JPH0810325B2 - Silver halide photographic material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide photographic light-sensitive material suitable for rapid processing and having improved color reproducibility and light fastness of dye images.

[Background of the Invention]

In recent years, a silver halide photographic light-sensitive material (hereinafter, simply referred to as a light-sensitive material) which has high image quality and can be processed quickly has been desired in the art.

In the image quality of a dye image obtained from a light-sensitive material, it is required that the color reproducibility is good and the light resistance is excellent.

By combining a silver halide emulsion having a high silver chloride composition and a pyrazoloazole-based magenta coupler, both rapid processing suitability and color reproducibility can be satisfied, but light resistance is poor. A technique for improving the light resistance of a magenta dye image by using a piperazine-based antioxidant is disclosed in JP-A-61-72246 and 61-7.
No. 3152, No. 61-189539, etc., these methods deteriorate the suitability for rapid processing. Further, the phenolic antioxidant does not impair the suitability for rapid processing (Japanese Patent Laid-Open No. 59-12573).
No. 2, No. 60-262159, No. 61-184543, No. 61-186960,
No. 61-194444, No. 61-241753, etc.), but the effect of improving light resistance is small.

Therefore, it is required to develop a color light-sensitive material having excellent color reproducibility and light fastness, and also having suitability for rapid processing.

[Object of the Invention]

An object of the present invention is to provide a color photographic material which has improved color reproducibility and light resistance of a dye image and is suitable for rapid processing.

[Structure of Invention]

The above object of the present invention is to provide silver halide grains containing at least 80 mol% of silver chloride in at least one of the silver halide emulsion layers of a light-sensitive material having at least one silver halide emulsion layer on a support. It was achieved by incorporating a magenta coupler represented by the following general formula [M-1] and a compound represented by the following general formula [I].

General formula [MI] In the formula, Z represents a group of non-metal atoms 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 capable of splitting off upon reaction with an oxidized product of a color developing agent, and R represents a hydrogen atom or a substituent.

General formula [I] In the formula, R ¹ represents an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, a bridged hydrocarbon group, an alkylsulfonyl group or an arylsulfonyl group, and R ² can be substituted on the benzene ring. Represents a group. m is 0
Represents an integer of 4; When m is 2 or more, plural R ^{2 s} may be the same or different, and R ^{2 s} may form a ring. R ² may form a ring with —OR ¹ . A represents a non-metal atomic group necessary for forming a 5- to 8-membered ring with a nitrogen atom.

 Next, the present invention will be specifically described.

General Formula [M-I] General Formula [M-I] In the magenta coupler represented by, Z represents a nonmetallic 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 capable of leaving by reaction with an oxidized form of a color developing agent.

 R represents a hydrogen atom or a substituent.

The substituent represented by R is not particularly limited, but typical examples thereof include alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, and cycloalkyl groups. Atoms and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl,
Carbamoyl, sulfamoyl, cyano, alkoxy,
Aryloxy, heterocyclic oxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio groups , And spiro compound residues, bridged hydrocarbon compound residues and the like.

The alkyl group represented by R preferably has 1 to 32 carbon atoms, and may be linear or branched.

The aryl group represented by R is preferably a phenyl group.

Examples of the acylamino group represented by R include an alkylcarbonylamino group and an arylcarbonylamino group.

Examples of the sulfonamide group represented by R include an alkylsulfonylamino group and an arylsulfonylamino group.

The alkyl component and the aryl component in the alkylthio group and the arylthio group represented by R include the alkyl group and the aryl group represented by R.

The alkenyl group represented by R has 2 to 32 carbon atoms, and the cycloalkyl group has 3 to 12 carbon atoms, especially 5
The alkenyl group may be linear or branched.

The cycloalkenyl group represented by R has 3 carbon atoms.
-12, especially 5-7 are preferred.

The sulfonyl group represented by R is an alkylsulfonyl group, an arylsulfonyl group, etc .; The sulfinyl group is an alkylsulfinyl group, an arylsulfinyl group, etc .; The phosphonyl group is an alkylphosphonyl group, an alkoxyphosphonyl group, an aryloxyphosphonyl group. , An arylphosphonyl group, etc .; an acyl group, an alkylcarbonyl group, an arylcarbonyl group, etc .; a carbamoyl group, an alkylcarbamoyl group, an arylcarbamoyl group, etc .; a sulfamoyl group, an alkylsulfamoyl group, an arylsulfamoyl group, etc .; As the acyloxy group, an alkylcarbonyloxy group, an arylcarbonyloxy group, etc .; As the carbamoyloxy group, an alkylcarbamoyloxy group, an arylcarbamoyloxy group, etc .; a ureido group Such as alkyl ureido groups and aryl ureido groups; sulfamoylamino groups such as alkylsulfamoylamino groups and arylsulfamoylamino groups; and heterocyclic groups having 5 to 7 members are preferred. Is a 2-furyl group, a 2-thienyl group, a 2-pyrimidinyl group, a 2-benzothiazolyl group or the like; As the heterocyclic oxy group, those having a 5- to 7-membered heterocyclic ring are preferable, and for example, 3,4,5,6 -Tetrahydropyranyl-2-oxy group, 1-phenyltetrazol-5-oxy group, etc .; As the heterocyclic thio group, a 5- to 7-membered heterocyclic thio group is preferable, for example, a 2-pyridylthio group, a 2-benzothiathio group. Zolylthio group, 2,4-diphenoxy-1,3,5-triazole-6-thio group, etc .; siloxy group includes trimethylsiloxy group, triethylsiloxy group, dimethylbutyl Proxy group or the like; succinimide imide group as a group, 3-heptadecyl succinic acid imide group, a phthalimide group, a glutarimide group and the like; spiro [3.3] As a spiro compound residue heptane -
1-yl, etc .; as a bridged hydrocarbon compound residue, bicyclo [2.2.1]
Examples include heptan-1-yl, tricyclo [3.3.1.1 ^3,7 ] decan-1-yl, 7,7-dimethyl-bicyclo [2.2.1] heptan-1-yl, and the like.

Examples of the group represented by X which can be eliminated by the reaction with the oxidized product of the color developing agent include, for example, a halogen atom (chlorine atom, bromine atom, fluorine atom, etc.), alkoxy, aryloxy,
Heterocyclic oxy, acyloxy, sulfonyloxy, alkoxycarbonyloxy, aryloxycarbonyl,
Alkyl oxalyloxy, alkoxy oxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonylthio, acylamino, sulfonamide, nitrogen-containing heterocyclic ring bonded by N atom, alkyloxycarbonylamino, aryloxycarbonylamino, carboxyl , (R ₁ ′ has the same meaning as R above, Z ′ has the same meaning as Z above, and R ₂ ′ and R ₃ ′ each represent a hydrogen atom, an aryl group, an alkyl group or a heterocyclic group). And a halogen atom, particularly a chlorine atom is preferable.

The nitrogen-containing heterocyclic ring 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 described above for R. Is mentioned.

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

General formula [M-II] General formula [M-III] General formula [M-IV] General formula [MV] General formula [M-VI] General formula [M-VII] In the general formulas [M-II] to [M-VII], R _{1 to} R ₈
And X have the same meanings as R and X described above.

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

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

Among the magenta couplers represented by the above general formulas [M-II] to [M-VII], the most preferable one is the general formula [M-I
I] is a magenta coupler.

The most preferable substituents R and R ₁ on the heterocycle are represented by the following general formula [M-IX].

General formula [M-IX] In the formula, R ₉ , R ₁₀ and R ₁₁ have the same meanings as R above.

Two of R ₉ , R ₁₀ and R ₁₁ , such as R ₉ and R _10, are linked to form a saturated or unsaturated ring (eg, cycloalkane,
(Cycloalkene, heterocycle), and R ₁₁ may be bonded to the ring to form a bridged hydrocarbon compound residue.

Among the general formula [M-IX], preferred is (i) R ₉ to
When at least two of R ₁₁ are alkyl groups, (ii) R
One example R ₁₁ in the ₉ to R ₁₁ is a hydrogen atom, a, if the other two R ₉ and R ₁₀ form a cycloalkyl together with the root carbon atom bonded.

Further preferred among (i) is 2 of R _{9 to} R _11.
One is an alkyl group and the other one is a hydrogen atom or an alkyl group.

Further, the ring formed by Z in the general formula [MI] and the substituent which the ring formed by Z ₁ in the general formula [M-VIII] may have, and the general formula [M-II] to [M
As R _{2 to} R ₈ in —VI], those represented by the following general formula [MX] are preferable.

The general formula [M-X] -R ₁₂ -SO ₂ -R ₁₃ formula in R ₁₂ is an alkylene group, R ₁₃ represents an alkyl group, a cycloalkyl group or an aryl group.

The alkylene group represented by R ₁₂ preferably has 2 or more carbon atoms in the straight chain portion, more preferably 3 to 6, and may be straight chain or branched.

The cycloalkyl group represented by R ₁₃ is preferably a 5- or 6-membered one.

 The typical examples of the compounds according to the present invention are shown below.

In addition to the typical examples of the compound according to the present invention described above, specific examples of the compound according to the present invention include compounds described on pages 66 to 122 of Japanese Patent Application No. 61-9791. And N
o.1-4,6,8-17,19-24,26-43,45-59,61-104,106-1
Compounds represented by 21,123 to 162,164 to 223 can be mentioned.

Also, the coupler is the Journal of the Chemical Societ.
y), Perkin I (1977), 2047-2052, U.S. Pat. No. 3,725,067, JP-A-59-99437, JP-A-58-42045.
No. 59-162548, 59-171956, 60-33552
No. 60-43659, No. 60-172982 and No. 60-190779.
No. etc. can be referred to for synthesis.

The coupler of the present invention usually contains 1 × per mol of silver halide.
10 ⁻³ mol to 1 mol, preferably 1 × 10 ⁻² mol to 8 × 10 ⁻¹
It can be used in the molar range.

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

Next, the anti-fading agent represented by the general formula [I] used in combination with the magenta coupler of the present invention will be described.

In the general formula [I], the alkyl group represented by R ¹ is, for example, a linear or branched alkyl group having 1 to 24 carbon atoms, the cycloalkyl group is, for example, a cycloalkyl group having 5 to 24 carbon atoms, and the alkenyl group is For example, alkenyl group having 3 to 24 carbon atoms, aryl group such as phenyl group, naphthyl group, heterocyclic group such as pyridyl group, imidazolyl group, thiazolyl group, acyl group such as acetyl group, benzoyl group and bridged hydrocarbon group. Examples include bicyclo [2.2.1] heptyl group and the like.

Each of these groups represented by R ¹ also includes those having a substituent.

The preferred ^one for R ¹ is an alkyl group.

The group capable of substituting on the benzene ring represented by R ² is typically a halogen atom and alkyl, aryl,
Alkoxy, aryloxy, alkylthio, arylthio, acyl, alkoxycarbonyl, carbamoyl (eg, alkylcarbamoyl, arylcarbamoyl, etc.), ureido (eg, alkylureido, arylureido, etc.), sulfamoyl (eg, alkylsulfamoyl, arylsulfamoyl, etc.) , Amino (including substituted amino), alkylsulfonyl, arylsulfonyl, nitro, cyano, carboxy and the like. Among these, preferred as R ² are halogen atom, alkyl group and alkylthio group. The group represented by R ² may further have a substituent.

m represents an integer of 0 to 4, preferably 0 to 2.

Examples of the 5- to 8-membered ring formed by A include rings such as pyrrolidine, piperidine, piperazine, morpholine and pyridine. These rings also include those having a substituent.

OR ¹ is It can be in any position relative to, but is preferably in the p-position.

The representative examples of the magenta dye fading preventive agent of the present invention represented by the general formula [I] are shown below, but the invention is not limited thereto.

In addition to the representative specific examples of the compound according to the present invention described above, examples of the compound used in the present invention include compounds described in Japanese Patent Application No. 61-241743.

The amount of the magenta dye fading-preventing agent of the present invention used is preferably 5 to 300 mol%, more preferably 10 to 200 mol%, based on the magenta coupler of the present invention.

Further, for the purpose of further improving the light resistance of the magenta coupler in the silver halide photographic light-sensitive material of the present invention, the following general formula [I
It is preferable to use the phenolic antioxidant represented by [I].

General formula [II] In the formula, R ³ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group, and R ⁴ , R ⁵ , R ⁷ and
R ⁸ is a hydrogen atom, a halogen atom, a hydroxy group,
It represents an alkyl group, an alkenyl group, an aryl group, an alkoxy group or an acylamino group, and R ⁶ represents an alkyl group, a hydroxy group, an aryl group or an alkoxy group. R ³
And R ⁴ may be ring-closed to each other to form a 5- or 6-membered ring, in which case R ⁶ represents a hydroxy group or an alkoxy group. Further, R ³ and R ⁴ may be closed to form a methylenedioxy ring. Further, R ⁵ and R ⁶ may be ring-closed to form a 5-membered hydrocarbon ring, in which case R ³ represents an alkyl group, an aryl group or a heterocyclic group. However, the case where R ³ is a hydrogen atom and R ⁶ is a hydroxy group is excluded.

Specific examples of the compound of the general formula [II] preferably used in the present invention are shown below.

The phenol compound or phenyl ether compound represented by the general formula [II] is preferably 1 × 10 ^{−2 to} 5 mol, and more preferably 1 × 10 ⁻¹ to ² mol based on 1 mol of the magenta coupler of the present invention. It is to be used in the molar range.

In the light-sensitive material of the present invention, the following general formula is used for the purpose of maintaining the effects of the present invention, that is, the effect of improving rapid processing suitability, color reproducibility, and light fastness, and further suppressing the minimum density of a dye image formed. It is preferable to use the compound represented by [S].

General formula [S] In the formula, examples of the heterocyclic ring which may be condensed with the benzene ring formed by Q include imidazole, tetrazole, thiazole, oxazole, selenazole, benzimidazole, naphthimidazole, benzothiazole, naphthothiazole, benzoselenazole, naphthoselenazole. , Benzoxazole, pyridine, pyrimidine, quinoline and the like, and these heterocycles include those having a substituent.

Typical specific examples of the compound represented by formula [S] are shown below.

The compound [S] is preferably added during chemical ripening, at the end of chemical ripening, or after the end of chemical ripening and before coating. The addition may be carried out all at once or may be added in a plurality of times.

Compound [S] is usually 1 × 10 ^-6 per mol of silver halide.
It is used in the range of ˜1 × 10 ⁻¹ , preferably 1 × 10 ⁻⁵ to 1 × 10 ⁻² mol.

The high-speed reactive yellow coupler preferably used in the present invention is a yellow coupler having a relative coupling reaction rate of 0.5 or more.

The coupling reaction rate of the coupler is determined by mixing two types of couplers M and N, which give different dyes which can be clearly separated from each other, and adding them to a silver halide emulsion for color development. It can be determined as a relative value by measuring the amount of each dye. This method is disclosed in Japanese Patent Application Nos. 61-20715, 61-20974 and 61-97513.
No. 61-97514, No. 61-135150, etc.

In the present invention, it means the coupling activity ratio (RM / RN) when the following coupler is used as the above N coupler.

Specific representative examples of high-speed yellow couplers are shown below.

The amount of yellow coupler added is 2 × 10 ^-3 per mol of silver
5 × 10 ^-1 mol is preferable, more preferably 1 × 10 ^{-2 to} 5
× 10 ^-1 mol.

The magenta coupler of the present invention is dissolved in a high-boiling point organic solvent having a boiling point of about 150 ° C. or more in combination with a low-boiling point and / or a water-soluble organic solvent as necessary, and has a surface active property in a hydrophilic binder such as a gelatin aqueous solution. It may be added to the desired hydrophilic colloid layer after emulsifying and dispersing using the agent.

The high boiling point organic solvent has a dielectric constant at 30 ° C.
It is preferable to use a compound of 7.0 or less, and the lower limit is preferably 2.0 or more. Examples of the compound having a dielectric constant of 7.0 or less include esters such as phthalic acid ester and phosphoric acid ester, organic acid amides, ketones, and hydrocarbon compounds.

As the high boiling point solvent having a dielectric constant of 7.0 or less, which is preferably used, dibutyl phthalate, dihexyl phthalate, di-2-ethylhexyl phthalate, dioctyl phthalate, dinonyl phthalate, didodecyl phthalate, di-
Examples thereof include i-octadecyl phthalate, tricresyl phosphate, trioctyl phosphate, tri-i-nonyl phosphate, tri-i-dodecyl phosphate and the like.

The magenta coupler of the present invention and the cyan coupler used with the high speed yellow coupler are not particularly limited,
JP-A-50-112038, 53-109630, 55-163537,
31935, 59-100440, 59-121332, 59-1243
No. 41, No. 59-139352, No. 59-146050, No. 59-166956
2,5-diacylaminophenol cyan couplers described in U.S. Pat. No. 2,895,826 and the like and JP-A-60-117249.
No. 60, No. 60-205447, No. 61-3142, No. 61-9652, No. 61-
9653, 61-27540, 61-39045, 61-50136,
No. 61-105545, U.S. Pat.No. 3,772,002, etc. 2-
An acylaminophenol cyan coupler can be preferably used.

These cyan couplers may be used alone or in combination, and are usually used in an amount of 1 × 10 ^-3 to 1 mol, preferably 1 × 10 ^-2 to 8 × 10 ^-1 mol per mol of silver halide. You can

The silver halide emulsion layer containing the magenta coupler of the present invention contains silver halide grains having a silver chloride content of 80 mol% or more.

The silver halide grain of the present invention has a silver chloride content of 80 mol% or more, preferably 90 mol% or more. The silver bromide content is preferably 10 mol% or less, and the silver iodide content is preferably 0.5 mol% or less. More preferably, the silver chloride content is 95 mol% or more.

The silver halide grains of the present invention may be used alone or in combination with other silver halide grains having different compositions. Further, it may be used by mixing with silver halide grains having a silver chloride content of less than 10 mol%.

Further, in a silver halide emulsion layer containing silver halide grains having a silver chloride content of 80 mol% or more according to the present invention, the silver chloride content in all silver halide grains contained in the emulsion layer. The proportion of silver halide grains of 80 mol% or more is 60 wt% or more, preferably 80 wt% or more.

The composition of the silver halide grain of the present invention may be uniform from the inside to the outside of the grain, or the composition inside and outside the grain may be different. When the composition inside and outside the particle is different, the composition may continuously change or may be discontinuous.

The grain size of the silver halide grains of the present invention is not particularly limited, but is preferably in the range of 0.2 to 1.6 μm, more preferably 0.25 to 1.2 μm, in consideration of other photographic properties such as rapid processing and sensitivity. .

The silver halide grains used in the emulsion of the present invention are preferably grains in which a latent image is mainly formed on the surface.

 The emulsion of the present invention is chemically sensitized by a conventional method.

The emulsion of the present invention can be spectrally sensitized in a desired wavelength region by using a sensitizing dye.

The silver halide grains used in emulsion layers other than the silver halide emulsion layer according to the present invention are not particularly limited, but preferably have the same silver chloride content of 80 as used in the silver halide emulsion layer according to the present invention. It contains more than mol% of silver halide grains.

The silver halide photographic light-sensitive material of the present invention having the above-mentioned constitution can be, for example, a negative and a positive film of color negative, a color photographic paper, and the like, and in particular, a color photographic paper provided for direct viewing was used. In this case, the effect of the method of the present invention is effectively exhibited.

The silver halide photographic light-sensitive material of the present invention may further contain additives such as a hardener, a plasticizer, a latex, a surfactant, a matting agent, a lubricant and an antistatic agent.

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

The pH value of the color developing solution is usually 7 or higher, most commonly about 10 to 13.

Color development temperature is usually 15 ℃ or higher, generally 20 ℃
The range is up to 50 ° C. For rapid development, it is preferably carried out at 30 ° C or higher. In the conventional processing, the time is 3 minutes to 4 minutes, but the color development time of the present invention for the purpose of rapid processing is generally preferably in the range of 20 seconds to 60 seconds,
More preferably, the range is 30 seconds to 50 seconds.

The silver halide photographic light-sensitive material of the present invention, after color development,
Bleached and fixed. The bleaching process may be performed simultaneously with the fixing process.

After the fixing process, a washing process is usually performed. Further, as a substitute for the water washing treatment, a stabilizing treatment may be performed, or both may be used in combination.

[Specific effects of the invention] In the silver halide photographic light-sensitive material of the present invention as described above, the color reproducibility is excellent, the color development and light fastness of the formed magenta dye image are simultaneously improved, and further rapid processing is performed. It was excellent in suitability.

〔Example〕

 Hereinafter, specific examples of the present invention will be described in detail.

Example 1 Various coupler dispersions having the compositions shown in Table 1 were prepared by the method shown below, and the obtained dispersions were mixed with 500 g of a green-sensitive silver halide emulsion prepared by the method shown below.
Samples 1 to 13 were obtained by adding 10 ml of a 10% aqueous solution of 2,4-dihydroxy-6-chloro-s-triazine.sodium as a hardener and coating and drying it on a polyethylene-coated paper support.

(Preparation of Coupler Dispersion) 40 g of the coupler shown in Table 1 was dissolved in a mixed solvent of 40 g of dioctyl phthalate (high boiling organic solvent) and 100 ml of ethyl acetate, and this solution was added to 300 ml of 5% gelatin aqueous solution containing sodium dodecylbenzenesulfonate. After the addition, the mixture was dispersed with an ultrasonic homogenizer to obtain a coupler dispersion.

(Preparation of Silver Halide Emulsion) EM-1 A silver nitrate aqueous solution and a sodium chloride aqueous solution were added to and mixed with an inert gelatin aqueous solution by a double jet method while stirring. At this time, control was performed so that the temperature was maintained at 60 ° C., pH = 3.0 and pAg = 7.8. Further, similarly, an aqueous silver nitrate solution and an aqueous potassium bromide solution were added. Then, desalting was performed by a conventional method to obtain EM-1. EM-1 has an average particle size of 0.5 μm
Cubic monodisperse silver chlorobromide emulsion (99.8% silver chloride, silver bromide 0.
2%).

EM-2 Silver nitrate aqueous solution and halide aqueous solution (mixed aqueous solution of potassium bromide and sodium chloride) by the double jet method,
It was added and mixed in an inert gelatin aqueous solution. At this time, 60
The temperature was controlled according to the method described in JP-A-59-45437 so that the temperature was maintained at pH = 3.0 and pAg = 7.8. Then, desalting was performed by a conventional method to obtain EM-2. EM-2 has an average particle size of 0.5μ
It was a monodisperse emulsion consisting of tetradecahedral silver chlorobromide grains containing 90 mol% of silver bromide.

Next, EM-1 and EM-2 were chemically sensitized under the following conditions to prepare green-sensitive silver halide emulsions EMB-1 and EMB-2, respectively. However, the compound [S] was added at the end of the chemical sensitization.

Sulfur sensitizer: sodium thiosulfate 2.5 mg / mol AgX chloroauric acid: 5 × 10 ⁻⁵ mol / mol AgX sensitizing dye: D-1 100 mg / mol AgX compound [S]: (shown in Table 1) 1.5 × 10 ^-3 mol / mol AgX Temperature: 60 ℃ Time: 60 minutes The sample obtained above was subjected to wedge exposure according to a conventional method, and then the following treatment was performed.

[Treatment process]

Temperature Time Color development 34.7 ± 0.3 ℃ 50 seconds Bleach-fixing 34.7 ± 0.5 ℃ 50 seconds Stabilization 30-34 ℃ 90 seconds Dry 60-80 ℃ 60 seconds (Color developer) Ethylene glycol 10ml N, N-diethylhydroxylamine 10ml Potassium chloride 2g N-Ethyl-N-β-methanesulfonamide Ethyl-3-methyl-4-aminoaniline sulfate 5g Sodium tetrapolyphosphate 2g Potassium carbonate 30g Optical brightener (4,4'-diaminostilbenedisulfonic acid derivative) Adjust the pH to 10.08 by adding 1g pure water to make the total amount 1.

(Bleaching fixer) 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, Add water to bring the total volume to 1.

(Stabilizing solution) 5-chloro-2-methyl-4-isothiazolin-3-one 1g 1-Hydroxyethylidene-1,1-diphosphonic acid 2g Add water to make 1 and adjust pH to 7 with sulfuric acid or potassium hydroxide.
Adjust to 0.

For each of the samples treated above, the color developability, light fastness, and color reproducibility (sub-absorption density and stain) were measured as described below. The results are also shown in Table-1.

<Color developability> Measure the maximum reflection density (Dmax) of each sample to obtain “color developability”
The characteristics of

<Light fastness> Each sample was exposed to sunlight for 30 days through an ultraviolet absorption filter using an underglass outdoor exposure table, and the initial concentration D _{0 was} 1.0 and the residual rate was shown.

Residual rate = D / D ₀ × 100 (%) (where D = density after fading) <Sub-absorption density> The spectral reflection spectrum of the color-developed sample is analyzed by a color analyzer.
It was measured using a model 607 (manufactured by Hitachi Ltd.). At this time, the maximum concentration of the absorption spectrum in the visible region of each sample was normalized to 1.0 and measured. The reflection density at 430 nm of each sample was used as an index of the color purity as the secondary absorption density.

<Stain> The reflection density (Dmin) of the unexposed area of each sample was measured.

As is apparent from Table-1, in Samples 1 and 2 using the comparative coupler, the sub-absorption density was high and the magenta image was turbid and the image was unclear. Further, in Sample 2 using silver halide grains having a high silver chloride content, the color developability is improved but it is insufficient. Sample 4, which uses the magenta coupler of the present invention and silver halide grains having a silver chloride content of 99.8 mol%, has good color development and color reproducibility but poor light resistance. Furthermore, Sample 5 using the comparative anti-fading agent has a small effect of improving the light resistance, and Sample 6 has a problem that the color developability is deteriorated, so that all the performances cannot be satisfied.

Only when the silver halide grains of the present invention, the magenta coupler of the present invention and the anti-fading agent of the present invention are used, the color developability, light fastness and color reproducibility are all improved.

Further, Samples 7 to 12 using the compound S-14 have better light resistance than the sample 13 using the compound SC-1 and have a small stain, which is preferable for image reproduction.

Example 2 18 kinds of samples which are the same as the sample 7 of Example 1 were prepared except that the magenta coupler, the anti-fading agent, the high boiling point organic solvent and the silver chloride content of the silver halide grains were changed as shown in Table 2. (Samples 14 to 31).

The same color development test as in Example 1 was performed on these samples.
A light resistance test and a color reproduction test were conducted. The results are shown in Table-2.
Shown in

As is clear from Table 2, in each of the samples of the present invention, a clear magenta color image excellent in light fastness and color developability and having a small secondary absorption density (low turbidity) was obtained.

Further, it is more preferable that the silver chloride content of the silver halide grains is 90 mol% or more and 99.9 mol% or less, because the color developability is good.

Samples 22, 23 and 24 using magenta couplers in which the 6-position is substituted with an isopropyl group or a t-butyl group
Has further improved light resistance.

Further, it can be seen that the sample using a high boiling point organic solvent having a dielectric constant of 7.0 or less has improved light resistance and color development.

Example 3 A multi-color color light-sensitive material was prepared by sequentially coating each layer having the following composition from the support side on a support made of polyethylene-coated paper. The amount of the compound is the amount per 100 cm ² .

First layer: Blue-sensitive silver chloride emulsion layer Yellow coupler (★) 8 mg, the following blue-sensitive silver chloride emulsion (Em.A) 3 mg in terms of silver, high boiling organic solvent (DNP)
3 mg and gelatin 16 mg.

Second layer: intermediate layer 0.45 mg of hydroquinone derivative (HQ-1) and 4 mg of gelatin.

Third layer: green light-sensitive silver chloride emulsion layer Magenta coupler (*) 4 mg, and green-sensitive silver chloride emulsion (Em.B, C or D) shown below in 2 mg (B,
D) or 4 mg (C), high boiling organic solvent (DOP) 4 mg, anti-fade agent (★) equimolar to magenta coupler and gelatin 16 mg.

4th layer: Intermediate layer UV absorber (UV-1) 3 mg, UV absorber (UV-
2) 3 mg, DNP 4 mg, HQ-1 0.45 mg and gelatin 14 m
g.

Fifth layer: Red-sensitive silver chloride emulsion layer Cyan coupler (*) 4 mg, DOP 4 mg, red-sensitive silver chloride emulsion (Em.E) shown below in terms of silver 3 mg and gelatin 14 mg.

Layer 6: Intermediate layer UV-12 mg, UV-22 mg, DNP 2 mg and gelatin
6 mg.

7th layer: protective layer 9 mg of gelatin.

Incidentally, (*) in the first to seventh layers is shown in Table-3. The silver halide emulsions Em.A to Em.E used are as follows.

As the sensitizing dyes for Em.B, Em.C and Em.D, D-1 (same as in Example 1) was used, Em.A was D-2, and Em.E was D-3.

Sensitometer (manufactured by Konishi Roku Photo Industry Co., Ltd.)
KS-7 type) was subjected to wedge exposure with white light, and then the same treatment as in Example 1 was performed.

The same test as in Example 1 was performed on the obtained sample.

 The results are shown in Table-3.

As is clear from Table 3, in the samples of the present invention, all of the light fastness, color developability and color reproducibility of the magenta color image were good. Also, the photobleaching balance and the coloring balance of yellow, magenta, and cyan images were good, and clear images were obtained.

On the contrary, in the sample 34 using the comparative anti-fading agent,
The light fastness of the magenta image is improved, but the color developability is deteriorated. Also, the color balance of yellow, magenta, and cyan is poor, and the neutral image is reproduced in a greenish color.

Further, when a phenolic antioxidant or a metal complex is used as the anti-fading agent in combination with the compound of the present invention, the light resistance of magenta images is improved, and the photo-fading balance is evenly obtained, and preferable results are obtained.

Claims (6)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein at least one of the silver halide emulsion layers contains 80 mol% or more of silver chloride. Particles, the following general formula [MI]
A silver halide photographic light-sensitive material comprising a magenta coupler represented by and a compound represented by the following general formula [I]. General formula [MI] [In the formula, Z represents a nonmetallic 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 capable of splitting off upon reaction with an oxidized product of a color developing agent, and R represents a hydrogen atom or a substituent. ] General formula [I] [In the formula, R ¹ represents an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, a bridged hydrocarbon group, an alkylsulfonyl group or an arylsulfonyl group, and R ² is a benzene ring. Represents a possible group. m is 0
Represents an integer of 4; When m is 2 or more, plural R ^{2 s} may be the same or different, and R ^{2 s} may form a ring. R ² may form a ring with —OR ¹ . A represents a non-metal atomic group necessary for forming a 5- to 8-membered ring with a nitrogen atom. However, the following cases (a), (b) or (c) are excluded. (A) The compound represented by the general formula [I] is represented by the following general formula [A] or general formula [B], and the general formula [A]
When the compound represented by and the compound represented by the general formula [B] are used in combination. General formula [A] [In the formula, R ¹¹ represents an aryl group, and Z ₁₁ and Z ₁₂ each represent an alkylene group having 1 to 3 carbon atoms. However, Z ₁₁
And the total number of carbon atoms of the alkylene group represented by Z ₁₂ is 3
~ 6. n represents 1 or 2. ] General formula [B] [In the formula, R ¹² represents an aryl group, and Y ₁ represents a nonmetallic atom group necessary for forming a piperazine ring or a homopiperazine ring together with a nitrogen atom. (B) The compound represented by the above general formula [I] is represented by the following general formula [XII], and the following general formulas [XIIIa] and [XIIIa]
When at least one compound selected from the compounds represented by b] is used in combination. General formula (XII) [In the formula, R ²¹ represents an aryl group, and Y ₂ represents a nonmetallic atom group necessary for forming a pyrrolidine ring, a piperidine ring or a homopiperidine ring together with a nitrogen atom. ] General formula [XIIIa] [In the formula, R ²² and R ²⁵ are each a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkenyloxy group, a hydroxy group, an aryl group, an aryloxy group, an acyl group, an acylamino group, an acyloxy group,
Represents a sulfonamide group, a cycloalkyl group or an alkoxycarbonyl group, R ²³ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an acyl group, a cycloalkyl group or a heterocyclic group, and R ²⁴ represents a hydrogen atom or a halogen atom. Represents an alkyl group, an alkenyl group, an aryl group, an aryloxy group, an acyl group, an acylamino group, an acyloxy group, a sulfonamide group, a cycloalkyl group or an alkoxycarbonyl group. R ²³ and R ²⁴ may be ring-closed to each other to form a 5- or 6-membered ring. Furthermore R ²³ and R ²⁴
May form a methylenedioxy ring. Y ₃ represents an atomic group necessary for forming a chroman or coumaran ring. ] General formula [XIIIb] [In the formula, R ³² and R ³⁴ are each a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, a hydroxy group, an aryl group, an aryloxy group, an acyl group, an acylamino group, an acyloxy group, a sulfonamide group, Represents a cycloalkyl group or an alkoxycarbonyl group,
R ³³ represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, a hydroxy group, an aryl group, an acyl group, an acylamino group, an acyloxy group, a sulfonamide group, a cycloalkyl group or an alkoxycarbonyl group. Also R
³³ and R ³⁴ may be ring-closed to each other to form a 5- or 6-membered hydrocarbon ring. Y ₄ represents an atomic group necessary for forming an indane ring. (C) The magenta coupler represented by the above general formula [MI] is represented by the following general formula [II]: 1H-pyrazolo [5,1-
c] -1,2,4-triazole and the compound represented by the above general formula [I] is a compound represented by the following general formula [IV]. General formula (II) [In the formula, R represents a hydrogen atom or a substituent, R ⁴¹ represents an alkylene group having a straight chain portion of 3 or more carbon atoms, R ⁴² represents an alkyl group, a cycloalkyl group or an aryl group, and X represents
Represents a hydrogen atom or a substituent capable of splitting off upon reaction with an oxidized product of a color developing agent. However, at least one of R and R ⁴¹ is bonded to the pyrazolotriazole mother nucleus via a branched carbon atom or a carbon atom on the ring. ] General formula [IV] [In the formula, R ⁴³ represents an aryl group, and Y ₅ represents a nonmetallic atom group necessary for forming a pyrrolidine ring, a piperidine ring, or a homopiperidine ring together with a nitrogen atom. ] 2. The halogen according to claim 1, wherein the magenta coupler represented by the general formula [MI] has at least one sulfonyl group or sulfonamide group in its structure. Silver halide photographic light-sensitive material. 3. A magenta coupler represented by the general formula [MI] has the structure Claim 1 characterized in that it has a group represented by (Ra, Rb and Rc each represent a hydrogen atom or an alkyl group, but at least two of Ra to Rc are alkyl groups). The silver halide photographic light-sensitive material as described in the item 2. 4. The silver halide according to claim 1, 2 or 3, wherein the silver halide emulsion layer containing the magenta coupler contains a phenolic antioxidant. Photographic material. 5. The silver halide according to claim 1, wherein the silver halide photographic light-sensitive material further contains a compound represented by the following general formula [S]. Photographic material. General formula [S] [In the formula, Q represents an atomic group necessary for forming a 5- or 6-membered heterocyclic ring which may be condensed with a benzene ring, M represents a hydrogen atom,
Represents an alkali metal atom or an ammonium group. ] 6. The silver halide according to any one of claims 1 to 5, wherein the silver halide photographic light-sensitive material contains a high-speed reaction yellow coupler having a relative coupling speed of 0.5 or more. Photographic material.