JPH026948A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To form a stable cyan dye by incorporating a specific cyan dye forming coupler into at least one layer of silver halide emulsion layers. CONSTITUTION:The cyan dye forming coupler expressed by the formula I is incorporated into at least one layer of the silver halide emulsion layers. In the formula I, X denotes an atom group necessary for forming a nitrogenous unsatd. 6-membered ring; Z denotes a hydrogen atom or a group which can be eliminated by coupling reaction with the oxidant of an arom. primary amine developing agent; R1, R2 respectively denote substituents on a nitrogenous unsatd. 6-membered ring and a naphthalene ring; m denotes 1-4 integer; n denotes 0-5 integer. This cyan coupler is usually added in an about 0.005-2mol, more preferably 0.01-0.5mol range per 1mol silver halide in case of adding said coupler into the silver halide emulsions. The stable cyan dye is formed in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide color photographic light-sensitive material containing a novel l-7 toll type cyan coupler.

[Background of the invention]

Conventionally, phenols or naphthols have been widely used as cyan dye-forming couplers; for example, U.S. Pat.
2,423.730, 2,474.293, 2,772,162, 2,895,826, 3
, No. 002.836, No. 3,034,892, No. 3,
No. 041,836, JP-A-56-65134, etc.

It has been widely used as a cyan coupler for color negative films; when naphthol compounds are processed in a tired bleach bath or bleach-fix bath, the cyan dye once formed during color development is reduced and returns to the leuco form. There was a drawback that the dye density decreased.

In order to improve this, a cyan coupler having a substituted phenylureido group at the 2-position of the phenol was developed, and the above dye density loss was dramatically improved.

However, although 2-substituted phenylureido phenol couplers are certainly superior to the conventionally known phenolic and naphthol cyan couplers in the above points, the spectral absorption waveform of the coloring dye changes depending on the coloring density. There was a problem in that color images with different tones were provided in high color density areas and low color density areas.

[Purpose of the invention]

Accordingly, a first object of the present invention is to provide a silver halide color photographic light-sensitive material which forms a cyan image with little loss of dye density even when developed using a fatigued bleach bath or a fatigued bleach-fix bath.

A second object of the present invention is to provide a silver halide color photographic material that does not change the spectral absorption waveform of a color image depending on the color density and forms a stable cyan image.

[Structure of the invention]

An object of the present invention is to provide a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, in which at least one of the silver halide emulsion layers is represented by the following general formula [I]. This was achieved using a silver halide color photographic material containing a cyan dye-forming coupler.

General formula (1) In the formula, X represents an atomic group necessary to form a nitrogen-containing unsaturated 6-membered ring, and Z is a hydrogen atom or a compound that is separated by a coupling reaction with an oxidized product of an aromatic primary amine developing agent. represents a possible group. R3 and R3 represent substituents on the nitrogen-containing unsaturated 6-membered ring and the 7talene ring, respectively, m represents an integer of 1 to 4, and n represents an integer of 0 to 5. When m and n are 2 or more, multiple R
, and R2 may be the same or different, adjacent R1 may be bonded to each other to form a ring, and the chain ring may further have a substituent.

The present invention will be explained in more detail below.

Examples of the nitrogen unsaturated 6-membered ring include a pyridine ring, a pyrimidine ring, a pyrazine ring, a pyridazine ring, and a 1.3°5-triazine ring. The bonding position of these heterocycles to the carbamoyl group is not particularly limited.

It is a pyridyl group having a group, and a pyridyl group having an electron-donating substituent is particularly preferable.

Examples of substituents on the nitrogen-containing unsaturated 6-membered ring represented by R2 include halogen atoms (chlorine, fluorine, etc.), cyano groups, nitro groups, alkyl groups having 1 to 20 carbon atoms (methyl, trifluoromethyl, ethyl, t-butyl, t-pentyl, t
-octyl, pentadecyl, etc.), alkoxy groups (methoxy, ethoxy, i-propoxy, butoxy, hexyloxy, dodecyloxy, etc.), alkylsulfonamide groups (methanesulfonamide, butanesulfonamide, octanesulfonamide, hexadecanesulfonamide, etc.)
, arylsulfonamide group (benzenesulfonamide F
, m-chlorosulfonamide, toluenesulfonamide, p-dodecyloxysulfonamide, etc.), alkylsulfamoyl groups (methylsulfamoyl, ethylsulfamoyl, t-butylsulfamoyl, dodecylsulfamoyl, etc.), Arylsulfamoyl group (benzenesulfamoyl, p-toluenesulfamoyl, p-dodecyloxybenzenesulfamoyl, etc.), alkylsulfonyl group (methanesulfonyl, propanesulfonyl, etc.)
, arylsulfonyl group (benzenesulfonyl, p-hydroxyphenylsulfonyl, etc.), alkoxycarbonyl group (ethoxycarbonyl, hexadecyloxycarbonyl, etc.), aryloxycarbonyl group (phenoxycarbonyl, p-tolyloxycarbonyl, etc.), phosphoric acid amide group (diethylphosphoamide, diphenylphosphoamide, etc.).

When m is 2 or more, a plurality of R1s may be the same or different, and adjacent R1s may be bonded to each other to form a ring.

Examples of chain rings include benzene rings, cycloalkenyl rings (cyclohexene, cyclooctene, etc.), unsaturated heterocycles (pyrrole, imidazole, furan, thiophene, etc.), and these include substituents as explained for R1. May have.

The leaving group represented by Z includes any group known as a leaving group for 2-equivalent phenolic cyan couplers and 2-equivalent naphthol-based cyan couplers, but more preferably halogen atoms (fluorine, chlorine, etc.) , substituted or unsubstituted alkoxy groups (methoxy, 2-methoxyethoxy, 3
- substituted or unsubstituted aryloxy group (phenoxy, 4-hydroxyphenoxy, 2,4-dimethanesulfonamidophenoxy, 2゜4-di(dimethylsulfamoylamino)phenoxy) , 2.3-dihydroxy-5-propylcarbonylamino-4-see-butylaminophenoxy, 4
-L-octylphenoxy, 3-pentadecylphenoxy, 4-(2-(tohydroxy-3,6-disulfo-8)
-acetylamino)su7tylazo)phenoxy, 1-naphthoxy, etc.), substituted or unsubstituted heterocyclic oxy groups (2,
Pyridyloxy, 4,6-simethoxy 1.3.5-1
-riazin-2-yloxy, etc.), substituted or unsubstituted alkylthio groups (methylthio, 2-carboxyethylthio, 2-methanesulfonylethylthio, dodecylthio, etc.)
, substituted or unsubstituted arylthio group (phenylthio, 4
-dodecylphenylthio, 2-methoxy-5・L-octylthio, etc.), heterocyclic thio groups (4-pyridylthio, 1-
phenyltetrasol-5-ylthio, etc.), substituted or unsubstituted alkylsulfonyl groups (methylsulfonyl, decylsulfonyl, 4-hydroxybutylsulfonyl, etc.),
Sulfonamide groups (methanesulfonamide, toluenesulfonamide, etc.), acyloxy groups (acetoxy, benzoyloxy, lauroyloxy, etc.), carbonamide groups (dichloroacetylamide, trifluoroacetamide, benzamide, pentafluorobenzamide, etc.),
Aromatic azo groups (phenylazo, 2-acetylphenylazo, 2-acetylnaphthylazo, 2-(see-hexadecyloxycarbonyl)phenylazo, 4-pivaloylaminophenylazo, etc.), alkyl dicarbonyloxy groups (ethoxycarbonyl oxy, dodecyloxycarbonyloxy, etc.), aryloxycarbonyloxyoxyphenoxycarbonyloxy, etc.), carbamoyloxy groups (methylcarbamoyloxy, dodecylcarbamoyloxy, phenylcarbamoyloxy, etc.), hetero groups connected to the active position of the coupler with a nitrogen atom Cyclic groups (succinimide, phthalimide, hydantoinyl, pyrazolyl, morpholino, 2-benzotriazolyl, ■-benzyl-5
-ethoxyhydantoin-3-yl, etc.).

Among these, preferred Z is a hydrogen atom, a chlorine atom,
Mention may be made of aryloxy groups, alkoxy groups, alkylthio groups, arylthio groups and heterocyclic thio groups, with alkoxy groups and aryloxy groups being particularly preferred.

Examples of substituents on the naphthalene ring represented by R2 include halogen atoms (chlorine, fluorine, etc.), cyano groups, nitro groups, hydroxyl groups, carboxyl groups, sulfo groups, halogenated alkyl groups (trifluoromethyl, trifluoromethyl, etc.). ), alkoxy groups (methoxy, ethoxy, butoxy,
dodecyloxy, etc.), aryloxy groups (phenoxy,
p-tolyloxy, etc.), alkylsulfonamide groups (methanesulfonamide, butanesulfonamide, etc.), arylsulfonamide groups (benzenesulfonamide, p-
methoxybenzenesulfonamide, etc.), alkylsulfamoyl groups (methylsulfamoyl, butylsulfamoyl, dodecylsulfamoyl, etc.), arylsulfamoyl groups (benzenesulfamoyl, p~dotesyloxybenzenesulfamoyl) etc.), alkylsulfonyl groups (methanesulfonyl, butanesulfonyl, etc.), arylsulfonyl groups (benzenesulfonyl, p-benzyloxyphenylsulfonyl, etc.), alkoxycarbonyl groups (
methoxycarbonyl, [-butoxycarbonyl, etc.), aryloxycarbonyl group (phenoxycarbonyl, p
-1-lyloxylponyl, etc.), acyloxy groups (acetamido, benzoyloxy, etc.), acylamino groups (
acetamide, benzamide, etc.), amino groups (amino,
methylamino, diethylamino, anilino, etc.), alkylcarbamoyl groups (methylcarbamoyl, !-propylcarbamoyl, etc.), arylcarbamoyl groups (phenylcarbamoyl, 4-methoxy/phenylcarbamoylcarbamoyltoxycarbamoyl, dobutyloxycarbamoyl, etc.)
, aryloxycarbonyl groups (phenoxycarbonyl, p-dodecylphenoxycarbamoyl, naphthoquinecarbamoyl, etc.), alkylthio groups (methylthio, ethylthio, dodecylthio, etc.), arylthio groups (phenylthio, p-t-butylphenylthio, naphthylthio, etc.), etc. Can be mentioned.

Typical specific examples of the compound represented by the general formula [I] (hereinafter referred to as the coupler of the present invention) are shown below, but the present invention is not limited thereto.

No.

COtC+=H2m No.

R R.

No.

R.

7 uncoupler of the present invention An example of synthesis is shown below.

Synthesis Example (Synthesis of Exemplary Coupler 3) Synthesis Scheme (Synthesis of Exemplary Coupler Intermediate ■) 16.3 g of Compound ■ and 10 g of N,N'-dicyclohexylcarbodiimide, 3 g of 1,4-dioxane 10
Dissolve in 0 mQ and cool with water to an internal temperature of 15°C. A solution of 17.5 g of compound (1) in 50 ml of 1°4 dioxane was added dropwise to this over 15 minutes, and the mixture was stirred for 2 hours.

After removing the insoluble matter by filtration, the filtrate was concentrated and the resulting t-residue was
Lyca gel column chromatography was performed. The desired product was obtained from the n-hexane:ethyl acetate 1=5 eluate. 25.
3g (77%) Synthetic Compound of Exemplary Coupler 3 25. 1.3 g of palladium-carbon catalyst was added to the mixture, and catalytic hydrogenation was performed. About 2.6Q of hydrogen is absorbed l-
Thereafter, the catalyst was distilled off and the filtrate was concentrated to obtain a crude intermediate (1). 24.2g (101%) Crude compound 24.
2g to 250m0. 462 g of succinic anhydride dissolved in 100 g of ethyl acetate and warmed to 40°C.
-The solution was added dropwise over 30 minutes, and after the addition was completed, the solution was stirred at 50'C for 2 hours. After removing insoluble matter by filtration, the filtrate was concentrated, and the residue was purified by licage gel column chromatography. The target product was obtained from the toluene:acetone-7=3 eluate. 17
．． The structure of 2g (62%) compound is determined by NMR, Mass
, confirmed by IR spectra.

The cyan coupler of the present invention has a silver halide emulsion layer and/or
The cyan coupler of the present invention is typically incorporated into a silver halide emulsion, and this emulsion is coated on a support.
It can be a silver halide color photographic light-sensitive material contained in a silver halide emulsion layer. This silver halide color photographic light-sensitive material may be monochromatic or multicolored.

In the case of multicolor, the cyan coupler of the present invention is usually contained in a red-sensitive emulsion, but it may also be contained in a non-sensitized emulsion or an emulsion layer sensitive to the three primary color regions of the spectrum other than red.

Each structural unit forming a dye image in the present invention is
It consists of a single-pore agent layer or a multilayer emulsion layer that is sensitive to a certain region of the spectrum.

The layers necessary for the yXr:I silver-genide color photographic light-sensitive material, including the layers of the image-forming units described above, can be arranged in various orders as known in the art.

A typical multicolor silver halide color photographic light-sensitive material comprises a Noan dye image-forming unit consisting of at least one red-sensitive/10 silver emulsion layer having at least one cyan dye-forming coupler, at least one magenta dye-forming coupler. a green-sensitive silver halide emulsion layer comprising at least one green-sensitive silver halide emulsion layer having at least one dye-forming coupler; Dingcy - Dye image forming constituent unit supported on support Tsuji I
-consists of things.

This photographic material can have additional layers, such as λ filter layers, interlayers, sublayers, etc.

Cyan coupler of the present invention and resultant force Z'→-
When added to a silver halide emulsion, it is usually about 0.005 to 2 mol per mol of silver halide, preferably about 0.005 to 2 mol, preferably 0.
It is added in a range of 1=0.5 mole.

As the silver halide used in the silver halide emulsion used in the present invention, common silver halide such as silver bromide, silver chloride, silver iodobromide, silver chlorobromide, silver chloroiodochide, etc. Includes anything used in silver oxide emulsions.

The silver halogenide emulsion constituting the silver fluoride emulsion layer according to the present invention can be prepared by all conventional manufacturing methods, as well as various manufacturing methods, such as those described in Japanese Patent Publication No. 7772/1983. method, i.e., forming an entire emulsion of silver salt grains consisting of at least some silver salts having higher solubility than silver bromide, and then converting at least a part of the grains to silver bromide or silver iodobromide, etc. A method for producing a so-called conversion emulsion, or o.
It can be prepared in the form of fine powder having an average particle size of less than 100 ml (by any manufacturing method such as the method of manufacturing an emulsion made of silver halogenide). Furthermore, the silver halide emulsion of the present invention may contain sulfur sensitizers, such as arylthiocarnomid, thiourea, insulin, etc., active or inactive selenium sensitizers, and reduction sensitizers, such as Precious metal sensitizers such as stannous salts and polyamines, such as gold sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate, 2-oresulfobenzothiazole methyl chloride, etc., or ruthenium, rhodium, iridium, etc. Chemical sensitization can be carried out by using water-soluble salt sensitizers such as ammonium chloroparadate, potassium chlorooleate, and sodium chloroparadite alone or in appropriate combinations.

Further, the silver halide emulsion used in the present invention can contain various known photographic additives. for example[
Research Disclosure JI December 978,
No. 17643.

The silver halide used in the present invention is spectral sensitized by selecting an appropriate sensitizing dye in order to impart photosensitivity in the required wavelength range. Various spectral sensitizing dyes are used, and these can be used alone or in combination of two or more.

Spectral sensitizing dyes advantageously used in the present invention include, for example, U.S. Pat.
0゜378, 2,442.710, 2,454
．． Typical examples include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in No. 620 and No. 2,776.280.

In the present invention, in addition to the couplers of the present invention, magenta couplers include 5-pyrazolone couplers, pyrazolopenzimidazole couplers, pyrazolotriazole couplers, cyanoacetylcoumarone couplers, open-chain acylacetonitrile couplers, etc., and yellow couplers include acylacetamide couplers (e.g. Examples of cyan couplers include naphthol couplers and phenol couplers. These couplers preferably have a hydrophobic group called a ballast group in the molecule. The coupler may be either 4-equivalent or 2-equivalent to silver ions. It may also be a colored coupler that has a color correction effect or a coupler that releases a development inhibitor during development (so-called DIR coupler).

In addition to the DIR coupler, the coupling reaction product may contain a colorless DIR coupling compound which is colorless and releases a development inhibitor.

In order to incorporate the cyan coupler of the present invention and each coupler into a silver halide photosensitive material, conventionally known methods may be followed. For example, after dissolving the cyan coupler of the present invention or each coupler according to the present invention in a mixture of a known high boiling point solvent and a low boiling point solvent such as butyl acetate or butyl propionate,
Mixing with an aqueous gelatin solution containing a surfactant, then emulsifying with a high-speed rotary mixer, colloid mill, or ultrasonic disperser, and then adding to silver halide to prepare the silver halide emulsion used in the present invention. I can do it.

Examples of high boiling point solvents include phthalic acid alkyl esters (dibutyl 7-talate, dioctyl 7-talate, etc.),
Phosphate esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (e.g. acetyl tributyl citrate), benzoic acid esters (e.g. octyl benzoate), alkyl amides (e.g. diethyl laurylamide), Fatty acid esters (eg, dibutoxyethylsuccinate, dioctyl azelate), phenols (eg, 2,4.-di-t-amylphenol), trimesic acid esters (eg, tributyl trimesate), and the like can be used.

Also, Special Publication No. 51-39853, Japanese Patent Publication No. 51-59943
The dispersion method using the compounds described in this issue can also be used.

When the coupler has an acid group such as carboxylic acid or sulfonic acid, it is introduced into the hydrophilic colloid as an alkaline aqueous solution.

Typical color developing agents include those based on p-phenylenediamine, such as diethyl-p-phenylenediamine hydrochloride, monomethyl-p-phenylenediamine hydrochloride, dimethyl-p-7 22-diamine hydrochloride, 2-
Amino-5-diethylaminotoluene hydrochloride, 2-amino-5-(N-ethyl-N-β-hydroxylethylamino)-toluene, 2-amino-5-(N-ethyl-N
-β-methanesulfonamidoethyl)amine toluene sulfate, 2-amino-5-(N-ethyl-N-β-methanesulfonamidoethylamino)toluene, 4-(N-ethyl-N-β-hydroxyethylamino) ) Aniline, 2-
Examples include amino-5-(N-ethyl β-methoxyethyl)aminotoluene.

These color developing agents may be used alone or in combination of two or more, and if necessary, in combination with a black and white developing agent such as hydroquinone. Furthermore, the color developing solution generally contains an alkaline agent such as sodium hydroxide, ammonium hydroxide, sodium carbonate, sodium sulfite, etc., and further contains various additives such as alkali metal halides,
Contains, for example, potassium bromide or a development regulator such as citradinic acid.1. But that's fine.

The silver halide color photographic light-sensitive material of the present invention is usually subjected to bleaching and fixing, bleach-fixing, and water washing after color development.

Many compounds are used as bleaching agents, among them polyvalent metal compounds such as iron (III), cobal) (I[[), and tin (II), especially those containing polyvalent metals and organic acids. Complex salts, such as aminopolycarboxylic acids such as ethyl-diaminetetraacetic acid, nitrilotriacetic acid, N-hydroxyethylenediaminediacetic acid, metal complex salts such as malonic acid, tartaric acid, malic acid, diglycolic acid, dithioglycolic acid, or ferric acid. Salts of salts, dichloromethane, acid salts, etc. can be used alone or in appropriate combinations.

The present invention will be specifically described below with reference to Examples.

〔Example〕

Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.

Example 1 As shown in Table 1, 0.03 mol of each cyan coupler of the present invention or comparison was taken per 1 mol of silver, and dibutyl 7-talate (high-boiling organic solvent) of the same weight as the coupler was mixed with 3
Add each to twice the amount of ethyl acetate and heat to 60°C to completely dissolve the solution containing 120+1lff of a 5% aqueous solution of alkanol B (alkylnaphthalene sulfone I-: manufactured by DuPont). 5% geladine aqueous solution 120
01il+2 and dispersed using an ultrasonic dispersion machine to obtain an emulsion.

This dispersion was added to 4 kg of a red-sensitive silver iodobromide emulsion (containing 7 mol% silver iodide), and a 2% solution of 1,2-bis(vinylsulfonyl) epitane (water:methanol=
l:l) 12011Ilf2 was added, coated and dried on the subbed transparent polyester base, and samples 1 to 9
(coated silver 113mg/100c+++2).

The sample thus obtained was subjected to wedge exposure according to a conventional method, and then subjected to the following development treatment.

Treatment process (38°C) Color development phenomenon 3 minutes 15 seconds bleaching 1 minute 30 seconds water washing 3 minutes 15 seconds fixing 6 minutes 30 seconds water washing 3 minutes 15 seconds stabilization 1 minute 30 seconds drying Used in each processing step The composition of the treatment solution was as follows.

[Coloring current east solution] 4-amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)- Aniline/sulfate anhydrous sodium sulfite hydroxylamine/1/2 sulfate anhydrous potassium carbonate sodium bromide 4. 75 g 4.25 g 2.0 g 37.5 g 1.3 g Nitrilo-acetic acid trisodium salt (l hydrate) 2.5 g
Add 1.0 g of potassium hydroxide to make IQ, and use potassium hydroxide to adjust the pH to 10.0.
Adjust to.

[Bleach solution (A)]

Ethylenediaminetetraacetic acid iron ammonium salt 100.0 g Ethylenediaminetetraacetic acid diammonium salt 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0ml adjust.

[Fixer]

Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Add water to 1Q
and adjust the pH to 6.5 using acetic acid.

[Stabilizing liquid]

Formalin (37% aqueous solution) 1.5mQ
Konidax (Konica Corporation) 7.5+af
Add fi water to make 112.

Separately, each sample was subjected to development geography under exactly the same conditions except that a fatigue bleaching solution (B) having the following composition was used in place of the above bleaching solution (A).

[Fatigue bleaching solution (B)]

Ethylenediaminetetraacetic acid iron ammonium salt 50.0 g Ethylenediaminetetraacetic acid diammonium salt 5.0 g Ammonium bromide 75.0 g Hydrosulfide 5.0 g Glacial acetic acid
10. Add omQ water to make ta, and adjust to pH 5.4 using ammonia water.

The maximum color density of each sample obtained was measured using a PDA-65 type densitometer (manufactured by Konica Corporation). Incidentally, the dye residual rate at the maximum density was determined using the following formula, and the degree of loss of cyan dye due to the fatigue bleaching solution was evaluated.

The results are also shown in Table 1.

Table 1 Comparative coupler A Comparative coupler D (Coupler described in JP-A No. 62-5239) Comparative coupler B Comparative coupler C Furthermore, for the developed samples 1 to 8 using bleaching solution (A), the color density was 0.4 The spectral absorption spectrum in the visible region at and 0.9 was measured, and the difference in λl1ax and half-width between the two was calculated from the following formula.

The results are shown in Table 2.

Δλwax−λl1aXo, +(n+a)−λmaX
o, , (nm)△(half-width)=(half-width). , − (half width),.

(Coupler described in JP-A No. 62-5239) Table 2 *As is clear from Table 1, which includes the secondary absorption at the shoulder with respect to the main absorption, the coupler of the present invention and the comparative coupler (B),
(c) is a coupler that shows little loss in dye density even when developed using a fatigue bleaching solution. Furthermore, as is clear from Table 2, only the couplers of the present invention exhibit small changes in color tone of dye images due to differences in color density, and have sufficient performance to achieve the object of the present invention.

Example 2 Multilayer color photographic element sample 10 was prepared by sequentially forming layers having the compositions shown below on a triacetyl cellulose film support from the support side.

Incidentally, the amount added in each layer is per 1 ln2 unless otherwise specified.

First layer; antihalation layer (HC-1) Gelatin layer containing black colloidal silver. Silver coating amount 0,2ε/ai'' Second layer: Intermediate layer (1, L, ) Gelatin layer containing an emulsified dispersion of 2,5-di-t-octylnohydroquinone.

3rd layer; low sensitivity red-sensitive silver halide emulsion layer (RL-1)
Average particle size (r) 0.40 μl Monodispersed emulsion (emulsion I) consisting of AgBr1 containing 16 mol% Ag... Silver coating amount 1.9 g/m2 Sensitizing dye I... For 1 mol of silver 5. OX 10-'molar sensitizing dye ■・
...0.8X per 1 mole of silver 10-'Morsian coupler (ax-1)...0.0 per mole of silver
85 mole colored cyan coupler (CC-1)...Silver 1
0.005 mol per mole DIN compound (D-1)... 0.0015 mol per mol silver DIR compound (D-2)... 0.0015 mol per mol silver 0.002 mol 4th layer; Highly sensitive red-sensitive silver halide emulsion W (R1!-
1) Average particle size (r) 0.8μs, AgL6.0mol%
A monodispersed emulsion (emulsion ■) consisting of AgBr1 containing: Silver coating amount: 14 g/m'' Sensitizing dye I... 2.5X 10-mol sensitizing dye ■... per 1 mole of silver
...... 0.8X 10-' mol cyan coupler for 1 mol of silver (comparison A) 0.007 mol cyan coupler for 1 mol of silver (CX-2)...... for 1 mol of silver 0.027 mol colored cyan coupler (CC-1) for silver 1
09 units 15 moles per mole DIR compound (D-2)...0.001 mole per mole of silver 5th layer; Intermediate layer (1,L,) Same as the 2nd layer, gelatin layer.

6th layer - low sensitivity green sensitive silver halide emulsion layer (GL~l)
Emulsion-I... Coated silver i 1.5 si/m" sensitizing dye... 2.OX 10-' mol sensitizing dye for 1 mole of silver...
... t, ox to -' mole per mole of silver Magenta coupler (M-1) ...0.09 per mole of silver
0 mole colored magenta coupler (CM-1)...
0.004 mol DIR compound (1)-1) per mol silver DIR compound (D-3) 0.0010 mol per mol silver DIR compound (D-3) 1 mol silver 0.0030 mol for 7th layer; high-sensitivity green-sensitive silver halide emulsion layer (GH-1)
Emulsion - ■... Coated silver amount 1.49/I11"
Sensitizing dye ■・・・・・・ 1.2X 10-' mol sensitizing dye ■・ per 1 mole of silver
...0.8X 10-' mole magenta coupler (M-1) for 1 mole of silver...0.01 for 1 mole of silver
5 molar colored magenta coupler (CIJ-1)...
0.002 mol per mol of silver DIR compound (D-3)...0.0010 mol per mol of silver 8th layer; Yellow filter layer (YC-1) Yellow colloidal silver and 2 . A gelatin layer comprising an emulsified dispersion of 5-di-t-octylhydroquinone. Silver coating amount: 0-1 g/m" 9th layer; low-sensitivity blue-sensitive silver halide emulsion layer (BL-1)
AgBr containing 15 mol% Ag with an average particle size of 0.48 μm
Monodisperse emulsion consisting of 1 (emulsion ■)...silver coating amount 0.99/II"
Sensitizing dye V...1.3X 10-' mol per mole of silver Yellow coupler (Y-1)...0.
29 mol 1st O layer; high sensitivity blue sensitive emulsion layer (BH-1) average grain size 0
．． Monodispersed emulsion (emulsion ■) consisting of AgBr I containing 8 μs and 17 mol% of Ag...silver coating amount 0.59/+02
Sensitizing dye V: 1.0% per mole of silver. OX 10-' mole Yellow coupler (Y-1)...0.08 per mole of silver
Mol DIR compound (D-2)...0,0030 mol per mol of silver 11th layer; 1st protective layer (Pro-1) Silver iodobromide (
Agl 1 mol% Average particle size 0.07 μm) Silver coating amount 0.
5g/+” Gelatin layer containing UV absorbers UV-1 and UV-2.

12th layer; second protective layer (Pro-2) Gelatin layer containing polymethyl methacrylate particles (diameter 1.5 μff1).

In addition to the above composition, each layer contains a gelatin hardener (H-
1) and (H-2) and a surfactant were added.

The compounds contained in each layer of sample IO are as follows.

Sensitizing dye I; anhydro 5,5'-dichloro-9-ethyl-3,3'-di (3-sulfopropyl)thiacarbocyanine hydroxide sensitizing dye ■;
3-sulfopropyl)-4,5.

4',5'-dibenzothiacarbocyanine hydroxide sensitizing dye ■; Anhydro 5,5'-diphenyl9-ethyl-3,3'-di (3-sulfopropyl)oxacarbocyanine hydroxide sensitizing dye ■; anhydro9-ethyl-3,3'di (
3-sulfopropyl)-5,6.

5',6'-dibenzoxacarbonanine hydroxide sensitizing dye V; anhydro 3,3'-di (3-sulfopropyl)-4,5-benzo-5'-methquinthiacyanine hydroxide M ■ M -1 I2 ■V Each sample was wedge-exposed with white light and then developed using two types of bleaching solutions in the same manner as in Example 1, and the dye residual rate of the obtained sample was determined. The results are shown in Table 3.

Table 3 V C2H.

[(CH2-C11SO□CH3)gccHzsO2(
CHJz)zN(CHz)2sOJTable 3 shows that even in multilayer color photographic materials, the couplers of the present invention show less loss of dye density in fatigue bleaching solutions and are excellent in color development.

Claims (1)

[Scope of Claims] In a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, at least one of the silver halide emulsion layers has the following general formula [I].
A silver halide color photographic material containing a cyan dye-forming coupler represented by: General formula [
I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, Represents a group that can be separated by a coupling reaction with an oxidant. R_1 and R_2 represent substituents on the nitrogen-containing unsaturated 6-membered ring and naphthalene ring, respectively, and m is 1 to 4.
, n represents an integer of 0 to 5. When m and n are 2 or more, a plurality of R_1 and R_2 may be the same or different, and adjacent R_1 may be bonded to each other to form a ring, and the ring may further have a substituent. ]