JPH0720618A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide color photographic sensitive material high in sensitivity and graininess and small in change of photographic performance due to storage after photographing by incorporating a specified coupler and a specified compound. CONSTITUTION:The silver halide photographic sensitive material having, on a support, at least one photosensitive silver halide emulsion layer, contains at least one of the compounds represented by formula I and at least one of the couplers represented by formula II. In formulae I and II, each of Ra1-Ra5 is H or an alkyl or the like, or each adjacent pair of them is a group necessary to combine with each other to form a chroman ring; R11 is a substituent; R12 is an electron-attractive group; m is an integer of 2-5, and when m is >=2, each of R11 may be the same as or different from each other; and X1 is a group to be released by coupling with the oxidation product of an aromatic primary amine color developing agent.

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, it has high sensitivity and excellent graininess, and has little change in photographic performance due to storage after photography. The present invention relates to a silver color photographic light-sensitive material.

[0002]

2. Description of the Related Art Silver halide color photographic light-sensitive materials, especially photographic light-sensitive materials, are required to have high image quality and small change in photographic performance due to storage, and have made remarkable progress in recent years. However, further progress is required for the image quality of sensitive materials and the storage performance of sensitive materials. JP-A-3-209469 discloses a color light-sensitive material which uses a specific magenta coupler and a monodisperse silver halide emulsion and has good color reproducibility and graininess and good storage stability. Although the light-sensitive material described in the publication has improved color reproducibility and graininess, it has a drawback of insufficient sensitivity, and further improvement in graininess and storage stability is desired. It was rare. Further, JP-A-5-61167 discloses a light-sensitive material which uses a specific magenta coupler and a phenolic compound, has high sensitivity, is excellent in color reproducibility, and is excellent in storage stability. However, although the light-sensitive material described in the publication has high sensitivity, further improvement is desired in terms of graininess and storability after photographing.

[0003]

SUMMARY OF THE INVENTION It is, therefore, an object of the present invention to provide a silver halide color photographic light-sensitive material having high sensitivity, excellent graininess, and small change in photographic performance due to storage after photography.

[0004]

Means for Solving the Problems As a result of earnest research, the present inventors have found that the above-mentioned problems can be achieved by the following means. Ie, at least 1 on the support
A silver halide color photographic light-sensitive material having a light-sensitive silver halide emulsion layer, which contains at least one compound selected from the compounds represented by the following general formula (A) and is represented by the following general formula (I). A silver halide color photographic light-sensitive material containing at least one selected from the group consisting of: General formula (A)

[0005]

[Chemical 4]

In the formula, Ra _{1 to} Ra ₅ may be the same or different and each represents a hydrogen atom, an alkyl group, or --X--R.
a ₀ or Ra _{1 to} Ra ₅ represents a group required for two groups in the ortho positions to bond to each other to form a chroman ring. Here, X is _{-C (Ra 6) (Ra 7} ) -, ─O─,
Alternatively, it represents -S-. Ra ₆ and Ra ₇ represent a hydrogen atom or an alkyl group. Ra ₀ represents a hydroxyphenyl group, X is —C (Ra ₆ ) (Ra ₇ ) —, Ra ₆ and Ra ₇ are simultaneously an alkyl group, and Ra ₁ and Ra ₅ are simultaneously —X—Ra _0.
When it is, it may be an alkyl group. However, Ra ₃ is not a hydrogen atom, and at least one of Ra _{1 to} Ra ₅ is the same as or above. Further, Ra ₃ is -X-Ra ₀ ,
And when Ra ₀ is a hydroxy phenyl group, Ra ₁ and
None of Ra ₅ is a hydrogen atom. General formula (I)

[0007]

[Chemical 5]

In the formula, R ₁₁ represents a substituent and R ₁₂ represents an electron-withdrawing group. m represents an integer of 1 to 5, and when m is 2 or more, R ₁₁ may be the same or different. n represents an integer of 2 to 5, and R ₁₂ may be the same or different. X ₁ 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. R
_{In 11} , R ₁₂ or X ₁ , a dimer or a multimer which is bound to each other via a divalent or divalent group may be formed.

The present invention will be described in more detail below. First, the compound of the general formula (A) of the present invention will be described specifically and in detail. General formula (A)

[0010]

[Chemical 6]

In the formula, R _{a1 to} R _a5 may be the same or different and each is a hydrogen atom, an alkyl group, or -X-.
R _a0 or R _{a1 to} R _a5 represents a group necessary for two groups in the ortho positions to be bonded to each other to form a chroman ring. Here, X is -C (R _a6 ) (R _a7 )-,
Represents -O- or -S-. R _a6 and R _a7 represent a hydrogen atom or an alkyl group. R _a0 represents a hydroxyphenyl group, X is —C (R _a6 ) (R _a7 ) —, R _a6 and R _a7 are simultaneously an alkyl group, and R _a1 and R _a5 are simultaneously —X—R _a0. When it is, it may be an alkyl group. However,
R _a3 is not a hydrogen atom, and at least one of R _{a1 to} R _a5 is the same as or above. In addition, R _a3 is -X-
When R _a0 and R _a0 is a hydroxyphenyl group, neither R _a1 nor R _a5 is a hydrogen atom.

The substituent described in the present invention may further have a substituent. In the general formula (A), R _{a1 to} R _a5 may be the same or different and each is a hydrogen atom or an alkyl group (for example, methyl, t-butyl, t-octyl, cyclohexyl, 2′-hydroxybenzyl, 4′-hydroxybenzyl). And the preferred carbon number is 1 to 30), (a)
-X-R _a0 or (b) represents a group necessary for forming a chroman ring by bonding two groups in the ortho positions to each other among R _{a1 to} R _a5 .

-X- is -C (R _a6 ) (R _a7 )-, -O
Represents-, or -S-. R _a6 and R _a7 represent a hydrogen atom or an alkyl group (for example, methyl, ethyl, propyl, isopropyl, octyl, cyclohexyl, benzyl, hexadecyl, methoxyethyl, preferably having 1 to 26 carbon atoms). In R _a0 , X is -C (R _a6 ) (R
_a7 ) _-and R _a6 and R _a7 are simultaneously an alkyl group, and further when -X-R _a0 is R _a1 or R _a5 , an alkyl group (for example, methyl, ethyl, propyl, isopropyl, octyl, cyclohexyl, benzyl). , Hexadecyl, methoxyethyl, preferably having 1 to 26 carbon atoms, and R _a0 is a hydroxyphenyl group (for example, o-hydroxyphenyl, m-hydroxyphenyl, p-hydroxyphenyl, 3-t) in other cases. -Butyl-2-hydroxy-5-methylphenyl and 3,5-di-t-butyl-4-hydroxyphenyl, with preferable carbon number of 6-30 hydroxyphenyl and substituted hydroxyphenyl). When R _a0 is an alkyl group, it is preferable that R _a5 and R _a3 are alkyl groups.

However, R _a3 is not a hydrogen atom, and at least one of R _{a1 to} R _a5 is (a) or (b).
Is. Of these, the compound formed by (a) is preferably bisphenol or trisphenol, more preferably bisphenol. Among the compounds represented by the general formula (A), particularly preferable compounds from the viewpoint of the effect of the present invention are the following general formulas (AI) and (A-II), and the most preferable compounds are the general formula (A-II). ).

[0015]

[Chemical 7]

In the general formula (AI), R _a1 , R _a4 and R _a5 represent the groups defined in the general formula (A). Z represents an atomic group necessary for forming a chroman ring. General formula (A
In -I), a compound in which R _a5 is an alkyl group is preferable from the viewpoint of the effect of the present invention. In the general formula (A-II),
X represents a group defined by the general formula (A). R _a10 ~ R _a13
Represents an alkyl group. In the general formula (A-II), a compound in which X is —CH (R _a6 ) — is preferable from the viewpoint of the effect of the present invention, and at this time, R _a6 is a hydrogen atom or has 1 to 1 carbon atoms.
Particularly preferred is an alkyl group of 11.

Specific examples of the compound represented by formula (A) of the present invention are shown below, but the compounds used in the present invention are not limited thereto.

[0018]

[Chemical 8]

[0019]

[Chemical 9]

[0020]

[Chemical 10]

[0021]

[Chemical 11]

[0022]

[Chemical 12]

[0023]

[Chemical 13]

[0024]

[Chemical 14]

[0025]

[Chemical 15]

[0026]

[Chemical 16]

[0027]

[Chemical 17]

[0028]

[Chemical 18]

[0029]

[Chemical 19]

[0030]

[Chemical 20]

[0031]

[Chemical 21]

[0032]

[Chemical formula 22]

[0033]

[Chemical formula 23]

The compound represented by formula (A) of the present invention may be contained anywhere in the light-sensitive material, but is preferably contained in the color-sensitive layer on the side farthest from the support.

As for the method of addition, it may be added after being dissolved in water, alcohol, ester or ketone or a mixed solvent thereof. Further, it may be added after being dissolved in a high-boiling point organic solvent and then dispersed. When this method is combined with the oil-soluble compound represented by the general formula (A), the added compound is preferably fixed in the layer to which it is added, which is preferable. A method of adding the so-called co-emulsifier with couplers is also preferable.

The addition amount of the compound represented by formula (A) of the present invention is 1 × per mol of silver halide in the layer to be added.
The range of 10 ⁻⁴ to 10 mol is preferable, more preferably 1 × 10 ⁻³ to 1 mol, and further preferably 5 × 10 ⁻³ to 1 ×.
It is 10 ^-1 .

Next, R ₁₁ , R ₁₂ and X _{1 in the} coupler represented by the formula (I) will be described in detail.

R ₁₁ represents a substituent. Specifically, it is a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxy group, a nitro group, a carboxy group, a sulfo group, an amino group, an alkoxy group or an aryloxy group. 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, hetero Ring oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonylamino group, imide group, heterocyclic thio group, sulfinyl group, phosphonyl group,
It represents an aryloxycarbonyl group, an acyl group or an azolyl group, and R ₁₁ may be a divalent group to form a bis form.

More specifically, R ₁₁ is each 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,
A cycloalkyl group or a cycloalkenyl group, 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 group), aryl group (eg, phenyl, 4-t-
Butylphenyl, 2,4-di-t-amylphenyl, 4
-Tetradecanamidophenyl), heterocyclic groups (e.g. 2-furyl, 2-thienyl, 2-pyrimidinyl, 2
-Benzothiazolyl), cyano group, hydroxy group, nitro group, carboxy group, amino group, alkoxy group (for example, methoxy, ethoxy, 2-methoxyethoxy, 2-
Dodecylethoxy, 2-methanesulfonylethoxy),
Aryloxy group (eg, phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 3-t-butyloxycarbamoylphenoxy, 3-methoxycarbamoyl), acylamino group (eg, acetamide, benzamide, tetradecane) Amide, 2- (2,4-di-t-amylphenoxy) butanamide, 2- (3-t-butyl-4-hydroxyphenoxy) butanamide, 2- {4- (4-hydroxyphenylsulfonyl) phenoxy} decanamide) , An alkylamino group (eg, methylamino, butylamino, dodecylamino, diethylamino, methylbutylamino), an anilino group (eg, phenylamino, 2-chloroanilino, 2-chloro-5-tetradecaneaminoanilino, 2-chloro-). 5- Decyloxycarbonyl anilino, N- acetyl anilino, 2-chloro-5- {2-
(3-t-butyl-4-hydroxyphenoxy) dodecanamide} anilino), ureido group (for example, phenylureido, methylureido, N, N-dibutylureido), sulfamoylamino group (for example, N, N-dipro). Pilsulfamoylamino, N-methyl-N-decylsulfamoylamino), alkylthio group

(Eg, methylthio, octylthio, tetradecylthio, 2-phenoxyethylthio, 3-phenoxypropylthio, 3- (4-t-butylphenoxy) propylthio), arylthio group (eg, phenylthio, 2-butoxy-). 5-t-octylphenylthio, 3-pentadecylphenylthio, 2-carboxyphenylthio, 4-tetradecanamidophenylthio),
Alkoxycarbonylamino group (eg, methoxycarbonylamino, tetradecyloxycarbonylamino), sulfonamide group (eg, methanesulfonamide, hexadecanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, octadecanesulfonamide, 2-methoxy- 5-t-butylbenzenesulfonamide), a carbamoyl group (eg, N-ethylcarbamoyl, N, N-dibutylcarbamoyl, N-
(2-dodecyloxyethyl) carbamoyl, N-methyl-N-dodecylcarbamoyl, N- {3- (2,4-
Di-t-amylphenoxy) propyl} carbamoyl), sulfamoyl group (eg, N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N- (2
-Dodecyloxyethyl) sulfamoyl, N-ethyl-N-dodecylsulfamoyl, N, N-diethylsulfamoyl), sulfonyl group (e.g., methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl), alkoxycarbonyl group ( For example, methoxycarbonyl, butyloxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl),
Heterocyclic oxy group (for example, 1-phenyltetrazole-5-oxy, 2-tetrahydropyranyloxy), azo group (for example, 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), aryl Oxycarbonylamino group (for example, phenoxycarbonylamino), imide group, for example, N-succinimide, N-phthalimide, 3-octadecenylsuccinimide, heterocyclic thio group (for example, 2-benzothiazolylthio, 2, Four Di-phenoxy-1,3,5-triazole-6-thio, 2-pyridylthio), sulfinyl group (for example, dodecanesulfinyl, 3-pentadecylphenylsulfinyl, 3-phenoxypropylsulfinyl), phosphonyl group (for example, phenoxyphosphon) Nyl, octyloxyphosphonyl, phenylphosphonyl), aryloxycarbonyl group (for example, phenoxycarbonyl), acyl group (for example, acetyl, 3-phenylpropanoyl, benzoyl, 4-dodecyloxybenzoyl), azolyl group (for example, Imidazolyl, pyrazolyl, 3-chloro-pyrazol-1-yl, triazolyl).

Among these substituents, the group capable of 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. Among these substituents, preferred R ₁₁ is a halogen atom, an alkoxy group, an aryloxy group, an acylamino group, a ureido group, a sulfamoylamino group, an alkoxycarbonylamino group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group. , A carbamoyloxy group, an imide group, or an acyl group.

R ₁₂ represents an electron-withdrawing group, specifically, a halogen atom, an aryl group, a heterocyclic group, a cyano group, a nitro group, a carboxy group, a sulfo group, an acylamino group, a ureido group, a sulfamoylamino group, an alkylthio group. Group, arylthio group, alkoxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, imide group, heterocyclic thio group, sulfinyl group, phosphonyl group, acyl group,
Represents an azolyl group. More particularly, these groups are R ₁₁
It is a group having the same meaning as the group specifically shown in. Preferably R ₁₂
Is a halogen atom, an acylamino group, or a carbamoyl group, and more preferably a halogen atom. n is preferably 4 or 5. Particularly, n is preferably 5. m is preferably 1 to 3.

X ₁ represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidation product of an aromatic primary amine color developing agent. The splitting-off group is specifically described by a halogen atom, an alkoxy group, an 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 There are a nitrogen-containing heterocyclic group, an imide group, an arylazo group, and the like, and these groups may be further substituted with a group acceptable as the substituent for R ₁₁ .

More specifically, halogen atom (eg, fluorine atom, chlorine atom, bromine atom), alkoxy group (eg, ethoxy, dodecyloxy, methoxyethylcarbamoylmethoxy, carboxypropyloxy, methylsulfonylethoxy, ethoxycarbonylmethoxy), aryl An oxy group (for example, 4-methylphenoxy, 4-
Chlorophenoxy, 4-methoxyphenoxy, 4-carboxyphenoxy, 3-ethoxycarboxyphenoxy, 3-acetylaminophenoxy, 2-carboxyphenoxy), acyloxy group (for example, acetoxy, tetradecanoyloxy, benzoyloxy), alkyl or aryl. Sulfonyloxy groups (eg, methanesulfonyloxy, toluenesulfonyloxy), acylamino groups (eg, dichloroacetylamino, heptafluorobutyrylamino), alkyl or aryl sulfonamide groups (eg, methanesulfonamino, trifluoromethanesulfonamino, p-toluenesulfonylamino), an alkoxycarbonyloxy group (eg, ethoxycarbonyloxy, benzyloxycarbonyloxy), aryl Oxycarbonyl group (e.g., phenoxycarbonyloxy), alkyl, aryl or heterocyclic thio group (e.g., dodecylthio,
1-carboxydodecylthio, phenylthio, 2-butoxy-5-t-octylphenylthio, tetrazolylthio), carbamoylamino group (for example, N-methylcarbamoylamino, N-phenylcarbamoylamino),
5- or 6-membered nitrogen-containing heterocyclic group (for example, imidazolyl, pyrazolyl, triazolyl, tetrazolyl,
1,2-dihydro-2-oxo-1-pyridyl), an imide group (eg, succinimide, hydantoinyl), an arylazo group (eg, phenylazo, 4-methoxyphenylazo), and the like. In addition to these, X ₁ 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 ₁ may contain a photographically useful group such as a development inhibitor or a development accelerator. Preferred X
₁ is a halogen atom, 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.

When the vinyl monomer contains the compound represented by the formula (1), the vinyl group may have a substituent other than that represented by the formula (1), and preferable substituents are a hydrogen atom, a chlorine atom, Alternatively, it represents a lower alkyl group having 1 to 4 carbon atoms (eg, methyl group, ethyl group).

Monomers including those represented by formula (1) may form a copolymer with a non-color forming ethylenic monomer that does not couple with the oxidation product of an aromatic primary amine developer.

As the non-color-forming, ethylene-like monomer which does not couple with the oxidation product of the aromatic primary amine developing agent, acrylic acid, α-chloroacrylic acid, α-alkylacrylic acid (for example, methacrylic acid) and their compounds are used. Esters or amides derived from acrylic acids (eg, acrylamide, n-butyl acrylamide, t-butyl acrylamide, diacetone acrylamide, methacrylamide, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl acrylate) , Iso-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and β-. Mud carboxymethyl methacrylate),
Methylenedibisacrylamide, vinyl esters (eg vinyl acetate, vinyl propionate and vinyl laurate), acrylonitrile, methacrylonitrile, aromatic vinyl compounds (eg styrene and its derivatives, vinyltoluene, divinylbenzene, vinylacetophenone and sulfostyrene). , Itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ether (eg vinyl ethyl ether),
Maleic acid, maleic anhydride, maleic acid ester, N
-Vinyl-2-pyrrolidone, N-vinylpyridine, and 2- and 4-vinylpyridine. The non-color-forming ethylenically unsaturated monomers used here may be used in combination of two or more kinds. For example, n-butyl acrylate and methyl acrylate, styrene and methacrylic acid, methacrylic acid and acrylamide, methyl acrylate and diacetone acrylamide, and the like.

As is well known in the polymer color coupler art, the non-chromogenic, ethylenically unsaturated monomers for copolymerization with the solid water-insoluble monomer coupler are the physical properties and / or chemistry of the copolymer formed. Properties such as solubility,
The compatibility of the binder of the photographic colloidal composition, such as gelatin, its flexibility, thermal stability, etc., can be selected to be favorably influenced. The polymer coupler used in the present invention may be water-soluble or water-insoluble, and among them, the polymer coupler latex is particularly preferable.

Specific examples of the coupler represented by formula (1) of the present invention are shown below, but the present invention is not limited thereto.

[0050]

[Chemical formula 24]

[0051]

[Chemical 25]

[0052]

[Chemical formula 26]

[0053]

[Chemical 27]

[0054]

[Chemical 28]

[0055]

[Chemical 29]

[0056]

[Chemical 30]

The synthesis of these couplers is described in British Patent 1,5
52,701 and European Patent Publication 348,135. These couplers of the present invention are described in British Patent 1,525,70.
1, European Published Patent No. 348,135, US Pat. Nos. 3,227,554, 4,351,897,
4,556,630, 4,584,266, 4,264,723, 4,308,343, 4,367,282 and 4,436,808. Can be synthesized by the method described above.

The coupler represented by the formula (I) of the present invention is selected so that the spectral absorption waveform of the dye obtained from the coupler by color development and the color-developing dye obtained from another coupler used in the same layer are similar. To be done. As a result, the printer suitability of various auto printers of various companies that use color filters with various spectral characteristics, light sources, and density sensors can be maintained stably even when the shooting conditions and exposure amount fluctuate, and good quality prints with constant quality can be obtained. Can be supplied. Further, the coupler represented by formula (I) of the present invention has improved photographic sensitivity and exhibits stable color development processability. The coupler represented by formula (I) of the present invention may be used in any layer in the silver halide light-sensitive material, but is preferably added to the green-sensitive emulsion layer and / or its adjacent layer. The total amount added is from 1 × 10 ^-3
1.0 g / m ² , preferably 5 × 10 ^{−3 to} 0.8 g / m
² , more preferably 1 × 10 ^{-2 to} 0.5 g / m ² . The method of adding the coupler of the present invention to the light-sensitive material is based on the method of other couplers described below, but the amount of the high boiling organic solvent used as the dispersion solvent to the magenta coupler is 0 to 3.0 as a weight ratio. Is preferred, and 0.3 to
2.0 is more preferable, and 0.5 to 1.2 is further preferable.

The coupler represented by the formula (I) of the present invention can be used with a known magenta coupler.
As known magenta couplers, 5-pyrazolone-based and pyrazoloazole-based compounds are preferable, and US Pat. Nos. 4,310,619, 4,351,897, EP 73,636, and US Pat. 3,061,43
No. 2, No. 3,725,067, Research Disclosure No. 24220 (June 1984), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-4
No. 3659, No. 61-72238, No. 60-3573.
No. 0, No. 55-118034, No. 60-185951
U.S. Pat. Nos. 4,500,630 and 4,54
0,654, 4,556,630, International Publication W
Those described in O88 / 04795 and the like are particularly preferable.

Next, the yellow dye-forming coupler (also referred to as a yellow coupler) represented by the formula [Y], which is preferably used in the invention, will be described. In the formula [Y], R ₁ is an aryl group, R ₂ is a hydrogen atom, a halogen atom (F, Cl, Br, I and below, the same in the description of the formula [Y]), an alkoxy group, an aryloxy group, an alkyl group. Or a dialkylamino group, R ₃ is a group capable of substituting on the benzene ring, and X is a group capable of splitting off by a coupling reaction with a hydrogen atom or an oxidized product of an aromatic primary amine developer (referred to as splitting group). And p represents an integer of 0 to 4, respectively. However, when p is plural, plural R ₃ may be the same or different.

Here, as examples of R _3, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbonamide group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, There are alkylsulfonyl groups, arylsulfonyl groups, ureido groups, sulfamoylamino groups, alkoxycarbonylamino groups, nitro groups, heterocyclic groups, cyano groups, acyl groups, acyloxy groups, alkylsulfonyloxy groups, arylsulfonyloxy groups, Examples of the leaving group include a heterocyclic group bonded to the coupling active position with a nitrogen atom, an aryloxy group, an arylthio group, an acyloxy group, an alkylsulfonyloxy group, a heterocyclic oxy group, and a halogen atom.

When the substituent in the formula [Y] is an alkyl group or contains an alkyl group and is not particularly defined, the alkyl group is unsaturated even if it is linear, branched or cyclic. An alkyl group which may contain a bond (for example, methyl, isopropyl, t-butyl, cyclopentyl, t-pentyl, cyclohexyl, 2-ethylhexyl, 1,1,3,3-tetramethylbutyl, dodecyl,
Hexadecyl, allyl, 3-cyclohexenyl, oleyl, benzyl, trifluoromethyl, hydroxymethyl, methoxyethoxy, ethoxycarbonylmethyl, phenoxyethyl).

When the substituent in the formula [Y] is or contains an aryl group and there is no particular limitation, the aryl group may be a monocyclic or condensed ring aryl group which may be substituted (eg phenyl, 1 -Naphthyl, p-tolyl, o-tolyl, p-chlorophenyl, 4-methoxyphenyl, 8-quinolyl, 4-hexadecyloxyphenyl, pentafluorophenyl, p-hydroxyphenyl, p-cyanophenyl, 3-pentadecylphenyl ,
2,4-di-t-pentylphenyl, p-methanesulfonamidophenyl, 3,4-dichlorophenyl).

When the substituent in the formula [Y] is a heterocyclic group or contains a heterocyclic group and is not particularly specified, the heterocyclic group is at least one of O, N, S, P, Se and Te. An optionally substituted 3- to 8-membered monocyclic or condensed-ring heterocyclic group containing a heteroatom in the ring (for example, 2-furyl, 2
-Pyridyl, 4-pyridyl, 1-pyrazolyl, 1-imidazolyl, 1-benzotriazolyl, 2-benzotriazolyl, succinimide, phthalimide, 1-benzyl-2,4-imidazolidinedione-3-yl) means. The substituents preferably used in formula [Y] will be described below.

In the formula [Y], R ₁ is preferably the total number of carbon atoms which may be substituted (hereinafter abbreviated as C number) 6 to 3
0 represents an aryl group, and examples of the substituent thereof include a halogen atom, an alkyl group, an alkoxy group, a nitro group, an amino group, a carbonamido group, and a sulfonamide group.

In the formula [Y], R ₂ is preferably a halogen atom, which may have a C number of 1 to 30 which may be substituted.
Alkoxy group, aryloxy group having 6 to 30 C, C
It represents an alkyl group having 1 to 30 or a dialkylamino group having 2 to 30 carbon atoms, and examples of the substituent thereof include a halogen atom, an alkyl group, an alkoxy group, and an aryloxy group.

In the formula [Y], R ₃ is preferably a halogen atom, an optionally substituted alkyl group having 1 to 30 C atoms, an aryl group having 6 to 30 C atoms, or an alkoxy group having 1 to 30 C atoms. , C2-30 alkoxycarbonyl group, C7-30 aryloxycarbonyl group, C1-30 carbonamido group, C1-30 sulfonamide group, C1-30 carbamoyl group , C number 0-3
0 sulfamoyl group, C 1-30 alkylsulfonyl group, C 6-30 arylsulfonyl group, C 1
To 30 ureido group, C number 0 to 30 sulfamoylamino group, C number 2 to 30 alkoxycarbonylamino group, C number 1 to 30 heterocyclic group, C number 1 to 30 acyl group, C number It represents an alkylsulfonyloxy group having 1 to 30 or an arylsulfonyloxy group having 6 to 30 carbon atoms, and the substituent thereof is, for example, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group,
Heterocyclic oxy group, alkylthio group, arylthio group, heterocyclic thio group, alkylsulfonyl group, arylsulfonyl group, acyl group, carbonamido group, sulfonamide group, carbamoyl group, sulfamoyl group, alkoxycarbonylamino group, sulfamoylamino group Group, ureido group, cyano group, nitro group, acyloxy group, alkoxycarbonyl group, aryloxycarbonyl group, alkylsulfonyloxy group, arylsulfonyloxy group.

In the formula [Y], p preferably represents an integer of 1 or 2, and the substitution position of R ₃ is

[0069]

[Chemical 31]

On the other hand, the meta position or the para position is preferable.

In the formula [Y], X preferably represents a heterocyclic group or an aryloxy group bonded to the coupling active position by a nitrogen atom.

When X represents a heterocyclic group, X is preferably an optionally substituted 5- to 7-membered monocyclic or condensed-ring heterocyclic ring, and examples thereof include succinimide, maleinimide, phthalimide and diglycol. Imido, pyrrole, pyrazole, imidazole, 1,2,4-triazole, tetrazole, indole, indazole, benzimidazole, benzotriazole, imidazolidine-2,4-dione, oxazolidine-2,4-dione,
Thiazolidine-2,4-dione, imidazolidine-2-
On, oxazoline-2-one, thiazolin-2-one, benzimidazolin-2-one, benzoxazoline-2-one, benzothiazolin-2-one, 2-pyrrolin-5-one, 2-imidazoline-5-one , Indoline-2,3-dione, 2,6-dioxypurine, parabanic acid, 1,2,4-triazolidine-3,5-dione, 2-pyridone, 4-pyridone, 2-pyrimidone, 6
-Pyridazone, 2-pyrazone, 2-amino-1,3,4
-Thiazolidine, 2-imino-1,3,4-thiazolidin-4-one and the like, and these heterocycles may be substituted. Examples of substituents of these heterocyclic groups include halogen atom, hydroxyl group, nitro group, cyano group, carboxyl group, sulfo group, alkyl group, aryl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, alkyl group. Sulfonyl group, arylsulfonyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, acyloxy group, amino group, carbonamido group, sulfonamide group, carbamoyl group, sulfamoyl group, ureido group, alkoxycarbonylamino group, sulfamoyl group There is an amino group.

When X represents an aryloxy group, X preferably represents an aryloxy group having a C number of 6 to 30,
It may be substituted with a group selected from the substituent group mentioned when X is a heterocyclic group. Substituents for the aryloxy group include halogen atom, cyano group, nitro group, carboxyl group, trifluoromethyl group, alkoxycarbonyl group, carbonamido group, sulfonamide group, carbamoyl group, sulfamoyl group, alkylsulfonyl group, arylsulfonyl group. Groups or acyl groups are preferred.

Substituents particularly preferably used in formula [Y] will be described below.

R ₁ is particularly preferably a phenyl group or a phenyl group substituted with a chlorine atom, a methyl group, a methoxy group, an ethoxy group or a butoxy group.

R ₂ is particularly preferably a chlorine atom, a fluorine atom, an alkyl group having a C number of 1 to 6 (eg methyl, trifluoromethyl, ethyl, isopropyl, t-butyl), C
An alkoxy group of the number 1 to 8 (for example, methoxy, ethoxy,
Methoxyethoxy, butoxy) or an aryloxy group having 6 to 24 carbon atoms (for example, phenoxy, p-tolyloxy, p-methoxyphenoxy), most preferably a chlorine atom or a methoxy group.

R ₃ is particularly preferably a halogen atom, an alkoxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbonamido group, a sulfonamide group, a carbamoyl group or a sulfamoyl group, and most preferably an alkoxy group, an alkoxycarbonyl group, A carbonamide group or a sulfonamide group.

X is particularly preferably a group represented by the following formula [Y-1] or [Y-2].

[0079]

[Chemical 32]

In the formula [Y-1], Z is

[0081]

[Chemical 33]

Or

[0083]

[Chemical 34]

Represents Here, R ₄ , R ₅ , R ₈ and R ₉ represent a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group or an amino group, R ₆ and R ₇ represent a hydrogen atom, an alkyl group, an aryl group, an alkylsulfonyl group, an arylsulfonyl group, or an alkoxycarbonyl group,
R ₁₀ and R ₁₁ represent a hydrogen atom, an alkyl group or an aryl group. R ₁₀ and R ₁₁ may combine with each other to form a benzene ring. R ₄ and R ₅ , R ₅ and R ₆ , R ₆ and R ₇ or R ₄ and R ₈ may combine with each other to form a ring (eg, cyclobutane, cyclohexane, cycloheptane, cyclohexene, pyrrolidine, piperidine). .

Among the heterocyclic groups represented by the formula [Y-1], a particularly preferred one is Z in the general formula [Y-1].

[0086]

[Chemical 35]

Is a heterocyclic group which is

The C number of the heterocyclic group represented by the formula [Y-1] is 2 to 30, preferably 4 to 20, and more preferably 5.
~ 16.

[0089]

[Chemical 36]

In the formula [Y-2], at least one of R ₁₂ and R ₁₃ is a halogen atom, a cyano group, a nitro group, a trifluoromethyl group, a carboxyl group, an alkoxycarbonyl group, a carbonamido group, a sulfonamide group or carbamoyl. A group selected from a group, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group or an acyl group, and the other may be a hydrogen atom, an alkyl group or an alkoxy group. R ₁₄ represents a group having the same meaning as R ₁₂ or R _13, and m represents an integer of 0-2. Formula [Y
-2], the C number of the aryloxy group is 6 to 3
It is 0, preferably 6 to 24, more preferably 6 to 15.

The coupler represented by the formula [Y] has substituents R ₁ , X or

[0092]

[Chemical 37]

In the above, a dimer or a multimer having a valence of two or more may be bonded to each other to form a multimer or more. In this case, the number of carbon atoms shown in each of the above substituents may be out of the specified range.

When the coupler represented by the formula [Y] forms a multimer, a typical example is a homopolymer or copolymer of an addition polymer ethylenically unsaturated compound (yellow coloring monomer) having a yellow dye-forming coupler residue. And is preferably represented by the formula [Y-3].

[0095]

[Chemical 38]

In formula [Y-3], G _i is a repeating unit derived from a color forming monomer, is a group represented by formula [Y-4], and H _j is a repeating unit derived from a non-color forming monomer. I is a positive integer, j is 0 or a positive integer, and gi and hj are weight fractions of G _i or H _j , respectively.
Here, when i or j is plural, G _i or H _j means containing plural kinds of repeating units.

[0097]

[Chemical Formula 39]

In the formula, R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a chlorine atom, and A represents -CONH-, -C.
OO- or a substituted or unsubstituted phenylene group, B represents a substituted or unsubstituted alkylene group, a phenylene group or an aralkylene group, L represents -CONH-,
-NHCONH-, -NHCOO-, -NHCO-,-
OCONH-, -NH-, -COO-, -OCO-,-
CO -, - O -, - S -, - SO 2 -, - NHSO
₂ -, or represents a -SO ₂ NH-. a, b, c are 0
Or 1 is shown. Q is R ₁ , X of the compound represented by the general formula [Y], or

[0099]

[Chemical 40]

A yellow coupler residue in which one hydrogen atom has been removed is shown below. Examples of the non-color forming ethylene type monomer that does not couple with the oxidation product of the aromatic primary amine developing agent that gives the repeating unit H _j include acrylic acid, α-chloroacrylic acid, α-alkylacrylic acid (for example, methacrylic acid, etc.). ) Amides or esters derived from these acrylic acids (eg, acrylamide, methacrylamide, n-butyl acrylamide, t-butyl acrylamide, diacetone acrylamide, methyl acrylate, ethyl acrylate, n-propyl acrylate)
, N-butyl acrylate, t-butyl acrylate
, Iso-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and β-hydroxymethacrylate. G)), vinyl esters (eg vinyl acetate, vinyl propionate and vinyl laurate), acrylonitrile, methacrylonitrile, aromatic vinyl compounds (eg styrene and its derivatives such as vinyltoluene, divinylbenzene, vinylacetophenone and sulfostyrene). , Itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ethers (eg vinyl ethyl ether), maleic acid esters, N-vinyl-2-pyrrolidone, N-vinyl pyridine and 2 And 4 there is vinylpyridine.

Acrylic acid esters, methacrylic acid esters and maleic acid esters are particularly preferred. Two or more kinds of non-color-forming ethylene type monomers used here can be used together. For example, methyl acrylate and butyl acrylate, butyl acrylate and styrene, butyl methacrylate and methacrylic acid, methyl acrylate and diacetone acrylamide, etc. can be used.

As well known in the field of polymer couplers, the ethylenically unsaturated monomer to be copolymerized with the vinyl monomer corresponding to the above formula [Y-4] is in the form of the copolymer to be formed, For example, solid, liquid, micellar or physical and / or chemical properties such as solubility (solubility in water or organic solvent), compatibility with photographic colloid composition binders such as gelatin, The flexibility, the thermal stability, the coupling reactivity with the oxidized form of the developing agent, the diffusion resistance in the photographic colloid, etc. can be selected so as to be favorably influenced.
These copolymers may be random copolymers or copolymers having a specific sequence (for example, block copolymer, alternating copolymer).

The number average molecular weight of the yellow polymer coupler used in the present invention is usually on the order of thousands to hundreds of thousands, but oligomeric polymer couplers of 5000 or less can also be used.

The yellow coupler used in the present invention is a lipophilic polymer soluble in an organic solvent (for example, ethyl acetate, butyl acetate, ethanol, methylene chloride, cyclohexanone, dibutyl phthalate, tricresyl phosphate) or an aqueous gelatin solution. It may be a hydrophilic polymer that is miscible with the hydrocolloid, or may be a polymer having a structure and properties capable of forming micelles in the hydrocolloid.

The yellow polymer coupler used in the present invention is obtained by dissolving a lipophilic polymer coupler obtained by polymerization of a vinyl-type monomer giving a coupler unit represented by the above formula [Y-4] in an organic solvent to obtain gelatin. It may be prepared by emulsion-dispersing it in the form of a latex in an aqueous solution, or may be prepared by a direct emulsion polymerization method.

US Pat. No. 3,451,820 for a method of emulsion-dispersing a lipophilic polymer coupler in the form of a latex in an aqueous gelatin solution, and US Pat. No. 4,084 for emulsion polymerization.
The methods described in Nos. 0,211 and 3,370,952 can be used.

Specific examples of each substituent in the formula [Y] are shown below.

[0108]

[Chemical 41]

[0109]

[Chemical 42]

[0110]

[Chemical 43]

[0111]

[Chemical 44]

[0112]

[Chemical formula 45]

[0113]

[Chemical formula 46]

[0114]

[Chemical 47]

[0115]

[Chemical 48]

[0116]

[Chemical 49]

Specific examples of the yellow coupler represented by the formula [Y] are shown below.

[0118]

[Chemical 50]

[0119]

[Chemical 51]

[0120]

[Chemical 52]

[0121]

[Chemical 53]

[0122]

[Chemical 54]

[0123]

[Chemical 55]

[0124]

[Chemical 56]

[0125]

[Chemical 57]

Examples of compounds other than the yellow couplers used in the present invention and / or methods for synthesizing these yellow couplers are described in, for example, US Pat. Nos. 3,227,554, 3,408,194, 3,644,498 and 3,770,445.
, No. 3,894,875, No. 3,933,501, No. 3,973,
No. 968, No. 4,022,620, No. 4,032,347, No. 4,
No. 046,575, No. 4,049,458, No. 4,057,432, No. 4,115,121, No. 4,133,958, No. 4,157,919
No. 4,201,584, No. 4,203,768, No. 4,248,
961, No. 4,266,019, No. 4,314,023, No. 4,
326,024, 4,327,175, 4,401,752, 4,420,556, 4,511,649, 4,617,256
No. 4, No. 4,711,837, No. 4,729,944, No. 4,758,
501, European Patent Nos. 30,747A, 272,041A, and
280,330A, 284,081A, 296,793A, 31
3,308A, British patent 1,040,710, West German patent 3,107,
173C, JP-A-58-42044, 59-174839, 60-696.
53, 62-200349, 62-276547, 63-23153
No. 63-43144, No. 63-123047, etc.

The yellow coupler represented by the formula [Y] of the present invention is contained in at least one layer of the light-sensitive material. At least one layer may be a photosensitive silver halide emulsion layer or a non-photosensitive layer (eg, antihalation layer, intermediate layer, yellow filter layer, protective layer). It is preferably a blue-sensitive emulsion layer and / or a non-light-sensitive layer adjacent thereto. More preferably, it is used in at least one of the blue-sensitive emulsion layers. The amount of the yellow coupler represented by the formula [Y] used in the light-sensitive material is 1.0 × 10 ⁻³ to 1 m ² of the light-sensitive material.
It is in the range of 3.0 g. Preferably 5.0 × 10 ⁻³ or more
2.0 g, and more preferably 1.0 × 10 ^-2 to 1.
It is in the range of 5 g.

The yellow coupler represented by the formula [Y] may be used alone or in combination of two or more kinds. Further, it may be divided into two or more layers and used alone or in combination of two or more kinds. Further, it can be used in combination with known photographic additives. The yellow coupler represented by the formula [Y] may be introduced into the light-sensitive material by any known dispersion method. Preferred is a method in which a high-boiling-point organic solvent described later is used and an oil-in-water dispersion method is applied to introduce the emulsion-dispersed dispersion into a photosensitive material.

Techniques and inorganic / organic materials that can be used in the color photographic light-sensitive material of the present invention are described in the following section of European Patent No. 436,938A2 and the patents cited below. 1. Layer structure: Page 146, line 34 to Page 147, line 25. Silver halide emulsion: Page 147, line 26 to line 14
Page 8, line 12 3. Yellow coupler: Page 137, line 35 to line 14
Page 6, line 33, page 149, lines 21-23. 4. Cyan coupler: page 149, lines 29-33; EP 432,804A2, page 3, line 28-page 40, line 2. Polymer couplers: page 149, lines 34-38; EP 435,334A2, page 113, 3
Line 9 to page 123, line 37 6. Colored Coupler: Page 53, Line 42 to 137
Page 34, line 34, page 149, lines 39 to 45 7. Other functional couplers: page 7, line 1-53
Page 41 line, page 149 line 46 to page 150 line 3;
7. European Patent No. 435,334A2, page 3, line 1 to page 29, line 50. Antiseptic / antifungal agent: Page 150, lines 25-28 9. Formalin scavenger: page 149, lines 15 to 17 10. Other additives: page 153, lines 38 to 47; European patent 421,453A1, page 75 21.
Line-Page 84, Line 56, Page 27, Line 40-Page 37, Line 40 11. Dispersion method: Page 150, lines 4 to 24 12. Support: Page 150, lines 32 to 34 13. Film thickness / film physical properties: Page 150, lines 35 to 49 14. Color development Process: Page 150, line 50 to Page 151, line 47, line 15. Desilvering process: Page 151, line 48 to page 152, 53
Line 16. Automatic processor: page 152 line 54 to page 153 2
Line 17. Water washing / stabilization process: Page 153, lines 3 to 37

[0130]

【Example】

Example 1 (Preparation of Sample 100) Onto an undercoated cellulose triacetate film support, each layer having the composition shown below was coated in multiple layers to prepare Sample 100 which is a multilayer color light-sensitive material. (Photosensitive layer composition) The main materials used for 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.

First Layer (Antihalation Layer) Black Colloidal Silver Silver 0.18 Gelatin 1.40 ExM-1 0.18 ExF-1 2.0 × 10 ^-3 HBS-1 0.20

[0132]

Third Layer (Low Sensitivity Red Sensitive Emulsion Layer) Emulsion A Silver 0.29 Emulsion B Silver 0.24 ExS-1 6.9 × 10 ^-5 ExS-2 1.8 × 10 ^-5 ExS-3 3.1 × 10 ^-4 ExC-1 0.17 ExC-3 0.030 ExC-4 0.10 ExC-5 0.020 ExC-7 0.0050 ExC-8 0.010 HBS-1 0.10 Gelatin 0.87

Fourth Layer (Medium Sensitivity Red Sensitive Emulsion Layer) Emulsion D Silver 0.70 ExS-1 3.5 × 10 ^-4 ExS-2 1.6 × 10 ^-5 ExS-3 5.1 × 10 ^-4 ExC-1 0.13 ExC-2 0.060 ExC-3 0.0070 ExC-4 0.090 ExC-5 0.025 ExC-7 0.0010 ExC-8 0.0070 HBS-1 0.10 Gelatin 0.75

Fifth Layer (High Sensitivity Red Sensitive Emulsion Layer) Emulsion E Silver 1.40 ExS-1 2.4 × 10 ^-4 ExS-2 1.0 × 10 ^-4 ExS-3 3.4 × 10 ^-4 ExC-1 0.12 ExC-3 0.045 ExC-6 0.020 ExC-8 0.025 HBS-1 0.22 HBS-2 0.10 Gelatin 1.20

Sixth Layer (Intermediate Layer) Cpd-1 0.10 HBS-1 0.50 Gelatin 1.10

Seventh Layer (Low Sensitivity Green Sensitive Emulsion Layer) Emulsion C Silver 0.35 ExS-4 3.0 × 10 ^-5 ExS-5 2.1 × 10 ^-4 ExS-6 8.0 × 10 ^-4 ExM-1 0.010 ExM-2 0.10 ExM-3 0.086 Exemplified coupler M-23 0.33 ExY-1 0.015 HBS-1 0.30 HBS-3 0.010 Gelatin 0.73

Eighth Layer (Medium Sensitivity Green Sensitive Emulsion Layer) Emulsion D Silver 0.80 ExS-4 3.2 × 10 ^-5 ExS-5 2.2 × 10 ^-4 ExS-6 8.4 × 10 ^-4 ExM-1 0.12 ExM-2 0.08 ExM-3 0.030 Exemplified coupler M-23 0.10 ExY-1 0.018 HBS-1 0.16 HBS-3 8.0 × 10 ^-3 gelatin 0.90

9th layer (high-sensitivity green-sensitive emulsion layer) Emulsion E Silver 1.25 ExS-4 3.7 × 10 ^-5 ExS-5 8.1 × 10 ^-5 ExS-6 3.2 × 10 ^-4 ExC-8 0.020 ExM-1 0.030 ExY-4 0.040 ExM-4 0.020 ExM-5 0.010 Exemplified coupler M-23 0.030 Cpd-2 0.040 HBS-1 0.25 HBS-2 0.10 Gelatin 1.44

10th layer (yellow filter layer) Yellow colloidal silver Silver 0.030 Cpd-1 0.16 HBS-1 0.60 Gelatin 0.60

Eleventh Layer (Low Sensitivity Blue Sensitive Emulsion Layer) Emulsion C Silver 0.15 ExS-7 8.6 × 10 ^-4 ExY-1 0.020 ExY-2 0.22 ExY-3 0.50 ExY-4 0.020 HBS-1 0.28 Gelatin 1.10

12th layer (medium-speed blue-sensitive emulsion layer) Emulsion D Silver 0.20 ExS-7 7.4 × 10 ^-4 ExC-7 7.0 × 10 ^-3 ExY-2 0.050 ExY-3 0.10 HBS-1 0.050 Gelatin 0.78

13th layer (high-sensitivity blue-sensitive emulsion layer) Emulsion F Silver 1.00 ExS-7 4.0 × 10 ^-4 ExY-2 0.10 ExY-4 0.040 ExY-3 0.10 HBS-1 0.070 Gelatin 0.86

Fourteenth layer (first protective layer) Silver iodobromide 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 1.7 μm) 5.0 × 10 ^-2 B-2 (diameter 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- may be used. 6, F
-1 to F-17 and iron salt, lead salt, gold salt, platinum salt,
It contains iridium salt and rhodium salt.

[0147]

[Table 1]

In Table 1, (1) Emulsions A to F were prepared according to the examples of JP-A-2-91938.
It is reduction-sensitized during grain preparation using thiourea dioxide and thiosulfonic acid. (2) Emulsions A to F were prepared according to the examples of JP-A-3-237450.
Gold sensitization, sulfur sensitization and selenium sensitization are performed in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate. (3) For the preparation of tabular grains, low molecular weight gelatin is used according to the examples 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 by using a high voltage electron microscope.

[0149]

[Chemical 58]

[0150]

[Chemical 59]

[0151]

[Chemical 60]

[0152]

[Chemical formula 61]

[0153]

[Chemical formula 62]

[0154]

[Chemical formula 63]

[0155]

[Chemical 64]

[0156]

[Chemical 65]

[0157]

[Chemical formula 66]

[0158]

[Chemical formula 67]

[0159]

[Chemical 68]

[0160]

[Chemical 69]

[0161]

[Chemical 70]

[0162]

[Chemical 71]

[0163]

[Chemical 72]

(Preparation of Sample 101) In Sample 101, M-23 and M-27 of the seventh, eighth and ninth layers were replaced with equimolar amounts of M-9 and M-18, respectively. (Preparation of Sample 102) The seventh, eighth, and ninth layers of Sample 100 are
Compound A-7 was added to 0.030 g / m ² , 0.0
30 g / m ^2, except for adding 0.060 g / m ^2, the sample 10
It was created in the same manner as 0. (Preparation of Samples 103 to 110) In Sample 102, compound A-7 and exemplified couplers M-23 and M-27 were replaced with equimolar compounds and couplers shown in "Table 2".
It was created in the same manner as the sample 102. Comparative compounds A and B are as follows.

[0165]

[Chemical formula 73]

(Preparation of Samples 111 to 115) Sample 100
And 102 to 105, 0.040 g / m ² of the compound shown in Table 2 was added to the third to fifth layers, respectively.
Samples prepared in the same manner as Samples 100 and 102 to 105 except that the compounds shown in Table 2 were added to the 11th to 13th layers at 0.080 g / m ² respectively. Samples 111 to 115 were prepared, respectively. (Preparation of Sample 116) In Sample 112, the seventh, eighth,
Nine layers of magenta coupler M-22 were mixed with an equimolar amount of E
Sample 112 was prepared in the same manner as in Example 112 except that xM-1 was substituted, and M-23 was substituted by an equimolar comparative coupler (1). (Preparation of Sample 117) The sample 112 was prepared in the same manner as the sample 112 except that the coupler ExY-2 of the eleventh layer to the thirteenth layer was removed and replaced with 1.4 times the molar amount of ExY-5. The samples 101 to 116 prepared as described above were exposed to 2000 lux at 1/100 seconds through an optical wedge using a tungsten light source of 4800 ° K. The exposed sample was subjected to the development processing described below, and then the density was measured. (Evaluation of Sensitivity) The sensitivity was evaluated by the logarithm of the reciprocal of the exposure amount which gives the minimum density of magenta + 0.2. (Evaluation of graininess) The grain size was evaluated by a conventional RMS (Root Mean Square) method. The evaluation of graininess by the RMS method is well known to those skilled in the art.
d Engineering "vol 19; No. 4 (1975) p.235-238.

After exposing the above color photographic light-sensitive material, it was processed by an automatic developing machine by the method described below until the cumulative replenishment amount of the developing solution became three times the tank capacity. (Processing process) Process processing time Processing temperature Replenishment amount ^* Tank capacity Color development 3 minutes 15 seconds 38 ℃ 22 ml 20 liters Bleach 3 minutes 00 seconds 38 ℃ 25 ml 40 liters Water wash (1) 15 seconds 24 ℃ (2 ) To (1) 10 liter counter-current piping system Washing (2) 15 seconds 24 ℃ 15 ml 10 liters fixed 3 minutes 00 seconds 38 ℃ 15 ml 30 liters water washing (3) 30 seconds 24 ℃ (4) From (3) to 10 L countercurrent piping system Washing with water (4) 30 sec 24 ℃ 1200 ml 10 liter Stability 30 sec 38 ℃ 20 ml 10 liter Dry 4 min 20 sec 55 ℃ * Replenishment amount is 35 mm width 1 m Per length

Next, the composition of the processing liquid will be described. (Color developer) Tank liquid (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1.0 1.2 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 2.2 Sodium sulfite 4.0 4.8 Potassium carbonate 30.0 39.0 Potassium bromide 1.4 0.3 Potassium iodide 1.5 mg-hydroxylamine sulfate 2.4 3.1 4- [N-ethyl-N- (β-hydroxyethyl) amino] -2-methylaniline sulfate 4.5 6.0 Add water 1.0 liter 1.0 liter pH (to potassium hydroxide and sulfuric acid 10.05 10.15

(Bleaching solution) Tank solution (g) Replenishing solution (g) Ethylenediaminetetraacetic acid sodium ferric trihydrate 100.0 120.0 Ethylenediaminetetraacetic acid disodium salt 10.0 11.0 3-Mercapto-1,2,4-triazole 0.03 0.08 Ammonium bromide 140.0 160.0 Ammonium nitrate 30.0 35.0 Ammonia water (27%) 6.5 ml 4.0 ml Add water 1.0 liter 1.0 liter pH (adjusted with ammonia water and nitric acid) 6.0 5.7

(Fixing liquid) Tank liquid (g) Replenishing liquid (g) Ethylenediaminetetraacetic acid disodium salt 0.5 0.7 Ammonium sulfite 20.0 22.0 Ammonium thiosulfate aqueous solution (700 g / l) 295.0 ml 320.0 ml acetic acid (90%) 3.3 4.0 Water In addition 1.0 liter 1.0 liter pH (adjusted with aqueous ammonia and acetic acid) 6.7 6.8

(Stabilizing Solution) Common Tank Solution / Replenishing Solution (unit: g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether (Average degree of polymerization: 10) 0.2 Ethylenediaminetetraacetic acid disodium salt 0.05 1, 2,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 Water was added to 1.0 liter pH 8.5 (Evaluation of preservability up to development processing after photographing) Samples 101 to 116 Each of the samples was exposed to 2000 lux for 1/100 seconds through an optical wedge using a tungsten light source of 4800 ° K, and one of the samples was stored in a freezer for 3 days, and one was stored at 50 ° C and 80%. After storing for 3 days RH,
The same development processing and density measurement as described above were performed. From this data, changes in fog and sensitivity during storage were determined. The above results are summarized in Table 2.

[0172]

[Table 2]

From Table 2, it can be seen that the combination of the coupler of the present invention and the compound has high sensitivity and good graininess, and the change in photographic performance after photographing is small.

Claims (2)

[Claims] 1. A silver halide color photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, containing a compound represented by the following general formula (A), and A silver halide color photographic light-sensitive material comprising a coupler represented by the formula (I). General formula (A): In the formula, Ra _{1 to} Ra ₅ may be the same or different and each is a hydrogen atom, an alkyl group, -X-Ra ₀ , or Ra.
_{1 to} Ra ₅ are groups necessary for forming a chroman ring by bonding two groups in the ortho positions to each other. Here, X is _{-C (Ra 6) (Ra 7} ) -, ─O─, or an -S-. Ra ₆ and Ra ₇ represent a hydrogen atom or an alkyl group. Ra ₀ represents a hydroxyphenyl group, and X is —C (Ra
₆ ) (Ra ₇ ) —, when Ra ₆ and Ra ₇ are simultaneously an alkyl group, and Ra ₁ and Ra ₅ are simultaneously —X—Ra ₀ , it may be an alkyl group. However, Ra ₃ is not a hydrogen atom, and at least one of Ra _{1 to} Ra ₅ is the same as or above. Further, when Ra ₃ is —X—Ra ₀ and Ra ₀ is a hydroxyphenyl group, neither Ra ₁ nor Ra ₅ is a hydrogen atom. General formula (I) In the formula, R ₁₁ represents a substituent and R ₁₂ represents an electron-withdrawing group. m represents an integer from 1 to 5, and when m is 2 or more, R
₁₁ may be the same or different. n represents an integer of 2 to 5, and R ₁₂ may be the same or different. X ₁ 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. A dimer or a multimer of R ₁₁ , R ₁₂ or X ₁ which are bonded to each other via a divalent or divalent or higher valent group may be formed. 2. The silver halide color photographic light-sensitive material according to claim 1, further comprising a coupler represented by the following general formula [Y]. General formula [Y] In the formula [Y], R ₁ is an aryl group, R ₂ is a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group,
An alkyl group or a dialkylamino group, R ₃ is a group capable of substituting on the benzene ring, X is a hydrogen atom or a group capable of leaving by a coupling reaction with an oxidized product of an aromatic primary amine developer (leaving group). , And p represents an integer of 0 to 4, respectively. However, when p is plural, plural R ₃
May be the same or different.