁻⁴ (mol per mol silver)
Magenta coupler (M-A)	0.05
Magenta coupler (M-B)	0.15
Colored magenta coupler (CM-2)	0.05
DIR compound (D-3)	0.01
High boiling solvent (Oiℓ-2)	0.5
Gelatin	1.0

8th Layer: Yellow filter layer (YC)
Yellow colloid silver	0.1
Anti-stain agent (SC-1)	0.1
High boiling solvent (Oiℓ-3)	0.1
Gelatin	0.8

9th Layer: low-speed blue-sensitive emulsion layer (BL)
Silver iodobromide emulsion (Em-1)	0.25
Silver iodobromide emulsion (Em-2)	0.25
Sensitizing dye (SD-10) 7 x 10⁻⁴ (mol per mol silver)
Yellow coupler (Y-1)	0.5
Yellow coupler (Y-2)	0.1
DIR compound (D-2)	0.01
High boiling solvent (Oiℓ-2)	0.3
Gelatin	1.0

10th Layer: high-speed blue-sensitive emulsion layer (BH)
Silver iodobromide emulsion (Em-4)	0.4
Silver iodobromide emulsion (Em-1)	0.4
Sensitizing dye (SD-9) 1 x 10⁻⁴ (mol per mol silver)
Sensitizing dye (SD-10) 3 x 10⁻⁴ (mol per mol silver)
Yellow coupler (Y-1)	0.30
Yellow coupler (Y-2)	0.05
High boiling solvent (Oiℓ-2)	0.15
Gelatin	1.1

11th Layer: 1st protective layer (PRO-1)
Fine-grained silver iodobromide emulsion (average gain size: 0.08 µm, AgI content: 2 mol%)	0.4
UV absorber (UV-1)	0.10
UV absorber (UV-2)	0.05
High boiling solvent (Oiℓ-1)	0.1
High boiling solvent (Oiℓ-3)	0.1
Formalin scavenger (HS-1)	0.5
Formalin scavenger (HS-2)	0.2
Gelatin	1.0

12th Layer: 2nd protective layer (PRO-2)
Surfactant (Su-1)	0.005
Alkaline-soluble matting agent (average grain size: 2 µm)	0.05
Polymethylmethacrylate (average grain size: 3 µm)	0.05
Lubricant (WAX-1)	0.04
Gelatin	0.6

Besides the above ingredients, a coating aid (Su-2), a dispersion aid (Su-3), hardeners (H-1 and H-2), a stabilizer (ST-1), antifoggants (AF-1, AF-2) were added to each layer.

Em-1: a monodispersed core/shell type silver halide emulsion having a grain size distribution of 14% and a low silver iodide content (2 mol%) in the outermost shell (average grain size: 0.46 µm, average silver iodide content: 7.0 mol%)
Em-2: a monodispersed core/shell type silver halide emulsion having a grain size distribution of 14% and containing silver bromide in the outermost shell (average grain size: 0.30 µm, average silver iodide content: 2.0 mol%)
Em-3: a monodispersed core/shell type silver halide emulsion having a grain size distribution of 14% and alow silver iodide content (1.0 mol%) in the outermost shell (average grain size: 0.81 µm, average silver iodide content: 7.0 mol%)
Em-4: a monodispersed core/shell type silver halide emulsion having a grain size distribution of 14% and alow silver iodide content (0.5 mol%) in the outermost shell (average grain size:0.95 µm, average silver iodide content: 8.0 mol%)

The grain size distribution is defined by the following equation:

Samples No. 2 to 14 were prepared in the same manner as in Sample No.1, except that the magenta couplers in the 6th and 7th layers were replaced as shown in Table 1 and that Compounds A-I were added to the 6th and 7th layers.

Table 1

Sample No.	6th layer				7th layer
	Coupler		Compound [A-I]		Coupler		Compound [A-I]
	No.	Amount	No.	Amount	No.	Amount	No.	Amount
1 (Comparison)	M-A	0.1	-	-	M-A	0.18	-	-
	M-B	0.2
2 (Comparison)	M-4	0.2	-	-	M-4	0.12	-	-
3 (Comparison)	M-57	0.2	-	-	M-57	0.1	-	-
4 (Invention)	M-4	0.2	A-16	0.1	M-A	0.18	-	-
5 (Invention)	M-4	0.2	A-16	0.1	M-4	0.12	A-16	0.05
6 (Invention)	M-4	0.2	A-17	0.1	M-4	0.12	A-17	0.05
7 (Invention)	M-4	0.2	A-2	0.1	M-4	0.12	A-2	0.05
8 (Invention)	M-4	0.22	A-24	0.15	M-4	0.12	A-13	0.05
9 (Invention)	M-1	0.2	A-12	0.1	M-1	0.12	A-12	0.05
10 (Invention)	M-5	0.2	A-19	0.12	M-5	0.12	A-19	0.06
11 (Invention)	M-10	0.2	A-18	0.1	M-10	0.12	A-18	0.05
12 (Invention)	M-57	0.2	A-16	0.1	M-57	0.12	A-16	0.05
13 (Invention)	M-58	0.2	A-16	0.1	M-58	0.12	A-16	0.05
14 (Invention)	M-59	0.2	A-11	0.09	M-59	0.12	A-11	0.05

Each sample was exposed to white light through an optical wedge for 1/100 seconds, and subjected to the following Processing.

Processing (38°C)
Color developing	3 min. 15 sec.
Bleaching	6 min. 30 sec.
Washing	3 min. 15 sec.
Fixing	6 min. 30 sec.
Washing	3 min. 15 sec.
Stabilizing	1 min. 30 sec.
Drying

The composition of each processing liquid is as follows:

Color developer
4-Amino-3-methyl-N-ethyl-N-(β-hydroxylethyl)-aniline sulfate	4.75 g
Sodium sulfite anhydrous	4.25 g
Hydroxylamine 1/2 sulfate	2.0 g
Potassium carbonate anhydrous	37.5 g
Potassium bromide	1.3 g
Trisodium nitrilotriacetate (monohydrate)	2.5 g
Potassium hydroxide	1.0 g
Water wa added to make a total quantity 1ℓ (pH=10.2)

Bleacher
Ferric ammonium ethylenediaminetetraacetate	100.0 g
Diammonium ethylenediaminetetraacetate	10.0 g
Ammonium bromide	150.0 g
Glacial acetic acid	10 mℓ
Water was added to make a total quantity 1ℓ and pH was adjusted to 6.0 with aqueous ammonia.

Fixer
Ammonium thiosulfate	175.0 g
Ammonium sulfite anhydrous	8.5 g
Sodium metasulfite	2.3 g
Water was added to make a total quantity 1ℓ and pH was adjusted to 6.0 with acetic acid.

Stabilizer
Formalin (37% solution)	1.5 mℓ
Konidax (manufactured by Konica Corp)	7.5 mℓ
Water was added to make a total quantity 1ℓ.

Graininess was evaluated in terms of RMS value. An RMS value was determined by a standard deviation of a variation of a density, which was observed when scanning a portion of 250 µm² on a magenta dye image having the density of the minimum density + 0.5 with a Sakura microdensitometer (model PDM-5, Type AR, manufactured by Konica Corp), and expressed by a value relative to that of Sample No. 1, which was set at 100.
Processing stability was evaluated by varying pH of the developer from 10.0 to 10.4 and observing a variation of a gamma value on the characteristic curve of a magenta dye image.
The gamma value variation is defined by the following equation, wherein A and B are the gamma values at pH 10.4 and 10.0 respectively:
Gamma value variation=(B/A-1) x 100

The smaller this value, the smaller the difference in gamma value. The results are shown in Table 2.

Table 2.

Sample No.	Graininess	Processing stability
1 (Comparison)	100	25
2 (Comparison)	92	36
3 (Comparison)	93	35
4 (Invention)	89	20
5 (Invention)	83	15
6 (Invention)	86	16
7 (Invention)	89	18
8 (Invention)	87	17
9 (Invention)	85	15
10 (Invention)	86	16
11 (Invention)	82	13
12 (Invention)	87	17
13 (Invention)	81	14
14 (Invention)	83	13

As is evident from the results, the samples of the invention are significantly improved in graininess and processing stability.

Example 2

The layers of the following constitutions were provided on a polyethylene-laminated paper support in sequence from the support to prepare Sample No. 15

1st Layer: blue-sensitive layer

Silver chlorobromide emulsion (silver chloride content: 99.3 mol%) 0.32

Yellow coupler (Y-3) 0.8

High boiling solvent (Oiℓ-1) 0.5

Gelatin 1.2

2nd Layer: anti-irradiation layer

Anti-irradiation dye (AI-1) 0.03

Anti-irradiation dye (AI-2) 0.02

Gelatin 0.7

3rd Layer: green-sensitive layer

Silver chlorobromide emulsion (silver chloride content: 99.7 mol%) 0.25

Magenta coupler (M-56) 0.6

High boiling solvent (Oiℓ-1) 0.3

Gelatin 1.25

4th Layer: interlayer

Gelatin 1.02

5th Layer: red-sensitive layer

Silver chlorobromide emulsion (silver chloride content: 99.7%) 0.3

Cyan coupler (C-3) 0.9

High boiling solvent (Oiℓ-1) 0.5

Gelatin 1.2

6th Layer: UV absorbing layer

UV absorber (UV-3) 0.3

High boiling solvent (Oiℓ-1) 0.2

Gelatin 1.0

7th Layer: protective layer

Gelatin 0.5
Sodium 4-dichloro-6-hydroxy-s-triazine was added as a hardener to each of the 2nd, 4th and 7th layers in an amount of 0.017 g per gram of gelatin.
Samples No. 16 to 19 of the invention were prepared in the same manner as above, except that the magenta coupler was replaced as shown in Table 3 and that Compounds A-I were added.

Each sample was exposed in the same manner as in Example 1 and subjected to the following processing, in which pH of the developer was varied from 10.0 to 10.4 to evaluate processing stability in the same manner as in Example 1.

Processing
	Temperature	Time
Color developer	34.7 ± 0.3°C	45 sec
Bleach-fixing	34.7 ± 0.5°C	50 sec
Stabilizing	30 to 34°C	90 sec
Drying	60 to 80°C	60 sec

Color developer
Pure water	800 mℓ
Triethanolamine	8 g
N,N-diethylhydroxylamine	5 g
Potassium chloride	2 g
N-ethyl-N-β-methanesulfonamidethyl-3-methyl-4-aminoaniline sulfate	5 g
Sodium tetrapolyphosphate	2 g
Potassium carbonate	30 g
Potassium sulfite	0.2 g

Fluorescent bleaching agent (4,4-diaminostilbene disulfonic acid derivative)	1 g
Water was added to make a total quantity 1ℓ.

Bleach-fixer
Ferric ammonium ethylenediaminetetraacetate dihydrate	60 g
Ethylenediaminetetraacetic acid	3 g
Ammonium thiosulfate (70% solution)	100 mℓ
Ammonium sulfite (40% solution)	27.5 mℓ
Water was added to make a total quantity 1ℓ and pH as adjusted to 5.7 with potassium carbonate or glacial acetic acid.

Stabilizer
5-Chloro-2-methyl-4-isothiazoline-3-one	1 g
1-Hydroxyethylidene-1,1-diphosphonic acid	2 g
Water was added to make a total quantity 1ℓ, and pH was adjusted to 7.0 with sulfuric acid or potassium hydroxide.

Table 3

Sample No.	Coupler		Compound A-I		Processing stability
	No.	Amount	No.	Amount
15 (Comparison)	M-56	0.6	-	-	45
16 (Invention)	M-56	0.6	A-3	0.3	25
17 (Invention)	M-56	0.6	A-16	0.3	19
18 (Invention)	M-56	0.6	A-19	0.3	21
19 (Invention)	M-60	0.6	A-17	0.3	20

As is evident from the results shown in Table 3, the samples of the invention were significantly improved in processing stability.

Claims

1. A silver halide light-sensitive photographic material comprising
a support and provided thereon plural and light-sensitive layers including
at least one green-sensitive layer
wherein the at least one green-sensitive layer contains a magenta coupler represented by Formula M-I and a compound represented by Formula A-I:

wherein Z represents the group of non-metallic atoms for forming a nitrogen-containing heterocyclic ring; X represents a hydrogen atom or a substituent capable of splitting off by a reaction with an oxidation product of a developer; and R represents a hydrogen atom or a substituent;
Formula A-I
H O (̵J)̵ C O O Y
wherein J represents a divalent organic group; Y represents an alkyl group, a cycloalkyl group, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkenyl group and a heterocycilc group.

2. The photographic material of claim 1, wherein the organic group represented by J is an alkylene group an alkenylene group, a cycloalkylene group, a carbonyl group, a carbonyloxy group, an arylene group and a heterocyclic group.

3. The photographic material of claim 2, wherein the organic group is an arylene group.

4. The photographic material of claim 3, wherein the organic group is a phenylene group.

5. The photographic material of claim 1, wherein the groups represented by Y excluding a heterocyclic group have 1 to 32 carbon atoms.

6. The photographic material of claim 1, wherein the heterocyclic group represented by Y is a nitrogen-containing heterocyclic group.

7. The photographic material of claim 6, wherein the nitrogen-containing heterocyclic group is pyrrolyl, pyrazolyl, imidazolyl, pyridyl, pyrrolinyl, imidazolidinyl, piperadinyl and piperidinyl.

8. The photographic material of claim 1, wherein an addition amount of the compound represented by Formula A-I is 0.01 to 10 g/g of a magenta coupler.

9. The photographic material of claim 8, wherein the addition amount is 0.1 to 3.0 g/g of a magenta coupler.

10. The photographic material of claim 1, wherein the substituent represnted by R is an alkyl group, an aryl group, an anilino group, an acylamino group, a sulfonamide group, an alkylthio group, an arylthio gruop, an alkenyl group, a cycloalkyl group, a halogen atom, a cycloalkenyl group, an alkynyl group, a heterocyclic group, a sulfonyl group, a sulfinyl group, a phosphonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a cyano group, an alkoxy group, an aryloxy group, a heterocyclicoxy group, a siloxy group, an acyloxy group, a carbamoyloxy group, an amino group, an alkylamino group, an imido group, a ureido group, a sulfamoylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclicthio group, a spiro compound residue, or a bridged hydrocarbon residue.

11. The photographic material of claim 1, wherein the group represnted by X is an alkoxy group, an aryloxy group, a heterocyclicoxy group, an acyloxy group, a sulfonyloxy group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an alkyloxalyloxy group, an alkoxyoxalyloxy group, an alkylthio group, an arylthio group, a heterocyclicthio group, an alkoxythiocarbonylthio group, an acylamino group, a sulfonamide group, a nitrogen-containing heterocyclic group having a bonding site at the nitrogen atom, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a carboxyl group, and

wherein R₁′ans Z′ are the same as those defined for R an Z, respectively; and R₂′ and R₃′ represent independently a hydrogen atom, an alkyl group, an aryl group and a heterocyclic group.

12. The photographic material of claim 1, wherein the nitrogen-containing heterocyclic ring formed by Z is a pyrazole ring, an imidazole ring, a triazole ring and tetrazole ring.

13. The photographic material of claim 1, wherein the magenta coupler is represnted by one of Formulas M-II to M-VII:

wherein R₁ to R₈ and X are the same as those defined for R and X in Fromula M-I, respectively.

14. The photographic material of claim 13, wherein the magenta coupler is represented by Formula M-II.

15. The photographic material of claim 13, wherein R₂ to R₆ represent independently a group represented by Formula IX:
wherein R¹ represents an alkylene group; R² represents an alkyl group, a cycloalkyl group or an aryl group.

16. The photographic material of claim 15, wherein R¹ or R² has at least one acid group.

17. The photographic material of claim 16, wherein the acid group is a carboxylic group or a sulfonic group.

18. The photographic material of claim 17, wherein the acid group is a carboxylic group or a salt thereof.