JP2779728B2 - Silver halide color photographic materials - Google Patents

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 containing a novel coupler.

[0002]

2. Description of the Related Art Silver halide color photographic light-sensitive materials are most widely used at present, in which a color image is formed by utilizing a reaction between a dye-forming coupler for forming yellow, magenta, and cyan and a color developing agent. ing.

In recent years, with respect to silver halide color photographic light-sensitive materials, studies on improvement of dye-forming couplers have been actively conducted from the viewpoints of improving color reproducibility and image fastness, but it is said that sufficient improvement has not yet been made. hard. In particular, phenol-based or naphthol-based couplers have been used consistently for cyan couplers, but the dyes produced from these couplers have unnecessary absorption in the blue and green regions, and color reproduction It has become a big barrier to improving the quality. The small molecular extinction coefficient of the cyan dye produced is also disadvantageous for improving the sharpness of the image.

[0004] Recently, research on cyan dye-forming couplers having a new skeleton having a nitrogen-containing heterocycle has been actively conducted.
Various heterocyclic compounds have been proposed. For example, diphenylimidazole couplers described in JP-A-63-226,653, JP-A-63-199,352.
Nos. 63-250,649 and 63-250,65
No. 0, No. 64-554, No. 64-555, and JP-A-1
-105,250 and 1-105,251 disclose pyrazoloazole couplers. All of these couplers claim to improve color reproducibility and are characterized by having excellent absorption characteristics of the formed dye.

However, the cyan dyes obtained from the above couplers have drawbacks such as short-wave absorption, poor fastness to light and heat, and low coupling activity of the couplers themselves. It had serious practical problems. The dark fading of the obtained cyan dye in a reducing atmosphere is described in, for example, Journal of the Photographic Society of Japan 5
0, 183 (1987).

[0006]

A first object of the present invention is to provide a silver halide color photographic light-sensitive material containing a novel cyan coupler and having a high color density of a cyan dye formed and excellent spectral absorption characteristics. To provide. A second object of the present invention is to form a cyan image with excellent heat resistance,
An object of the present invention is to provide a silver halide color photographic light-sensitive material which is less susceptible to reductive fading.

[0007]

The above object is achieved by a silver halide color photographic light-sensitive material characterized in that at least one layer on a support contains at least one coupler represented by the following general formula (I). Was done.

[0008]

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(Wherein, R ¹ represents a hydrogen atom or a substituent, R ² represents a substituent, X represents a hydrogen atom or a group capable of leaving during a coupling reaction with an oxidized form of a color developing agent; Z ¹ represents a group of nonmetallic atoms necessary for forming a nitrogen-containing 6-membered heterocyclic ring, provided that the heterocyclic ring has at least one dissociating group and Z ¹ is —C (＝ O) —N
(R) -C (= O) -NH-, and Z
^The 6-membered nitrogen-containing heterocyclic ring formed by ¹ has no further fused ring. R represents a substituent. )

Hereinafter, the general formula (I) will be described in detail. R ¹ represents a hydrogen atom or a substituent, and R and R ² represent a substituent. As the substituents for R, R ¹ and R ² ,
Aryl group, alkyl group, cyano group, acyl group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, formylamino group, acylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamide group, ureido group, sulfo Famoylamino group, alkylamino group, arylamino group,
Alkoxy group, aryloxy group, heteryloxy group,
Alkylthio group, arylthio group, heterylthio group, heterocyclic group, halogen atom, hydroxy group, nitro group, sulfamoyl group, sulfonyl group, acyloxy group, carbamoyloxy group, imide group, sulfinyl group, phosphoryl group, carboxyl group, phosphono group, Examples include an unsubstituted amino group. Among these, the group which can have a substituent may be further substituted with the above-mentioned substituent. As the substituents for R, R ¹ and R ² , specifically, an aryl group (preferably having 6 to 30 carbon atoms, for example, phenyl, m-acetylaminophenyl, p-methoxyphenyl), an alkyl group (preferably having 1 carbon atom) ~ 30, for example methyl, trifluoromethyl, ethyl, isopropyl,
Heptafluoropropyl, t-butyl, n-octyl,
n-dodecyl), cyano group, acyl group (preferably having 1 to 30 carbon atoms, for example, acetyl, pivaloyl, benzoyl, furoyl, 2-pyridylcarbonyl), carbamoyl group (preferably having 1 to 30 carbon atoms, for example, methylcarbamoyl, ethyl) Carbamoyl, dimethylcarbamoyl,
n-octylcarbamoyl), an alkoxycarbonyl group (preferably having 1 to 30 carbon atoms such as methoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl), an aryloxycarbonyl group (preferably having 7 to 30 carbon atoms such as phenoxycarbonyl, p-methoxy) Phenoxycarbonyl, m-chlorophenoxycarbonyl, o-methoxyphenoxycarbonyl), formylamino group, acylamino group (preferably an alkylcarbonylamino group having 1 to 30 carbon atoms (eg, acetylamino, propionylamino, cyanoacetylamino), preferably Is an arylcarbonylamino group having 7 to 30 carbon atoms (e.g., henzoylamino, p-toluylamino, pentafluorobenzoylamino, m-methoxybenzoylamino), preferably Heterylcarbonylamino group having a prime number of 4 to 30 (eg, 2-pyridylcarbonylamino, 3-pyridylcarbonylamino, furoylamino)], alkoxycarbonylamino group (preferably having 2 to 30 carbon atoms, for example, methoxycarbonylamino, ethoxycarbonylamino) Methoxyethoxycarbonylamino), an aryloxycarbonylamino group (preferably having 7 to 30 carbon atoms, for example, phenoxycarbonylamino, p-methoxyphenoxycarbonylamino, p-methylphenoxycarbonylamino, m-chlorophenoxycarbonylamino), sulfonamide Group (preferably having 1 to 30 carbon atoms, for example, methanesulfonamide, benzenesulfonamide, p-toluenesulfonamide), and ureido group (preferably having 1 to 30 carbon atoms, for example, Ruureido, dimethyl ureido, p- cyanophenylureido), a sulfamoylamino group (preferably 1 to carbon atoms
30, eg methylaminosulfonylamino, ethylaminosulfonylamino, anilinosulfonylamino),
Alkylamino group (preferably having 0 to 30 carbon atoms, for example, amino, methylamino, dimethylamino, ethylamino, diethylamino, n-butylamino), arylamino group (preferably having 6 to 30 carbon atoms, for example, anilino), alkoxy group (Preferably having 1 to 30 carbon atoms such as methoxy, ethoxy, isopropoxy, n-butoxy, methoxyethoxy, n-dodecyloxy), an aryloxy group (preferably having 6 to 30 carbon atoms such as phenoxy, m-chlorophenoxy, p-methoxyphenoxy, o-methoxyphenoxy), heteryloxy group (preferably having 3 to 30 carbon atoms, for example, tetrahydropyranyloxy, 3-pyridyloxy, 2- (1,3-benzimidazolyl) oxy), alkylthio group (preferably 1-30 carbon atoms, for example methyl O, ethylthio, n-butylthio, t-butylthio), an arylthio group (preferably having 6 to 30 carbon atoms, for example, phenylthio), a heterylthio group (preferably having 3 to 30 carbon atoms, for example, 2-pyridylthio, 2- (1,3 -Benzoxazolyl) thio, 1
-Hexadecyl-1,2,3,4-tetrazolyl-5
Thio, 1- (3-N-octadecylcarbamoyl) phenyl-1,2,3,4-tetrazolyl-5-thio), a heterocyclic group (preferably having 3 to 30 carbon atoms, for example, 2-benzoxazolyl, -Benzothiazolyl, 1-phenyl-2-benzimidazolyl, 5-chloro-1-tetrazolyl, 1-pyrrolyl, 2-furanyl, 2-pyridyl,
-Pyridyl), halogen atoms (fluorine, chlorine, bromine),
Hydroxy group, nitro group, sulfamoyl group (preferably having 0 to 30, for example, methylsulfamoyl, dimethylsulfamoyl), sulfonyl group (preferably having 1 to 30, for example, methanesulfonyl, benzenesulfonyl, toluenesulfonyl) An acyloxy group (preferably having 1 to 30 carbon atoms such as formyloxy, acetyloxy and benzoyloxy), a carbamoyloxy group (preferably having 1 to 30 carbon atoms such as methylcarbamoyloxy and diethylcarbamoyloxy), and an imide group (preferably C4-30, for example, succinimide, phthalimide), sulfinyl group (preferably, C1-30, for example, diethylaminosulfinyl), phosphoryl group (preferably C0-30, for example, dimethoxyphosphoryl), Hexyl group, a phosphono group, an unsubstituted amino group.

Preferably, at least one of R ¹ and R ² is an electron-withdrawing group having a Hammett's substituent constant σ _p value of 0.35 or more, and more preferably at least ^one of R ¹ and R ² . One is an electron-withdrawing group having a value of σ _p of 0.60 or more, and particularly preferably at least one of R ¹ and R ² is a cyano group.

Here, the Hammett's substituent constant used in the present specification will be described briefly. The Hammett's rule is an empirical rule proposed by LP Hammett in 1935 to quantitatively discuss the effect of substituents on the reaction or equilibrium of a benzene derivative, and is widely accepted today. The substituent constants determined by Hammett's rule include σ _p and σ _m values, which can be found in many general books. For example, JADean, “La
nge's Handbook of Chemistry ”, 12th edition, 1979 (McGraw-Hill) and“ Chemical Realm ”special edition, No. 122, 9
See pages 6-103, 1979 (Nankodo). In addition,
In the present invention, each substituent is defined or described by Hammett's substituent constant σ _p, but this is found in the above-mentioned textbook, in the sense that it is limited only to a substituent having a known value in the literature. Needless to say, even if the value is unknown in the literature, it also includes a substituent that would be included in the range when measured based on the Hammett rule.

The electron-withdrawing groups having a σ _p value of 0.35 or more include a cyano group (σ _p value of 0.66) and a nitro group (0.7 _p value).
8), carboxyl group (0.45), perfluoroalkyl group (eg, trifluoromethyl (0.54), perfluorobutyl), acyl group (eg, acetyl (0.50), benzoyl (0.43) ), Formyl group (0.42), sulfonyl group (for example, trifluoromethanesulfonyl (0.92), methanesulfonyl (0.
72), benzenesulfonyl (0.70)), a sulfinyl group (eg, methanesulfinyl (0.49)),
A carbamoyl group (eg, carbamoyl (0.36),
Methylcarbamoyl (0.36), phenylcarbamoyl, 2-chloro-phenylcarbamoyl), an alkoxycarbonyl group (for example, methoxycarbonyl (0.4
5), ethoxycarbonyl, diphenylmethylcarbonyl), a heterocyclic residue (for example, pyrazolyl (0.37),
1-tetrazolyl (0.50)), alkylsulfonyloxy group (for example, methanesulfonyloxy (0.3
6), a phosphoryl group (eg, dimethoxyphosphoryl (0.60), diphenylphosphoryl), a sulfamoyl group (0.57), a pentachlorophenyl group, a pentafluorophenyl group, or a sulfonyl group-substituted aromatic group (eg, 2,4- Dimethanesulfonylphenyl) and the like.

Preferred examples of the electron-withdrawing group having a value of σ _p of 0.60 or more include a cyano group, a nitro group and a sulfonyl group.

X represents a hydrogen atom or a group capable of leaving by a coupling reaction with an oxidized form of a color developing agent such as an aromatic primary amine developing agent (hereinafter referred to as a coupling-off group).

Specific examples of the coupling-off group include:
Halogen atoms (eg, fluorine, chlorine, bromine), alkoxy groups (eg, ethoxy, dodecyloxy, methoxyethylcarbamoylmethoxy, carboxypropyloxy,
Methylsulfonylethoxy), aryloxy groups (eg, 4-chlorophenoxy, 4-methoxyphenoxy,
-Carboxyphenoxy), acyloxy groups (eg, acetoxy, tetradecanoyloxy, benzoyloxy, sulfonyloxy groups (eg, methanesulfonyloxy, toluenesulfonyloxy), acylamino groups (eg, dichloroacetylamino, heptafluorobutyrylamino), sulfonamides) Groups (eg, methanesulfonamide, p-toluenesulfonamide), alkoxycarbonyloxy groups (eg, ethoxycarbonyloxy, benzyloxycarbonyloxy), aryloxycarbonyloxy groups (eg, phenoxycarbonyloxy), alkylthio groups (eg, carboxymethylthio), Arylthio group (for example, 2-butoxy-5-tert
-Octylphenylthio), a heterocyclic thio group (eg, tetrazolylthio), a carbamoylamino group (eg, N-methylcarbamoylamino, N-phenylcarbamoylamino), a 5- or 6-membered nitrogen-containing heterocyclic group (eg, imidazolyl, pyrazolyl, Triazolyl, tetrazolyl, 1,2-dihydro-2-oxo-1-pyridyl),
Imido groups (eg succinimide, hydantoinyl),
Aromatic azo group (eg, phenylazo), sulfinyl group (eg, 2-butoxy-5-tert-octylphenylsulfinyl), sulfonyl group (eg, 2-butoxy-5)
-Tert-octylphenylsulfonyl) and the like, and these groups may be further substituted with a group permitted as a substituent of R ¹ .

As the leaving group bonded via a carbon atom, there is a bis-type coupler obtained by condensing a 4-equivalent coupler with an aldehyde or a ketone. The leaving group of the present invention may contain a photographically useful group such as a development inhibitor and a development accelerator.

Z ¹ represents a group of non-metallic atoms necessary for forming a nitrogen-containing 6-membered heterocyclic ring, and has at least one dissociating group. The four divalent linking groups for constituting the nitrogen-containing 6-membered heterocyclic ring include -NH-, -N (R)-, -N
=, -CH (R)-, -CH =, -C (R) =, -CO
-, - S -, - SO -, - SO 2 - , and the like.
(R represents a substituent, and examples thereof include the substituents described for R ^1. ) Examples of the dissociating group include those having an acidic proton such as -NH-, -CH (R)-, and preferably pKa in water. It has a value of 3 to 12.

The dye-forming couplers represented by formula (I) can be preferably represented by formulas (II) to (XIX).

[0020]

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[0021]

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[0022]

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(Wherein R ¹ , R ² and X have the same meanings as in formula (I). R ³ , R ⁵ , R ⁶ ,
R ⁷ and R ⁸ represents a hydrogen atom or a substituent, R ⁴
Represents a substituent. EWG is the Hammett's substituent constant σ
An electron-withdrawing group having a value of _p of 0.35 or more. )

Examples of the substituents of R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are the same as those described for R ¹ .

The coupler represented by the general formula (I) is a compound represented by R ₁
Has in the base of to R ₈ residue of the coupler represented by formula (I), may form a dimer or higher polymer, also groups are polymer chains R ₁ to R ₈ And may form a homopolymer or a copolymer. The homopolymer or copolymer bonded to the polymer chain is typically a homopolymer or copolymer of an addition polymer ethylenically unsaturated compound having a coupler residue represented by the general formula (I). in this case,
The polymer may contain one or more kinds of color-forming repeating units having a coupler residue represented by the general formula (I), and the copolymer component may be, for example, an acrylate, a methacrylate or a maleate. It may be a copolymer containing one or more non-color-forming ethylene-type monomers.

Next, typical examples of the coupler used in the present invention are shown below, but the present invention is not limited to these. The substituents used in the compound examples are described below in numerical order.

[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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The following are examples of typical compounds of the coupler of the present invention, but the present invention is not limited thereto.

[0035]

[Table 1]

[0036]

[Table 2]

[0037]

[Table 3]

[0038]

[Table 4]

[0039]

[Table 5]

Next, a synthesis example of a representative coupler of the present invention will be described.

(Synthesis Example 1) Synthesis of coupler (III) -1

[0042]

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18.3 g of 2-amino-3-cyano-4-phenylpyrrole (compound a), which is easily obtained by condensing 2-aminoacetophenone hydrochloride and malononitrile in the presence of an alkali, and diethyl ethoxyethylidenemalonate 25. 3 g are dispersed in 300 ml of ethanol,
To this, sodium methylate 28% methanol solution 2
2.0 ml was added and the mixture was heated under reflux for 5 hours. After cooling, ethyl acetate was added, and the mixture was washed with water. The organic solvent was concentrated, and the precipitated crystals were collected by filtration to obtain 11.6 g of Compound b. Next, 50 ml of Fineoxocol 1600 and 2.0 g of titanium isopropoxide (Ti (Oi-Pr) ₄ ) were added thereto, and the mixture was heated at an oil bath temperature of 130 to 140 ° C for 6 hours. After cooling,
13. Purification by silica gel chromatography (hexane / ethyl acetate = 1/1), Coupler (III) -1
7 g were obtained as a pale yellow oil.

(Synthesis Example 2) Synthesis of coupler (III) -3

[0045]

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18.3 g of 2-amino-3-cyano-4-phenylpyrrole (compound a) and 24.0 g of diethyl ethoxymethylenemalonate were dispersed in 400 ml of ethanol, and 22.0 ml of a 28% methanol solution of sodium methylate was added thereto. Was added and heated under reflux for 1 hour. After cooling, the precipitated crystals were collected by filtration to obtain 28.0 g of a compound c. Then, fine oxo call 1600 was added to this for 150 m.
l, 4.0 g of Ti (Oi-Pr) ₄ were added, and the oil bath temperature was 130-
Heated at 140 ° C. for 2 hours. After cooling, the mixture was purified by silica gel chromatography to give coupler (III) -33
6.2 g were obtained.

Synthesis Example 3 Synthesis of Coupler (II) -1

[0048]

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18.3 g of 2-amino-3-cyano-4-phenylpyrrole (compound a) and 46.0 g of ethyl p-octadecyloxybenzoyl acetate were dispersed in 300 ml of acetic acid, and the mixture was heated under reflux for 8 hours. After cooling, 1 liter of ethyl acetate and 1 liter of water were added, and the precipitated crystals were collected by filtration to obtain 29.0 g of coupler (II) -1. Other compounds can be synthesized in a similar manner.

The light-sensitive material of the present invention may have at least one layer containing the coupler of the present invention on a support.
The layer containing the coupler of the present invention may be a hydrophilic colloid layer on a support. A general light-sensitive material can be constituted by coating a support with a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer in this order. However, the order may be different from this. Further, an infrared-sensitive silver halide emulsion layer can be used in place of at least one of the above-mentioned photosensitive emulsion layers. These photosensitive emulsion layers contain a silver halide emulsion having sensitivity in each wavelength region and a color coupler which forms a dye having a complementary color with the light to be exposed, thereby performing color reduction by the subtractive color method. be able to. However, the photosensitive emulsion layer and the color hue of the color coupler may not have the above correspondence. When the coupler of the present invention is applied to a light-sensitive material, it is particularly preferable to use it in a red-sensitive silver halide emulsion layer. The content of the coupler of the present invention in the light-sensitive material is suitably 1 × 10 ^-3 mol to 1 mol, preferably 2 × 10 ^-3 mol to 3 × 10 ^-1 mol per mol of silver halide. is there.

The coupler of the present invention can be introduced into a light-sensitive material by various known dispersion methods, dissolved in a high-boiling organic solvent (optionally using a low-boiling organic solvent in combination), emulsified and dispersed in an aqueous gelatin solution, and halogenated. An oil-in-water dispersion method to be added to a silver emulsion is preferred. Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in U.S. Pat. No. 2,322,027. Further, the steps and effects of the latex dispersion method as one of the polymer dispersion methods and specific examples of the latex for impregnation are described in US Pat. No. 4,199,363 and West German Patent Application (OLS) 2,541,274. And 2,541,23
No. 0, JP-B-53-41091 and European Patent Publication No. 0
No. 29104, etc., and the dispersion with an organic solvent-soluble polymer is described in PCT International Publication No. WO8.
No. 08/00723.

Examples of the high-boiling organic solvent which can be used in the above-described oil-in-water dispersion method include phthalic acid esters (for example, dibutyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis ( 2,4-di-tert
-Amylphenyl) isophthalate, bis (1,1-di-ethylpropyl) phthalate), esters of phosphoric or phosphonic acids (e.g., diphenyl phosphate, triphenyl phosphate, trichryl phosphate,
2-ethylhexyl diphenyl phosphate, dioctyl butyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, di-2-ethylhexyl phenyl phosphate), benzoic acid esters (for example, 2-ethylhexyl benzoate, 2,4- Dichlorobenzoate, dodecylbenzoate, 2-ethylhexyl-p-
Hydroxybenzoate), amides (eg, N, N
-Diethyldodecaneamide, N, N-diethyllaurylamide), alcohols or phenols (isostearyl alcohol, 2,4-di-tert-amylphenol, etc.), aliphatic esters (for example, dibutoxyethyl succinate, Di-2-ethylhexyl succinate, 2-hexyldecyl tetradecanoate, tributyl citrate, diethyl azelate, isostearyl lactate, trioctyl citrate), aniline derivative (N, N-dibutyl-2-butoxy-5-tert-) Octylaniline, etc.), chlorinated paraffins (chlorine content 10% to 80%)
Parames) trimesic esters (eg, tributyl trimesate), dodecylbenzene, diisopropylnaphthalene, phenols (eg, 2,4-di-tert-amylphenol, 4-dodecyloxyphenol, 4-dodecyloxycarbonylphenol) , 4-
(4-dodecyloxyphenylsulfonyl) phenol), carboxylic acids (for example, 2- (2,4-di-tert)
-Amylphenoxybutyric acid, 2-ethoxyoxytandecanoic acid), alkyl phosphoric acids (for example, di-2 (ethylhexyl) phosphoric acid, diphenylphosphoric acid) and the like.
As an auxiliary solvent, an organic solvent having a boiling point of 30 ° C. or more and about 160 ° C. or less (for example, ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone,
2-ethoxyethyl acetate, dimethylformamide) may be used in combination. The high boiling organic solvent is used in an amount of 0 to 10.0 times, preferably 0 to 4.0 times by weight the coupler.
Can be used in double amounts.

The light-sensitive material of the present invention is not particularly limited in the number and order of the silver halide emulsion layer and the non-light-sensitive layer.
A typical example is a photosensitive material having at least one photosensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support, The photosensitive layer is a unit photosensitive layer having color sensitivity to any of blue light, green light, and red light. In a multilayer silver halide color photographic material, the arrangement of the unit photosensitive layers is generally supported. The red-sensitive layer, the green-sensitive layer, and the blue-sensitive layer are arranged in this order from the body side. However, depending on the purpose, the order of installation may be reversed, or the order of installation may be such that different photosensitive layers are sandwiched between layers of the same color sensitivity. Non-light-sensitive layers such as various intermediate layers may be provided between the silver halide light-sensitive layers and as the uppermost layer and the lowermost layer. In the intermediate layer, JP-A-61-43748, JP-A-59-113438, and JP-A-59-11344
The couplers and DIR compounds as described in JP-A Nos. 0, 61-20037 and 61-20038 may be contained, and a color-mixing inhibitor may be contained as usually used. The plurality of silver halide emulsion layers constituting each unit photosensitive layer are described in West German Patent No. 1,121,470 or British Patent No. 923,
As described in No. 045, a two-layer structure of a high-speed emulsion layer and a low-speed emulsion layer can be preferably used. Usually, it is preferable to arrange them so that the light sensitivity decreases sequentially toward the support, and a non-photosensitive layer may be provided between the respective halogen emulsion layers. Also, JP-A-57-112751,
62-200350, 62-206541, 62-206543, as described in the low-speed emulsion layer on the side away from the support,
A high-sensitivity emulsion layer may be provided on the side close to the support. As specific examples, from the farthest side from the support, a low-sensitivity blue-sensitive layer (BL) / a high-sensitivity blue-sensitive layer (BH) / a high-sensitivity green-sensitive layer (GH) / a low-sensitivity green-sensitive layer (GL) / High-sensitivity red-sensitive layer (RH) / low-sensitivity red-sensitive layer (RL) or BH / BL /
They can be installed in the order of GL / GH / RH / RL or BH / BL / GH / GL / RL / RH. Further, as described in JP-B-55-34932, the layers may be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the side farthest from the support. Further, as described in JP-A-56-25738 and JP-A-62-63936, the layers can be arranged in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support. . Also, as described in JP-B-49-15495, the upper layer is the most sensitive silver halide emulsion layer, the middle layer is the less sensitive silver halide emulsion layer, and the lower layer is more sensitive than the middle layer. An arrangement in which a silver halide emulsion layer having a low degree of sensitivity is arranged, and three layers having different sensitivities are sequentially reduced in sensitivity toward a support, may be mentioned. Even in the case of such three layers having different sensitivities, Japanese Patent Application Laid-Open No. 59-202464
As described in the specification, in the same color-sensitive layer, a medium-speed emulsion layer / a high-speed emulsion layer / a low-speed emulsion layer may be arranged in this order from the side away from the support. In addition, the layers may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer. The arrangement may be changed as described above even in the case of four or more layers. To improve color reproducibility,
U.S. Patent Nos. 4,663,271, 4,705,744, 4,7
No. 07,436, JP-A-62-160448, and JP-A-63-89850, a main photosensitive layer such as BL, GL, RL, etc., and a donor layer (CL) having a multilayer effect having a different spectral sensitivity distribution from the main photosensitive layer. Preferably, it is located adjacent or close to the layer. as mentioned above,
Various layer configurations and arrangements can be selected according to the purpose of each photosensitive material.

As the silver halide used in the present invention, silver chloride, silver bromide, silver chlorobromide, silver iodochlorobromide, silver iodobromide, silver iodochloride and the like can be used. Silver halide grains in photographic emulsions include those having regular crystals such as cubic, octahedral and tetradecahedral, those having irregular crystal forms such as spheres and plates, twin planes, etc. Or a composite form thereof. The silver halide may be fine grains having a grain size of about 0.2 μm or less or large grains having a projected area diameter of about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion. Silver halide photographic emulsions that can be used in the present invention are described, for example, in Research Disclosure (RD) No. 17643 (December 1978), pp. 22-23,
"I. Emulsionpreparation and type
s) ”, and No. 18716 (November 1979), p. 648, N
o.307105 (November 1989), pp.863-865, and Grafkid, "Physics and Chemistry of Photography", published by Paul Montell (P.Gl.
afkides, Chemie et Phisique Photographique, Paul M
ontel, 1967), Duffin's "Photographic Emulsion Chemistry", Focal Press (GFDuffin, Photographic Emulsion Che)
mistry (Focal Press, 1966)), "Manufacture and coating of photographic emulsions" by Zerikman et al., published by Focal Press (VL Ze
likman et al., Making and Coating Photographic Emu
lsion, Focal Press, 1964).

Monodisperse emulsions described in US Pat. Nos. 3,574,628 and 3,655,394 and British Patent 1,413,748 are also preferable. Tabular grains having an aspect ratio of about 3 or more can also be used in the present invention. Tabular grains are described by Gatoff, Photographic Science and Engineering (Gutoff, PhotographicScience
and Engineering), Vol. 14, pp. 248-257 (1970);
U.S. Pat.Nos. 4,434,226, 4,414,310, 4,433,0
No. 48, 4,439,520 and British Patent No. 2,112,157. The crystal structure may be uniform, the inside and the outside may be composed of different halogen compositions, may have a layered structure, and even if silver halides having different compositions are joined by epitaxial junction. Also, it may be bonded to a compound other than silver halide such as, for example, silver rhodan or lead oxide. Also, a mixture of particles of various crystal forms may be used. The above emulsion may be either a surface latent image type in which a latent image is mainly formed on the surface, an internal latent image type in which the latent image is formed inside the grains, or a type having a latent image on both the surface and the inside. It is necessary to be. Among the internal latent image type emulsions, core / shell type internal latent image type emulsions described in JP-A-63-264740 may be used. A method for preparing this core / shell type internal latent image type emulsion is described in JP-A-59-133542. The thickness of the shell of this emulsion varies depending on the development process and the like, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

As the silver halide emulsion, usually, those subjected to physical ripening, chemical ripening and spectral sensitization are used. Additives used in such a process are described in Research Disclosure No. 17643, No. 18716 and No. 307105, and the relevant portions are summarized in the table below. The light-sensitive material of the present invention comprises two or more types of emulsions having at least one characteristic different from one another in the grain size, grain size distribution, halogen composition, grain shape, and sensitivity of the photosensitive silver halide emulsion.
They can be mixed and used in the same layer. U.S. Patent No.
No. 4,082,553, silver halide grains having a fogged surface, U.S. Pat.No. 4,626,498, silver halide grains having a fogged interior described in JP-A-59-214852, and photosensitive silver halide It can be preferably used for a silver emulsion layer and / or a substantially light-insensitive hydrophilic colloid layer. The term “silver halide particles having a fogged inside or surface” refers to silver halide grains that can be uniformly (non-imagewise) developed regardless of unexposed portions and exposed portions of the photosensitive material. . A method for preparing silver halide grains having the inside or the surface of the grains fogged is described in U.S. Pat.
No. 9-214852. The silver halides forming the internal nuclei of the core / shell type silver halide grains whose insides are fogged may have the same halogen composition or different halogen compositions. As the silver halide having the inside or surface of the grain fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. There is no particular limitation on the grain size of these fogged silver halide grains, but the average grain size is
It is preferably from 0.01 to 0.75 μm, particularly preferably from 0.05 to 0.6 μm. Also,
The grain shape is not particularly limited, and may be regular grains or polydisperse emulsions, but may be monodispersed (at least 95% of the weight or the number of silver halide grains is within ± 40% of the average grain size). Having a particle size of 1).

In the present invention, it is preferable to use non-photosensitive fine grain silver halide. Non-photosensitive fine grain silver halide is silver halide fine grains that are not exposed during imagewise exposure to obtain a dye image and are not substantially developed in the developing process, and are preferably not fogged in advance. . The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may contain silver chloride and / or silver iodide as needed. Preferably, it contains 0.5 to 10 mol% of silver iodide. Fine grain silver halide, average grain size (average value of projected area equivalent circle diameter)
Is preferably 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm. Fine grain silver halide can be prepared by the same method as that for ordinary photosensitive silver halide. In this case, the surface of the silver halide grains does not need to be chemically sensitized, and no spectral sensitization is required. However, prior to adding this to the coating solution, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, or mercapto-based compound or a zinc compound in advance. Colloidal silver can be preferably contained in the layer containing fine silver halide grains.

Known photographic additives that can be used in the present invention are also described in the above three Research Disclosures, and the relevant portions are shown in the following table. Additive type RD17643 RD18716 RD307105 1. Chemical sensitizer page 23, page 648, right column, page 866 2. Sensitivity enhancer 648, right column 3. Spectral sensitizer, page 23-24, page 648, right column, pages 866-868 Color sensitizer 〜page 649 right column 4. Brightening agent page 24 page 647 right column page 868 5. Fogging prevention page 24-25 page 649 right column 868-870 agent, stabilizer 6.Light absorber, 25- Page 26 649 Right column Page 873 Filter ~ Page 650 Left column Dye, UV absorber 7.Stain 25 Page Right column 650 Page Left column 872 Inhibitor ~ Right column 8. Dye image 25 Page 650 Page Left column 872 Stabilizer 9. Hardener page 26 page 651 left column 874-875 10. Binder page 26 page 651 left column 873-874 11. Plasticizer, page 27 page 650 right column page 876 Lubricant 12. Coating aid Pp. 26-27 650 right column 875-876 Surfactant 13. Stat. 27 page 650 right column 876-877 Inhibitor 14. Matsuto 878-879

Further, in order to prevent deterioration of photographic performance due to formaldehyde gas, it is preferable to add a compound which can react with formaldehyde described in US Pat. Nos. 4,411,987 and 4,435,503 and can be fixed to the photosensitive material. . U.S. Pat.No. 4,740,454
No. 4,788,132, JP-A-62-18539, JP-A-1-28
It is preferable to include a mercapto compound described in No. 3551. In the light-sensitive material of the present invention, compounds described in JP-A-1-06052, which release a fogging agent, a development accelerator, a silver halide solvent or a precursor thereof irrespective of the amount of developed silver produced by development processing Is preferably contained. In the light-sensitive material of the present invention, International Publication WO88 / 04794, dyes dispersed by the method described in JP-A-1-502912 or
EP 317,308A, U.S. Pat.No. 4,420,555, JP-A 1-2593
The dye described in No. 58 is preferably contained. Various color couplers can be used in the present invention, and specific examples thereof are described in Research Disclosure No. 1764, supra.
No. 307105, VII-CG, and VII-CG
The patent is described in US Pat. As the yellow coupler, for example, U.S. Pat.
No. 2,620, No. 4,326,024, No. 4,401,752, No.
No. 4,248,961, Japanese Patent Publication No. 58-10739, British Patent No. 1,425,
No. 020, No. 1,476,760, U.S. Pat.No. 3,973,968,
Nos. 4,314,023 and 4,511,649, European Patent 24
Those described in 9,473A and the like are preferred.

As magenta couplers, 5-pyrazolone and pyrazoloazole compounds are preferable, and US Pat. Nos. 4,310,619 and 4,351,897, and EP 73,63.
No. 6, U.S. Pat.Nos. 3,061,432, 3,725,067,
Research Disclosure No.24220 (June 1984
), JP-A-60-33552, Research Disclosure No.24230 (June 1984), JP-A-60-43659, 61-7
No. 2238, No. 60-35730, No. 55-118034, No. 60-185951
No. 4,500,630, U.S. Pat.No. 4,540,654, U.S. Pat.
Those described in 4,556,630, International Publication WO88 / 04795 and the like are particularly preferred. As the cyan coupler, a phenol-based coupler and a naphthol-based coupler can also be used in combination, as described in U.S. Patent Nos. 4,052,212, 4,146,396 and 4,228,2.
No. 33, No. 4,296,200, No. 2,369,929, No. 2,8
No. 01,171, No. 2,772,162, No. 2,895,826, No.
No. 3,772,002, No. 3,758,308, No. 4,334,011,
No. 4,327,173, West German Patent Publication No. 3,329,729, European Patent Nos. 121,365A and 249,453A, U.S. Pat.
Nos. 446,622, 4,333,999, 4,775,616, 4,451,559, 4,427,767, 4,690,889
No. 4,254,212, No. 4,296,199, JP-A-61-
Those described in No. 42658 are preferred. In addition, JP
-553, 64-554, 64-555 and 64-556, and imidazole couplers described in U.S. Pat. No. 4,818,672 can also be used in combination. Typical examples of polymerized dye-forming couplers include U.S. Patent Nos. 3,451,820; 4,080,211;
Nos. 7,282, 4,409,320, 4,576,910, British Patent 2,102,137 and European Patent 341,188A.

US Pat. No. 4,366,237 and British Patent No. 2,12 are examples of couplers whose coloring dyes have an appropriate diffusibility.
No. 5,570, European Patent No. 96,570, West German Patent (public) No.
Those described in 3,234,533 are preferred. Colored couplers for correcting unnecessary absorption of color-forming dyes are described in Research Disclosure No. 17643, Sections VII-G and 307.
105, paragraphs VII-G, U.S. Pat.No. 4,163,670, JP-B-57
-39413, U.S. Patent Nos. 4,004,929 and 4,138,258
And those described in British Patent No. 1,146,368 are preferred.
Further, a coupler that corrects unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in U.S. Pat. It is also preferable to use a coupler having a precursor group as a leaving group.
Compounds that release a photographically useful residue upon coupling can also be preferably used in the present invention. DIR couplers that release development inhibitors are described in RD 17643, VII-F above.
No. 307105, Patents described in Sections VII-F, JP-A-57-151944, JP-A-57-154234, JP-A-60-184248,
63-37346, 63-37350, U.S. Patent 4,248,962,
Preferred are those described in US Pat. No. 4,782,012. RDNo.1
The bleaching accelerator releasing couplers described in 1449, 24241, JP-A-61-201247, etc. are effective in shortening the processing time having a bleaching ability, and in particular, the tabular silver halide grains described above. The effect is great when it is added to a photosensitive material using. Couplers which release a nucleating agent or development accelerator imagewise during development are described in GB 2,097,1
No. 40, No. 2,131,188, JP-A No. 59-157638, No. 59-1
Those described in No. 70840 are preferred. In addition, Japanese Unexamined Patent Publication
7029, 60-252340, JP-A-1-44940, 1-456
No. 87, compounds which release a fogging agent, a development accelerator, a silver halide solvent or the like by an oxidation-reduction reaction with an oxidized form of the developing agent are also preferable.

Other compounds that can be used in the light-sensitive material of the present invention include competing couplers described in US Pat. No. 4,130,427 and US Pat. Nos. 4,283,472 and 4,3
Nos. 38,393, 4,310,618, etc., multi-equivalent couplers described in JP-A-60-185950, DIR redox compound releasing couplers described in JP-A-62-24252, etc., DIR coupler releasing couplers, DIR coupler releasing redox compounds Or a DIR redox-releasing redox compound, a coupler releasing a dye capable of recoloring after detachment described in European Patent Nos. 173,302A and 313,308A, a ligand releasing coupler described in U.S. Pat. -75747 Leuco dye releasing couplers, U.S. Pat.
No. 181 which emits a fluorescent dye.

The coupler used in the present invention can be introduced into a light-sensitive material by the above-mentioned various known dispersion methods.

In the color light-sensitive material of the present invention, phenethyl alcohol and JP-A-63-257747, JP-A-62-272248,
And JP-A-1-80941, 1,2-benzisothiazolin-3-one, n-butyl p-hydroxybenzoate,
It is preferable to add various preservatives or fungicides such as phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol, and 2- (4-thiazolyl) benzimidazole. The present invention can be applied to various color light-sensitive materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films, and color reversal papers.
Suitable supports that can be used in the present invention include, for example, the aforementioned R
D. No. 17643, page 28, No. 18716, page 647, right column, 648
No. 307105, page 879. In the light-sensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or less, more preferably 23 μm or less, still more preferably 18 μm or less, and particularly preferably 16 μm or less. The film swelling speed T
_1/2 is preferably 30 seconds or less, more preferably 20 seconds or less.
The film thickness means a film thickness measured under humidity control at 25 ° C. and a relative humidity of 55% (2 days), and the film swelling rate T _1/2 can be measured according to a method known in the art. For example, Photographic Science and Engineering by A. Green et al. (Photog
r.Sci.Eng.), 19 vol., No. 2, by using the type of Swellometer described (swelling meter) pp 124-129, can be measured, T _1/2 is 30 ° C. with a color developer 90% of the maximum swollen film thickness reached when the treatment is performed for 3 minutes and 15 seconds is defined as the saturated film thickness, and is defined as the time required to reach 1/2 of the saturated film thickness. Film swelling speed T
_{The ratio} of _1/2 can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating. The swelling ratio is preferably from 150 to 400%. The swelling ratio can be calculated from the maximum swelling film thickness under the conditions described above according to the formula: (maximum swelling film thickness-film thickness) / film thickness. In the light-sensitive material of the present invention, a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm is preferably provided on the side opposite to the side having the emulsion layer.
In this back layer, the above-mentioned light absorber, filter dye,
It is preferable to contain an ultraviolet absorber, an antistatic agent, a hardener, a binder, a plasticizer, a lubricant, a coating aid, a surfactant, and the like. The swelling ratio of this back layer is 150 ~ 500
% Is preferred.

The color photographic light-sensitive material according to the present invention is prepared according to the RD. No. 17643, pages 28 to 29, No. 18716, page 651, left column to right column, and No. 307105, pages 880 to 881, can be used for development. The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution mainly containing an aromatic primary amine color developing agent. As the color developing agent,
Aminophenol compounds are also useful, but p-phenylenediamine compounds are preferably used, and typical examples thereof are 3-methyl-4-amino-N, N-diethylaniline and 3-methyl-4-amino-N- Ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N
-Ethyl-β-methoxyethylaniline, 4-amino-3-
Methyl-N-methyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-ethyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-ethyl- N-
(2-hydroxypropyl) aniline, 4-amino-3-ethyl-N-ethyl-N- (3-hydroxypropyl) aniline, 4-
Amino-3-ethyl-N-ethyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-propyl-N- (3-
(Hydroxypropyl) aniline, 4-amino-3-propyl
-N-methyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-methyl-N- (4-hydroxybutyl) aniline, 4-amino-3-methyl-N-ethyl-N -(4-hydroxybutyl) aniline, 4-amino-3-methyl-N-propyl
-N- (4-hydroxybutyl) aniline, 4-amino-3-ethyl-N-ethyl-N- (3-hydroxy-2-methylpropyl) aniline, 4-amino-3-methyl-N, N-bis (4-hydroxybutyl) aniline, 4-amino-3-methyl-N, N-bis (5-
Hydroxypentyl) aniline, 4-amino-3-methyl-N
-(5-hydroxypentyl) -N- (4-hydroxybutyl) aniline, 4-amino-3-methoxy-N-ethyl-N- (4-hydroxybutyl) aniline, 4-amino-3-ethoxy-N, Examples include N-bis (5-hydroxypentyl) aniline, 4-amino-3-propyl-N- (4-hydroxybutyl) aniline, and sulfates, hydrochlorides or p-toluenesulfonates thereof. Among them, in particular, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 4-amino-3-methyl-N-ethyl-N- (3-hydroxypropyl)
Aniline, 4-amino-3-methyl-N-ethyl-N- (4-hydroxybutyl) aniline, and their hydrochlorides, p-toluenesulfonates or sulfates are preferred. These compounds can be used in combination of two or more depending on the purpose. The color developing solution may be a pH buffer such as an alkali metal carbonate, borate or phosphate, a chloride salt, a bromide salt, an iodide salt, a benzimidazole, a benzothiazole or a mercapto compound. It generally contains an inhibitor or an antifoggant. Also, if necessary,
Various preservatives such as hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazide, triethanolamine, catecholsulfonic acid,
Organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, 1-phenyl-3-
Auxiliary developing agents such as pyrazolidone, viscosity-imparting agents, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, various chelating agents represented by phosphonocarboxylic acids, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, Diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-
Hydroxyethylidene-1,1-diphosphonic acid, nitrilo-
N, N, N-trimethylenephosphonic acid, ethylenediamine-N,
N, N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof can be mentioned as typical examples.

When the reversal process is performed, color development is usually performed after black and white development. Known black-and-white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone or aminophenols such as N-methyl-p-aminophenol are used alone in the black-and-white developer. Alternatively, they can be used in combination. The pH of these color developing solutions and black-and-white developing solutions is generally 9 to 12. The replenishing amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per square meter of the photographic material, and is reduced to 500 ml or less by reducing the bromide ion concentration in the replenishing solution. You can also. When the replenishment rate is reduced, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the processing tank with the air. The contact area between the photographic processing solution and air in the processing tank can be represented by the aperture ratio defined below. That is, aperture ratio = [contact area between treatment liquid and air (cm ² )] ÷ [volume of treatment liquid (cm ³ )] The above-mentioned aperture ratio is preferably 0.1 (cm ^-1 ) or less, more preferably Preferably it is 0.001-0.05. As a method of reducing the aperture ratio in this manner, in addition to providing a shield such as a floating lid on the photographic processing liquid surface of the processing tank, a method using a movable lid described in JP-A-1-82033, 63-216050 can be mentioned. The reduction of the aperture ratio is preferably applied not only to both the color development and black-and-white development steps but also to the following various steps, for example, all the steps such as bleaching, bleach-fixing, fixing, washing and stabilization. The amount of replenishment can also be reduced by using means for suppressing the accumulation of bromide ions in the developer. The time for color development processing is usually 2 to 5
The processing time can be further shortened by setting the temperature at a high temperature and a high pH and using a color developing agent at a high concentration.

The photographic emulsion layer after color development is usually subjected to bleaching. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. In order to further speed up the processing, a processing method of performing bleach-fixing after bleaching may be used. Further, processing in two successive bleach-fixing baths, fixing before bleach-fixing, or bleaching after bleach-fixing can be arbitrarily performed according to the purpose. As the bleaching agent, for example, compounds of polyvalent metals such as iron (III), peracids, quinones, nitro compounds and the like are used. Typical bleaching agents are organic complex salts of iron (III),
For example, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid, or complex salts such as citric acid, tartaric acid, and malic acid Etc. can be used. Among these, iron (III) aminopolycarboxylates including iron (III) complex salts of ethylenediaminetetraacetate and 1,3-diaminopropanetetraacetate complex
Complex salts are preferred from the viewpoint of rapid processing and prevention of environmental pollution. Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in a bleaching solution and a bleach-fixing solution. The pH of the bleaching solution or bleach-fixing solution using these iron (III) complex salts of aminopolycarboxylic acid is usually from 4.0 to 8, but the processing can be carried out at a lower pH to speed up the processing.

In the bleaching solution, the bleach-fixing solution and the prebath thereof, a bleaching accelerator can be used if necessary.
Specific examples of useful bleach accelerators are described in the following specification: US Pat. No. 3,893,858, West German Patent 1,290,812.
No. 2,059,988, JP-A-53-32736, JP-A-53-57831
Nos. 53-37418, 53-72623, 53-95630, 53
-95631, 53-104232, 53-124424, 53-141
No. 623, No. 53-28426, Research Disclosure
Compounds having a mercapto group or a disulfide group described in No. 17129 (July, 1978);
No. 45-8506, JP-A-52-20832 and JP-A-53-32735, U.S. Pat. No. 3,706,561
No. 1,127,715, thiourea derivatives described in US Pat.
Iodide salts described in JP-A-58-16,235; West German Patent No. 966,
Polyoxyethylene compounds described in Nos. 410 and 2,748,430; polyamine compounds described in JP-B No. 45-8836; and other JP-A Nos. 49-40,943, 49-59,644 and 53-94,92.
No. 7, 54-35,727, 55-26,506, 58-163,940
Compounds described in (1); bromide ions and the like can be used. Among them, a compound having a mercapto group or a disulfide group is preferable in view of a large accelerating effect, and in particular, U.S. Pat.
3,858, West German Patent No. 1,290,812, JP-A-53-95,630
Are preferred. Further, U.S. Pat.
The compounds described in 834 are also preferred. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color photographic material for photography. The bleaching solution and the bleach-fixing solution preferably contain an organic acid in order to prevent bleaching stain in addition to the above compounds. Particularly preferred organic acids have an acid dissociation constant (pKa) of 2
-5, specifically, acetic acid, propionic acid,
Hydroxyacetic acid and the like are preferred. Examples of the fixing agent used in the fixing solution or the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas, a large amount of iodides, and the like. In particular, ammonium thiosulfate can be used most widely. It is also preferable to use a combination of a thiosulfate and a thiocyanate, a thioether-based compound, thiourea, or the like. Examples of preservatives for the fixing solution and the bleach-fixing solution include sulfites, bisulfites, carbonyl bisulfite adducts and EP No. 294.
The sulfinic acid compounds described in 769A are preferred. Furthermore,
It is preferable to add various aminopolycarboxylic acids or organic phosphonic acids to the fixing solution or the bleach-fixing solution for the purpose of stabilizing the solution. In the present invention, the fixing solution or the bleach-fixing solution contains pH.
For the adjustment, a compound having a pKa of 6.0 to 9.0, preferably imidazoles such as imidazole, 1-methylimidazole, 1-ethylimidazole, and 2-methylimidazole is used.
It is preferable to add 1 to 10 mol / l.

It is preferable that the total time of the desilvering step is shorter as long as the desilvering failure does not occur. Preferred time is 1 minute to 3
Minutes, more preferably 1 to 2 minutes. The processing temperature is from 25 ° C to 50 ° C, preferably from 35 ° C to 45 ° C. In a preferable temperature range, the desilvering speed is improved, and generation of stain after processing is effectively prevented. In the desilvering step, it is preferable that the stirring is strengthened as much as possible.
As a specific method of strengthening the stirring, a method of impinging a jet of a processing solution on an emulsion surface of a photosensitive material described in JP-A-62-183460, or a method of stirring using a rotating means described in JP-A-62-183461. A method for improving the effect, a method for moving the photosensitive material while bringing the wiper blade provided in the solution into contact with the emulsion surface, and making the emulsion surface turbulent to improve the stirring effect, and a circulation of the entire processing solution. There is a method of increasing the flow rate. Such a stirring improving means is effective for any of the bleaching solution, the bleach-fixing solution and the fixing solution. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film, and consequently increases the desilvering speed. Further, the above-mentioned means for improving the stirring is more effective when a bleaching accelerator is used, and can significantly increase the accelerating effect or eliminate the fixing inhibiting effect of the bleaching accelerator. The automatic developing machine used for the light-sensitive material of the present invention is disclosed in JP-A-60-191257.
It is preferable to have the photosensitive material conveying means described in JP-A Nos. 60-191258 and 60-191259. Japanese Patent Laid-Open No. Sho 6
As described in Japanese Patent Application No. 0-191257, such a transport means can significantly reduce the carry-in of the processing liquid from the pre-bath to the post-bath, and is highly effective in preventing the performance of the processing liquid from deteriorating. Such an effect is particularly effective for reducing the processing time in each step and reducing the replenishing amount of the processing solution.

The silver halide color photographic light-sensitive material of the present invention generally undergoes a washing and / or stabilizing step after desilvering. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, the material used such as a coupler), the use, the rinsing water temperature, the number of rinsing tanks (number of stages), the replenishment method such as countercurrent, forward flow, and other various conditions. Can be set widely.
Of these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is described in the Journal of the Society of Motion Picture a.
nd Television Engineers Vol. 64, pp. 248-253 (1955
May issue). According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced.However, due to an increase in the residence time of water in the tank, bacteria are propagated, and the generated suspended matter adheres to the photosensitive material. Problem arises. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, the method of reducing calcium ions and magnesium ions described in JP-A-62-288838 can be used very effectively. Also, isothiazolone compounds and thiabendazoles described in JP-A-57-8,542, chlorine-based disinfectants such as chlorinated sodium isocyanurate, and other benzotriazoles, etc. (1986) Sankyo Publishing, Sanitary Technology Association, "Microbial Sterilization, Sterilization, and Antifungal Technology" (1982) Industrial Technology Association, Japan Society of Antimicrobial and Antifungal Activities, "Encyclopedia of Antimicrobial and Antifungal Agents" (1986) The bactericides described can also be used. PH of washing water in processing the photosensitive material of the present invention
Is 4 to 9, preferably 5 to 8. Washing water temperature and washing time can also be set variously depending on the characteristics of the photosensitive material, the application, etc.
A range of 30 seconds to 5 minutes at 25-40 ° C is selected. Further, the light-sensitive material of the present invention can be processed directly with a stabilizing solution instead of the above-mentioned washing. In such a stabilization treatment, any of the known methods described in JP-A-57-8543, JP-A-58-14834 and JP-A-60-220345 can be used. Further, after the water washing treatment, a stabilization treatment may be further carried out. As an example, a stabilizing bath containing a dye stabilizer and a surfactant, which is used as a final bath of a color light-sensitive material for photography, is exemplified. be able to. As a dye stabilizer,
Aldehydes such as formalin and glutaraldehyde,
N-methylol compounds such as dimethylol urea, N-methylol pyrazole, N-methylol-1,2,4-triazole, hexamethylenetetramine, 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine Azolylmethylamines or aldehyde sulfite adducts. Various chelating agents and fungicides can also be added to this stabilizing bath.

The overflow solution accompanying the washing and / or replenishment of the stabilizing solution can be reused in other steps such as a desilvering step. In the processing using an automatic developing machine or the like, when each of the above processing solutions is concentrated by evaporation,
It is preferable to correct the concentration by adding water. The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up the processing. In order to incorporate the color developing agent, it is preferable to use various precursors of a color developing agent. For example, indoaniline-based compounds described in U.S. Pat. Described metal salt complex, JP-A-53-135
Urethane compounds described in No. 628 can be mentioned.
The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-3-
Pyrazolidones may be incorporated. Typical compounds are described in JP-A-56-64339, JP-A-57-144547 and JP-A-58-115438. Various processing solutions in the present invention are 10 ° C
Used at 5050 ° C. Usually, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature promotes the processing and shortens the processing time, and conversely, lowers the temperature to achieve the improvement of the image quality and the stability of the processing solution. be able to.

When the silver halide color photographic light-sensitive material of the present invention is applied to a film unit with a lens described in JP-B-2-32615, JP-B-3-39784, etc., the effect is more easily exhibited. It is valid.

[0073]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto.

Example 1 Using the couplers (III) -1, (II) -1, the comparative coupler (C-1) and the developing agent (D) of the present invention, cyan dyes (A), (B), (C) C) was synthesized, and the reduction potential was measured. A THF solution of the dye and a Briton-Robinson buffer were mixed at a volume ratio of 3: 2, and the concentration of the dye was 1 × 10 ⁻⁴ mol /
A liter, pH 7.0 solution was prepared and measured. (Voltammetric analyzer P-1000: manufactured by Yanagimoto Seisakusho; mercury drop electrode) The smaller the value, the less the reduction.

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[Table 6]

As shown in Table 6, the dye obtained from the coupler of the present invention is hardly reduced. Conventionally,
It has been pointed out that the dark heat fastness of the cyan dye tends to occur in a reducing atmosphere, indicating that the dye obtained from the coupler of the present invention is very excellent in this respect.

Example 2 (Preparation of Sample 101) An emulsified dispersion of the exemplified coupler (I) -1 was prepared by the method described below. 1.03 g of the exemplified coupler (I) -1 and 0.9 cc of tris (2-ethylhexyl) phosphate were added to 10 parts of ethyl acetate.
cc, and completely dissolved while maintaining the liquid temperature at about 40 ° C. Separately, at room temperature, 4.2 g of gelatin was added to 26 cc of water to sufficiently swell, and then completely dissolved at a temperature of about 40 ° C. While keeping this aqueous gelatin solution at about 40 ° C., 3 cc of 5% sodium dodecylbenzenesulfonate and all the oil phase liquid prepared above were added, and emulsified and dispersed by a homogenizer to obtain an emulsified dispersion. Using this emulsified dispersion, a coating solution having the following composition was prepared, and coated on an undercoated cellulose triacetate support so that the coupler was 1 mmol / m ² . In addition, 1.5
g / m ² of gelatin was applied as a protective layer to prepare Sample 101.

(Coating liquid) Emulsion (silver chlorobromide (Br 30 mol%)) 13 g 10% gelatin 28 g Emulsified dispersion 22 g Water 37 cc 1-oxy-3,5-dichloro-s-triazine sodium salt 4% aqueous solution 5 cc

(Preparation of Samples 102 to 117) Sample 101
Was prepared in the same manner as in Sample 101 except that the couplers shown in Table 7 were added in an equimolar amount to the exemplified coupler (I) -1 instead of the exemplified coupler (I) -1. Sample 10
2 to 117.

The sample prepared as described above was subjected to wedge exposure with white light, and color development was performed in the following processing step (I). Next, these samples were subjected to 80 ° C., 70 ° C.
The specimen was allowed to stand in a% RH for 3 days and subjected to a compulsory test. The density after the test where the density before the test was 1.0 was used as a measure of image fastness. The results are summarized in Table 7.

Processing Step (I) Processing Step Temperature Time Color Development 35 ° C. 1 minute Bleach-fix 30-36 ° C. 45 seconds Stable 30-37 ° C. 20 seconds Stable 30-37 ° C. 20 seconds Stable 30-37 ° C. 20 seconds Dry Drying 70 to 85 ° C for 60 seconds (four tank countercurrent method to stable →) The composition of each treatment liquid is as follows.

(Color developing solution) Water 800 ml Ethylenediaminetetraacetic acid 2.0 g Triethanolamine 8.0 g Sodium chloride 1.4 g Potassium bromide 0.6 g Potassium carbonate 25 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 5.0 g N, N-diethylhydroxylamine 4.2 g 5,6-dihydroxybenzene-1,2,4-trisulfonic acid 0.3 g Fluorescent brightener (4 4'-diaminostilbene type) 2.0 g Add water and 1000 ml pH (25 ° C) 10.25

(Bleach-fixing solution) Water 400 ml Ammonium thiosulfate (700 g / l) 100 ml Sodium sulfite 18 g Ammonium iron (III) ethylenediaminetetraacetate 55 g Disodium ethylenediaminetetraacetate 3 g Glacial acetic acid 8 g .5

(Stabilizing solution) Formalin (37%) 0.1 g Formalin-sulfite adduct 0.7 g 5-chloro-2-methyl-4-isothiazolin-3-one 0.02 g 2-methyl-4-isothiazoline-3 -On 0.01 g Copper sulfate 0.005 g Add water 1000 ml pH (25 ° C) 4.0

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[Table 7]

As is clear from Table 7, the couplers of the present invention are excellent in image fastness. Couplers (IV) -2, (V) -2, (VI) -2, (VII) of the present invention
-2, (IX) -2, (X) -2, (XI) -2, (XII)-
2, (XIII) -2, (XIV) -2, (XV) -2, (XVI)-
2, (XVII) -2, (XVIII) -2, and (XIX) -2 gave almost the same results.

Example 3 On an undercoated cellulose triacetate film support,
Each layer having the composition shown below was applied in multiple layers to prepare a sample 101 as a multilayer color photosensitive material. (Composition of photosensitive layer) The main materials used for each layer are classified as follows: ExC: cyan coupler UV: ultraviolet absorber ExM: magenta coupler HBS: high boiling point organic solvent ExY: yellow coupler H: gelatin Curing agent ExS: Sensitizing dye The number corresponding to each component indicates the coating amount in g / m ² , and for silver halide, it indicates the coating amount in terms of silver. However, as for the sensitizing dye, the coating amount is shown in mol unit with respect to 1 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 HBS-1 0.20

Second layer (intermediate layer) Emulsion G silver 0.065 2,5-di-t-pentanadecyl 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 × 10 ^-5 ExS-2 1.8 × 10 ^-5 ExS-33 0.1 × 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 Cpd-2 0.025 HBS- 1 0.10 Gelatin 0.87

Fourth Layer (Medium Speed 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 Cpd-2 0.023 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 Cpd-2 0.050 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 0.33 ExM-3 0.086 ExY-1 0.015 HBS-1 0.30 HBS-3 0.010 Gelatin 0.73

Eighth Layer (Medium Speed 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-2 0.13 ExM-3 0.030 ExY-1 0.018 HBS-1 0.16 HBS-3 8.0 × 10 ^-3 Gelatin 0.90

Ninth 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-1 0.010 ExM-1 0.030 ExM-4 0.040 ExM-5 0.019 Cpd-3 0.040 HBS-1 0.25 HBS-2 0.10 Gelatin 1.44

Tenth 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 0.18 ExS-7 8.6 × 10 ^-4 ExY-1 0.020 ExY-2 0.022 ExY-3 0.050 ExY- 4 0.020 HBS-1 0.28 Gelatin 1.10

Twelfth 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 0.050 ExY-30 .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-3 0.10 HBS-1 0.070 Gelatin 0 .86

Fourteenth 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 (1.7 μm in diameter) 5.0 × 10 ^-2 B-2 (1.7 μm in diameter) 0.10 B-30 .10 S-1 0.20 gelatin 1.20

Further, in order to improve the storability, processability, pressure resistance, fungicide / antibacterial property, antistatic property and coatability of each layer, W-1 to W-3, B-4 to B -6, F
-1 to F-17, and iron salts, lead salts, gold salts, platinum salts,
Contains iridium and rhodium salts.

[0106]

[Table 8]

In Table 8, (1) Emulsions A to F were subjected to reduction sensitization during the preparation of grains using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-191938. (2) Emulsions A to F 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. Have been. (3) For preparing 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 are observed in tabular grains and normal crystal grains having a grain structure using a high-pressure electron microscope.

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Next, the third, fourth and fifth layers of the cyan coupler E
Except that xC-1 and ExC-4 were equimolarly replaced with the couplers shown in Table 9, samples 302 to 302 were prepared in the same manner as sample 301.
310 was created. The obtained samples 301 to 310 were subjected to gradation exposure with red light, and then processed in the following processing step II using an automatic developing machine.

(Processing Step II) Step Processing time Processing temperature Replenishment amount * Tank capacity Color development 3 minutes 5 seconds 38.0 ° C 600 ml 17 liter Bleaching 50 seconds 38.0 ° C 140 ml 5 liter Bleaching and fixing 50 seconds 38.0 ° C -5 liter Arrival 50 seconds 38.0 ℃ 420ml 5l Rinse 30 seconds 38.0 ℃ 980ml 3l Stable (1) 20 seconds 38.0 ℃-3l Stable (2) 20 seconds 38.0 ℃ 560ml 3l Dry 1 minute 60 ℃ * Refill The amount was the amount per m ² of the photosensitive material. The stabilizing solution was of the countercurrent type from (2) to (1), and the overflow of the washing water was all introduced into the fixing bath. For replenishment to the bleach-fix bath, a cut is provided at the top of the bleach tank and the top of the fixing tank of the automatic processor, and all the overflow generated by the supply of the replenisher to the bleach tank and the fixing tank is transferred to the bleach-fix bath. It was made to flow in. The amount of the developer brought into the bleaching process, the amount of the bleaching solution brought into the bleach-fixing process, the amount of the bleach-fixing solution brought into the fixing process, and the amount of the fixing solution brought into the washing process are each per 1 m ² of the photosensitive material. 65 ml, 50 ml, 50 ml, 5
It was 0 ml. The crossover time is 6 seconds in each case, and this time is included in the processing time of the previous step. Each replenisher was replenished with the same liquid as the respective tank liquid.

The composition of the processing liquid is shown below. (Color developing solution) (Unit g) Diethylenetriaminepentaacetic acid 2.0 1-Hydroxyethylidene-1,1-diphosphonic acid 3.3 Sodium sulfite 3.9 Potassium carbonate 37.5 Potassium bromide 1.4 Potassium iodide 3 mg hydroxylamine sulfate 2.4 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 4.5 Water and 1.0 liter pH 10.15

(Bleaching solution) (unit: g) Ferric ammonium 1,3-diaminopropanetetraacetate monohydrate 130 Ammonium bromide 80 Ammonium nitrate 15 Hydroxyacetic acid 50 Acetic acid 40 Add water and add 1.0 L pH [Ammonia water 4.4)

(Bleach-fixing solution) A mixture of the above-mentioned bleaching solution and the following fixing solution in a ratio of 15:85 (by volume). (PH 7.0)

(Fixing solution) (Unit g) Ammonium sulfite 19 Aqueous ammonium thiosulfate solution (700 g / L) 280 mL Imidazole 15 Ethylenediaminetetraacetic acid 15 Add water 1.0 L pH [prepared with aqueous ammonia and acetic acid] 7.4

(Washing water) Tap water was replaced with H-type strongly acidic cation exchange resin (Amberlite IR- manufactured by Rohm and Haas Company).
120B) and a mixed bed column packed with an OH type strongly basic anion exchange resin (Amberlite IR-400) to reduce the calcium and magnesium ion concentration to 3 mg.
Per liter or less, followed by 20 mg / liter of sodium diisocyanurate and 150 mg of sodium sulfate.
mg / l was added. The pH of this solution is 6.5 to 7.
5 range.

(Stabilizing Solution) (Unit g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.2 Disodium ethylenediaminetetraacetate 0.05 1, 2,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) pidazine 0.75 1.0 liter with water added pH 8.5 Colored sample 301- 310 was measured for red density using a Fuji densitometer.
The gradient G of a straight line connecting 5 and fog density +1.0 was determined, and evaluated as a relative value when G = 1.00 of the sample 301. The color image storability was evaluated in the same manner as in Example 1 except that a point of cyan density 1.5 was obtained. Table 9 shows the results.

[0131]

[Table 9]

From Table 9, it can be seen that the cyan coupler of the present invention has a high relative activity and a good color image preservability even in a multilayer color light-sensitive material for photography (color negative film).

Couplers (IV) -3, (V) -3, (VI)
-3, (VII) -3, (IX) -3, (X) -3, (XI)-
3, (XII) -3, (XIII) -3, (XIV) -3, (XV)-
3, (XVI) -3, (XVII) -3, (XVIII) -3, (XIX)
About -3, almost the same result was obtained.

After a corona discharge treatment was applied to the surface of a paper support laminated on both sides with polyethylene, a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided, and various photographic constituent layers were further coated to form a layer structure shown below. Was prepared (sample 401). The coating solution was prepared as follows.

Preparation of coating solution for first layer 153.0 g of yellow coupler (ExY), 15.0 g of color image stabilizer (Cpd-1), color image stabilizer (Cpd-2)
7.5 g, 16.0 g of color image stabilizer (Cpd-3), 25 g of solvent (Solv-1), 25 g of solvent (Solv-2)
g and ethyl acetate (180 cc).
Emulsified dispersion A was prepared by emulsifying and dispersing in 1000 g of a 10% aqueous gelatin solution containing 60 cc of sodium dodecylbenzenesulfonate and 10 g of citric acid. On the other hand, silver chlorobromide emulsion A (cubic, 3: 7 mixture of large-size emulsion A having an average grain size of 0.88 μm and small-size emulsion A having an average grain size of 0.80 μm (silver molar ratio). , 0.08 and 0.10, respectively, and silver bromide in each size emulsion.
3 mol% was localized on part of the particle surface).
In this emulsion, blue-sensitive sensitizing dyes A and B shown below were used in an amount of 2.0.times.
10 ^-4 and for small size emulsion A, respectively.
5 × 10 ^-4 mol is added. The chemical ripening of this emulsion was carried out by adding a sulfur sensitizer and a gold sensitizer. The emulsified dispersion A and the silver chlorobromide emulsion A are mixed and dissolved,
A first layer coating solution was prepared so as to have the composition described below.

Preparation of Coating Solution for Fifth Layer 33.0 g of cyan coupler (ExC), 18.0 g of ultraviolet absorber (UV-2), color image stabilizer (Cpd-1) 3
0.0 g, color image stabilizer (Cpd-9) 15.0 g, color image stabilizer (Cpd-10) 15.0 g, color image stabilizer (Cp-9)
d-11) 1.0 g, color image stabilizer (Cpd-8) 1.0
g, color image stabilizer (Cpd-6) 1.0 g, solvent (Sol
v-6) 22.0 g of a solvent (Solv-1) and 1.0 g of a solvent were dissolved by adding 60.0 cc of ethyl acetate. This solution was added to 500 cc of a 20% aqueous gelatin solution containing 8 cc of sodium dodecylbenzenesulfonate. Emulsified dispersion C was prepared by emulsifying and dispersing with an ultrasonic homogenizer. On the other hand, silver chlorobromide emulsion C (cubic, average grain size 0.50
μm large size emulsion C and 0.41 μm small size emulsion C
1: 4 mixture with Ag mole ratio. The coefficient of variation of the grain size distribution was adjusted to 0.09 and 0.11, respectively, and 0.8 mol% of AgBr was locally contained in a part of the grain surface for each size emulsion.). This emulsion C contains a red-sensitive sensitizing dye E
Is 0.9 × 1 for large emulsion E per mole of silver.
^0-4 moles, and 1.1 × 10
^-4 mol is added. Further, 2.6 × 10 ^-3 mol of compound F is added per mol of silver halide. Emulsion C was chemically ripened by adding a sulfur sensitizer and a gold sensitizer. The above-mentioned emulsified dispersion and this red-sensitive silver chlorobromide emulsion C were mixed and dissolved, and a fifth layer coating solution was prepared so as to have the following composition.

Coating solutions for the second to fourth, sixth, and seventh layers were prepared in the same manner as the coating solution for the first layer. As a gelatin hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. The total amount of Cpd-14 and Cpd-15 was 25.
0 mg / m ² and 50 mg / m ² were added. The spectral sensitizing dye used for the silver chlorobromide emulsion in each photosensitive emulsion layer is shown below.

[0138]

[Table 10]

[0139]

[Table 11]

[0140]

[Table 12]

The blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer were treated with 1- (5-methylureidophenyl).
8.5 × 10 ^-5 mol, 7.7 × 10 ^-4 mol and 2.5 × 10 ^-4 mol of ^-5 -mercaptotetrazole were added per mol of silver halide, respectively. Further, 4-hydroxy-6-methyl-to-blue-sensitive emulsion layer and green-sensitive emulsion layer
1,3,3a, 7-Tetrazaindene were added in an amount of 1 × 10 ^-4 mol and 2 × 10 ^-4 mol, respectively, per mol of silver halide. To prevent irradiation, the following dyes were added to the emulsion layer (the values in parentheses indicate the coating amount).

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(Layer Structure) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver.

[0144]

[Table 13]

[0145]

[Table 14]

[0146]

[Table 15]

[0147]

[Table 16]

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(Preparation of Samples 402 to 407) Sample 401
The cyan coupler ExC was replaced with an equimolar number of the cyan coupler shown in Table 20 in place of EXC.
01.

First, each sample was exposed according to the method described in Example 1. The exposed sample was exposed to red light (sample 4) using a paper processor.
No. 01 was continuously processed (running test) until it was replenished in the next processing step (III) with twice the capacity of the tank for color development. After completion of the running test, samples 401 to 407 for evaluation were processed, and the color development and image fastness were evaluated in the same manner as in Example 1. The result
Table 20 summarizes them.

[0158]

[Table 17]

The composition of each processing solution is as follows.

[0160]

[Table 18]

[0161]

[Table 19]

[0162]

[Table 20]

Table 20 shows that even when a color developer from which benzyl alcohol was removed was used, the color paper using the coupler of the present invention was excellent in color developability and image fastness.

The pH of the bleach-fix solution in the processing step (III)
Was the same as the treatment step (III) except that
V) was carried out, and the maximum density value was used to determine the difference between the maximum density values in the processing in which the pH of the bleach-fixing solution was previously set to 6.0, and this was used as a measure of poor color reproduction. The results are shown in Table 21.

[0165]

[Table 21]

From these results, it can be seen that the light-sensitive material using the coupler of the present invention is excellent in poor recoloring even when a processing solution having bleaching ability with reduced oxidizing power is used.

(IV) -2, (V) -2, (VI) -2,
(VII) -2, (IX) -2, (X) -2, (XI) -2,
(XII) -2, (XIII) -2, (XIV) -2, (XV) -2,
(XVI) -2, (XVII) -2, (XVIII) -2, (XIX) -2
Approximately the same result was obtained for.

Example 5 Sample 601 of Example 6 described in JP-A-2-139544
A sample having the same configuration as that of the photosensitive material shown in FIG. Next, a sample was prepared in which the cyan couplers C-1, C-2, and C-3 of the fourth, fifth, and sixth layers of this sample were replaced with the couplers shown in Table 22. Was evaluated.

[0169]

[Table 22]

Further, C of the 16th and 17th layers of the above sample
-6 to an equimolar C-10, and the ninth to eleventh layers of C-
4. A sample was prepared in which C-8 was replaced with C-8 so that the total of C-7 was 80 mol%, and the same evaluation was performed. In this case, almost the same result was obtained.

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As described above, by using the cyan coupler of the present invention, the color reversal light-sensitive material can exhibit color developing properties,
It can be seen that the color image fastness is excellent.

(IV) -1, (V) -1, (VI) -1,
(VII) -1, (IX) -1, (X) -1, (XI) -1,
(XII) -1, (XIII) -1, (XIV) -1, (XV) -1,
(XVI) -1, (XVII) -1, (XVIII) -1, (XIX) -1
Approximately the same result was obtained for.

[0174]

The cyan image obtained from the coupler of the present invention has excellent light fastness and heat fastness. The silver halide color photographic light-sensitive material using the coupler of the present invention has a color image of light,
It is robust against heat, humidity and the like, and has an excellent effect that the dye formation rate and the maximum color density in the color developing solution are high, and they are sufficiently high especially in the color developing solution excluding benzyl alcohol. Further, according to such a silver halide color photographic light-sensitive material, a processing solution having a bleaching ability having a low oxidizing power (for example, a processing solution having a bleaching ability containing an EDTA iron (III) Na salt or an EDTA iron (III) NH ₄ salt) ) Or a processing method of a silver halide color photographic light-sensitive material which hardly causes a decrease in density when processed with a processing solution having a bleaching ability which is fatigued.

Claims (1)

(57) [Claims] 1. A silver halide color photographic light-sensitive material characterized in that at least one layer on a support contains at least one coupler represented by the following general formula (I). Embedded image (Wherein, R ¹ represents a hydrogen atom or a substituent, R ² represents a substituent, X represents a hydrogen atom or a group capable of leaving during a coupling reaction with an oxidized form of a color developing agent, and Z ¹ represents Represents a group of non-metallic atoms necessary to form a nitrogen-containing 6-membered heterocyclic ring, provided that the heterocyclic ring has at least one dissociating group and Z ¹ is —C (＝ O) —N (R) -C
It cannot be (＝ O) —NH— and the nitrogen-containing 6-membered heterocycle formed by Z ¹ has no further fused rings. R represents a substituent. )