JPH01201657A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a cyan image having high sensitivity and high optical density by incorporating a specified cyan dye forming coupler in the photosensitive material. CONSTITUTION:The cyan dye forming coupler shown by formula I is incorporated in at least one layer of silver halide emulsion layers. In formula I, R1 is alkyl or aryl group which may be substd., R2 is a monovalent org. group capable of substituting on a benzene ring, (m) is an integer of 1-4, when (m) is >=2, R2 may be the same or the different with each other, R2 and R4 are each hydrogen atom or alkyl, acyl, alkylsulfonyl or arylsulfonyl group which may be substd., and R2 and R4 may be the same or the different with each other, R3 and R4 together with each other may form a ring, J is a divalent bonding group. Thus, the cyan image having the high sensitivity and the high optical density is formed.

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 cyan coupler, particularly a silver halide color photographic material that can form cyan images with high sensitivity and high density. Regarding photographic materials.

[Background of the invention]

In silver halide color photographic materials, generally the photosensitive silver halide is exposed to light, then subjected to color development treatment, and a dye is formed by reacting an oxidized aromatic primary amine developing agent with a dye-forming coupler. Normally, when an image is formed by this method, yellow, magenta, and cyan dye images are formed, and a color photographic image is obtained by a so-called subtractive color method. Among these, phenols or naphthols have been widely used as cyan dye-forming couplers. For example, U.S. Pat.
No. 9, No. 2,423.730, No. 2,474,293
No. 2.772.162, No. 2,895.826, No. 2,367.531, No. 3,002.836,
It is described in No. 3,034,892, No. 3,041,836, JP-A-56-65134, etc. When the above-mentioned naphthol compounds, which have been widely used as cyan couplers for color negative films, are processed in a tired bleach bath or bleach-fix solution, the dyes once formed in the color developing solution are reduced and become leuco-containing. The drawback was that it returned to the body and the pigment concentration decreased. In order to improve this drawback, a cyan coupler having a substituted phenylureido group at the 2-position of the phenol in a phenolic compound was developed, and the above dye loss was dramatically improved.

However, these phenolic couplers are still insufficient for increasing the sensitivity and speeding up the development process of photographic materials.

In particular, among those skilled in the art, desilvering performance in the bleaching process is the biggest problem in rapid processing, and improvements have been desired.

The inventors of the present invention have conducted various studies on the above-mentioned problems associated with increasing the sensitivity of photographic light-sensitive materials and speeding up the development process. The present inventors have discovered that the present invention has extremely excellent effects, and have completed the present invention.

[Purpose of the invention]

A first object of the present invention is to provide a silver halide color photographic material that is highly sensitive and forms cyan images of high density.

A second object of the present invention is to provide a silver halide photographic material containing a cyan coupler that exhibits little dye loss even when using a bleach bath or a bleach-fix bath that is fatigued and degraded by running processing.

A third object of the present invention is to provide a silver halide photographic material with excellent desilvering properties and rapid processability using a cyan coupler with excellent silver bleaching ability.

[Structure of the invention]

The above-mentioned object of the present invention is to provide a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support. This was achieved using a silver halide color photographic material characterized by containing a cyan dye-forming coupler.

[In the formula, R3 represents a substituted or unsubstituted alkyl group or aryl group. R represents a monovalent organic group that can be substituted on the benzene ring. m represents an integer of 1 to 4, and when m is 2 or more, R2 may be the same or different. R
3 and R4 represent a hydrogen atom, a substituted or unsubstituted alkyl group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group, and these may be the same or different, and R3 and R4 are mutually exclusive. may be linked to form a ring. J represents a divalent linking group. ] [Specific structure of the invention] R+, Rz, R3, R4 in the above-maximum (1)
and J will be described in detail below.

- R1 in maximum (1) represents an alkyl group or an aryl group. The alkyl group is an alkyl group having 1 to 20 carbon atoms, and may have a substituent (particularly preferred is a group represented by the following general formula (n)).

However, in this -maximum (n), Y is 10-, -S-.

-3Offi-, and Rs is an alkylene group having 1 to 20 carbon atoms (methylene, 1.1-ethylene, 1.2-
Ethylene, 1.1-propylene, 1. 3-propylene, 2-methyl-1,1-propylene, 1.1-pentylene, 1,1-heptylene, 1゜1-nonylene, 1.1-
undecylene, 1,1-tridecylene, 1,1-bentade, silene, etc.), and R6 represents a halogen atom (chlorine atom, fluorine atom, etc.), a hydroxy group, or a carbon atom number of 1 to 20.
Alkyl groups (methyl group, ethyl group, tert-butyl group, tert-pentyl group, cyclopentyl group, cyclohexyl group, tert-octyl group, pentadecyl group, etc.), alkoxy groups (methoxy group, ethoxy group, isopropyloxy group, butoxy group) group, hexyloxy group, dodecyloxy group, etc.), alkylsulfonamide group (methanesulfonamide group, ethanesulfonamide group, butane-sulfonamide group, octanesulfonamide group, hexadecanesulfonamide group, etc.), arylsulfonamide group ( benzenesulfonamide group, m-chlorobenzenesulfonamide group, toluenesulfonamide group, p-methoxybenzenesulfonamide group, p-dodecyloxybenzenesulfonamide group, etc.), alkylsulfamoyl group (methylsulfamoyl group, ethylsulfamoyl group, etc.) famoyl group,
butylsulfamoyl group, tert-butylsulfamoyl group, dodecylsulfamoyl group, etc.), arylsulfamoyl group (benzenesulfamoyl group, toluenesulfamoyl group, dodecyloxybenzenesulfamoyl group, etc.), Alkylsulfony group (methanesulfonyl group,
butanesulfonyl group, etc.), arylsulfonyl group (benzenesulfonyl L p-benzyloxyphenylsulfonyl group, p-hydroxyphenylsulfonyl group, etc.), alkoxycarbonyl group (ethoxycarbonyl group, butoxycarbonyl group, hexadecyloxycarbonyl group, etc.)
can be mentioned. β represents an integer of 1 to 5, preferably 1 or 2. When l is 2 or more, R8 may be the same or different. ) In the present invention, when R in -maximum (1) is an aryl group, it is preferably a phenyl group, and the phenyl group is the above-mentioned -maximum (II).
It may be substituted with R6 shown by.

R2 in general formula (1) represents a monovalent organic group that can be substituted on a benzene ring. For example, halogen atoms (fluorine atoms,
chlorine atom, bromine atom, etc.), nitro group, number of carbon atoms 1 to 2
0 alkyl group, (methyl group, trifluoromethyl group,
ethyl group, tert-butyl group, tert-pentyl group, tert-octyl group, pentadecyl group, etc.), aryl group (phenyl group, naphthyl group, etc.), heterocyclic group (pyhelicine group, piperazine group, etc.), hydroxyl group, alkoxy groups (methoxy group, ethoxy group, isopropoxy group,
butoxy group, hexyloxy group, dodecyloxy group, etc.)
, aryloxy group, (substituted or unsubstituted phenoxy group, etc.), acyloxy group (acetoxy group, isobutyryloxy group, valeryloxy group, stearoyloxy group,
benzoyloxy group, etc.), alkylcarbonyl group (methylcarbonyl group, isobutylcarbonyl group, dodecylcarbonyl group, etc.), carbonyl group (benzenecarbonyl group, etc.), amino group, (unsubstituted amino group, methylamino group, ethylamino group, tert-butylamino group, dimethylamino group, diethylamino group, etc.), acylamine group (acetylamino group, propionylamino group, pivaloylamino group, benzoylamino group, etc.), alkylcarbamoyl group (methylcarbamoyl group, ethylcarbamoyl group) , tert-butylcarbamoyl group, dodecylcarbamoyl group, etc.), arylcarbamoyl group (benzenecarbamoyl group, p-methylbenzenecarbamoyl group, p-dodecyloxybenzenecarbamoyl group, etc.), alkylsulfonamide group, (methanesulfonamide group,
ethanesulfonamide group, butanesulfonamide group, octanesulfonamide group, hexadecanesulfonamide group, etc.), arylsulfonamide group (benzenesulfonamide group, m-chlorobenzenesulfonamide group, toluenesulfonamide group, p-methoxybenzenesulfonamide group) group, p-dodecyloxybenzenesulfonamide group, etc.), alkylsulfamoyl group (methylsulfamoyl group, ethylsulfamoyl group, butylsulfamoyl group, tert-butylsulfamoyl group, dodecylsulfamoyl group) etc.), arylsulfamoyl groups (benzenesulfamoyl group, p-toluenesulfamoyl group, p-dodecyloxybenzenesulfamoyl group, etc.),
Alkylsulfonyl groups (methanesulfonyl, propanesulfonyl, butanesulfonyl, etc.), arylsulfonyl groups (benzenesulfonyl, p-benzyloxyphenylsulfonyl, p-hydroxybenzenesulfonyl, etc.), alkoxycarbonyl groups (ethoxycarbonyl) , butoxycarbonyl group, hexadecyloxycarbonyl group, etc.), aryloxycarbonyl group (phenoxycarbonyl group, p-)lyloxycarbonyl group, etc.), phosphoric acid amide group (diethyl phosphoric acid amide group, diphenyl phosphoric acid amide group, etc.) can be mentioned. R2 is preferably a halogen atom or a lower alkyl group.

m in maximum (1) above is an integer from 1 to 4, m
is 2 or more, R1 may be the same or different.

R3 and R4 in the above-maximum (1) are hydrogen atoms,
Represents an alkyl group, acyl group, alkylsulfonyl group or arylsulfonyl group. The alkyl group is an alkyl group having 1 to 20 carbon atoms, and may further have a substituent. Examples of substituents include hydroxy group,
Carboxy group, halogen atom (chlorine atom, bromine atom, etc.)
Alkoxy group (methoxy group, ethoxy group, butoxy group,
hexyloxy group, dodecyloxy group, etc.), aryloxy group (phenoxy group, p-)lyloxy group, etc.), alkylsulfonyl group (methanesulfonyl group, ethanesulfonyl group, butanesulfonyl group, etc.), arylsulfonyl group (benzenesulfonyl group, etc.) , p-benzyloxyphenylsulfonyl group, p-hydroxyphenylsulfonyl group, etc.), acyl group (acetyl group, propionyl group, pivaloyl group, stearoyl group, benzoyl group, etc.), alkoxycarbonyl group (methoxycarbonyl group, ethoxycarbonyl group, tert-butoxycarbonyl group,
hexadecylcarbonyl group, etc.), aryloxycarbonyl group (phenoxycarbonyl group, p-)lyloxycarbonyl group, etc.), alkylamino group (methylamino group,
Typical examples include ethylamino group, dimethylamino group, etc.) and alkylthio groups (methylthio group, butylthio group, etc.).

Acyl groups include acetyl, propionyl, and stearoyl groups; alkylsulfonyl groups include methanesulfonyl, propanesulfonyl, and butanesulfonyl; and arylsulfonyl groups include benzenesulfonyl and p-hydroxybenzenesulfonyl groups. , 2-
Examples include butoxy-4-tert-octylbenzenesulfonyl group.

R3 and R4 may be linked to each other to form a ring,
Further, R8 and R4 may be the same or different.

R3 and R6 are preferably an alkyl group, an acyl group, or an alkylsulfonyl group, and particularly preferably an alkyl group.

As the divalent linking group represented by J, for example, a carbon number of 1
~20 alkylene groups are mentioned, which may be branched or unbranched. Further, J may be represented by -J, -X-J, - (wherein, X represents an oxygen atom or a sulfur atom, and Jl and J2 represent an alkylene group). J is preferably an alkylene group having 10 or less carbon atoms.

Representative examples of the cyan coupler represented by the general formula [I] of the present invention are shown below, but the present invention is not limited thereto.

(Margin below) (Image bottom margin) A typical synthesis example of the cyan coupler of the present invention is shown below.

Synthesis example (example coupler l) Synthesis scheme 2) POC13/DMF (example coupler N11Ll) (blank below) (1) 2-amino-5-nitrophenol [1] 15,
After dissolving 4 g in 200 m It of acetonitrile, 0.50 g of imidazole and 27.2 g of phenyl 3-cyano-4-chlorophenylcarbamate were added,
The reaction solution heated under reflux for 3 hours was cooled, the precipitated crystals were collected by filtration, and further recrystallized from acetonitrile to obtain 28.2 g of [2]. (Yield 85.0%
) (2) 25.0 g of compound [2] was dissolved in 300 mJ of ethanol, 2.0 g of 5% palladium-carbon catalyst was added, and catalytic hydrogenation was performed at room temperature and pressure.

After the reaction was completed, the catalyst was filtered off, and the mother liquor was concentrated under reduced pressure to obtain 22.0 g of a crude product of compound [3].

(3) 22.0 g of compound [3] and 250 liters of ethyl acetate
7.5 g of triethylamine and 2-(2,
26.8 g of 4-di-tert-amylphenoxy)hexanoyl chloride was added, and the mixture was heated under reflux for 2 hours.

After the reaction was completed, the precipitated triethylamine hydrochloride was filtered off.

Next, the mother liquor was concentrated under reduced pressure and then recrystallized from acetonitrile to obtain 34.6 g of compound [4].

(Yield 75%) (4) 31.6 g of compound [4] was dissolved in chloroform 10
4.0 ml of chlorosulfonic acid at room temperature
was dripped. After the mixture was stirred at room temperature for 2 hours, the mixture was further heated under reflux for 1 hour. To this reaction solution, 4.7 ml of phosphorus oxychloride and 15 ml of dimethylformamide were added, and the mixture was heated under reflux for 1 hour.

After the reaction was completed, chloroform was distilled off under reduced pressure, and the residue was extracted with water and ethyl acetate to obtain compound [5].
] 23.8 g of crudely purified product was obtained.

(5) 23.0 g of compound [5] was dissolved in 150 m of toluene, and 15 g of powdered zinc was added and stirred.

50 ml of concentrated hydrochloric acid was added dropwise to this and stirred at room temperature for 1 hour.
After the reaction was completed, the solid was filtered off, and the mother liquor was extracted with water and ethyl acetate. By distilling off the solvent under M pressure, 16.0 g of crudely purified compound [6] was obtained. (yield 74%
) (6) Dimethyl-(2-chloroethyl)amine2.
After dissolving 4g in pyridine 100mj+, compound [6
] Log was added in small portions at room temperature over about 10 minutes. After stirring as it is for 3.5 hours, after the zero reaction, fishing for 300m
1 and extracted with ethyl acetate. The target exemplary coupler N was obtained by distilling off the solvent under reduced pressure and recrystallizing the obtained residue from a mixed solvent of n-hexane and ethyl acetate.
6.8g of O,1 was obtained. (Yield 63%) The structure of the target compound was confirmed by NMR, IR and MASS spectrum data.

The cyan coupler of the present invention has a silver halide emulsion layer and/or
The cyan coupler of the present invention is typically blended into a silver halide emulsion, and this emulsion is coated onto a support to form a silver halide layer. It can be a silver halide color photographic light-sensitive material containing silver halide in an 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-hole emulsion layer or a multilayer emulsion layer that is sensitive to a certain region of the spectrum.

The layers necessary for silver halide color photographic materials, including the layers of 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 cyan dye image-forming building block consisting of at least one red-sensitive silver halide emulsion layer having at least one cyan dye-forming coupler, at least one magenta dye-forming coupler. a magenta dye image-forming unit consisting of at least one green-sensitive silver halide emulsion layer having a support, and a yellow dye image-forming unit consisting of at least one blue-sensitive silver halide emulsion layer having at least one yellow dye-forming coupler; It consists of something carried by

This photographic material may have additional layers, such as filter layers, interlayers, subbing layers, etc.

When the cyan coupler of the present invention and each coupler according to the present invention are added to a silver halide emulsion, it is usually about 0.005 to 2 mol, preferably 0.01 mol per mol of silver halide.
It is added in a range of 0.5 mol.

The silver halide used in the silver halide emulsion used in the present invention may include ordinary silver halide emulsions such as silver bromide, silver chloride, silver iodobromide, silver chlorobromide, and silver chloroiodobromide. Includes anything used.

The silver halide emulsion constituting the silver halide emulsion layer according to the present invention can be produced by various manufacturing methods including the usual manufacturing method, such as the method described in Japanese Patent Publication No. 46-7772,
That is, forming an emulsion of silver salt grains consisting of a small amount of silver salt whose solubility is higher than that of silver bromide, and then converting at least a part of the grains to silver bromide or silver iodobromide, etc. The manufacturing method of so-called conversion emulsion, or 0.1
It can be produced by any production method such as the production method of Lippmann emulsion consisting of fine grain silver halide having an average grain size of .mu.m or less. Furthermore, the silver halide emulsions of the present invention may contain sulfur enhancers such as arylthiocarbamide, thiourea, cystine, etc., active or inactive selenium sensitizers, and reduction sensitizers such as stannous salts, polyamines, etc. etc., noble metal sensitizers, such as gold sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate,
2-oresulfobenzthiazole methyl chloride, etc.
Alternatively, chemical sensitization can be carried out using water-soluble salt sensitizers such as ruthenium, rhodium, and iridium, specifically ammonium chloroparadate, potassium chlorooleate, and sodium chlorovaradite, alone or in combination as appropriate. be able to.

Further, the silver halide emulsion used in the present invention can contain various known photographic additives. For example, "Research Disclosure" December 1978,
A photographic additive such as that described in Magnet 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 may 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.
No. 270,378, No. 2,442,710, No. 2
．． Typical examples include cyanine dyes, merocyanine dyes and composite cyanine dyes as described in Patent No. 454.620 and No. 2,776.280.

In the present invention, in addition to the coupler of the present invention, a compound that can develop color by oxidative coupling with an aromatic primary amine developer (for example, a phenylene diamine derivative, an aminophenol derivative, etc.) in other color development processing is used in combination. Can be used.

Magenta couplers include 5-pyrazolone couplers, pyrazolobenzimidazole couplers, pyrazolotriazole couplers, cyanoacetyl coumaron couplers, open-chain acylacetonitrile couplers, etc. Yellow couplers include acylacetamide couplers (e.g. benzoylacetanilides, pivaloyl 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 product of the camping reaction is colorless and may contain an uncolored DIR camping compound that releases a development inhibitor.

In order to incorporate the cyan coupler of the present invention and each coupler according to the present invention into a silver halide photosensitive material, conventionally known methods may be followed. After dissolving the cyan coupler of the present invention or each coupler according to the present invention in a mixture of boiling point solvents, it is mixed with an aqueous gelatin solution containing a surfactant, and then emulsified using a high-speed rotating mixer, a colloid mill, or an ultrasonic disperser. After that, it can be added to silver halide to prepare a silver halide emulsion for use in the present invention.

Examples of high boiling point solvents include phthalic acid alkyl esters (e.g., dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (e.g., diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate, etc.), and citric acid esters. (e.g. acetyl tributyl citrate etc.),
Benzoic acid esters (e.g. octyl benzoate, etc.), alkylamides (e.g. diethyl laurylamide, etc.), fatty acid esters (e.g. dibutoxyethyl succinate, etc.)
dioctyl azelate, etc.), phenols (e.g. 2.
(4-ditertiary-amylphenol, etc.), trimesic acid esters (eg, tributyl trimesate, etc.), and the like can be used.

Also, Japanese Patent Publication No. 57-39853, Japanese Patent Publication No. 51-5994
A dispersion method using a polymer described in publications such as No. 3 can also be used. Furthermore, when the coupler has an acid group such as carboxylic acid or sulfonic acid, it is introduced into the hydrophobic colloid as an alkaline aqueous solution.

Typical color developing agents include those based on p-phenylenediamine, such as diethyl-phenylenediamine hydrochloride, monomethyl-p-phenylenediamine hydrochloride, dimethyl-p-phenylenediamine hydrochloride, and 2-amino-5-phenylenediamine hydrochloride. -diethylaminotoluene hydrochloride, 2-amino-
5-(N-ethyl-N-β-hydroxylethylamino)-toluene, 2-amino-5-(N-ethyl-N-β
-methanesulfonamidoethyl)aminotoluene sulfate, 2-amino-5-(N-ethyl-N-β-methanesulfonamidoethylamino)toluene, 4-(N-ethyl-N-β-hydroxyethylamino)aniline , 2-amino-5-(N-ethyl-β-methoxyethyl)-aminotoluene, and the like. 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 contains an alkaline agent such as sodium hydroxide, ammonium hydroxide/sodium carbonate, sodium sulfite, etc. in -IC, and various additives such as an alkali metal halide such as potassium bromide, or a development control agent. It may also contain agents such as citradinic acid.

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 (■), cobalt (■), and tin (II), especially complex salts of these polyvalent metal cations and organic acids, such as ethylenediamine. Aminopolycarboxylic acids such as tetraacetic acid, nitrilotriacetic acid, N-hydroxyethylenediaminediacetic acid, metal complexes such as malonic acid, tartaric acid, malic acid, diglycolic acid, dithioglycolic acid, ferricyanates, dichromates, etc. These can be used alone or in appropriate combinations.

〔Example〕

The present invention will be specifically described below with reference to Examples, but the embodiment B of the present invention is not limited thereto.

Example-1 As shown in Table 1, each cyan coupler of the present invention was weighed in an amount of 0.03 mol per 1 mol of silver, and phthalic acid diptyle ester (as a high boiling point solvent) of the same weight as the coupler was weighed. Each was added to 3 times the amount of ethyl acetate and heated to 60°C to completely dissolve.

In addition, for comparison, conventionally known comparative couplers were each mixed with 1 silver.
It was weighed out in units of 0.03 mol per mole, added to phthalic acid diptyle ester of the same weight as the coupler weight and 3 times the amount of ethyl acetate, and heated to 60°C to completely dissolve. This solution was mixed with alkanol B (alkylnaphthalene sulfonate:
1200 mj of 5% gelatin aqueous solution containing 120 ml of 5% aqueous solution (manufactured by DuPont)! and dispersed with an ultrasonic disperser to obtain an emulsion. Thereafter, this dispersion was added to 4 kg of red-sensitive silver iodobromide emulsion (containing 7 mol% silver iodide), and 1,2-bis(vinylsulfonyl) was added as a hardening agent.
2% solution of ethane (water:methanol=1:1) 120m
To obtain a sample with a stable coating film, coated silver amount was 18 mg/100 cm") and coated on a subbed transparent polyester base and dried. The thus obtained sample was wedged according to a conventional method. After exposure, the following development process was performed.

The results are shown in Table 1.

In addition, the sensitivity and maximum color density are for PDA manufactured by Konica Corporation.
Measured using a -65 type concentration meter.

[Processing process] (38℃), Processing time Color development
3 minutes 15 seconds, bleach
Wash with water for 1 minute and 30 seconds
Fixed for 3 minutes and 15 seconds 6
Wash with water for 30 minutes 3 minutes 15 minutes
Second stabilization bath The composition of the treatment liquid used in the 1 minute 30 second treatment step was as follows.

[Color developer composition]

4-Amino-3-methyl-N-ethyl-N-(β-hydroxyethyl) monoaniline sulfate 4.75 g Anhydrous sodium sulfite 4.25 g Hydroxyamine 1/2 sulfate 2.0 g Anhydrous potassium carbonate 37. 5 g sodium bromide
1.3g potassium hydroxide
Add 1.0 g of water to make IIl, and adjust the pH to 10.0 using potassium hydroxide.

[Bleach solution composition]

Ammonium bromide 150.0g Glacial acetic acid 10.0+*j! Add water to make 1 i, and adjust to pH 6.0 using aqueous ammonia.

[Fixer composition]

Ammonium thiosulfate (50% aqueous solution) 162mj! Add 12.4 g of anhydrous lithium sulfite to bring the solution to 11 and adjust the pH to 6.5 using acetic acid.

[Stabilizing liquid composition]

Formalin (37% aqueous solution) 5.0wl1
Konida Fukus (manufactured by Konica Corporation) 7.5mj2
Add water to make 11.

(Leaving space below) Table 1 Comparative coupler A (Coupler described in JP-A-62-173467) Comparative coupler B 4Hv (Coupler described in JP-A-60-50533) Comparative coupler C (JP-A-55-25056 Coupler listed in issue) In the table,
Sensitivity was expressed as relative sensitivity when comparison coupler A was taken as 100.

From Table 1, it was found that the couplers of the present invention had superior performance in both sensitivity and maximum density compared to the comparative couplers.

Example-2 After performing edge exposure on the sample obtained in Example-1,
The development process of Example-1 was performed. On the other hand, the bleaching solution was treated with a fatigue bleaching solution having the composition shown below, and the discoloration of cyan dye by the fatigue bleaching solution was investigated.

[Fatigue bleaching solution composition]

Ammonium bromide 75.0 g Hydrosulfide 5.0 g Glacial acetic acid
Add 10.0ml water and make 1
1 and adjust the pH to 5.4 using aqueous ammonia.

The maximum color density of the obtained sample was measured. The results are shown in Table 2. Incidentally, the dye residual rate at the maximum density was determined as follows.

As is clear from Table 2 (Table 2), the cyanide coupler of the present invention is characterized by a phenolic cyan coupler having a ureido group at the 2-position, which makes it possible to remove tired bleaching solutions. It can be seen that the characteristic of low dye loss is maintained even when used, and the degree of dye loss is also lower than that of the comparative couplers. Furthermore, from Tables 1 and 2, it can be seen that the cyan coupler of the present invention has the effect of not only having high color development but also having little loss of dye in fatigue bleaching solutions.

Example 3 Sample 12, a multilayer color photographic element, was prepared by sequentially forming layers having the compositions shown below on a triacetyl cellulose film support from the support side.

1st layer; antihalation layer (HC-1) gelatin layer containing black colloidal silver (silver coating amount 0.2 g/m") 2nd layer; intermediate layer (1, L, ) 2.5-di-t- Gelatin layer containing an emulsified dispersion of octylhydroquinone.

3rd layer: low-sensitivity red-sensitive silver halide emulsion layer (RL average grain size (r) 0.40 μm, monodispersed emulsion (emulsion I) consisting of AgBr1 containing 16 mol% Ag (emulsion I)... Silver coating Amount 1.9g/m" Sensitizing dye!... 5X10-'MoJ per 1R1 mole Sensitizing dye...
...0.8x10-'Morsian coupler (C-1) for 1 mole of silver...0.085 for 1 mole of silver
Molar colored cyan coupler (CC-1)... o, o o s mol per 1 mol of silver DIR compound (D-1).
... 0.0015 mol per 1 mol of SR DIR compound (D-2) 0.002 mol per 1 mol of silver 4th layer; Highly sensitive red-sensitive silver halide emulsion layer (Monodispersed emulsion (emulsion ■) consisting of AgBr1 containing RH average grain size (r) 0.8 μm and 16.0 mol% Ag... Primate coating amount 1.4 g/% Sensitizing dye I. ... 2.5 x 10-' mol sensitizing dye for 1 mol of silver...
・・・・0.8×10−′ molsian coupler (C-2) for 1 mole of silver ・・・・0.007 molsian coupler (C-3) for 1 mol of silver ...0.027 mol per mol of silver Colored cyan coupler (CC-1) 0.0015 mol per mol of silver DIR compound (D-2)... 1 mol of silver 0.001 mol 5th layer; middle layer (1, L,) Same as 2nd N, gelatin layer.

6th layer: Low sensitivity green-sensitive silver halide emulsion layer (GL-1) Emulsion - ■... Coated silver amount 1.6 g/rrr Sensitizing dye ■...... i = 1 mole 2.0×10-' molar sensitizing dye ■・
... 1.0 x 10 to 4 moles magenta coupler (M-1) for 1 mole of silver...0.090 for 1 mole of silver
Mol color magenta coupler (CM-1)...i
ff 0.004 mol DIR compound (D
-1)... 0.0010 mol per mol of silver DIR compound (D-3)... 0.0030 mol per mol of 1R 7N; High sensitivity green sensitive halogenated Silver emulsion layer (GH-1) Emulsion -] Coated silver amount 1.4 g/rd Enhancing element ■... Per 1 mole of silver! , 2X10-' molar enhancing dye ■...
...0.8 x 10-' moles per mole of silver Magenta coupler (M-1) ...0.015 per mole of silver
Mol color magenta coupler (CM-1)...i
0.002 mol DIR compound CD-3 per 1 mol
)... 8th layer: 0.0010 mol per mol of silver; Yellow filter layer (YC-1) Contains an emulsified dispersion of yellow colloidal silver and 2.5-di-t-octylhydroquinone gelatin layer. Silver coating amount 0.1g/rr
r 9th layer; low-speed blue-translucent silver halide emulsion layer (BL-1
) Average particle size 0.48 pm, A containing 16 mol% Ag
Monodispersed emulsion (emulsion ■) consisting of gBr1... Silver coating amount 0.9 / rJ Sensitizing dye ■... 1.0 x 10-' mol yellow coupler (Y -1)...0.29 mol per mol of silver 10th layer; high sensitivity blue sensitive emulsion layer (BH-1) average grain size 0
．． Monodispersed emulsion (emulsion ■) consisting of AgBr1 containing 8 μm and 17 mol % of Ag... Silver coating amount 0.5 g/rd Sensitizing dye ■... 1. 0X10-'Mo/L/Yellow coupler (Y-1)...0.0% per mole of silver.
08 mol DIR compound (D-2) 0.0030 mol per mol of i 11th layer; 1st protection J! 1 (pro-1) silver iodobromide (A
g11 mol% Average particle size 0.07. trm) il application 510. 5g/
n (gelatin layer containing ultraviolet absorbers UV-1 and UV-2.

12th layer; second protective layer (pro-2) gelatin layer containing polymethyl methacrylate particles (diameter 1.5 μm) In addition to the above composition, each layer contains a gelatin hardening agent (H-1
) and (H-2) and a surfactant were added.

The compounds contained in each layer of Sample 1 are as follows.

Sensitizing dye I; Thiandro-5,5'-dichloro-9-ethyl-3,3'-di(3-sulfopropyl)thiacarbocyanine hydroxide sensitizing dye ■; Thiandro-9-ethyl-3,3'- Di(3-sulfopropyl)-4゜5.4',5'-dibenzothiacarbocyanine hydroxide sensitizing dye ■; Thiandro-5,5'-diphenyl-9-
Ethyl-3,3'-di(3-sulfopropyl)oxacarbocyanine hydroxide sensitizing dye■tthiandro9-Ethyl-3,3'-di(3-sulfopropyl)-5゜6.5',6 '-Dibenzooxalpocyanine hydroxide sensitizing dye ■; Thiandro-3,3'-di(3-sulfoprobyl)-4,5-benzo-5'-methoxythiacyanine anhydroxide space below 4H9 C-1 ph M-1 Shil V-1 V-2 zHs ((CTo = CH30□CHz) 1ceI□SO
□(Clb)z) J(CHz)zsOJNext, each sample was prepared in the same manner except that the coupler was changed as shown in Table 3, and after each sample was wedge exposed with white light, the same procedure as in Example 1 was carried out. The remaining silver amount of each sample was treated in the same manner, and the desilvering rate was determined using sample 12 as a reference (0%) by fluorescent X-ray analysis.

However, the desilvering rate shall be the value determined by the following formula.

Desilvering rate (%) Residual charge in Sample 12 x 100 (Hereinafter blank) Table 3 As is clear from Table 3, compared to Comparative coupler B, the coupler of the present invention has a lower concentration than Comparative coupler B as shown in Examples 1 and 2. Sensitivity to,
It has been found that the coupler of the present invention not only exhibits good performance at the highest concentration, but also has excellent color development in fatigue bleaching solutions, and also has desilvering properties. Comparative coupler A is good in terms of desilvering properties, but it cannot be said to be sufficient in terms of sensitivity and maximum density.

[Effects of the present invention]

In the present invention, by using a cyan coupler represented by maximum [I], the obtained photographic image not only has excellent sensitivity and maximum density and good desilvering property, but also has the color of the present invention. The photosensitive material also provides photographic images with excellent color development in fatigue bleaching solutions.

Applicant: Konica Co., Ltd. Agent Patent attorney: Miki Nakajima Authorized proceedings by two other persons (spontaneous) 1. Indication of the case Patent Application No. 26974 of 1988 2. Name of the invention Silver halide color photographic light-sensitive material 3 , Relationship with the case of the person making the amendment Patent applicant address 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name (1
27) Konica Corporation Representative Keio Ide 4, Agent ° Address 2-42-1 Kabukicho, Shinjuku-ku, Tokyo 160
No. 1 No. 6, Detailed Description of the Invention Column 7 of the Specification Subject to Amendment, Contents of the Amendment As shown in Attachment 7, Contents of the Amendment 1) The odor of the compound No. 25 is amended in the table on page 21 of the specification.

2) Correct the odor of compound No. 27 in the table on page 21 of the specification.

3) The compound of comparative coupler A on page 42 of the specification is corrected as follows.

Claims (1)

[Scope of Claims] A silver halide color photographic light-sensitive material characterized by containing a cyan dye-forming coupler represented by the general formula [I]. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1 represents a substituted or unsubstituted alkyl group or aryl group. R_2 represents a monovalent organic group that can be substituted on the benzene ring. m represents an integer from 1 to 4, and m is 2
In the above case, R_2 may be the same or different. R_3 and R_4 represent a hydrogen atom, a substituted or unsubstituted alkyl group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group, and these may be the same or different, and R_3 and R_4 are mutually They may be connected to form a ring. J represents a divalent linking group. ]