JPH0728209A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide color photographic sensitive material having high sensitivity and excellent color reproducibility and showing little increase in fog during the photosensitive material is stored by incorporating one kind of benzoimidazolocarbocyanine die and one kind of magenta coupler into at least one green-sensitive layer. CONSTITUTION:This silver halide color photographic sensitive material has at least each one layer of red-sensitive, green-sensitive and blue-sensitive emulsion layer on a base body. At least one green-sensitive layer contains at least one kind of benzoimidazolocarbocyanine dye expressed by formula and at least one kind of magenta coupler. In formula, V1-V4 are hydrogen atoms or electron withdrawing groups, R11 is -(CH2)k(CF2)mH or -(CH2)k(CF2)mF group, R12, R13, R14 are -(CH2)p(CF2)qH or -(CH2)p(CF2)qF groups, alkyl groups, or alkenyl groups of <=10 total carbon number which may have substituents.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material, and more specifically, a silver halide having high sensitivity, little fog increase during storage of the light-sensitive material, and excellent color reproducibility. The present invention relates to a color photographic light-sensitive material.

[0002]

2. Description of the Related Art In recent years, color photographic light-sensitive materials have been remarkably improved in image quality such as graininess, sharpness and color reproducibility.
However, in addition to the demand for higher sensitivity and higher image quality of the sensitive material, the toughness of the sensitive material (fog during storage of the sensitive material), less sensitivity fluctuation, and fogging, sensitivity, gradation fluctuation However, there is a strong demand for that there is little variation in color tone, and improvement in stability over time has been long desired.

By the way, as one of the techniques for producing a photographic light-sensitive material, a cyanine dye of a certain kind is added to a silver halide photographic emulsion to extend its light-sensitive wavelength region to the long-wave side, that is, a spectral sensitization technique is used. well known. Among the spectral sensitization techniques, particularly the sensitization in the green wavelength region is important in connection with the fact that human visibility is high in the green region.

It is well known that the addition of certain benzimidazolocarbocyanine dyes is effective as a means of increasing the green sensitivity of silver halides. In this case, the dye added to the silver halide photographic emulsion is adsorbed to the silver halide in the emulsion and added to the absorption band specific to silver halide and the absorption band of longer wavelength. That is, spectral sensitization by the dye can be obtained. These matters are described, for example, in U.S. Pat. Nos. 2,912,329, 2,739,149, British Patents 654,690, 815,172, and Japanese Examined Patent Publication No.
3-4936 and the like. However, in the above method, the improvement in color reproducibility is insufficient, and when the silver halide photographic light-sensitive material is stored under high temperature or high temperature and high humidity, fog increases during storage and sensitivity decreases. It had the major drawback of causing performance changes.

On the other hand, silver halide emulsions used in silver halide photographic light-sensitive materials are usually chemically sensitized with various chemical substances in order to obtain desired sensitivity, gradation and the like. Typical methods include sulfur sensitization, selenium sensitization,
Various sensitization methods by sensitizing precious metals such as gold, reduction sensitization, and combinations thereof are known. In addition, various improvements have been made to these sensitizing methods for increasing the sensitivity and improving the graininess.

Among the above sensitizing methods, the selenium sensitizing method is described in US Pat. Nos. 1,574,944 and 160,259.
No. 2, No. 1623499, No. 3297446,
No. 3297447, No. 3320069, No. 3
No. 408196, No. 3408197, No. 3442
No. 653, No. 3420670, No. 3591385.
No., French Patent No. 2693038, No. 20932.
09, Japanese Patent Publication Nos. 52-34491 and 52-3449.
No. 2, No. 53-295, No. 57-22090, No. 59-180536, No. 59-185330, No. 59-181337, No. 59-187338, No. 5;
9-192241, 60-150046, 60
-151637, 61-246738, British Patents 255558, 861984 and HESpen.
cer et al., Journal of Photographic Science, 31
Vol., Pp. 158-169 (1983).

In general, selenium sensitization has a greater sensitizing effect than sulfur sensitization which is usually carried out in the art, but it tends to cause a large amount of fog and tend to be softened. Although many of the above-mentioned known patents improve these drawbacks, they have still obtained insufficient results, and in particular, a basic improvement for suppressing the occurrence of fogging has been eagerly desired.

[0008] Further, particularly when sulfur sensitization or selenium sensitization is used in combination with gold sensitization, a marked increase in sensitivity can be obtained.
At the same time, the fogging also rises. Compared with gold-sulfur sensitization, gold-selenium sensitization has a particularly large increase in fog, and there has been a strong demand for technological development for suppressing the occurrence of fog.

On the other hand, the exposed aromatic silver halide is used as an oxidizing agent, and the oxidized aromatic primary amine type color developing agent and the coupler react to give indophenol, indoaniline, indamine, azomethine, phenoxazine, phenazine and It is well known that similar dyes are formed and color images are formed.

Of these, 5-pyrazolone, cyanoacetophenone, indazolone, pyrazolobenzimidazole and pyrazolotriazole couplers are used for forming a magenta image.

Most of the 5-pyrazolones that have been widely put into practical use as magenta image-forming couplers and have been studied have hitherto been studied. The 5-pyrazolone coupler is excellent in dye forming speed and efficiency, and the formed azomethine dye is excellent in fastness to light and heat, but has absorption of a yellow component around 430 nm which is not preferable as a magenta dye. It was known that this is the cause of color turbidity.

[0012] As a magenta color image-forming bone nucleus which reduces the yellow component, a pyrazolobenzimidazole bone nucleus described in British Patent No. 1,047,612 and US Pat. No. 3,725,067 are described. Pyrazolotriazole bone nucleus, Pyrazoloimidazole bone nucleus described in JP-A-59-162548, Pyrazolopyrazole bone nucleus described in JP-A-60-43659, and Pyrazolotriazole bone described in JP-A-59-171956 Nuclear, ibid. 60-3355
The pyrazolotetrazole bone nucleus described in No. 2 is known.

The dyes formed by these pyrazoloazole-based magenta couplers are certainly superior to 5-pyrazolomagenta couplers in that they absorb unnecessary yellow components.

However, since these pyrazoloazole-based magenta couplers have the property of easily interacting with silver ions in the coating film, they are sufficient in terms of storage stability and processing dependence of the light-sensitive material. The current situation is that they have not been able to master them properly.

JP-A-61-32840 and 63-
206739 discloses an example in which a specific benzimidazolocarbocyanine dye is used for improving the storage stability and a specific pyrazoloazole magenta coupler is used, but it is still unsatisfactory from the viewpoint of storage stability and color reproducibility. It was enough.

[0016]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a silver halide color photographic light-sensitive material which has high sensitivity, little increase in fog during storage of the light-sensitive material, and excellent color reproducibility.

[0017]

The above objects of the present invention can be achieved by a light-sensitive material having the following constitution. That is, (1) in a silver halide color photographic light-sensitive material having at least one red-sensitive, green-sensitive and blue-sensitive emulsion layer on a support, at least one of the green-sensitive layers has the following general formula [ [I] containing at least one benzimidazolocarbocyanine dye and at least one magenta coupler represented by the following general formula [M], and a silver halide color photographic light-sensitive material and ( 2) It can be achieved by the silver halide color photographic light-sensitive material of the above (1), wherein at least one kind of silver halide grains contained in the green-sensitive layer is selenium-sensitized.

[0018]

[Chemical 3]

In the formula, V ₁ , V ₂ , V ₃ and V ₄ represent a hydrogen atom or an electron-withdrawing group, and V ₁ , V ₂ , V ₃ and V
_At least two or more of the substituents represented by ₄ are electron withdrawing groups. V ₁ , V ₂ , V ₃ , and V ₄ may be the same or different. R ₁₁ is-(CH ₂ ) _l (C
F _{2) m} H or - represents _{(CH 2) l (CF 2} ) a group represented by _m F, l is 0 or 1, m represents an integer of 1 to 8. R ₁₂ , R ₁₃ and R ₁₄ may be the same or different, and are — (CH ₂ ) _p (CF ₂ ) _q H group or — (CH ₂ ) _p (CF ₂ ) _q.
F group represents an optionally substituted alkyl group or alkenyl group having 10 or less carbon atoms, and at least one of R ₁₂ , R _{13 and} R ₁₄ is a group having a sulfo group or a carboxy group. . p represents 0 or 1, and q represents an integer of 1 to 8. X ₁₁ represents a counter ion necessary for neutralizing the electric charge. n ₁₁ represents 0 or 1, and is 0 in the case of an inner salt.

[0020]

[Chemical 4]

R ₁ in the formula represents a hydrogen atom or a substituent. Z represents a nonmetallic atom group necessary for forming a 5-membered azole ring containing 2 to 3 nitrogen atoms, and the azole ring may have a substituent (including a condensed ring). X represents a hydrogen atom or a group capable of splitting off upon a coupling reaction with an oxidized product of a developing agent. However, at the same time, the case where R ₁ is a methyl group and X is a chlorine atom is excluded.

The present invention will be described in detail below.

In the general formula [I], V ₁ , V ₂ , V ₃
And a preferable electron-withdrawing group represented by V ₄ is a halogen atom, a lower perfluoroalkyl group (more preferably a total carbon number of 5 or less, for example, a trifluoromethyl group, 2,
2,2-trifluoroethyl group, 2,2,3,3-tetrafluoropropyl group and the like), acyl group (total carbon number is preferably 8 or less, for example, acetyl group, propionyl group, benzoyl group, mesityl Group and a benzenesulfonyl group), an alkylsulfamoyl group (more preferably a total carbon number of 5 or less, and examples thereof include a methylsulfamoyl group and an ethylsulfamoyl group), a carboxy group, an alkylcarbonyl group. A group (more preferably a total carbon number of 5 or less, for example, a methoxycarbonyl group, an ethoxycarbonyl group, a butoxycarbonyl group and the like) and a cyano group and the like can be mentioned.

The alkyl group and alkenyl group represented by R ₁₂ , R ₁₃ or R ₁₄ preferably has a total carbon number of 10 to 1.
Further, as the more preferable substituents other than the sulfo group and the carboxy group, the following groups can be mentioned. Halogen atom (eg, fluorine atom, chlorine atom, bromine atom), hydroxy group, alkoxy group having 6 or less carbon atoms (eg, methoxy group, ethoxy group, propoxy group, butoxy group, etc.), substituted with 8 or less carbon atoms Optionally substituted aryl group (eg, phenyl group, tolyl group, sulfophenyl group, carboxyphenyl group, etc.), heterocyclic group (eg, furyl group, thienyl group, etc.), optionally substituted aryl having 8 or less carbon atoms Oxy group (eg, chlorophenoxy group, phenoxy group, sulfophenoxy group, hydroxyphenoxy group), acyl group having 8 or less carbon atoms (eg, benzenesulfonyl group, methanesulfonyl group, acetyl group, propionyl group), carbon number 6 The following alkoxycarbonyl groups (eg, ethoxycarbonyl group, butoxycarbonyl group, etc.), Group, an alkylthio group having 6 or less carbon atoms (eg, methylthio group, ethylthio group, etc.), an optionally substituted arylthio group having 8 or less carbon atoms (eg, phenylthio group, tolylthio group, etc.), An optionally substituted carbamoyl group (eg, carbamoyl group, N-ethylcarbamoyl group, etc.), acylamino group having 8 or less carbon atoms (eg, acetylamino group, methanesulfonylamino group, etc.), ureido group having 6 or less carbon atoms. (For example, ureido group, 3-methylureido group, 3-ethylureido group, etc.), acylaminocarbonyl group having 8 or less carbon atoms (eg, acetylaminocarbonyl group, propionylaminocarbonyl group, etc.), 8 or less carbon atoms Alkyl- or aryl-substituted sulfonylaminocarbonyl groups (eg benzenesulfonyl group) Bruno carbonyl group, methanesulfonylamino group, etc. ethanesulfonylamino group) and the like can be more preferable. Two or more of these substituents may be included.

Particularly preferred specific examples include, for example, methyl group, ethyl group, propyl group, allyl group, pentyl group,
Hexyl group, methoxyethyl group, ethoxyethyl group, phenethyl group, tolylethyl group, sulfophenethyl group,
2,2-difluoroethyl group, 2,2,2-trifluoroethyl group, 2,2,3,3-tetrafluoropropyl group, carbamoylethyl group, hydroxyethyl group, 2-
(2-hydroxyethoxy) ethyl group, carboxymethyl group, carboxyethyl group, ethoxycarbonylmethyl group, sulfoethyl group, 2-chloro-3-sulfopropyl group, 3-sulfopropyl group, 2-hydroxy-3-sulfopropyl group , 3-sulfobutyl group, 4-sulfobutyl group, 2- (2,3-dihydroxypropyloxy) ethyl group, 2- [2- (3-sulfopropyloxy) ethoxy] ethyl group, acetylaminocarbonylethyl group, acetylamino Examples thereof include a carbonylmethyl group, a methylsulfonylaminocarbonylethyl group and an ethylsulfonylaminocarbonylethyl group.

Further,-(CH ₂ ) _l (CF ₂ ) _m H represented by R _{11
Group, - (CH 2) l (} CF 2) m F _{group, - (CH 2) p (} CF 2) q H group, and _{- (CH 2) p (CF} 2) q F group R _12, R ₁₃ and It is more preferably used as the alkyl group represented by R ₁₄ .

Specific examples of the group represented by R ₁₁ include, for example,
Difluoromethyl group, trifluoromethyl group, 1,1,
2,2-tetrafluoroethyl group, 2,2-difluoroethyl group, 2,2,2-trifluoroethyl group, 2,
2,3,3-tetrafluoropropyl group, 2,2,3
3,3-pentafluoropropyl group, 2,2,3,3,
4,4-hexafluorobutyl group, 2,2,3,3,
4,4,5,5-octafluoropentyl group, 2,2
3,3,4,4,5,5,6,6-decafluorohexyl group, 2,2,3,3,4,4,5,5,6,6,7,
7-dodecafluoroheptyl group, 2,2,3,3,4
Examples include 4,5,5,6,6,7,7,8,8,9,9-hexadecafluorononyl group.

In the sensitizing dye represented by the general formula [I], the groups represented by V ₁ , V ₂ , V ₃ and V ₄ are Hammett (Ham).
It is particularly preferable that the sum of the substituent constants (σ _p ) of mett) is 0.5 or more, and the polarographic half-wave oxidation potential (Eox ^1/2 ) of the sensitizing dye is 0.7 V vs SC.
More preferably, it is more noble than E. The polarographic half-wave oxidation potentials of sensitizing dyes are T. Tani, K. Ohzeki, K. Sek.
i, Journal of the Electrochemical Scoiety, 138
Vol. 1411-1415 and J. Lenhard, Journal of.
It may be measured by the phase discrimination second harmonic AC voltammetry method described in Imaging Science, Volume 30, p. 27 to 35.

In order to incorporate the spectral sensitizing dye represented by the general formula [I] used in the present invention in the silver halide emulsion of the present invention, they may be dispersed directly in the emulsion or water. , Methanol, ethanol, propanol, acetone, methyl cellosolve, 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, 3-methoxy-1-propanol, 3-methoxy-
It may be added to the emulsion by dissolving it in a solvent such as 1-butanol, 1-methoxy-2-propanol, acetonitrile, tetrahydrofuran, N, N-dimethylformamide or a mixed solvent. In addition, US Pat.
No. 987, etc., a method in which a dye is dissolved in a volatile organic solvent, the solution is dispersed in water or a hydrophilic colloid, and the dispersion is added to an emulsion.
No. 24,185, etc., a method in which a water-insoluble dye is dispersed in a water-soluble solvent without being dissolved, and the dispersion is added to an emulsion.
No. 4, Japanese Patent Publication No. 44-27, 555, Japanese Patent Publication No. 57-22,
No. 091, etc., a method in which a dye is dissolved in an acid and the solution is added to the emulsion, or an acid or a base is coexisted to form an aqueous solution, and the solution is added to the emulsion. US Pat.
No. 822,135, US Pat. No. 4,006,025, etc., a method of adding an aqueous solution or colloidal dispersion in the presence of a surfactant into an emulsion, JP-A-53-102. , 733, JP-A-58-10
No. 5,141, a method of directly dispersing a dye in a hydrophilic colloid and adding the dispersion to an emulsion,
As described in JP-A-51-74624, it is possible to use a method in which a dye is dissolved using a compound that causes red shift and the solution is added to the emulsion. Also, ultrasonic waves can be used for dissolution.

The sensitizing dye used in the present invention may be added to the silver halide emulsion at any step during the preparation of the emulsion which has been found to be useful so far. For example, US Pat. No. 2,735,766 and US Pat.
28,960, U.S. Pat. No. 4,183,756, U.S. Pat. No. 4,225,666, JP-A-58-184,14.
No. 2, JP-A-60-196749, and the like, as disclosed in the specification such as silver halide grain formation step and / or before desalting, during desalting step and / or after desalting step. From the beginning to the start of chemical aging, JP-A-58-113,9
As disclosed in the specification of No. 20, etc., it may be added at any time or step immediately before chemical ripening or during the step, before the emulsion is coated until after the chemical ripening and before coating. good. Also, US Pat. No. 4,225,666,
As disclosed in the specification of JP-A-58-7,629 and the like, the same compound alone or in combination with a compound having a different structure is used, for example, in the same step or during the grain formation step and chemical aging. It may be added separately in different steps such as during the process or after completion of the chemical aging, or before the chemical aging or during the process and after completion, and the compound and the combination of compounds to be added in a divided manner may be added. The kind may be changed and added. In addition, a predetermined amount may be added in a short time, or continuously for a long time, for example, from the nucleation in the particle forming process to the completion of particle formation or most of the chemical ripening process in any step. You may add. In such a case, the addition speed may be a constant flow rate, or the flow rate may be accelerated or decelerated.

The addition amount of the spectral sensitizing dye represented by the general formula [I] used in the present invention varies depending on the shape and size of silver halide grains, but is 4 × 10 ^-6 per mol of silver halide. It can be used at up to 8 × 10 ⁻³ mol. For example, the silver halide grain size is 0.2 to 1.3.
In the case of μm, the total amount of the sensitizing dye added is 2 × 10 ^{−8 to} 3.5 × 10 ⁻⁶ per 1 m ² of the surface area of silver halide grains.
The molar addition amount is preferably 2.5 × 10 ^{−7 to} 2.0 × 1
The addition amount of 0 ^-6 is more preferable.

Examples of compounds represented by the general formula [I] are shown in Table-
1 to Table 5, but not limited thereto.

[0033]

[Table 1]

[0034]

[Table 2]

[0035]

[Table 3]

[0036]

[Table 4]

[0037]

[Table 5]

Next, the compound of the formula [M] according to the present invention will be explained in detail.

Among the coupler skeletons represented by the general formula [M] used in the present invention, preferred ones are 1H-imidazo [1,2-b] pyrazole and 1H-pyrazolo [1,5.
-B] [1,2,4] triazole, 1H-pyrazolo [5,1-c] [1,2,4] triazole and 1H
-Pyrazolo [1,5-d] tetrazole, which are represented by the following formulas [M-I], [M-II], and [M
-III] and [M-IV].

More preferably, [M-II] and [M-II]
I]].

[0041]

[Chemical 5]

Substituents R ₁₁ , R ₁₂ , R in these formulas
₁₃ and X will be described in detail.

R ₁₁ is a hydrogen atom, halogen atom, alkyl group, aryl group, heterocyclic group, cyano group, hydroxyl group, nitro group, carboxyl group, amino group, alkoxy group, aryloxy group, acylamino group, alkylamino group. , Anilino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamide group, carbamoyl group,
Sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonylamino group, imide group, heterocyclic thio group, sulfinyl group, phosphonyl group, aryloxy It represents a carbonyl group, an acyl group, or an azolyl group, and R ₁₁ may be a divalent group to form a bis form.

More specifically, each R ₁₁ is a hydrogen atom, a halogen atom (eg, chlorine atom, bromine atom), an alkyl group (eg, a straight chain or branched chain alkyl group having 1 to 32 carbon atoms, an aralkyl group, an alkenyl group, Alkynyl group, cycloalkyl group, cycloalkenyl group, and more specifically, for example, methyl, ethyl, propyl, isopropyl, t-butyl, tridecyl, 2-methanesulfonylethyl, 3-
(3-pentadecylphenoxy) propyl, 3- {4-
{2- [4- (4-hydroxyphenylsulfonyl) phenoxy] dodecanamide} phenyl} propyl, 2-
Ethoxytridecyl, trifluoromethyl, cyclopentyl, 3- (2,4-di-t-amylphenoxy) propyl), aryl groups (eg phenyl, 4-t-butylphenyl, 2,4-di-t-amylphenyl) , 4-tetradecanamidophenyl), a heterocyclic group (for example, 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an amino group, an alkoxy group (for example, methoxy). , Ethoxy, 2-methoxyethoxy, 2-dodecylethoxy, 2-methanesulfonylethoxy), aryloxy groups (eg phenoxy, 2-methylphenoxy, 4
-T-butylphenoxy, 3-nitrophenoxy, 3-
t-butyloxycarbamoylphenoxy, 3-methoxycarbamoyl), acylamino group (eg acetamide, benzamide, tetradecanamide, 2- (2,4)
-Di-t-amylphenoxy) butanamide, 4- (3
-T-butyl-4-hydroxyphenoxy) butanamide, 2- {4- (4-hydroxyphenylsulfonyl)
Phenoxy} decane amide), alkylamino group (eg methylamino, butylamino, dodecylamino, diethylamino, methylbutylamino), anilino group (eg phenylamino, 2-chloroanilino, 2-chloro-
5-tetradecaneaminoanilino, 2-chloro-5-dodecyloxycarbonylanilino, N-acetylanilino, 2-chloro-5- {α- (3-t-butyl-4-hydroxyphenoxy) dodecaneamide} anilino ), A ureido group (eg, phenylureido, methylureido,
N, N-dibutylureido), sulfamoylamino group (for example, N, N-dipropylsulfamoylamino, N
-Methyl-N-decylsulfamoylamino), alkylthio group (eg methylthio, octylthio, tetradecylthio, 2-phenoxyethylthio, 3-phenoxypropylthio, 3- (4-t-butylphenoxy) propylthio), arylthio Groups (eg phenylthio, 2,
-Butoxy-5-t-octylphenylthio, 3-pentadecylphenylthio, 2-carboxyphenylthio,
4-tetradecanamidophenylthio), an alkoxycarbonylamino group (for example, methoxycarbonylamino,
Tetradecyloxycarbonylamino), a sulfonamide group (for example, methanesulfonamide, hexadecanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, octadecanesulfonamide, 2-methyloxy-5-t-butylbenzenesulfonamide),
A carbamoyl group (for example, N-ethylcarbamoyl, N,
N-dibutylcarbamoyl, N- (2-dodecyloxyethyl) carbamoyl, N-methyl-N-dodecylcarbamoyl, N- {3- (2,4-di-t-amylphenoxy) propyl} carbamoyl), sulfamoyl group ( For example, N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N- (2-dodecyloxyethyl)
Sulfamoyl, N-ethyl-N-dodecylsulfamoyl, N, N-diethylsulfamoyl), sulfonyl group (eg, methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl), alkoxycarbonyl group (eg, methoxycarbonyl, butyloxy) Carbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl), a heterocyclic oxy group (for example, 1-
Phenyltetrazole-5-oxy, 2-tetrahydropyranyloxy), azo group (eg phenylazo, 4-
Methoxyphenylazo, 4-pivaloylaminophenylazo, 2-hydroxy-4-propanoylphenylazo), acyloxy group (eg acetoxy), carbamoyloxy group (eg N-methylcarbamoyloxy,
N-phenylcarbamoyloxy), silyloxy group (eg trimethylsilyloxy, dibutylmethylsilyloxy), aryloxycarbonylamino group (eg phenoxycarbonylamino), imide group (eg N
-Succinimide, N-phthalimide, 3-octadecenylsuccinimide), a heterocyclic thio group (for example, 2-benzothiazolylthio, 2,4-di-phenoxy-1,
3,5-triazole-6-thio, 2-pyridylthio), a sulfinyl group (for example, dodecanesulfinyl,
3-pentadecylphenylsulfinyl, 3-phenoxypropylsulfinyl), phosphonyl group (eg phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), aryloxycarbonyl group (eg phenoxycarbonyl), acyl group (eg acetyl,
3-phenylpropanoyl, benzoyl, 4-dodecyloxybenzoyl), azolyl groups (eg imidazolyl, pyrazolyl, 3-chloro-pyrazol-1-yl,
Triazolyl).

Among these substituents, the group capable of further having a substituent may further have an organic substituent or a halogen atom linked by a carbon atom, an oxygen atom, a nitrogen atom or a sulfur atom.

Of these substituents, preferred R ₁₁ is an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, a ureido group, a urethane group,
An acylamino group can be mentioned.

R ₁₂ is the same group as the substituent exemplified for R ₁₁ , and is preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, a sulfinyl group or an acyl group. And a cyano group.

R ₁₃ is a group having the same meaning as the substituent exemplified for R ₁₁ , and preferably a hydrogen atom, an alkyl group,
An aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkoxycarbonyl group, a carbamoyl group and an acyl group, more preferably an alkyl group, an aryl group, a heterocyclic group, an alkylthio group and an arylthio group. It is a base.

X represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidized product of an aromatic primary amine color developing agent. The splittable group is a halogen atom if it is described in detail.
Alkoxy group, aryloxy group, acyloxy group, alkyl or aryl sulfonyloxy group, acylamino group, alkyl or aryl sulfonamide group,
Alkoxycarbonyloxy group, aryloxycarbonyloxy group, alkyl, aryl or heterocyclic thio group, carbamoylamino group, 5-membered or 6-membered nitrogen-containing heterocyclic group, imide group, arylazo group, etc.,
These groups may be further substituted with a group acceptable as the substituent for R ₁₁ .

More specifically, a halogen atom (for example,
Fluorine atom, chlorine atom, bromine atom), alkoxy group (eg ethoxy, dodecyloxy, methoxyethylcarbamoylmethoxy, carboxypropyloxy, methylsulfonylethoxy, ethoxycarbonylmethoxy), aryloxy group (eg 4-methylphenoxy, 4-chloro) Phenoxy, 4-methoxyphenoxy, 4-carboxyphenoxy, 3-ethoxycarboxyphenoxy,
3-acetylaminophenoxy, 2-carboxyphenoxy), acyloxy group (eg acetoxy, tetradecanoyloxy, benzoyloxy), alkyl or arylsulfonyloxy group (eg methanesulfonyloxy, toluenesulfonyloxy), acylamino group (eg dichloro). Acetylamino, heptafluorobutyrylamino), alkyl or aryl sulfonamide groups (eg methanesulfonamino, trifluoromethanesulfonamino, p-toluenesulfonylamino), alkoxycarbonyloxy groups (eg ethoxycarbonyloxy, benzyloxycarbonyloxy), Aryloxycarbonyloxy groups (eg phenoxycarbonyloxy), alkyl, aryl or heterocyclic thio groups (eg Decylthio, 1-carboxy-dodecyl thio, phenylthio, 2-butoxy -5-t
-Octylphenylthio, tetrazolylthio), carbamoylamino group (for example, N-methylcarbamoylamino, N-phenylcarbamoylamino), a 5- or 6-membered nitrogen-containing heterocyclic group (for example, imidazole, pyrazolyl, triazolyl, tetrazolyl, 1,2) -Dihydro-2-oxo-1-pyridyl), an imide group (for example, succinimide, hydantoinyl), an arylazo group (for example, phenylazo, 4-methoxyphenylazo), and the like. In addition to these, X may take the form of a bis-type coupler obtained by condensing a 4-equivalent coupler with an aldehyde or a ketone as a leaving group bonded via a carbon atom. Further, X may contain a photographically useful group such as a development inhibitor or a development accelerator. Preferred X is a halogen atom,
It is an alkoxy group, an aryloxy group, an alkyl or arylthio group, or a 5- or 6-membered nitrogen-containing heterocyclic group bonded to the coupling active position with a nitrogen atom.

Compound examples of the magenta coupler represented by the above-mentioned general formula [M] are shown in the following chemical formulas 6 to 16, but not limited thereto.

[0052]

[Chemical 6]

[0053]

[Chemical 7]

[0054]

[Chemical 8]

[0055]

[Chemical 9]

[0056]

[Chemical 10]

[0057]

[Chemical 11]

[0058]

[Chemical 12]

[0059]

[Chemical 13]

[0060]

[Chemical 14]

[0061]

[Chemical 15]

[0062]

[Chemical 16]

Documents which describe a method for synthesizing the coupler represented by the general formula [M] are listed below. The above formula [M-
The compound of [I] is a compound of US Pat. No. 4,500,630,
The compound of formula [M-II] is described in US Pat. No. 4,540,654.
No. 4,705,863, JP-A-61-65245.
No. 62-209457, No. 62-249155 and the like, the compound of the formula [M-III] is disclosed in JP-B-47-2741.
1, U.S. Pat. No. 3,725,067 and the like [M-
The compound of [IV] can be synthesized by the method described in JP-A-60-33552.

The magenta coupler represented by the general formula [M] of the present invention is added to the green-sensitive emulsion layer and / or its adjacent layer, and the total amount thereof is 0.01 to 1.0 g.
/ M ² , preferably 0.05 to 0.8 g / m ² , and more preferably 0.1 to 0.5 g / m ² . The method of adding the magenta coupler of the present invention to the light-sensitive material is in accordance with the method of other couplers described below, but the amount of the high boiling point organic solvent used as the dispersion solvent is the weight relative to all the couplers added to the magenta coupler-containing layer. The ratio is 0 to 5.0, preferably 0 to 3.0, and more preferably 0.1 to 1.5.

Next, selenium sensitization in the present invention will be described. As the selenium sensitizer used in the present invention, selenium compounds disclosed in conventionally known patents can be used. That is, usually, an unstable selenium compound and / or a non-unstable selenium compound is added at high temperature,
It is preferably used by stirring the emulsion at 40 ° C. or higher for a certain period of time. Examples of unstable selenium compounds include Japanese Examined Patent Publication Nos. 44-15748 and 43-13489.
No. 2, Japanese Patent Application No. 2-130976, Japanese Patent Application No. 2-22930
It is preferable to use the compounds described in No. 0. Specific examples of the unstable selenium sensitizer include, for example, isoselenocyanates (eg, aliphatic isoselenocyanates such as allyl isoselenocyanate), selenoureas, selenoketones, selenamides, selenocarboxylic acids (eg, 2 -Selenopropionic acid, 2-selenobutyric acid), selenoesters, diacyl selenides (eg bis (3
-Chloro-2,6-dimethoxybenzoyl) selenide), selenophosphates, phosphine selenides,
Examples include colloidal metal selenium.

Particularly preferred unstable selenium compounds are shown below.

I. Colloidal metal selenium II. Organic selenium compound (selenium atom is double-bonded to carbon atom of organic compound by covalent bond) a. Isoselenocyanates, for example aliphatic isoselenocyanates such as allyl isoselenocyanate b. Selenoureas (including enol type) For example, methyl, ethyl, propyl, isopropyl, butyl, hexyl, octyl, dioctyl, tetraoctyl, N- (β-carboxyethyl) -N ′, N′-dimethyl, N, N -Aliphatic selenoureas such as dimethyl, diethyl, dimethyl; aromatic selenoureas having one or more aromatic groups such as phenyl, tolyl; heterocyclic groups having heterocyclic groups such as pyridyl, benzothiazolyl Selenourea c. Selenoketones, for example, selenoacetone, selenoacetophenone, selenoketone having an alkyl group bonded to> C = Se, selenobenzophenone d. Selenoamides For example, selenoacetamide e. Selenocarboxylic acids and esters For example, 2-selenopropionic acid, 3-selenobutyric acid, methyl-3-selenobutyrate III. Others a. Selenides For example, diethyl selenide, diethyl diselenide,
Triphenylphosphine selenide b. Selenophosphates, for example, tri-p-tolyl selenophosphate, tri-p-tolyl
The preferred types of n-butylselenophosphate labile selenium compounds have been described above, but are not limiting. Stable selenium compounds as sensitizers for photographic emulsions are known to those skilled in the art, as long as selenium is unstable, the structure of the compounds is not so important, and organic compounds of selenium sensitizer molecules are not important. It is generally understood that the moieties carry selenium and have no role other than allowing it to be present in the emulsion in an unstable form. In the present invention, the labile selenium compound having such a broad concept is advantageously used.

Examples of the non-labile selenium compound used in the present invention are JP-B-46-4553 and JP-B-52-34.
The compounds described in JP-B No. 492 and JP-B-52-34491 are used. Examples of non-labile selenium compounds include selenious acid, potassium selenocyanide, selenazoles, quaternary salts of selenazoles, diaryl selenides, diaryl diselenides, dialkyl selenides, dialkyl diselenides, 2-selenazolidinediones, Examples include 2-selenooxazolidinethione and derivatives thereof.

The non-labile selenium sensitizer and thioselenazolidinedione compound described in JP-B-52-38408 are also useful.

Of these selenium compounds, the following general formulas [I] and [II] are preferable. General formula [II]

[0071]

[Chemical 17]

In the formula, Z ₁ and Z ₂ may be the same or different, and are an alkyl group (eg, methyl, ethyl, t-butyl, adamantyl, t-octyl), an alkenyl group (eg, vinyl, propenyl). , Aralkyl groups (eg, benzyl, phenethyl), aryl groups (eg, phenyl, pentafluorophenyl, 4-chlorophenyl, 3-nitrophenyl, 4-octylsulfamoylphenyl, α-naphthyl), heterocyclic groups (eg, pyridyl group, a thienyl group, a furyl group, an imidazolyl _{group), - NR 1 (R 2} ), - represents the oR ₃ or -SR _4.

R ₁ , R ₂ , R ₃ and R _{4, which} may be the same or different, each represents an alkyl group, an aralkyl group, an aryl group or a heterocyclic group. Examples of the alkyl group, aralkyl group, aryl group or heterocyclic group are the same as those for Z ₁ .

However, R ₁ and R ₂ are a hydrogen atom or an acyl group (for example, acetyl, propanoyl, benzoyl, heptafluorobutanoyl, difluoroacetyl,
4-nitrobenzoyl, α-naphthoyl, 4-trifluoromethylbenzoyl) may be used.

In the general formula [II], preferably Z ₁ represents an alkyl group, an aryl group or --NR ₁ (R ₂ ), and Z ₂ represents-
Represents NR ₅ (R ₆ ). R ₁ , R ₂ , R ₅ and R _{6, which} may be the same or different, each represents a hydrogen atom, an alkyl group, an aryl group or an acyl group.

In the general formula [II], more preferably N, N-
Dialkylselenourea, N, N, N'-trialkyl-
N'-acyl selenoureas, tetraalkyl selenoureas,
Represents N, N-dialkyl-arylselenoamide, N-alkyl-N-aryl-arylselenoamide. General formula [III

[0077]

[Chemical 18]

In the formula, Z ₃ , Z ₄ and Z ₅ may be the same or different and each is an aliphatic group, an aromatic group, a heterocyclic group, -OR ₇ , -NR ₈ (R ₉ ), -SR. ₁₀ , -Se
R ₁₁ , X and a hydrogen atom are represented.

R ₇ , R ₁₀ and R ₁₁ represent an aliphatic group, an aromatic group, a heterocyclic group, a hydrogen atom or a cation, and R ₈ and R ₉ represent an aliphatic group, an aromatic group, a heterocyclic group or hydrogen. Represents an atom, and X represents a halogen atom.

In the general formula [III], Z ₃ , Z ₄ , Z
_The aliphatic group represented by ₅ , R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ is a linear, branched or cyclic alkyl group, an alkenyl group, an alkynyl group or an aralkyl group (for example, methyl, ethyl, n -Propyl, isopropyl, t-butyl, n-
Butyl, n-octyl, n-decyl, n-hexadecyl, cyclopentyl, cyclohexyl, allyl, 2-butenyl, 3-pentenyl, propargyl, 3-pentynyl, benzyl, phenethyl).

In the general formula [III], Z ₃ , Z ₄ , Z
_The aromatic group represented by ₅ , R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ is a monocyclic or condensed aryl group (for example, phenyl, pentafluorophenyl, 4-chlorophenyl, 3
-Sulfophenyl, α-naphthyl, 4-methylphenyl).

In the general formula [III], Z ₃ , Z ₄ , Z
_The heterocyclic group represented by ₅ , R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ is a saturated or unsaturated 3-10 membered ring containing at least one of a nitrogen atom, an oxygen atom or a sulfur atom. Heterocyclic group (for example, pyridyl group, thienyl group, furyl group,
Thiazolyl group, imidazolyl group, benzimidazolyl group).

In the general formula [III], the cation represented by R ₇ , R ₁₀ and R ₁₁ represents an alkali metal atom or ammonium, and the halogen atom represented by X is, for example, a fluorine atom, a chlorine atom or a bromine atom. Or represents an iodine atom.

In the general formula [III], preferably Z ₃ and Z ₄
Or Z ₅ represents an aliphatic group, an aromatic group or -OR _7, R ₇ represents an aliphatic group or an aromatic group.

In the general formula [III], a trialkylphosphine selenide, a triarylphosphine selenide, a trialkylselenophosphate or a triarylselenophosphate is more preferable.

Specific examples ("Chemical formula 19" to "Chemical formula 23") of the compounds represented by the general formulas [I] and [II] are shown below, but the present invention is not limited thereto.

[0087]

[Chemical 19]

[0088]

[Chemical 20]

[0089]

[Chemical 21]

[0090]

[Chemical formula 22]

[0091]

[Chemical formula 23]

Regarding the selenium sensitization method, for example, US Pat. Nos. 1,574,944, 1,602,592 and 16,
No. 23499, No. 3297446, No. 32974
No. 47, No. 3320069, No. 3408196.
No. 3,408,197, No. 3442653, No. 3420670, No. 3591385, French Patent No. 2693038, No. 2093209, Japanese Patent Publication No. 52-34491, No. 52-34492, No. 53.
-295, 57-22090, JP-A-59-18.
0536, 59-185330, 59-181.
No. 337, No. 59-187338, No. 59-1922.
No. 41, No. 60-150046, No. 60-15163.
7, 61-246738, JP-A-3-42221.
Japanese Patent Application Nos. 1-287380 and 1-250950.
No. 1-254441, No. 2-334090, No. 2
-110558, 2-130976, 2-13
No. 9183, No. 2-229300, British Patent Nos. 255546, 861984, and HESpenc.
er et al., Journal of Photographic Science, 31
Vol. 158-169 (1983).

These selenium sensitizers are dissolved in water or an organic solvent such as methanol and ethanol, alone or in a mixed solvent, or in Japanese Patent Application Nos. 2-264447 and 2-26.
It is added at the time of chemical sensitization in the form described in No. 4448.
It is preferably added before the start of chemical sensitization. The selenium sensitizer used is not limited to one type, and two or more types of the above selenium sensitizers can be used in combination. The unstable selenium compound and the non-unstable selenium compound may be used in combination.

The addition amount of the selenium sensitizer used in the present invention varies depending on the activity of the selenium sensitizer used, the kind and size of silver halide, the temperature and time of ripening, etc.
It is preferably 1 × 10 ⁻⁸ mol or more per mol of silver halide. More preferably 1 × 10 ⁻⁷ mol or more and 1 × 10
^-4 mol or less. The temperature of chemical ripening when a selenium sensitizer is used is preferably 45 ° C. or higher. More preferably, pAg and pH of 50 ° C. or higher and 80 ° C. or lower are arbitrary. For example, the effect of the present invention can be obtained in a wide range of pH from 4 to 9.

The silver halide emulsion of the present invention is sensitized with gold-selenium, but by sensitizing gold-sulfur-selenium in combination with sulfur sensitization, higher sensitivity and lower fog can be achieved. .

The sulfur sensitization in the present invention is usually carried out by adding a sulfur sensitizer and stirring the emulsion at a high temperature, preferably 40 ° C. or higher for a certain period of time.

The gold sensitization in the present invention is usually carried out by adding a gold sensitizer and stirring the emulsion at a high temperature, preferably 40 ° C. or higher for a certain period of time.

Known sulfur sensitizers can be used for the above-mentioned sulfur sensitization. Examples thereof include thiosulfates, thioureas, allyl isothiocyanates, cystines, p-toluene thiosulfonates, and rhodanines. Other US Pat. Nos. 1,574,944 and 2,41
No. 0,689, No. 2,278,947, No. 2,7
No. 28,668, No. 3,501,313, No. 3,
656,955 specifications, German Patent 1,422,8
No. 69, Japanese Patent Publication No. 56-24937, and Japanese Patent Laid-Open No. 55-45.
The sulfur sensitizers described in JP-A No. 016, etc. can also be used. The sulfur sensitizer may be added in an amount sufficient to effectively increase the sensitivity of the emulsion. This amount is pH,
Although it varies over a considerable range under various conditions such as temperature and size of silver halide grains, it is preferably 1 × 10 ⁻⁷ mol or more and 5 × 10 ⁻⁴ mol or less per mol of silver halide.

As the gold sensitizer for the above-mentioned gold sensitization, the oxidation number of gold may be +1 valence or +3 valence, and a gold compound usually used as a gold sensitizer can be used. Typical examples include chloroaurate, potassium chloroaurate,
Auric trichloride, potassium auriothiocyanate, potassium iodoaurate, tetracyano auric acid, ammonium aurothiocyanate,
Pyridyl trichlorogold is mentioned. The amount of the gold sensitizer added varies depending on various conditions, but as a guide, it is preferably 1 × 10 ^{−7 to} 1 × 10 ⁻⁴ mol per mol of silver halide.

In chemical ripening, there is no particular limitation on the timing and order of addition of a silver halide solvent and a selenium sensitizer or a sulfur sensitizer and / or a gold sensitizer which can be used in combination with a selenium sensitizer. There is no need to provide it,
For example, the above compounds can be added at the same time as the initial (preferably) chemical ripening or during the progress of chemical ripening, or at different addition points. In addition, at the time of addition, the above compound may be dissolved in water or an organic solvent capable of mixing with water, for example, a single liquid or a mixed liquid of methanol, ethanol, and acetone, and then added.

The chemical sensitization by gold-selenium sensitization or gold-sulfur-selenium sensitization of the present invention is more effective when carried out in the presence of a silver halide solvent.

The silver halide solvent which can be used in the present invention is, for example, US Pat. No. 3,271,
No. 157, No. 3,531,289, No. 3,57.
4,628, JP-A-54-1019 and 54-15.
(A) Organic thioethers described in 8917, JP-A Nos. 53-82408, 55-77737, and 5
(B) thiourea derivative described in JP-A-5-2982, and (c) a silver halide solvent having a thiocarbonyl group sandwiched between an oxygen or sulfur atom and a nitrogen atom, described in JP-A-53-144319. , (D) imidazoles, (e) sulfites described in JP-A No. 54-100717,
(F) Thiocyanate.

Particularly preferred silver halide solvents are:
Examples thereof include thiocyanate, tetramethylthiourea, and thiocyanate. The silver halide emulsion of the present invention contains thiocyanate. The amount of the solvent used varies depending on the kind, but in the case of thiocyanate, the preferable amount is 1 × 10 ⁻⁴ mol or more and 1 × 10 ⁻² mol per mol of silver halide.
It is less than or equal to mol.

As the thiocyanate, for example, ammonium salt, potassium salt and sodium salt are preferably used.

The thiocyanate may be used alone or in combination with a gold sensitizer at the time of chemical sensitization. The thiocyanate may be added dividedly or continuously.

In the present invention, thiocyanate is more preferably used not only during chemical sensitization but also during grain formation or during the desalting step. For the use of thiocyanate in grain formation, see US Pat.
No. 434226.

Research Disclosure No. 308119 (Generally, about various techniques and inorganic / organic materials which can be used for the silver halide photographic emulsion of the present invention and the silver halide photographic light-sensitive material using the same. 1
989) can be used.

In addition to this, more specifically, for example,
Techniques and inorganic / organic materials that can be used for color photographic light-sensitive materials to which the silver halide photographic emulsion of the present invention can be applied are described in the following parts of EP 436,938A2 and the patents cited below. There is.

Item This section 1) Layer structure Page 146, line 34 to page 147, line 25 2) Silver halide emulsion Page 147, line 26 to page 148, line 12 3) Yellow coupler No. Page 137, line 35 to page 146, line 33, page 149, line 21 to line 23 4) Combined use, page 149, line 24 to line 28; European patent No. 42 magenta coupler 1,453A1 Page 3, line 5 to page 25, line 55) Cyan coupler page 149, lines 29 to 33; European patent 432,804A2, page 3, line 28 to page 40, line 2 6) Polymer coupler, page 149, lines 34 to 38; EP 113, line 39, line 39 to page 123, line 37; 7) Colored coupler, page 53, line 42 to 137. Page 34 line, page 149 page 39 line -Line 45 to 8) Other functionality Page 7, line 1 to page 53, line 41, page 149, line 46, coupler line to page 150, line 3; European Patent 435,334A3, 3rd line Page 1, line 1 to page 29, line 50 9) Antiseptic and antifungal agent Page 150, line 25 to line 28 10) Formalin Page 149, line 15 to line 17 Scavenger 11) Other additives 153 Page 38, line 47 to line 47; European Patent No. 421,453A1 page 75, line 21 to page 84, line 56 12) Dispersion method page 150, line 4 to line 13) Support 150. Page 32 line 34-line 14) Film thickness and film physical properties page 150 Page 35 line 35-49 line 15) Color development step page 150 line 50-page 151 line 47 16) Desilvering step 151 Page 48, line 48 to page 152, line 53 17) Automatic processor Page 152, line 54 to page 153, line 2 18) Washing and stabilization process page 153, line 3 to 37 row

[0110]

【Example】

Example 1 Hereinafter, the present invention will be specifically described with reference to examples, but the invention is not limited thereto. Preparation of Sample 101 A multilayer color light-sensitive material composed of each layer having the following composition was prepared on an undercoated cellulose triacetate film support having a thickness of 127 μm to prepare Sample 101. The numbers represent the amount added per m ² . The effect of the added compound is not limited to the described use.

First layer: antihalation layer Black colloidal silver 0.20 g Gelatin 1.90 g UV absorber U-1 0.10 g UV absorber U-3 0.040 g UV absorber U-4 0.10 g High boiling organic solvent Oil-1 0.10 g Microcrystalline solid dispersion of Dye E-1 0.10 g

Second layer: intermediate layer Gelatin 0.40 g Compound Cpd-C 5.0 mg Compound Cpd-J 5.0 mg Compound Cpd-K 3.0 mg High boiling point organic solvent Oil-3 0.10 g Dye D-4 0.80 mg

Third Layer: Intermediate Layer Finely grained silver iodobromide emulsion with the surface and inside fogged (average grain size 0.06 μm, coefficient of variation 18%, AgI content 1 mol%) silver amount 0.050 g yellow colloidal silver silver amount 0.050g Gelatin 0.40g

Fourth layer: low-sensitivity red-sensitive emulsion layer Emulsion A Silver amount 0.30 g Emulsion B Silver amount 0.20 g Gelatin 0.80 g Coupler C-1 0.150 g Coupler C-2 0.050 g Coupler C-3 0.050 g Coupler C-8 0.050 g Compound Cpd-C 5.0 mg Compound Cpd-J 5.0 mg High boiling point organic solvent Oil-2 0.10 g Additive P-1 0.10 g

Fifth layer: Medium-sensitive red-sensitive emulsion layer Emulsion B Silver amount 0.20 g Emulsion C Silver amount 0.30 g Gelatin 0.80 g Coupler C-1 0.20 g Coupler C-2 0.050 g Coupler C-3 0.20 g High boiling point organic solvent Oil-2 0.10 g Additive P-1 0.10 g

Sixth layer: High-sensitivity red-sensitive emulsion layer Emulsion D Silver amount 0.40 g Gelatin 1.10 g Coupler C-1 0.30 g Coupler C-2 0.10 g Coupler C-3 0.70 g Additive P-1 0.10 g

Seventh layer: intermediate layer Gelatin 0.60 g Additive M-1 0.30 g Color mixing inhibitor Cpd-I 2.6 mg Dye D-5 0.020 g Dye D-6 0.010 g Compound Cpd-J 5.0 mg High boiling organic solvent Oil -1 0.020 g

Eighth layer: intermediate layer Silver iodobromide emulsion with fogged surface and inside (average grain size 0.06 μm, variation coefficient 16%, AgI content 0.3 mol%) Silver amount 0.020 g Yellow colloidal silver Silver amount 0.020 g Gelatin 1.00 g Additive P-1 0.20 g Color mixture inhibitor Cpd-A 0.10 g Compound Cpd-C 0.10 g

Ninth layer: low-sensitivity green-sensitive emulsion layer Emulsion E Silver amount 0.10 g Emulsion F Silver amount 0.25 g Emulsion G Silver amount 0.20 g Gelatin 0.50 g Coupler C-7 0.16 g Compound Cpd-B 0.030 g Compound Cpd-D 0.020 g Compound Cpd-E 0.020 g Compound Cpd-F 0.040 g Compound Cpd-J 10 mg Compound Cpd-L 0.020 g High boiling point organic solvent Oil-1 0.10 g High boiling point organic solvent Oil-2 0.10 g

Layer 10: Medium-speed green-sensitive emulsion layer Emulsion G Silver amount 0.25 g Emulsion H Silver amount 0.10 g Gelatin 0.60 g Coupler C-4 0.10 g Coupler C-7 0.10 g Compound Cpd-B 0.030 g Compound Cpd-D 0.020 g Compound Cpd-E 0.020 g Compound Cpd-F 0.050 g Compound Cpd-L 0.050 g High boiling point organic solvent Oil-2 0.010 g

Eleventh layer: High-sensitivity green-sensitive emulsion layer Emulsion I Silver amount 0.90 g Gelatin 1.00 g Coupler C-4 0.50 g Coupler C-7 0.10 g Compound Cpd-B 0.080 g Compound Cpd-E 0.020 g Compound Cpd-F 0.040g Compound Cpd-K 5.0 mg Compound Cpd-L 0.020 g High boiling point organic solvent Oil-1 0.020 g High boiling point organic solvent Oil-2 0.020 g

Twelfth layer: intermediate layer Gelatin 0.60 g Compound Cpd-L 0.050 g High boiling point organic solvent Oil-1 0.050 g

Thirteenth layer: Yellow filter layer Yellow colloidal silver Amount of silver 0.070 g Gelatin 1.10 g Color-mixing inhibitor Cpd-A 0.010 g Compound Cpd-L 0.010 g High boiling point organic solvent Oil-1 0.010 g Fine crystals of dye E-2 Solid dispersion 0.050g

14th layer: intermediate layer 0.60 g of gelatin

Fifteenth layer: low-sensitivity blue-sensitive emulsion layer Emulsion J Silver amount 0.20 g Emulsion K Silver amount 0.30 g Gelatin 0.80 g Coupler C-5 0.20 g Coupler C-6 0.10 g Coupler C-9 0.40 g

Sixteenth layer: Medium sensitivity blue-sensitive emulsion layer Emulsion L Silver amount 0.30 g Emulsion M Silver amount 0.30 g Gelatin 0.90 g Coupler C-5 0.10 g Coupler C-6 0.10 g Coupler C-9 0.60 g

Layer 17: High-sensitivity blue-sensitive emulsion layer Emulsion N Silver amount 0.20 g Emulsion O Silver amount 0.20 g Gelatin 1.20 g Coupler C-5 0.10 g Coupler C-6 0.10 g Coupler C-9 0.60 g High boiling point organic solvent Oil-2 0.10 g

Eighteenth layer: First protective layer Gelatin 0.70 g UV absorber U-1 0.20 g UV absorber U-2 0.050 g UV absorber U-5 0.30 g Formalin scavenger Cpd-H 0.40 g Dye D-1 0.15 g Dye D-2 0.050 g Dye D-3 0.10 g

19th layer: Second protective layer Colloidal silver Silver amount 0.10 mg Fine grain silver iodobromide emulsion (average particle size 0.06 μm, AgI content 1 mol%) Silver amount 0.10 g Gelatin 0.40 g

20th layer: 3rd protective layer Gelatin 0.40 g Polymethylmethacrylate (average particle size 1.5 μ) 0.10 g Copolymer of methylmethacrylate and acrylic acid 4: 6 (average particle size 1.5 μ) 0.10 g Silicone oil 0.030g Surfactant W-1 3.0mg Surfactant W-2 0.030g

In addition to the above composition, additives F-1 to F-8 were added to all emulsion layers. In addition to the above composition, gelatin hardener H-1 and coating and emulsifying surfactants W-3, W-4, W-5 and W-6 were added to each layer. Further, phenol, 1,2-benzisothiazolin-3-one, 2-phenoxyethanol, phenethyl alcohol, and p-benzoic acid butyl ester were added as antiseptic and antifungal agents.

[0132]

[Table 6]

[0133]

[Table 7]

[0134]

[Table 8]

[0135]

[Chemical formula 24]

[0136]

[Chemical 25]

[0137]

[Chemical formula 26]

[0138]

[Chemical 27]

[0139]

[Chemical 28]

[0140]

[Chemical 29]

[0141]

[Chemical 30]

[0142]

[Chemical 31]

[0143]

[Chemical 32]

[0144]

[Chemical 33]

[0145]

[Chemical 34]

[0146]

[Chemical 35]

[0147]

[Chemical 36]

[0148]

[Chemical 37]

[0149]

[Chemical 38]

Next, in the same manner as in Sample 101, except that the sensitizing dye S-5 and the magenta coupler in the ninth, tenth and eleventh layers of Sample 101 were changed, Samples 102 to 102 were prepared.
112 was created. These contents are summarized in Table-9. The sensitizing dye was replaced with an equimolar amount, and the coupler was replaced with a 0.7-fold molar amount so that the maximum color density measured by the green filter after the treatment was almost the same as that of the sample 101.

The storability of the obtained samples 101 to 112 under high temperature and high humidity conditions was evaluated. Two sets of samples were prepared, one set under the condition of 20 ° C. and 50% RH, and the other set.
After standing for 3 days at 50 ° C. and 75% RH, each sample was exposed through a sensitometric wedge with a white light source at 4800 ° K. The exposed sample was subjected to a reversal process by the following process steps.

Processing Step Time Temperature First development 6 minutes 38 ° C. Water washing 2 minutes 38 ° C. Inversion 2 minutes 38 ° C. Color development 6 minutes 38 ° C. Pre-bleaching 2 minutes 38 ° C. Bleach 6 minutes 38 ° C. Settling 4 minutes 38 ℃ Water wash 4 minutes 38 ℃ Final rinse 1 minute 25 ℃

The composition of each treatment liquid was as follows. [First developer] Nitrilo-N, N, N-trimethylenephosphonic acid / 5-sodium salt 1.5 g Diethylenetriaminepentaacetic acid / 5-sodium salt 2.0 g Sodium sulfite 30 g Hydroquinone / potassium monosulfonate 20 g Potassium carbonate 15 g Sodium carbonate 12 g 1-Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 1.5 g Potassium bromide 2.5 g Potassium thiocyanate 1.2 g Potassium iodide 2.0 mg Diethylene glycol 13 g Water added 1000 ml pH 9.60 pH is Adjusted with sulfuric acid or potassium hydroxide.

[Inversion Liquid] Nitrilo-N, N, N-trimethylenephosphonic acid-5 sodium salt 3.0 g stannous chloride dihydrate 1.0 g p-aminophenol 0.1 g sodium hydroxide 8 g glacial acetic acid 15 ml Water was added to 1000 ml pH 6.00 The pH was adjusted with acetic acid or sodium hydroxide.

[Color Developer] Nitrilo-N, N, N-trimethylenephosphonic acid / 5 sodium salt 2.0 g sodium sulfite 7.0 g phosphoric acid trisodium dodecahydrate 36 g potassium bromide 1.0 g potassium iodide 90 mg Sodium hydroxide 3.0 g Citrazine acid 1.5 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline / 3/2 sulfuric acid monohydrate 11 g 3,6-dithiaoctane- 1,8-diol 1.0 g Water was added to 1000 ml pH 11.80 The pH was adjusted with sulfuric acid or potassium hydroxide.

[Pre-bleaching] Ethylenediamine tetraacetic acid / disodium salt / dihydrate 8.0 g Sodium sulfite 6.0 g 1-Thioglycerol 0.4 g Sodium formaldehyde bisulfite adduct 30 g Water 1000 ml pH 6.20 pH is acetic acid or Adjusted with sodium hydroxide.

[Bleach] Ethylenediaminetetraacetic acid ・ disodium salt ・ dihydrate 2.0 g Ethylenediaminetetraacetic acid ・ Fe (III) ・ Ammonium ・ dihydrate 120 g Potassium bromide 100 g Ammonium nitrate 10 g Water was added to 1000 Milliliter pH 5.70 pH was adjusted with nitric acid or sodium hydroxide.

[Fixing Solution] Ammonium thiosulfate 80 g Sodium sulfite 5.0 g Sodium bisulfite 5.0 g Water was added to 1000 ml pH 6.60 pH was adjusted with acetic acid or aqueous ammonia.

[Final Rinse Solution] 1,2-Benzisothiazolin-3-one 0.02 g Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 g Polymaleic acid (average molecular weight 2,000) 0.1 g Water was added. 1000 ml pH 7.0

After the treatment, the density was measured with a green filter to evaluate the maximum density (Dmax / G) of the green photosensitive layer.
The decrease in the maximum density here means that the fog is increasing. The obtained results are summarized in Table 9.

Next, the color reproducibility was evaluated. Sample 101 except that a cellulose triacetate base having a base thickness of 205 μ was used and a curling prevention layer was coated on the side opposite to the emulsion layer.
Sample Nos. 101 ′ to 1 coated with an emulsion layer in the same manner as No. 112 to No. 112
12 'was produced. These were processed into a size of 4 × 5, and a color checker manufactured by Macbeth and a subject mainly composed of reddish color were photographed by a camera, and the same processing as described above was performed. The obtained practical sample was subjected to sensory evaluation to evaluate the red color reproducibility. The results are summarized in Table-9.

[0162]

[Table 9]

As is clear from the results of Table 9, in the samples according to the present invention, Dmax caused by fogging with time
There is little variation in / G and color reproducibility is improved at the same time. On the other hand, R _{1 of the} general formula II is a methyl group and
The comparative couplers A and B in which X is a fluorine atom cannot produce the effects of the present invention.

Example 2 [Preparation of Emulsion I] (i) 0.05 mol of potassium bromide (per liter of solution,
The same shall apply hereinafter) 1.0 liter of 0.7% aqueous solution of inert bone gelatin containing the same was kept at 60 ° C. and stirred. (ii) To this was added a 1.95 molar aqueous solution of potassium bromide and a 1.9 molar aqueous solution of silver nitrate by the double jet method at the same constant flow rate for 80 seconds (consuming 4.4% of gold-silver-nitrate). (iii) 400% 9% deionized gelatin solution
After adding ml, the temperature was raised to 75 ° C. (iv) After adding 1.52 mol of silver nitrate aqueous solution to adjust pBr to 2.25 (consuming 3.1% of total silver nitrate), add 14.7N ammonia aqueous solution to adjust pH to 8.3 and adjust the physical properties. After aging, 1N nitric acid was added to adjust the pH again to 5.2. (v) Simultaneously increasing the flow rate of an aqueous solution containing 1.34 mol of potassium bromide and 0.16 mol of potassium iodide and an aqueous solution of 1.9 mol silver nitrate (the flow rate at the end was 3.5 times that at the start). ) Added over 40 minutes keeping pBr at 1.56 (consumed 62.4% of total silver nitrate). (vi) Potassium iodide 0.
250 ml of an 11 molar aqueous solution was added over 5 minutes, and 10 minutes after the addition was completed, a 1.34 molar aqueous solution of potassium bromide and a 1.9 molar aqueous solution of silver nitrate were simultaneously added at a constant flow rate for 15 minutes while maintaining pBr at 2.42. (Consumed 30.1% of total silver nitrate). (vii) Next, the tabular silver iodobromide grains having an average grain diameter / thickness ratio of 6.0 and a sphere-equivalent diameter of 0.85 μm were desalted by an ordinary flocculation method (average silver iodide content: 8. 9 mol%) was prepared.

Emulsion I was mixed with spectral sensitizing dyes ExS-5 and ExS-5.
Emulsions Ia and Ib were prepared by adding S-6 and optimally chemically sensitizing it by either of the following two methods. Here, “optimal” means that the sensitivity is highest when exposed for 1/100 second. Emulsion Ia. (Gold-sulfur sensitization): per mol of silver halide,
Sodium thiocyanate 2.2 × 10 ^-3 mol, chloroauric acid 1.5 × 10 ^-6 mol and sodium thiosulfate 1.4 ×
Optimum chemical sensitization was carried out at 56 ° C. by adding 10 ⁻⁵ mol. Emulsion Ib. (Gold-Sulfur-Selenium sensitized): 2.2 × 10 ^-3 mol of sodium thiocyanate per mol of silver halide,
Chloroauric acid 2.2 × 10 ⁻⁶ mol, sodium thiosulfate 1.
0 × 10 ⁻⁵ mol and selenium sensitizer (compound 40)
Optimal chemical sensitization was carried out at 56 ° C. by adding 5 × 10 ⁻⁶ mol.

[Preparation of Emulsions II and III] In the same manner as in the preparation method of Emulsion I, except that the amount of gelatin (i), the temperature, the amount of aqueous silver nitrate solution (ii), the addition time and the like were changed, the procedure was almost the same. Emulsions II and III were prepared. Emulsion II was a tabular silver iodobromide grain having an average grain diameter / thickness ratio of 5.8 and an equivalent spherical diameter of 0.63 μm (average silver iodide content was 6.0 mol%), and Emulsion III was an average grain diameter / thickness. It was a tabular silver bromide grain having a ratio of 5.9 and an equivalent spherical diameter of 0.47 μm (average silver iodide content: 2.5%).

Emulsions II and III were mixed with the spectral sensitizing dye ExS-
4, ExS-5 was added, and gold-sulfur sensitized emulsions IIa, IIIa and gold- were prepared in the same manner as in the preparation of the emulsions Ia, Ib.
Sulfur-selenium sensitized emulsions IIb and IIIb were prepared.

[0168]

[Chemical Formula 39]

[Preparation of Light-Sensitive Material and Its Evaluation] On the undercoated cellulose triacetate film support, each layer having the composition shown below was coated in multiple layers to prepare Sample 201, which is a multilayer color light-sensitive material. (Photosensitive layer composition) The main components used in each layer are classified as follows: ExC: Cyan coupler UV: UV absorber ExM: Magenta coupler HBS: High boiling point organic solvent ExY: Yellow coupler H: Gelatin Curing agent ExS: Sensitizing dye The numbers corresponding to the respective components indicate the coating amount expressed in units of g / m ² , and for silver halide, the coating amount in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown in mol unit per mol of silver halide in the same layer. (Sample 101) First layer (antihalation layer) Black colloidal silver Silver 0.18 Gelatin 1.40 ExM-1 0.18 ExF-1 2.0 × 10 ^-3 Second layer (intermediate layer) Emulsion G Silver 0.065 2,5-di-t- Pentadecyl hydroquinone 0.18 ExC-2 0.020 UV-1 0.060 UV-2 0.080 UV-3 0.10 HBS-1 0.10 HBS-2 0.020 Gelatin 1.04 Third layer (low-sensitivity red-sensitive emulsion layer) Emulsion A Silver 0.25 Emulsion B Silver 0.25 ExS -1 6.9 x 10 ^-5 ExS-2 1.8 x 10 ^-5 ExS-3 3.1 x 10 ^-4 ExC-1 0.17 ExC-4 0.17 ExC-7 0.020 UV-1 0.070 UV-2 0.050 UV-3 0.070 HBS-1 0.060 Gelatin 0.87

Fourth Layer (Medium Sensitivity Red Sensitive Emulsion Layer) Emulsion D Silver 0.80 ExS-1 3.5 × 10 ^-4 ExS-2 1.6 × 10 ^-5 ExS-3 5.1 × 10 ^-4 ExC-1 0.20 ExC-2 0.050 ExC-4 0.20 ExC-5 0.050 ExC-7 0.015 UV-1 0.070 UV-2 0.050 UV-3 0.070 Gelatin 1.30 Fifth layer (high-sensitivity red-sensitive emulsion layer) Emulsion E Silver 1.40 ExS-1 2.4 × 10 ^-4 ExS -2 1.0 x 10 ^-4 ExS-3 3.4 x 10 ^-4 ExC-1 0.097 ExC-2 0.010 ExC-3 0.065 ExC-6 0.020 HBS-1 0.22 HBS-2 0.10 Gelatin 1.63 6th layer (intermediate layer) Cpd- 1 0.040 HBS-1 0.020 Gelatin 0.80

Seventh Layer (Low Sensitivity Green Sensitive Emulsion Layer) Emulsion IIIa Silver 0.30 ExS-4 6.4 × 10 ^-4 ExS-5 3.0 × 10 ^-4 ExM-1 0.021 ExM-2 0.26 ExM-3 0.030 ExY-1 0.025 HBS-1 0.10 HBS-3 0.010 Gelatin 0.63 Eighth layer (medium speed green emulsion layer) Emulsion IIa Silver 0.50 ExS-4 5.1 × 10 ^-4 ExS-5 2.5 × 10 ^-4 ExM-2 0.010 ExM-3 0.026 ExY -1 0.018 HBS-1 0.16 HBS-3 8.0 × 10 ^-3 Gelatin 0.50

Ninth Layer (High Sensitivity Green Sensitive Emulsion Layer) Emulsion IIa Silver 1.25 ExS-5 2.1 × 10 ^-4 ExS-6 3.3 × 10 ^-4 ExC-1 0.015 ExM-1 0.023 ExM-4 0.10 ExM-5 0.018 Cpd-2 0.011 HBS-1 0.20 HBS-2 0.10 Gelatin 1.34 10th layer (yellow filter layer) Yellow colloidal silver 0.027 Cpd-1 0.075 HBS-1 0.080 Gelatin 0.55 11th layer (low sensitivity blue emulsion layer) Emulsion C Silver 0.18 ExS-7 8.6 × 10 ^-4 ExY-1 0.042 ExY-2 0.72 HBS-1 0.28 Gelatin 1.10

12th layer (medium-speed blue-sensitive emulsion layer) Emulsion D Silver 0.40 ExS-7 7.4 × 10 ^-4 ExC-7 7.0 × 10 ^-3 ExY-2 0.15 HBS-1 0.050 Gelatin 0.78 13th layer (high sensitivity) Blue-sensitive emulsion layer) Emulsion F Silver 0.70 ExS-7 2.8 × 10 ^-4 ExY-2 0.20 HBS-1 0.070 Gelatin 0.69 14th layer (first protective layer) Emulsion G Silver 0.20 UV-4 0.11 UV-5 0.17 HBS- 1 5.0 × 10 ^-2 Gelatin 1.00 Fifteenth layer (second protective layer) H-1 0.40 B-1 (diameter about 1.7 μm) 5.0 × 10 ^-2 B-2 (diameter about 1.7 μm) 0.10 B-3 0.10 S-1 0.20 Gelatin 1.20

Further, in order to improve the storability, processability, pressure resistance, antifungal / antibacterial property, antistatic property and coating property of each layer, W-1 to W-3, B-4 to B are appropriately added. -6, F
-1 to F-17 and iron salt, lead salt, gold salt, platinum salt,
It contains iridium salt and rhodium salt.

[0175]

[Table 10]

In Table 10, (1) Emulsions A to F were reduction-sensitized at the time of grain preparation using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-91938. (2) Emulsions AF were subjected to gold sensitization, sulfur sensitization and selenium sensitization in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate according to the examples of JP-A-3-237450. It has been subjected. Specifically, each emulsion was sensitized with gold and chalcogen under the conditions shown in Table 2 below. (3) Low molecular weight gelatin was used for the preparation of tabular grains according to the example of JP-A 1-158426. (4) Dislocation lines as described in JP-A-3-237450 have been observed in tabular grains and normal crystal grains having a grain structure using a high voltage electron microscope.

[0177]

[Chemical 40]

[0178]

[Chemical 41]

[0179]

[Chemical 42]

[0180]

[Chemical 43]

[0181]

[Chemical 44]

[0182]

[Chemical formula 45]

[0183]

[Chemical formula 46]

[0184]

[Chemical 47]

[0185]

[Chemical 48]

[0186]

[Chemical 49]

[0187]

[Chemical 50]

[0188]

[Chemical 51]

[0189]

[Chemical 52]

Then, following the method for preparing Emulsions Ib, IIb and IIIb, the sensitizing dye ExS-5 was replaced with I-22 of the present invention in an equimolar amount to prepare the corresponding emulsions Ic, IIc and IIIc. Further, Samples 202, 2 were prepared in the same manner as Sample 201, except that the emulsions, sensitizing dyes and magenta couplers of the 7th, 8th and 9th layers of Sample 201 were changed as shown in Table 11.
03 was created. The amount of the coupler added was adjusted so that the color density was matched. Sample 201 to be obtained in this way
Wedge exposure (1/100 second exposure) was given to 203 with white light (color temperature 5500 ° K), and the following color development processing was performed.

[0191]

Next, the composition of the processing liquid will be described. (Color developer) (Unit: g) Diethylenetriaminepentaacetic acid 1.0 1-Hydroxyethylidene-1,1-diphosphonic acid 3.0 Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide 1.5 mg Hydroxylamine sulfate 2.4 4- [N- Ethyl-N-β-hydroxyethyl 4.5 amino] -2-methylaniline sulphate Water was added to 1.0 liter pH 10.05 (bleaching solution) (unit: g) Ethylenediaminetetraacetic acid ferric sodium trihydrate 100.0 Ethylenediaminetetraacetic acid disodium salt Salt 10.0 3-Mercapto-1,2,4-triazole 0.08 Ammonium bromide 140.0 Ammonium nitrate 30.0 Ammonia water (27%) 6.5 ml Water is added to 1.0 liter pH 6.0 (fixer) (unit g) Ethylenediaminetetraacetic acid disodium salt 0.5 Ammonium sulfite 20.0 Ammonium thiosulfate Water soluble Liquid (700 g / liter) 290.0 ml Water was added to 1.0 liter pH 6.7 (Stable liquid) (Unit: g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl 0.2 ether (Average degree of polymerization 10) Ethylene diamine tetra Acetic acid disodium salt 0.05 1,2,4-triazole 1.3 1,4-bis (1,2,4-triazole-1-0.75 ylmethyl) piperazine Water was added to 1.0 liter pH 8.5

The processed sample was subjected to density measurement through a green filter, the reciprocal of the exposure amount giving the density of fog of each sample +0.2 was found, and the relative value when the value of sample 201 was set to 100 was used to evaluate the relative sensitivity. Was done.

Next, two sets of samples 201 to 203 were separately prepared, and one set was stored under the conditions of 50 ° C. and 60% RH for 7 days.
The other set was for these samples after storage at room temperature,
The same wedge exposure as that described above was applied and development processing was performed. The fog density of the treated sample was measured with a green filter, and the fog evaluation was performed by the difference in fog value between the sample stored at 50 ° C. and 60% RH and the sample stored at room temperature. Separately from the above evaluation, samples 201 to 203 were processed into a 135 format, and the same practical shooting as in Example 1 was performed.
It was printed on a cut-out size color paper, and sensory evaluation was performed for color reproducibility. The above results are summarized in Table 11. It is clear that the sample 203 according to the present invention has a high degree of fog but little increase in fogging with time, and has a high color saturation in the reddish range.

[0195]

[Table 11]

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] October 1, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 1

[Correction method] Change

[Correction content]

[Chemical 1] In the formula, V ₁ , V ₂ , V ₃ and V ₄ represent hydrogen atoms or electron withdrawing groups, and at least two or more of the substituents represented by V ₁ , V ₂ , V ₃ and V ₄ are electron withdrawing groups. Represents a group. V ₁ , V ₂ , V ₃ , and V ₄ may be the same or different. R ₁₁ is _{- (CH 2) k (CF} 2) m H or _{- (CH 2) k (CF} 2) a group represented by _m F, k is 0 or 1, m is 1 to 8 of Represents an integer. R ₁₂ , R ₁₃ and R ₁₄ may be the same or different and are — (CH ₂ ) _p (C
F ₂ ) _q H group or − (CH ₂ ) _p (CF ₂ ) _q F group, total carbon number 1
It represents 0 or less optionally substituted alkyl group or alkenyl group, and at least one of R ₁₂ , R _{13 and} R ₁₄ is a group having a sulfo group or a carboxy group. p represents 0 or 1, and q represents an integer of 1 to 8. X ₁₁ represents a counter ion necessary for neutralizing the electric charge. n ₁₁ represents 0 or 1, and is 0 in the case of an inner salt.

[Chemical 2] R ₁ in the formula represents a hydrogen atom or a substituent. Z represents a nonmetallic atom group necessary for forming a 5-membered azole ring containing 2 to 3 nitrogen atoms, and the azole ring may have a substituent (including a condensed ring). X represents a hydrogen atom or a group capable of splitting off upon a coupling reaction with an oxidized product of a developing agent. However, at the same time, the case where R ₁ is a methyl group and X is a chlorine atom is excluded.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0002

[Correction method] Change

[Correction content]

[0002]

2. Description of the Related Art In recent years, color photographic light-sensitive materials have been remarkably improved in image quality such as graininess, sharpness and color reproducibility.
However, in addition to the demand for higher sensitivity and higher image quality of the sensitive material, the toughness of the sensitive material (fogging during storage of the sensitive material, less variation in sensitivity, variation in processing factors, fogging, sensitivity, gradation variation, or There is also a strong demand for that there is little variation in color tone), and improvement in stability over time has been long desired.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0004

[Correction method] Change

[Correction content]

It is well known that the addition of certain benzimidazolocarbocyanine dyes is effective as a means of increasing the green sensitivity of silver halides. In this case, the dye added to the silver halide photographic emulsion is adsorbed to the silver halide in the emulsion, and a longer wavelength absorption band is added to the absorption band specific to silver halide. That is, spectral sensitization by the dye can be obtained. These matters are described, for example, in U.S. Pat. Nos. 2,912,329, 2,739,149, British Patents 654,690, 815,172, and Japanese Examined Patent Publication No.
3-4936 and the like. However, in the above method, the improvement in color reproducibility is insufficient, and when the silver halide photographic light-sensitive material is stored under high temperature or high temperature and high humidity, fog increases during storage and sensitivity decreases. It had the major drawback of causing performance changes.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0019

[Correction method] Change

[Correction content]

In the formula, V ₁ , V ₂ , V ₃ and V ₄ represent a hydrogen atom or an electron-withdrawing group, and V ₁ , V ₂ , V ₃ and V
_At least two or more of the substituents represented by ₄ are electron withdrawing groups. V ₁ , V ₂ , V ₃ , and V ₄ may be the same or different. R ₁₁ is-(CH ₂ ) _k (C
F _{2) m} H or - represents _{(CH 2) k (CF 2} ) a group represented by _m F, k is 0 or 1, m represents an integer of 1 to 8. R ₁₂ , R ₁₃ and R ₁₄ may be the same or different, and are — (CH ₂ ) _p (CF ₂ ) _q H group or — (CH ₂ ) _p (CF ₂ ) _q.
F group represents an optionally substituted alkyl group or alkenyl group having 10 or less carbon atoms, and at least one of R ₁₂ , R _{13 and} R ₁₄ is a group having a sulfo group or a carboxy group. . p represents 0 or 1, and q represents an integer of 1 to 8. X ₁₁ represents a counter ion necessary for neutralizing the electric charge. n ₁₁ represents 0 or 1, and is 0 in the case of an inner salt.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0026

[Correction method] Change

[Correction content]

Further,-(CH ₂ ) _k (CF ₂ ) _m H represented by R _{11
Group, - (CH 2) k (} CF 2) m F group, the alkyl group represented by R _12, R ₁₃ and R _14, more preferably used.

[Procedure correction 6]

[Document name to be amended] Statement

[Name of item to be corrected] 0032

[Correction method] Change

[Correction content]

Examples of compounds represented by the general formula [I] are shown in Table-
1 to Table-5, but not limited thereto.

[Procedure Amendment 7]

[Document name to be amended] Statement

[Name of item to be corrected] 0070

[Correction method] Change

[Correction content]

Of these selenium compounds, the following general formulas [II] and [III] are preferable. General formula [II]

[Procedure Amendment 8]

[Document name to be amended] Statement

[Correction target item name] 0086

[Correction method] Change

[Correction content]

Specific examples ("Chemical formula 19" to "Chemical formula 23") of the compounds represented by the general formulas [II] and [III] are shown below, but the present invention is not limited thereto.

[Procedure Amendment 9]

[Document name to be amended] Statement

[Correction target item name] 0092

[Correction method] Change

[Correction content]

These selenium sensitizers are dissolved in water or an organic solvent such as methanol and ethanol, alone or in a mixed solvent, or in Japanese Patent Application Nos. 2-264447 and 2-26.
It is added at the time of chemical sensitization in the form described in No. 4448.
It is preferably added before the start of chemical sensitization.

[Procedure Amendment 10]

[Document name to be amended] Statement

[Correction target item name] 0093

[Correction method] Change

[Correction content]

The selenium sensitizer used is not limited to one kind, and two or more kinds of the above selenium sensitizers can be used in combination. The unstable selenium compound and the non-unstable selenium compound may be used in combination.

[Procedure Amendment 11]

[Document name to be amended] Statement

[Correction target item name] 0161

[Correction method] Change

[Correction content]

Next, the color reproducibility was evaluated. Sample 101 except that a cellulose triacetate base having a base thickness of 205 μ was used and a curling prevention layer was coated on the side opposite to the emulsion layer.
Sample Nos. 101 ′ to 1 coated with an emulsion layer in the same manner as No. 112 to No. 112
12 'was produced. These were processed into a size of 4 × 5, and a color checker manufactured by Macbeth and a subject mainly composed of reddish color were photographed by a camera, and the same processing as described above was performed. The color reproducibility of reddish color was evaluated by sensory evaluation of the obtained practical sample. The results are summarized in Table-9.

[Procedure Amendment 12]

[Document name to be amended] Statement

[Correction target item name] 0163

[Correction method] Change

[Correction content]

As is clear from the results of Table 9, in the samples according to the present invention, Dmax caused by fogging with time
There is little variation in / G and color reproducibility is improved at the same time. On the other hand, the comparative couplers A and B in which R ₁ in the general formula [M] is a methyl group and X is a chloro atom cannot produce the effects of the present invention.

Claims (2)

[Claims] 1. A silver halide color photographic light-sensitive material having at least one red-sensitive, green-sensitive and blue-sensitive emulsion layer on a support, wherein at least one of the green-sensitive layers has the following general formula: I], containing at least one benzimidazolocarbocyanine dye,
A silver halide color photographic light-sensitive material containing at least one magenta coupler represented by the following general formula [M]. [Chemical 1] In the formula, V ₁ , V ₂ , V ₃ and V ₄ represent hydrogen atoms or electron withdrawing groups, and at least two or more of the substituents represented by V ₁ , V ₂ , V ₃ and V ₄ are electron withdrawing groups. Represents a group. V ₁ , V ₂ , V ₃ , and V ₄ may be the same or different. R ₁₁ is _{- (CH 2) l (CF} 2) m H or _{- (CH 2) l (CF} 2) a group represented by _m F, l is 0 or 1, m is 1 to 8 of Represents an integer. R ₁₂ , R ₁₃ and R ₁₄ may be the same or different and are — (CH ₂ ) _p (C
F ₂ ) _q H group or − (CH ₂ ) _p (CF ₂ ) _q F group, total carbon number 1
Representing 0 or less optionally substituted alkyl group or alkenyl group, and at least one of R ₁₂ , R _{13 and} R ₁₄ is a group having a sulfo group or a carboxy group. p represents 0 or 1, and q represents an integer of 1 to 8. X ₁₁ represents a counter ion necessary for neutralizing the electric charge. n ₁₁ represents 0 or 1, and is 0 in the case of an inner salt. [Chemical 2] R ₁ in the formula represents a hydrogen atom or a substituent. Z represents a nonmetallic atom group necessary for forming a 5-membered azole ring containing 2 to 3 nitrogen atoms, and the azole ring may have a substituent (including a condensed ring). X represents a hydrogen atom or a group capable of splitting off upon a coupling reaction with an oxidized product of a developing agent. However, at the same time, the case where R ₁ is a methyl group and X is a chlorine atom is excluded. 2. The silver halide color photographic light-sensitive material according to claim 1, wherein at least one kind of silver halide grains contained in the green-sensitive layer is selenium-sensitized.