JPH07122740B2 - Silver halide color photographic light-sensitive material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a cyan dye-forming coupler for color light-sensitive materials (hereinafter abbreviated as cyan coupler), particularly a sulfamoyl group at the 2-position and an amino group or a substituted amino group at the 5-position. The present invention relates to a silver halide color photographic light-sensitive material containing the novel 1-naphthol cyan coupler.

(Prior Art) An aromatic primary amine developer oxidized by color development after exposure of a silver halide photographic light-sensitive material reacts with a dye-forming coupler (hereinafter referred to as a coupler) to form a color image. It is formed.

Various requirements have been imposed on couplers used in silver halide color photographic light-sensitive materials in recent years. For example, excellent stability, excellent processability, excellent color development, excellent hue of color image, robust color image, inexpensive and excellent in manufacturing suitability. Being there.

Conventionally, a phenol coupler or a naphthol coupler has been used as a cyan coupler. Especially, the 1-naphthol coupler has an absorption maximum (λma
x) is a long wave, has little secondary absorption in the green region, is excellent in color reproduction, and many couplers with excellent color development are also found. Moreover, it is inexpensive and excellent in manufacturing suitability, and widely used in color negative photosensitive materials. Has been transformed.

However, phenol-type couplers and naphthol-type couplers, which have been widely used in the past, particularly 2-alkylcarbamoyl-1-naphthol-type couplers, bleaching or bleach-fixing solutions are tired or oxidized in the bleaching or bleach-fixing step of color development processing. If it has a weak force, it has a drawback that a sufficient color image cannot be obtained. This phenomenon is considered to be due to the reduction fading of the cyan dye due to ferrous ions generated in the bleaching or bleach-fixing process. Further, the cyan image formed by these couplers has a defect that the fastness is low.

The former drawback of the naphthol coupler is to change the substituent of the carbamoyl group at the 2-position from an alkyl group to an aryl group to give a 2-arylcarbamoyl-1-naphthol coupler (for example, described in US Pat. No. 3488193). However, the latter drawback is still insufficient with the use of the coupler, and the use of 100% of the coupler as a cyan coupler was not always preferable in terms of image storability.

On the other hand, US Pat. No. 4,333,999, JP-A-57-204543
In the phenol cyan couplers having a ureido group at the 2-position described in JP-A Nos. 57-204544, 57-204545, etc., the former two drawbacks have been solved, but these couplers are aromatic. Since the activity of the primary amine developing agent in the coupling reaction with the oxidant is low and the color developability is not sufficient, it cannot be said that it is suitable for recent high-sensitivity and high-quality color photographic light-sensitive materials.

Similarly, JP-A-60-237448, 61-145557 and 61-153.
In the 1-naphthol type cyan coupler having an amino group or a substituted amino group at the 5-position described in No. 640, the former two drawbacks have been solved, but the coloring property is higher than that of the conventional naphthol type cyan coupler. It was inferior in the low point.

(Object of the Present Invention) The first object of the present invention is to provide a silver halide color photographic light-sensitive material which is free from deterioration in cyan color density when processed with a bleaching or bleach-fixing solution which is tired or has a weak oxidizing power. Especially.

Secondly, the object of the present invention is to provide a silver halide color photographic light-sensitive material having high sensitivity and high image quality by improving the coloring property of a cyan coupler.

(Means for Achieving the Purpose) These objects of the present invention are represented by at least one of the following general formula [I] in a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support. Was achieved in a silver halide color photographic light-sensitive material characterized by containing a cyan dye-forming coupler.

General formula [I] In the formula, R ₁ represents a hydrogen atom —COR ₆ , —CO ₂ R ₈ or —SO ₂ R ₈ , and R ₆ and R ₈ are an aliphatic group having 1 to 30 carbon atoms or 6 to 30 carbon atoms. Represents an aromatic group. R ₂ is a group capable of substituting on a naphthalene ring, m is an integer of 0 to 3, R ₃ and R ₄ are each independently a hydrogen atom, an aliphatic group, or an aromatic group,
X represents a hydrogen atom or a group capable of splitting off by a coupling reaction with an oxidation product of an aromatic primary amine developing agent. Here, when m is plural, R ₂ may be the same or different.
R ₁ and R ₂ , R ₁ and X, or R ₃ and R ₄ may be bonded to each other to form a ring.

Here, the aliphatic group refers to a linear, branched, or cyclic alkyl group, alkenyl group, or alkynyl group, which may be substituted or unsubstituted. The aromatic group represents a substituted or unsubstituted aryl group, which may be a condensed ring. The heterocycle means a substituted or unsubstituted monocyclic or condensed ring heterocyclic group.

Next, each substituent in the general formula [I] will be described in detail below.

R ₂ represents a group capable of substituting on a naphthalene ring (including atoms, the same applies hereinafter), and representative examples thereof include a halogen atom, a hydroxy group, an amino group, a carboxy group, a sulfonic acid group, a cyano group, an aromatic group, and a heterocyclic group. , Carbonamide group, sulfonamide group, carbamoyl group, sulfamoyl group, ureido group, acyl group, acyloxy group, aliphatic oxy group, aromatic oxy group, aliphatic thio group, aromatic thio group, aliphatic sulfonyl group, aromatic Group sulfonyl groups, sulfamoylamino groups, nitro groups, imide groups and the like can be mentioned, and the number of carbon atoms contained in R ₂ is 0-30. An example of cyclic R ₂ when m = 2 is a dioxymethylene group.
Examples of the combination of R ₁ and R ₂ include 2-hydroxynaphthoxazole, 2-hydroxynaphthoimidazole and 2
-Hydroxynaphthopyrrole and the like.

R ₃ and R ₄ are each independently a hydrogen atom or a carbon atom number of 1 to 36.
Or an aromatic group having 6 to 36 carbon atoms. R ₃ and R ₄ may combine with each other to form a nitrogen-containing heterocycle (eg, morpholine ring, piperidine ring, pyrrolidine ring, etc.).

X represents a hydrogen atom or a coupling-off group (including a leaving atom; the same applies hereinafter). Examples of coupling-off groups include halogen atoms (fluorine atom, chlorine atom, bromine atom,
Iodine atom, etc.), thiocyanato group, -OR ₉ , -SR ₉ , -NHCOR ₉ , Aromatic azo group having 6 to 30 carbon atoms and 1 to 30 carbon atoms
And a heterocyclic group (for example, a succinimide group, a phthalimido group, a hydantoinyl group, a pyrazolyl group, an imidazolyl group, a triazolyl group, a 2-benzotriazolyl group, etc.) which is bonded to the coupling active position of the coupler with a nitrogen atom. , R ₉ represents an aliphatic group having 1 to 30 carbon atoms, an aromatic group having 6 to 30 carbon atoms, or a heterocyclic group having 2 to 30 carbon atoms.

Examples of the aliphatic group in the present invention include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a t-butyl group, a cyclohexyl group,
2-ethylhexyl group, n-octyl group, n-decyl group, n-dodecyl group, 3,5,5-trimethylhexyl group,
t-octyl group, n-tetradecyl group, adamantyl group, n-hexadecyl group, 2-hexyldecyl group, n-
Octadecyl group, vinyl group, allyl group, 5-hexenyl group, oleyl group, crotyl group, trifluoromethyl group,
Trichloromethyl group, hydroxyethyl group, methoxyethyl group, benzyl group, phenethyl group, phenoxyethyl group, propargyl group, phthalimidomethyl group, methylthioethyl group, methylsulfonylethyl group, carboxymethyl group, hydroxymethyl group, carboxymethylthioethyl group, Methoxyethoxycarbamoylmethyl group, 3-
Decyloxypropyl group, 3-dodecyloxypropyl group, 3- (2,4-di-t-pentylphenoxy) propyl group, 4- (2,4-di-t-pentylphenoxy) butyl group, 3- (2-ethylhexyloxy) propyl group and the like.

Examples of the aromatic group in the present invention include phenyl group, tolyl group, 4-chlorophenyl group, 4-t-butylphenyl group, 4-nitrophenyl group, 2-acetamidophenyl group, 4-dodecylphenyl group, 4- ( 4-hydroxyphenylsulfonyl) phenyl group, pentafluorophenyl group, 2,4,6-trichlorophenyl group, 3,5-didodecyloxycarbonylphenyl group, 4-t-octylphenyl group, 4- Cyanophenyl group, 4-methoxyphenyl group, 4-dodecyloxyphenyl group, 2-tetradecyloxyphenyl group, 3-hydroxyphenyl group, 4-hydroxyphenyl group, 2-chloro-5-dodecyloxycarbonyl group Phenyl group, 5-tetradecyloxycarbonyl-2-methoxyphenyl group, 1-naphthyl group, 2-
There are naphthyl groups and the like.

Examples of the heterocyclic group in the present invention include pyrrolidino group, piperidino group, morpholino group, hydantoinyl group, succinimide group, phthalimido group, pyrazolyl group, imidazolyl group, triazolyl group, 2-pyridyl group, 4-pyridyl group, 2 -Furyl group, 2-thienyl group, 2-benzotriazolyl group and the like.

Next, specific examples of each substituent of the compound represented by formula (I) are shown below.

Examples of R ₁ are aliphatic or aromatic acyl groups (eg, acetyl group, trifluoroacetyl group, 2-ethylhexanoyl group, dodecanoyl group, benzoyl group, perfluorobenzoyl group, p-nitrobenzoyl group, p-chloro). Benzoyl group, etc.), aliphatic or aromatic sulfonyl group (for example, methylsulfonyl group, n-butylsulfonyl group, n-dodecylsulfonyl group, trifluoromethylsulfonyl group, phenylsulfonyl group, p-tolylsulfonyl group, p -Dodecylphenylsulfonyl group, etc.),
Or an aliphatic oxycarbonyl group (for example, methoxycarbonyl group, ethoxycarbonyl group, n-butoxycarbonyl group, i-butoxycarbonyl group, benzyloxycarbonyl group, 2-ethyloxycarbonyl group, n-octyloxycarbonyl group, n-dodecyl Oxycarbonyl group, etc.) and the like.

Examples of R ₂ include a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, etc.), aliphatic group (eg, methyl group, i-
Propyl group, t-butyl group, sec-butyl group, cyclopentyl group, cyclohexyl group, etc., nitro group, cyano group, carbonamido group (eg acetamide group, trifluoroacetamido group, benzamide group etc.), sulfonamide group (eg Methylsulfonamide group, trifluoromethylsulfonamide group, p-tolylsulfonamide group, etc.), acyl group (eg acetyl group, benzoyl group etc.), aliphatic oxy group (eg methoxy group, benzyloxy group, ethoxy group etc.) Etc.

Examples of amino group, N, N-dimethylamino group, N, N-
Diethylamino group, N, N-dibutylamino group, N, N-dihexylamino group, N, N-dioctylamino group, N-octadecyl-N-methylamino group, pyrrolidino group, morpholino group, piperidino group, N-methylamino group Group, N-ethylamino group, N-butylamino group, N-cyclohexylamino group, N- (2-ethylhexyl) amino group, N-
Dodecylamino group, N-tetradecylamino group, N-hexadecylamino group, N-octadecylamino group, N-
[3- (2-Ethylhexyloxy) propyl] amino group, N- (3-decyloxypropyl) amino group, N-
(3-dodecyloxypropyl) amino group, N- [3-
(2,4-Di-t-pentylphenoxy) propyl] amino group, N- [4- (2,4-di-t-pentylphenoxy) butyl] amino group, N-phenylamino group, N-
(2-tetradecyloxyphenyl) amino group, N-
(4-tetradecyloxyphenyl) amino group, N-
(3,5-di-dodecyloxycarbonylphenyl) amino group, N- (2-chloro-5-dodecyloxycarbonylphenyl) amino group, N- (2-chloro-5-tetradecanamidophenyl) amino group , N- (2-butoxyphenyl) amino group and the like.

Examples of X include a hydrogen atom, a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, etc.), an aliphatic oxy group (eg, methoxy group, ethoxy group, methoxyethoxy group, hydroxyethoxy group, 3-hydroxypropyl group, 2-
(2-hydroxyethoxy) ethoxy group, carboxymethoxy group, 1-carboxyethoxy group, 1-triazolylmethyl group, 2-carboxyethoxy group, 3-carboxypropoxy group, N-methoxyethoxycarbamoylmethoxy group, methylsulfonylethoxy group Group, methylsulfonamide ethoxy group, 2- (carboxymethylthio) ethoxy group, 2- (1-carboxytridecylthio) ethoxy group, etc.), aromatic oxy group (for example, phenoxy group, 4
-Nitrophenoxy group, 2-nitrophenoxy group, 4-
Methylsulfonamidophenoxy group, 2-acetamidophenoxy group, etc.), aliphatic thio group (methylthio group, hydroxyethylthio group, carboxymethylthio group, 1-carboxyethylthio group, 2-carboxyethylthio group,
3-carboxypropylthio group, n-dodecylthio group,
1-carboxytridecylthio group, etc.), aromatic thio group (for example, phenylthio group, p-nitrophenylthio group,
p-carboxyphenylthio group, 4-methylsulfonamidophenylthio group, p-dodecylphenylthio group, etc.), heterocyclic thio group (1-phenyl-1,2,3,4-tetrazol-5-ylthio group) Group, 1-ethyl-1,2,3,4-tetrazol-5-ylthio group, 1- (4-hydroxyphenyl) -1,2,3,4-tedrazol-5-ylthio group, 5
-Methyl-1,3,4-oxadiazol-2-ylthio group, 5-methylthio-1,3,4-thiadiazol-2-ylthio group, 5-methyl-1,3,4-thiadiazol-2-
Ilthio group, 5-phenyl-1,3,4-oxadiazol-2-ylthio group, benzoxazol-2-ylthio group, benzothiazol-2-ylthio group, 1-methylbenzimidazol-2-ylthio group, 4 -Pyridylthio group, etc.), aromatic azo group (for example, phenylazo group, 4-methoxyphenylazo group, 3,4-dimethoxyphenylazo group, 4-pivaloylaminophenylazo group, 1-naphthylazo group, 2 -Ethoxycarbonylphenylazo group, etc.), a heterocyclic group (eg, succinimide group, phthalimido group, 3-hydantoinyl group, pyrazolyl group, imidazolyl group, 2-benzotriazolyl group, etc.) and the like.

Next, the substituents preferably used in the present invention will be described.

In (R ₂ ) m, preferably m = 0, and then m =
It is preferable that R _{2 in} 1 is a fluorine atom, a chlorine atom, a cyano group or a trifluoromethyl group. The substituent R ₂ is R ₁ NH
Is preferably in the second or fourth position.

Preferably, one of R ₃ and R ₄ is a hydrogen atom and the other is an aliphatic group.

X is preferably a hydrogen atom, a halogen atom, an aliphatic oxy group, an aliphatic thio group or a heterocyclic thio group.

The coupler represented by the general formula [I] has substituents R ₁ , R ₂ ,
A dimer or a multimer of R ₃ , R ₄ or X, which is bonded via a divalent or divalent or higher polyvalent group, may be formed. In this case, the number of carbon atoms shown in each of the above substituents may be out of the range. When the coupler represented by the general formula [I] forms a multimer,
A typical example is a homopolymer or copolymer of an addition-polymerizable ethylenically unsaturated compound (cyan color-forming monomer) having a cyan dye-forming coupler residue. In this case, the multimer contains a repeating unit represented by the general formula [III], and one or more cyan color-forming repeating units represented by the general formula [III] may be contained in the monomer. It may be a copolymer containing one or more non-color-forming ethylene-like monomers.

General formula (III) In the formula, R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a chlorine atom, A represents -CONH-, -COO- or a substituted or unsubstituted phenylene group, and B represents a substituted or unsubstituted alkylene group. Group, a phenylene group or an aralkylene group, L is -CONH-, -NHCONH-, -NHCOO-, -N
HCO-, -OCONH-, -NH-, -COO-, -OCO-, -CO
-, - O -, - SO 2 -, - NHSO 2 - or represents a -SO ₂ NH-. a, b, and c represent 0 or 1. Q represents a cyan coupler residue in which a hydrogen atom other than the hydrogen atom of the hydroxyl group at the 1-position is eliminated from the compound represented by the general formula [I].

As the multimer, a copolymer of a cyan color-forming monomer giving a coupler unit of the general formula [III] and the following non-color-forming ethylene-like monomer is preferable.

As the non-color-forming, ethylene-like monomer that does not couple with the oxidation product of the aromatic primary amine developing agent, acrylic acid,
α-Chloroacrylic acid, α-alkylacrylic acid (eg methacrylic acid) Esters or amides derived from these acrylic acids (eg acrylamide, methacrylamide, n-butylacrylamide, t)
-Butylacrylamide, N- (1,1-dimethyl-2-
(Sulfonate ethyl) acrylamide, diacetone acrylamide, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl acrylate, iso-butyl acrylate, 2-ethylhexyl acrylate, 3-sulfonate propyl acrylate, n- Octyl acrylate,
Lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and β-
Hydroxymethacrylate,), vinyl esters (eg vinyl acetate, vinyl propionate and vinyl laurate), acrylonitrile, methacrylonitrile, aromatic vinyl compounds (eg styrene and its derivatives, eg vinyltoluene, divinylbenzene, vinylacetophenone). And sulfonate styrene), 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. -Vinyl pyridine and the like.

In order to obtain a lipophilic polymer coupler, acrylic acid ester, methacrylic acid ester, maleic acid ester and vinylbenzene are particularly preferable as the non-color forming ethylene-like monomer. Two or more kinds of the non-color-forming ethylenic 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.

Further, in order to obtain a neutral or alkaline water-soluble hydrophilic polymer coupler, N- (1,1-dimethyl-2-
Sulfonate ethyl) acrylamide, 3-sulfonate propyl acrylate, sodium styrene sulfonate, potassium styrene sulfonate, acrylamide,
It is preferable to use a hydrophilic non-color-forming ethylene-like monomer such as methacrylamide, acrylic acid, methacrylic acid, N-vinylpyrrolidone, N-vinylpyridine as a copolymerization component.

As well known in the field of polymer couplers, the above general formula [III]
An ethylenically unsaturated monomer for copolymerization with a vinylic monomer corresponding to the physical and / or chemical properties of the copolymer formed, such as solubility, binder of a photographic colloid composition, such as It can be selected so that its compatibility with gelatin, its flexibility, thermal stability, etc. are favorably influenced.

Cyan polymer coupler used in the present invention A lipophilic polymer coupler obtained by polymerization of a vinylic monomer which gives a coupler unit represented by the general formula [III] is dissolved in an organic solvent to prepare a latex solution in a gelatin aqueous solution. It may be prepared by emulsifying and dispersing in the form, or may be prepared directly by the emulsion polymerization method.

U.S. Pat.No. 3,451, for a method of emulsifying and dispersing a lipophilic polymer coupler in the form of a latex in an aqueous gelatin solution.
820, U.S. Pat.No. 4,080,211 for emulsion polymerization,
The method described in No. 3,370,952 can be used.

The hydrophilic polymer coupler can be added to the coating solution as an aqueous solution, and is also a mixed solvent of water and an organic solvent miscible with water such as lower alcohol, tetrahydrofuran, acetone, ethyl acetate, cyclohexanone and ethyl lactate. It can also be dissolved in and added. Further, it may be added after being dissolved in an alkaline aqueous solution or an organic solvent containing alkaline water. A small amount of surfactant may be added.

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

Next, a synthesis example of the cyan dye-forming coupler of the present invention is shown below.

Synthesis Example 1 Synthesis of Exemplified Coupler (7) 5-Amino-1-naphthol-2-sulfonic acid 60 g obtained by reaction of 5-amino-1-naphthol and sulfuric acid
Acetonitrile (500 ml) was added to sodium acetate (46 g) and acetic anhydride (250 ml) was added dropwise with heating under reflux, and the mixture was further refluxed for 3 hours. The reaction solution was cooled and the precipitated crystals were dried in excess to give 109 g of 5-acetamido-1-acetoxynaphthalene-2-sulfonic acid crude crystals.

To 60 g of 5-acetamido-1-acetoxynaphthalene-2-sulfonic acid, 100 ml of dimethylacetamide and 300 ml of acetonitrile were added, and phosphorus oxychloride was added while stirring at 40 ° C.
20 ml was added dropwise. After stirring for 2 hours, the reaction solution was added to 3 l of ice water with stirring. The precipitated crystals are washed with water, washed with water, and dried to give 5-acetamido-1-acetoxynaphthalene-
35 g of 2-sulfonyl chloride was obtained.

17.1 g of 5-acetamido-1-acetoxynaphthalene-2-sulfonyl chloride was dissolved in 100 ml of dimethylacetamide, and 12.2 g of 3-dodecyloxypropylamine was added dropwise at room temperature. The reaction solution was stirred at 50 ° C for 3 hours and then cooled.
300 ml of water was added, and 200 ml of ethyl acetate was added for extraction.
The ethyl acetate layer was washed with 300 ml of water, dried and concentrated.
Next, 300 ml of ethanol was added to the concentrate to dissolve it, and an aqueous solution of 6 g of sodium hydroxide was added with stirring at room temperature, followed by stirring for 1 hour. A solution of concentrated hydrochloric acid (15 ml) in water (200 ml) was added dropwise to the reaction solution. 18.7 g of the target Exemplified Compound (7) was obtained by filtering the precipitated crystals and recrystallizing them from acetonitrile.
Obtained. Melting point 118 to 120 ° C. Synthesis Example 2 Synthesis of Exemplified Coupler (8) Exemplified Coupler (7) 9.9 g, concentrated hydrochloric acid 8.4 ml and ethanol 1
00 ml was added and the mixture was heated under reflux for 5 hours. The reaction solution was cooled and a sodium hydroxide aqueous solution was added dropwise for neutralization, and then 100 ml of water was added little by little. The precipitated crystals were washed with water, dried and dried. 9 g of the obtained crystal was dissolved in 80 ml of dimethylacetamide, 2.9 g of isobutyl chlorocarbonate was added dropwise with stirring at room temperature, and the mixture was further stirred for 2 hours. 200 ml of water was added to the reaction solution, and the precipitated crystals were filtered and recrystallized from acetonitrile to obtain 8.9 g of the desired exemplary coupler (8). Melting point 71 to 72 ° C. Synthesis example 3 Synthesis of exemplified coupler (14) 5-acetamido-1-acetoxynaphthalene-2-sulfonyl chloride (54.7 g) was added with acetonitrile (147 ml) and heated under reflux with diisopropylamine (32 ml). The precipitated crystals are filtered off, washed with acetonitrile and then with water, and dried to give 5-acetamide-
28 g of 2 (N, N-diisopropylsulfamoyl) -1-naphthol was obtained.

Dissolve 28 g of sodium hydroxide in 260 ml of water, then
28 g of acetamido-2- (N, N-diisopropylsulfamoyl) -1-naphthol was added, and the mixture was heated under reflux for 6 hours. The reaction mixture is cooled, acetic acid is added to adjust the pH to 6, and the precipitated crystals are washed with water, dried and washed with 5-amino-2-
21.8 g of (N, N-diisopropylsulfamoyl) -1-naphthol was obtained.

5-Amino-2- (N, N-diisopropylsulfamoyl) -1-naphthol (12.9 g) was added to dimethylacetamide (80 m).
l-octyl chlorocarbonate (8.5 g) was added dropwise to the solution while stirring at room temperature. After stirring for 5 hours, add 300 ml of water and add 200 ml.
It was extracted with ethyl acetate. The ethyl acetate layer was washed twice with 200 ml of water and then concentrated, and 150 ml of acetonitrile was added for crystallization. 14.8 g of the target Exemplified Compound (14) was obtained by over-drying the precipitated crystals. Melting point 110-112.
5 ° C. The cyan coupler of the present invention can be added to both photosensitive and non-photosensitive layers of a light-sensitive material, and when added to a photosensitive layer, any of a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer can be used. Can be added to the layer, but especially red-sensitive layer (red-sensitive silver halide emulsion layer)
Is preferred.

The addition amount of the cyan coupler of the present invention to the light-sensitive material is 0.01 to
1 g / m ^2, preferably from 0.05 to 0.5 g / m ^2, more preferably 0.1
~ 0.3 g / m ² .

The cyan couplers of the present invention may be used as a mixture of two or more kinds, and other known cyan couplers such as 2-alkylcarbamoyl-1-naphthol cyan couplers, 2
-Arylcarbamoyl-1-naphthol cyan couplers and 2-ureidophenol cyan couplers (for example, U.S. Pat. No. 4,333,999, JP-A-57-204543, 57-2).
No. 04544 and No. 57-204545, etc.).

The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is silver iodobromide, silver iodochloride or silver iodochlorobromide containing about 30 mol% or less of silver iodide.
Particularly preferred is silver iodobromide containing from about 2 mol% to about 25 mol% silver iodide.

The silver halide grains in a photographic emulsion have regular crystal forms such as cubes, octahedra and tetradecahedrons, irregular crystal forms such as spheres and plates, and twin planes. It may have a crystal defect such as, or a composite form thereof.

The grain size of silver halide may be fine grains having a diameter of about 0.1 micron or less or large grains having a projected area diameter of up to about 10 microns, and may be a polydisperse emulsion or a monodisperse emulsion.

The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (RD), No. 17643 (1978.
December), pages 22-23, I. Emulsion preparation
and types) ”and ibid., No. 18716 (November 1979), 64
P.Glafkides, Chimie et Physique Photograp, "Physics and Chemistry of Photography" by Graphide, page 8.
hique Paul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Forcal Press (GFDuffin, Photograhic
Emulsion Chemistry (Focal Press, 1966), "Production and Coating of Photographic Emulsions" by Zelikman et al., VLZelikman et al, Making and Coating Photogra
Phic Emulsion, Focal Press, 1964) and the like.

Monodisperse emulsions described in US Pat. Nos. 3,574,628 and 3,655,394 and British Patent 1,413,748 are also preferable.

Further, tabular grains having an aspect ratio of about 5 or more can be used in the present invention. Tabular grains are described by Gatov, Gutoff, Photographic Science and Engineering,
Volume 14, Pages 248-257 (1970); U.S. Pat. No. 4,434,226.
No. 4,414,310, No. 4,433,048, No. 4,439,520, and British Patent No. 2,112,157, and the like.

The crystal structure may be uniform, may have different halogen compositions inside and outside, or may have a layered structure. Further, silver halides having different compositions may be joined by epitaxial joining, or may be joined with compounds other than silver halides such as silver rhodanide and lead oxide.

Also, a mixture of particles having various crystal forms may be used.

The silver halide emulsion is usually one which has been physically ripened, chemically ripened and spectrally sensitized. Additives used in such processes are Research Disclosure No.176.
43 and No. 18716, and the relevant parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above-mentioned two research disclosures, and the locations described in the table below are shown.

Various color couplers can be used in the present invention, specific examples of which are described in the patents described in Research Disclosure (RD) No. 17643, VII-CG.

Examples of the yellow coupler include, for example, U.S. Pat.
No. 501, No. 4,022,620, No. 4,326,024, No. 4,40
Those described in 1,752, JP-B-58-10739, British Patents 1,425,020, 1,476,760 and the like are preferable.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat. No. 4,310,
619, 4,351,897, European Patent 73,636, U.S. Patents 3,061,432, 3,725,067, Research Disclosure No. 24220 (June 1984), JP-A-60-33552.
Issue, Research Disclosure No. 24230 (6 June 1984)
JP-A-60-43659, U.S. Pat. Nos. 4,500,630 and 4,540,654 are particularly preferable.

Examples of cyan couplers that can be used in combination with the cyan coupler of the present invention include phenol type and naphthol type couplers, and U.S. Pat.Nos. 4,052,212, 4,146,396, 4,228,233, 4,296,200, and 2,369,929. ,
No. 2,801,171, No. 2,772,162, No. 2,895,826
No. 3, No. 3,772,002, No. 3,758,308, No. 4,334,01
No. 1, 4,327,173, West German Patent Publication No. 3,329,729,
European Patent 121,365A, U.S. Patent 3,446,622, and
Those described in 4,333,999, 4,451,559, 4,427,767, etc. are preferable.

Colored couplers for correcting unwanted absorption of color forming dyes are Research Disclosure No. 17643 VII-
Section G, U.S. Pat. No. 4,163,670, Japanese Patent Publication No. 57-39413, U.S. Pat. Nos. 4,004,929, 4,138,258, and British Patent 1,14.
Those described in 6,368 are preferable.

As the coupler in which the color forming dye has an appropriate diffusibility, those described in U.S. Pat. No. 4,366,237, British Patent 2,125,570, European Patent 96,570 and West German Patent (Publication) 3,234,533 are preferable.

Typical examples of polymerized dye-forming couplers are U.S. Pat.Nos. 3,451,820, 4,080,211 and 4,367,282.
No. 2,102,173 and the like.

A coupler which releases a photographically useful residue upon coupling is also preferably used in the present invention. The DIR coupler which releases the development inhibitor is RD17643, the patents described in the paragraphs VII to F, JP-A-57-151944, 57-154234 and 60.
-184248, those described in U.S. Pat. No. 4,248,962 are preferred.

Examples of couplers that release an image-like nucleating agent or a development accelerator during development include British Patent Nos. 2,097,140 and 2,13.
Those described in 1,188, JP-A-59-157638 and JP-A-59-170840 are preferable.

Other couplers that can be used in the light-sensitive material of the present invention include competitive couplers described in U.S. Pat.No. 4,130,427, U.S. Pat.Nos. 4,283,472, 4,338,393, and
Multiequivalent couplers described in 4,310,618 and the like, JP-A-60-1859
50 and the like, and DIR redox compound releasing couplers and the couplers described in EP 173,302A, which release dyes that recover color after withdrawal.

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

Examples of the high boiling point organic solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027.

The steps of the latex dispersion method, effects, and specific examples of the latex for impregnation are described in US Pat. No. 4,199,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.

Suitable supports that can be used in the present invention include, for example, the aforementioned R
Page 28 of D.No.17643 and page 647 of the same, No.18716 From right column 6
See page 48, left column.

The color photographic light-sensitive material according to the present invention has the above-mentioned RD, No. 1
Development can be carried out by a usual method described in pages 28 to 29 of 7643 and 651 left column to right column of No. 18716.

The color developing solution used for the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. Although aminophenol compounds are also useful as the color developing agent, p-phenylenediamine compounds are preferably used, and typical examples thereof include 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-N-
Examples include β-methoxyethylaniline and their sulfates, hydrochlorides or P-toluenesulfonates. Two or more of these compounds can be used in combination depending on the purpose.

The color developer contains a pH buffer such as an alkali metal carbonate, borate or phosphate, a bromide salt, an iodide salt, a benzimidazole, a benzothiazole or a mercapto compound or a development inhibitor or a fog. Generally, it contains an inhibitor and the like. If necessary, hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenylsemicarbazides, triethanolamine, catecholsulfonic acids, triethylenediamine (1,4-diazabicyclo [2,2,2] octane) Various preservatives such as, 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, fogging agents such as sodium boron hydride. Agent, 1-
Auxiliary developing agents such as phenyl-3-pyrazolidone, tackifiers, 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 their salts can be mentioned as representative examples.

When the reversal process is performed, black and white development is usually performed before color development. In this black-and-white developing solution, 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. Alternatively, they can be used in combination.

The color developing solution and the black and white developing solution generally have a pH of 9 to 12. The replenishment amount of these developers is
Although it depends on the color photographic light-sensitive material to be processed, it is generally 3 l or less per 1 m 2 of the light-sensitive material and can be reduced to 500 ml or less by reducing the bromide ion concentration in the replenisher. When the replenishment amount is reduced, the contact area with the air in the processing tank is reduced to evaporate the liquid,
It is preferable to prevent air oxidation. Further, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developing solution.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. Further, in order to speed up the processing, a processing method of bleach-fixing processing after bleaching processing may be used. Further processing with two continuous bleach-fix baths,
The fixing treatment before the bleach-fixing treatment or the bleaching treatment after the bleach-fixing treatment can be optionally carried out according to the purpose.
As the bleaching agent, compounds of polyvalent metals such as iron (III), cobalt (III), chromium (VI), copper (II), peracids, quinones, nitro compounds and the like are used. Typical bleaching agents include ferricyanide; dichromate; iron (II
I) or cobalt (III) organic complex salts such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexyldiaminetetraacetic acid, methyliminodiacetic acid, 1,3
-Aminopolycarboxylic acids such as diaminopropane tetraacetic acid and glycol ether diamine tetraacetic acid or complex salts such as citric acid, tartaric acid and malic acid; persulfates; bromates; permanganates; nitrobenzenes and the like can be used. it can. Of these, aminopolycarboxylic acid iron (II) including ethylenediaminetetraacetic acid iron (III) complex salts
I) Complex salts and persulfates are preferable from the viewpoint of rapid processing and prevention of environmental pollution. Furthermore, iron (III) aminopolycarboxylate
Complex salts are particularly useful in both bleaching solutions and bleach-fixing solutions. The pH of the bleaching solution or bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 5.5 to 8, but a lower pH can be used for speeding up the processing.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath. Specific examples of useful bleach accelerators are described in the following specifications: US Pat. No. 3,893,858, West German Patents 1,290,812, 2,059,988.
No. 53 / 32,736, 53-57,831, 53-37,418
No. 53, 72, 623, No. 53-95, 630, No. 53-95, 631,
53-104,232, 53-124,424, 53-141,623,
53-28,426, Research Disclosure No.17,129
Compounds having a mercapto group or a disulfide group described in JP-A No. 1978, July 1978; thiazolidine derivatives described in JP-A Nos. 50-140,129; JP-B-45-8,506 and JP-A-52-2.
0,832, 53-32,735, thiourea derivatives described in US Pat. No. 3,706,561; West German Patent No. 1,127,715, JP-A-5
Iodide salts described in 8-16,235; West German Patent No. 966,410,
Polyoxyethylene compounds described in No. 2,748,430;
Polyamine compounds described in JP-B-45-8,836; Other JP-A-49-42,434, 49-59,644, 53-94,927, 54-
Compounds described in Nos. 35,727, 55-26,506, and 58-163,940; bromide ion and the like can be used. Among them, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of a large accelerating effect, and the compounds described in U.S. Pat. No. 3,893,858, West German Patent 1,290,812 and JP-A-53-95,630 are particularly preferable. Further, the compounds described in US Pat. No. 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color light-sensitive material for photographing.

Examples of the fixing agent include thiosulfates, thiocyanates, thioether compounds, thioureas, and a large amount of iodide salts, but thiosulfates are generally used, and ammonium thiosulfate is the most widely used. Can be used for As a preservative for the bleach-fix solution, sulfite, bisulfite or carbonyl bisulfite adduct is preferable.

The silver halide color photographic light-sensitive material of the present invention is generally washed with water and / or stabilized after the desilvering process.
The amount of rinsing water in the rinsing process depends on the characteristics of the light-sensitive material (for example, depending on the materials used such as couplers), application, and further, the rinsing water temperature, the number of rinsing tanks (steps), countercurrent, normal flow replenishment method, etc. It can be set in a wide range according to various conditions.
Of these, the relationship between the number of washing tanks and the water volume in the multi-stage countercurrent system is described in the Journal of the Society of Motion Picture a
nd Television Engineers Volume 64, P.248-253 (May 1955)
It can be obtained by the method described in (Month issue).

According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate, and the suspended matter produced adheres to the photosensitive material, etc. Problem arises. In the color light-sensitive material of the present invention, Japanese Patent Application No.
The method for reducing calcium ion and magnesium ion described in 61-131,632 can be used very effectively. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8,542, chlorine-based bactericides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., Hiroshi Horiguchi "Chemistry of antifungal agents" The sterilizing agents described in "Microbial Sterilization, Sterilization, and Antifungal Technologies" edited by the Society of Hygiene Technology and "Encyclopedia of Antibacterial and Antifungal Agents" edited by Japan Society for Antibacterial and Antifungal Agents can also be used.

The pH of washing water in the processing of the light-sensitive material of the present invention is 4-9.
And preferably 5-8. The washing water temperature and washing time can be variously set depending on the characteristics and use of the light-sensitive material, but in general, the range is 20 seconds to 10 minutes at 15-45 ° C, and preferably 30 seconds to 5 minutes at 25-40 ° C. To be selected. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such stabilization treatment, Japanese Patent Laid-Open No.
All known methods described in Nos. -8,543, 58-14,834 and 60-220,345 can be used.

Further, there is a case where a stabilizing treatment is further performed after the water washing treatment, and an example thereof is a stabilizing bath containing formalin and a surfactant, which is used as a final bath of a color light-sensitive material for photographing. . Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow solution accompanying the above washing with water and / or supplementation of the stabilizing solution can be reused in other steps such as the desilvering step.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents. For example, indaniline compounds described in U.S. Pat.No. 3,342,597, No. 3,342,599, Schiff base type compounds described in Research Disclosure Nos. 14,850 and 15,159, aldol compounds described in No. 13,924, and U.S. Pat.No. 3,719,492 described. Metal salt complex of
The urethane compound described in 3-135,628 can be mentioned.

The silver halide color light-sensitive material of the present invention contains various 1-phenyl-type light-sensitive materials for the purpose of promoting color development, if necessary.
You may incorporate 3-pyrazolidones. Typical compounds are JP-A-56-64,339, JP-A-57-144,547, and JP-A-58-11.
No. 5,438 is listed.

The various treatment liquids in the present invention are used at 10 ° C to 50 ° C. Normally, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature accelerates the processing to shorten the processing time, and a lower temperature lowers the image quality to improve the stability of the processing liquid. be able to. Further, in order to save silver in the light-sensitive material, processing using cobalt intensification or hydrogen peroxide intensification described in West German Patent No. 2,226,770 or US Pat. No. 3,674,499 may be performed.

The present invention can be applied to various color light-sensitive materials. Typical examples include carnega films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers. The present invention also relates to Research Disclosure 17123 (July 1978).
It is also applicable to a black and white light-sensitive material using a mixture of three-color couplers described in (Mon.).

[Examples] The present invention is described in detail below with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1 Samples 101 to 110, which are light-sensitive materials each having the following composition, were prepared on a cellulose triacetate film support.

(Sample 101) First layer: Red-sensitive emulsion layer Silver iodobromide emulsion (5 mol% silver iodide, average grain size 0.4 μ) Silver coating amount 1.79 g / m ² Sensitizing dye I 4.5 per 1 mol silver × 10 ^-4 mol Sensitizing dye II 1.5 mol to 1 mol silver × 10 ^-4 mol Coupler A 0.06 mol to 1 mol silver Dibutyl phthalate Coupler 0.6 g to 1 g Second layer: protective layer Polymethylmethacrylate particles Gelatin layer containing (about 1.5 μm in diameter) In addition to the above composition, a gelatin hardening agent H-1 and a surfactant were added to each layer.

The sample manufactured as described above was designated as Sample 101.

Samples 102 to 110 are each a coupler B, a coupler C, a coupler D, a coupler (1), instead of the coupler A of the sample 101.
It was prepared in the same manner as in Sample 101, except that the coupler (2), the coupler (3), the coupler (4), the coupler E and the coupler (20) were added in equimolar amounts to the coupler A.

Compound used to prepare the sample Sensitizing dye I: Anhydro-5,5'-dichloro-3,3'-di-
(Γ-Sulfopropyl) -9-ethyl-thiacarbocyanine hydroxide / pyridinium salt Sensitizing dye II: anhydro-9-ethyl-3,3′-di- (γ
-Sulfopropyl) -4,5,4 ', 5'-dibenzothiacarbocyanine hydroxide triethylamine salt coupler A Coupler B JP-A-60-237448 Exemplified Compound (2) Coupler C JP-A-60-237448 Exemplified Compound (3) Coupler D JP-A-61-153640 Exemplified Compound (8) Coupler E Included in U.S. Pat. No. 4,333,999 H-1 (CH ₂ = CHSO ₂ CH ₂ CONHCH _{2 2 The} obtained samples 101 to 110 were exposed for sensitometry and then developed as described below [A] 38. Performed at ℃.

1. Color development 3 minutes 15 seconds 2. Bleaching 6 minutes 30 seconds 3. Water washing 3 minutes 15 seconds 4. Fixing 4 minutes 20 seconds 5. Water washing 3 minutes 15 seconds 6. Stability 1 minute 5 seconds Each treatment The composition of the treatment liquid used in the process is as follows.

Color developer Sodium nitrilotriacetate 1.0g Sodium sulfite 4.0g Sodium carbonate 30.0g Potassium bromide 1.4g Hydroxylamine sulfate 2.4g 4- (N-ethyl-N-β-hydroxyethylamino)
2-Methylaniline sulfate 4.5g Water added 1 Bleach Ammonium bromide 160.0g Ammonia water (28%) 25.0ml Ethylenediamine-tetraacetic acid sodium iron salt 130.0g Glacial acetic acid 14.0ml Water added 1 Fixer Tetra Sodium polyphosphate 2.0g Sodium sulfite 4.0g Ammonium thiosulfate (70%) 175.0ml Sodium bisulfite 4.6g Add water 1 Stabilizer Formalin 8.0ml Add water 1 Next, bleaching during development [A] The development treatment [B] was performed in the same manner as the development treatment [A] except that the treatment liquid for the treatment was changed to the following treatment liquid formulation. This bleaching solution is a schematic reproduction of a state in which the processing solution is fatigued as a result of processing a large amount of light-sensitive material.

Treatment process [B] (D-1) Ammonium bromide 160.0 g Ammonia water (28%) 7.1 ml Ethylenediamine-tetraacetic acid sodium iron salt 117 g Glacial acetic acid 14 ml Water 900 ml (D-2) Ethylenediamine-tetraacetic acid sodium acetate Steel wool was added to 130 g of salt (D-2), tightly capped, and left to stand for Fe (III) -EDTA to become Fe (II) -EDTA.
The same treatment as in the treatment step [A] was carried out except that l was added to (D-1) to give a bleaching solution in the treatment step [B].

The densities of the samples 101 to 110 processed in the processing steps [A] and [B] were measured with red light. The results are shown in Table 1.

From Table 1, in the sample 101 using the coupler A, the treatment [B] treated with the fatigued bleaching solution causes a remarkable decrease in color density, whereas the coupler (1) of the present invention,
Samples (105), (106), (107), (108), (110), (11) using (3), (4), (8), (20) and (12)
It can be seen that in 1) there is almost no decrease in color density.
Further, when comparing the maximum color density Dm [A] and the relative sensitivity of the 4-equivalent coupler, compared with the samples (101), (102), (103) and (104) using the conventional couplers A, B, C and D. Samples (105), (106), (107), (108) (11) using the couplers (1), (3), (4) and (8) of the present invention
In 1), all of them are high, which shows that the coupler of the present invention is excellent in color forming property.

Samples (109) and (11) comparing two equivalent couplers
Regarding 0), it is understood that the coupler (20) of the present invention is superior in color forming property to the conventional coupler E.

The relative sensitivity in Table 1 is cyan density (fog +0.5).
Is a relative value with respect to the value of the sample (101) as 100.

Example 2 On a subbed cellulose triacetate film support,
A multilayer color light-sensitive material 201 was prepared by applying each layer having the following composition in multiple layers.

(Photosensitive Layer Composition) The numbers corresponding to the respective components indicate the coating amount in g / m ² unit, and for silver halide, the coating amount in terms of silver.
However, for the sensitizing dye and the coupler, the coating amount is shown in mol unit per mol of silver halide in the same layer.

(Sample 201) First layer; anti-halation layer Black colloidal silver ...... Silver 0.18 gelatin ...... 1.40 Second layer; Intermediate layer 2,5-di-t-pentadecyl hydroquinone ...... 0.18 C-1 ...... 0.07 C-3 ...... 0.02 U-1 ...... 0.08 U-2 ...... 0.08 HBS-1 ...... 0.10 HBS-2 ...... 0.02 Gelatin ...... 1.04 Third layer; First red-sensitive emulsion layer Silver iodobromide emulsion (silver iodide) 6 mol%, average particle size 0.8μ)
Silver 1.00 Sensitizing dye IX 6.9 × 10 ^-5 Sensitizing dye II …… 1.8 × 10 ^-5 Sensitizing dye III …… 3.1 × 10 ^-4 Sensitizing dye IV …… 4.0 × 10 ^-5 C-2… … 0.250 HBS-1 …… 0.10 C-10 …… 0.020 Gelatin ・ ・ ・ 1.20 Fourth layer; second red-sensitive emulsion layer Silver iodobromide emulsion (silver iodide 5 mol%, average grain size 0.85 µ) ……
Silver 1.15 Sensitizing dye IX …… 5.1 × 10 ^-5 Sensitizing dye II …… 1.4 × 10 ^-5 Sensitizing dye III …… 2.3 × 10 ^-4 Sensitizing dye IV …… 3.0 × 10 ^-5 C-2… ... 0.060 C-3 ... 0.008 C-10 ... 0.004 HBS-1 ... 0.30 Gelatin ... 1.50 Fifth layer; third red emulsion layer Silver iodobromide emulsion (silver iodide 10 mol%, average grain size 1.5μ) ……
Silver 1.50 Sensitizing dye IX ...... 5.4 × 10 ^-5 Sensitizing dye II …… 1.4 × 10 ^-5 Sensitizing dye III …… 2.4 × 10 ^-4 Sensitizing dye IV …… 3.1 × 10 ^-5 C-5… … 0.012 C-3 …… 0.003 C-4 …… 0.32 HBS-1 …… 0.32 Gelatin …… 1.62 6th layer; Intermediate layer Gelatin …… 1.06 7th layer; 1st green sensitive emulsion layer Silver iodobromide emulsion ( 6 mol% silver iodide, average grain size 0.8μ)
Silver 0.35 Sensitizing dye V …… 3.0 × 10 ^-5 Sensitizing dye VI …… 1.0 × 10 ^-4 Sensitizing dye VII …… 3.8 × 10 ^-4 C-6 …… 0.180 C-1 …… 0.010 C-7 ...... 0.042 C-8 ...... 0.025 HBS-1 ...... 0.20 Gelatin ...... 0.70 Eighth layer; Second green-sensitive emulsion layer Silver iodobromide emulsion (5 mol% silver iodide, average grain size 0.85 µ) ......
Silver 0.75 Sensitizing dye V …… 2.1 × 10 ^-5 Sensitizing dye VI …… 7.0 × 10 ^-5 Sensitizing dye VII …… 2.6 × 10 ^-4 C-6 …… 0.035 C-8 …… 0.004 C-1 ...... 0.002 C-7 ...... 0.015 HBS-1 ...... 0.15 Gelatin ...... 0.80 9th layer; 3rd green sensitive emulsion layer Silver iodobromide (silver iodide 10 mol%, average grain size 1.5 µ) ...... Silver 1.8
0 Sensitizing dye V …… 3.5 × 10 ^-5 Sensitizing dye VI …… 8.0 × 10 ^-5 Sensitizing dye VII …… 3.0 × 10 ^-4 C-11 …… 0.012 C-1 …… 0.001 HBS-2… … 0.69 Gelatin …… 1.74 10th layer; Yellow filter layer Yellow colloidal silver …… Silver 0.05 2,5-di-t-pentadecylhydroquinone …… 0.03 Gelatin …… 0.95 11th layer; 1st blue emulsion layer Iodour Silver halide emulsion (6 mol% silver iodide, average grain size 0.6μ)
Silver 0.24 Sensitizing dye VIII …… 3.5 × 10 ^-4 C-9 …… 0.27 C-8 …… 0.005 HBS-1 …… 0.28 Gelatin …… 1.28 12th layer; 2nd blue sensitive emulsion layer Silver iodobromide emulsion (Silver iodide 10 mol%, average grain size 1.0μ)
Silver 0.45 Sensitizing dye VIII …… 2.1 × 10 ^-4 C-9 …… 0.098 HBS-1 …… 0.03 Gelatin …… 0.46 13th layer; 3rd blue emulsion layer Silver iodobromide emulsion (silver iodide 10 mol %, Average particle size 1.8μ)
Silver 0.77 Sensitizing dye VIII …… 2.2 × 10 ^-4 C-9 …… 0.036 HBS-1 …… 0.07 Gelatin …… 0.69 14th layer: 1st protective layer Silver iodobromide (silver iodide 1 mol%, average) Grain size 0.07μ) …… Silver 0.
5 U-1 ...... 0.11 U-2 ...... 0.17 Butyl P-hydroxybenzoate ...... 0.012 HBS-1 ...... 0.90 Gelatin ...... 1.0 15th layer; 2nd protective layer Polymethylmethacrylate particles (diameter about 1.5 μm ) ...
0.54 S-1 0.15 S-2 0.10 Gelatin 0.72 In addition to the above composition, a gelatin hardener H-1 and a surfactant were added to each layer.

The coupler C-2 of the third layer and the fourth layer of the sample (201) is the couplers C and D described in Example-1 and the couplers (3), (4), (8) and (15) of the present invention, Samples (202) to (208) were prepared in the same manner as sample (201), except that equimolar amounts were substituted for (12).

The color temperature of these samples was 4800 with a filter using the A light source.
After adjusting the temperature to ° K and performing imagewise exposure so that the maximum exposure amount was 10 CMS, color development processing was carried out at 38 ° C using the following Bleach-A solution.

The results are shown in Table 1.

Color development 2 minutes 45 seconds Bleach-A 6 minutes 30 seconds (or bleach-B) Water wash 2 minutes 10 seconds Settling 4 minutes 20 seconds Water wash 3 minutes 15 seconds Stability 1 minute 05 seconds Treatment liquid used for each step The composition was as follows.

Color developer Diethylenetriaminepentaacetic acid 1.0g 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0g Sodium sulfite 4.0g Potassium carbonate 30.0g Potassium bromide 1.4g Potassium iodide 1.3mg Hydroxylamine sulfate 2.4g 4- (N- Ethyl-N-β-hydroxyethylamino)
-2-Methylaniline sulfate 4.5g Add water 1.0l pH10.0 Bleach-A solution Ethylenediaminetetraacetic acid ferric ammonium salt 100.0g Ethylenediaminetetraacetic acid disodium salt 10.0g Ammonium bromide 150.0g Ammonium nitrate 10.0g Water Addition 1.0l pH6.0 Fixer Ethylenediaminetetraacetic acid disodium salt 1.0g Sodium sulfite 4.0g Ammonium thiosulfate aqueous solution (70%) 175.0ml Sodium bisulfite 4.6g Add water 1.0l pH6.6 Stabilizer Formalin (40% ) 2.0 ml Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization ≈ 10) 0.3 g Water was added to 1.0 l Next, the bleach-A solution during the development processing was changed to the following processing solution formulation. Was similarly developed. The bleach-B solution is a model in which a state in which a large amount of a light-sensitive material is processed and fatigued is adjusted as a model forced deterioration solution.

Bleach-B solution is a mixture of 900 ml of (B-1) solution and 100 ml of (B-2) solution.

Bleach solution composition (B-1) (B-2 ') Steel wool is put into (B-2 '), and the container is sealed and left to change Fe (III) -EDTA to Fe (II) -EDTA, and this solution is referred to as solution (B-2). Table 2 shows the concentration reduction rate of Bleach-B solution which is a forced fatigue solution at the exposure amount of 2.00 when developed with fresh Bleach-A solution.

From Table 2, the samples of the present invention have high sensitivity and high contrast,
Moreover, it is clear that the concentration is less reduced under the forced deterioration condition.

Structure of the compound used in Example-2 HBS-1 Tricresyl Phosphate HBS-2 Dibutyl Phthalate HBS-3 Tri-n-hexyl Phosphate Sensitizing dye Example-3 Samples (201) to (207) produced in Example-2 were exposed for sensitometry (color temperature of 48
It was adjusted to 00 ° K and the maximum exposure was adjusted to 10 CMS. ), The color development process below is performed at 38 ℃.
I went to. The results of sensitometry are shown in Table 3.

 Process Treatment time Treatment temperature Color development 3 minutes 15 seconds 38 ℃ Bleach 6 minutes 30 seconds 38 ℃ Water wash 2 minutes 10 seconds 24 ℃ Settlement 4 minutes 20 seconds 38 ℃ Water wash (1) 1 minute 05 seconds 24 ℃ Water wash (2 ) 1 minute 00 seconds 24 ℃ Stability 1 minute 05 seconds 38 ℃ Dry 4 minutes 20 seconds 55 ℃ Next, describe the composition of the treatment liquid.

(Color developer) (Unit: g) Diethylenetriaminepentaacetic acid 1.0 1-Hydroxyethylidene-1,1-diphosphonic acid 3.0 Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide 1.5 mg Hydroxylamine sulfate 2.4 4- (N- Ethyl-N-β-hydroxyethylamino)
-2-Methylaniline sulfate 4.5 Water was added to 1.0l pH 10.05 (bleaching solution) (unit: g) Ethylenediaminetetraacetic acid ferric sodium trihydrate 100.0
Ethylenediaminetetraacetic acid disodium salt 10.0 Ammonium bromide 140.0 Ammonium nitrate 30.0 Ammonia water (27%) 6.5ml Add water 1.0l pH 6.0 (fixer) (Unit g) Ethylenediaminetetraacetic acid disodium salt 0.5 Sodium sulfite 7.0 Sodium bisulfite 5.0 Aqueous ammonium thiosulfate solution (70%) 170.0 ml Add water 1.0 l pH 6.7 (Stable solution) (Unit: g) Formalin (37%) 2.0 ml Polyoxyethylene-p-monononylphenyl ether (Average degree of polymerization 10) 0.3 Ethylenediaminetetraacetic acid disodium salt 0.05 Add water 1.0l pH 5.0-8.0 As is clear from Table 3, the light-sensitive material of the present invention has high sensitivity and high contrast.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-55-33439 (JP, A) JP-A-60-237448 (JP, A) JP-A 61-153640 (JP, A) JP-A 62- 3253 (JP, A) JP 61-179438 (JP, A) JP 62-121456 (JP, A) JP 61-179436 (JP, A) JP 62-91947 (JP, A)

Claims (1)

[Claims] 1. A silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, containing at least one cyan dye-forming coupler represented by the following general formula [I]. And a silver halide color photographic light-sensitive material. General formula [I] In the formula, R ₁ represents a hydrogen atom, —COR ₆ , —CO ₂ R ₈ or —SO ₂ R ₈ , and R ₆ and R ₈ are an aliphatic group having 1 to 30 carbon atoms or 6 to 6 carbon atoms. Represents 30 aromatic groups. R ₂ is a group capable of substituting on the naphthalene ring, m is an integer of 0 to 3, R ₃ and R ₄
Each independently represent a hydrogen atom, an aliphatic group, or an aromatic group, and X represents a hydrogen atom or a group capable of splitting off by a coupling reaction with an oxidation product of an aromatic primary amine developing agent.